Determination of atomistic deformation of tricalcium silicate paste with high-volume fly ash

We examined the effect of incorporating high-volume fly ash on the atomic arrangement and interatomic deformation behavior of calcium silicate hydrates in tricalcium silicate paste upon exposure to external forces. The interatomic structural changes and strains under compressive load were assessed using synchrotron in situ high-energy X-ray scattering-based atomic pair distribution function analysis. Three different types of strains, which were (a) macroscopic strains from gauges on the surfaces of specimen, (b) strains in a reciprocal space (Bragg peak shift), and (c) strains in real space (PDF peak shift), were compared to each other. All monitored and calculated strains for tricalcium silicate-fly ash (50 wt% fly ash) paste were compared with the counterparts of the pure tricalcium silicate paste. Pair distribution function analysis in the range of r < 10 Å indicated that the atomic arrangement of tricalcium silicate-fly ash was similar to that of synthetic calcium silicate hydrates followed by that of pure tricalcium silicate paste. Moreover, the pair distribution function refinement results revealed that the calcium silicate hydrate structure in tricalcium silicate-fly ash paste was similar to tobermorite 11 Å, unlike that in pure tricalcium silicate paste. The interatomic strain of tricalcium silicate-fly ash in the real space (r < 20 Å) was smaller than that of tricalcium silicate under compression, which suggested that the incompressibility of calcium silicate hydrates at atomistic scale was enhanced by the incorporation of fly ash into it. This was likely to be caused by the increased silicate polymerization of calcium silicate hydrates, which was attributed to the increase in the amount of silicate in their structure via the addition of fly ash.     

电阻层析成像技术及其在水合物开采模拟实验中的应用

电阻层析成像是一种可视化的无损测量手段,可以为天然气水合物开采过程室内模拟实验提供有效的监测途径。首先介绍了电阻层析成像技术的工作原理、发展历程与应用现状,重点对电阻层析成像技术在天然气水合物室内模拟实验方面的主要应用进行了综述,并分析了存在的问题,在此基础上给出了解决问题的建议,为下一步开展水合物的电阻层析成像实验提供参考。     

海洋天然气水合物储层拉削开采新方法及可行性分析

针对深水浅层非成岩天然气水合物借鉴刨煤机刨削采煤过程提出一种新的拉削开采方法，参照拉刀结构特点设计了一种集开采、收集和输送为一体的拉削管。建立了拉削开采三维模型，对其工作原理和工作步骤进行了说明。用有限元仿真对采空区和拉削管受力进行了分析。结果表明，岩土力学仿真下采空区开采半径和开采角度的增大都会引起剪切应力的增加，最大剪切应力发生在采空区上部的起始位置和终止位置；在不发生剪切破坏的采空区中选择体积较大者作为理想采空区，估算出拉削开采方法的日产气量为142000 m3，具有应用潜力；开采工况下，拉削管的最大等效应力小于管材的屈服极限，表明开采过程中拉削管处于弹性形变，满足方法需求。     

基于宽频复电阻率的含黏土沉积物中水合物饱和度计算方法

天然气水合物沉积物中的黏土成分显著影响沉积物的电学特性以及水合物饱和度的计算模型。以自主设计开发的复电阻率参数测量装置为实验平台,在20 Hz ~ 100 kHz频率范围内测试了黏土条件下含水合物海沙体系的复电阻率,分析了复电阻率的频散特性、黏土影响以及主导的电极化机制,利用泥质修正Archie公式建立了基于宽频复电阻率的水合物饱和度计算模型。研究结果表明：（1）含水合物海沙体系的复电阻率呈现出显著的频散特性,双电层极化和界面极化分别是20 Hz ~ 1 kHz和1 ~ 100 kHz频段主导的极化机制;（2）黏土颗粒表面的双电层发生形变增强了含水合物沉积物双电层极化作用,提高了复电阻率相角和虚部的绝对值;（3）在20 Hz ~ 100 kHz频率范围内泥质修正Archie公式岩性系数较为稳定,而胶结指数和饱和度指数与测试频率之间的关系在20 Hz ~ 1 kHz和1 ~ 100 kHz频段差异显著,因此应分频段建立水合物饱和度计算模型。本研究为探讨含水合物沉积物的低频电学特性和建立含黏土沉积物中水合物饱和度计算模型提供了新的途径。     

Quantitative analysis of CO2 hydrate formation in porous media by proton NMR

Gas hydrate is a nonstoichiometric crystal compound formed from water and gas. Most nonvisual studies on gas hydrate are unable to detect how much water is converted to hydrates, and thus, the hydrate stoichiometry calculations are inaccurate. This study investigated the CO₂ hydrate formation process in porous media directly and quantitatively. The characteristics of the time-variable consumption of hydrate formation indicated a two-stage formation, hydrate enclathration and continuous occupancy. The enclathration stage occurred in the first 20 min of the formation when considerable heat is released. The continuous occupancy stage lasted longer than the hydrate enclathration because the empty cages in previously formed hydrates would also be occupied. The higher formation pressures can accelerate water consumption and increase cage occupancy. The compositions of completely formed CO₂ hydrates at 2.7, 3.0, and 3.3 MPa and 275.15 K were determined as CO₂·6.90H₂O, CO₂·6.70H₂O, and CO₂·6.49H₂O, respectively.     

多相流管输体系中水合物沉积机理研究进展

国内外对多相流管输体系中水合物沉积的研究虽然很多，但水合物沉积机理仍有待进一步研究。本文根据水合物沉积实验开展条件的不同，将多相流管输体系分为气体主导体系、油基体系、部分分散体系、水主导体系，总结了各体系的水合物沉积的主要机理，并提出了未来的发展方向。管输体系中水合物沉积机理包括水润湿沉积表面、水合物颗粒聚并、水合物的管壁膜生长、水合物颗粒的管壁粘附和水合物的颗粒着床沉积等。大多数学者认为：水合物的管壁膜生长是气体主导体系水合物沉积的主要机理；油基体系水合物沉积的主要机理是水合物颗粒的着床沉积；而部分分散体系和水主导体系的水合物沉积机理尚无统一定论，需进一步研究。多相流管输体系中水合物沉积研究未来的发展方向如下。①搭建全透明的流动环路，观测水合物在管路内实际的形成过程及沉积过程，对水合物沉积机理进行深入研究。②量化研究油水分层、油包水(或水包油)乳状液、自由水层对水合物沉积、堵塞的影响。③对于气体主导体系，除环状流和分层流外，有必要对段塞流、气泡流等其他常见的流型下沉积机理进行研究，重点在于开发一个综合模型来描述水合物沉积过程。④对于水主导体系，水合物形成过程出现的油水破乳的具体机理应是未来水合物沉积过程进行定量研究的方向。⑤国内外对垂直管、弯管及管阀件处水合物沉积堵塞理论研究较少，未来应着重这方面。     

Reactivity of industrial wastes as measured through ICP-OES: A case study on siliceous Indian biomass ash

An untapped source of amorphous SiO₂, industrially generated Indian biomass ash (SA)—90% amorphous, with composition of ~60% SiO₂ and ~20% unburnt carbon—can be used to produce cementitious and alkali-activated binders. This study reports dissolution of amorphous Si from SA in 0.5 mol/L and 1 mol/L aqueous NaOH, with and without added Ca(OH)₂, at SA:Ca(OH)₂ wt% ratios of 100:0, 87.5:12.5, and 82.5:17.5. Monitoring of elemental dissolution and subsequent/simultaneous product uptake by ICP-OES offers an effective process for evaluating utility of industrial wastes in binder-based systems. After 28 days in solution, up to 68% of total Si is dissolved from SA in 1 mol/L NaOH, with values as much as 38% lower in the presence of Ca(OH)₂, due to the formation of tobermorite-like C-S-H. FTIR, ²⁹Si MAS-NMR, and XRD are used to characterize solid reaction products and observe reaction progress. Product chemistries calculated from ICP-OES results and verified by selective dissolution in EDTA/NaOH—namely, Ca/Si of 0.6-1 and Na adsorption of 1-2 mmol/g—are found to be consistent with those indicated by aforementioned techniques. This indicates the efficacy of ICP-OES in estimating product chemistry via such a methodology.     

Improving the gas recovery and separation efficiency of a hydrate-based gas separation

Efficient gas recovery and separation in a hydrate-based system was investigated for a model gaseous mixture of R22 and nitrogen. The formed hydrate settled in the recovery vessel; excess water was recycled and the hydrate was subsequently decomposed by releasing pressure from the vessel. The gas uptake rate of R22 gas from the vapor phase and the gas recovery rate from the hydrate were determined from hydrate formation and decomposition, respectively. The gas recovery rate of R22 gas gradually increased with time. On the contrary, the nitrogen gas recovery rate was a maximum in the initial stage of hydrate decomposition. A high separation factor (S.F.) was achieved by first separating the N₂-rich gas generated during initial hydrate decomposition. An efficient hydrate-based gas separation and recovery process is proposed.     

二氧化碳水合物浆在圆管中的流动特性

实验研究了固相分数为8.2%～23.1%的CO₂水合物浆在内径为8 mm的圆管中的流动特性。结果发现水合物浆在管内的流动压降随着流速的增加而增大。当流速低于0.60 m·s^-1时,浆体流变指数小于1,且随着固相体积分数的增大而减小,CO₂水合物浆为H-B流体,其表观黏度随着流速的增大而减小,呈剪切变稀特性。剪切速率为600 s^-1时,CO₂水合物浆的表观黏度为8.5～10.6 mPa·s。实验得到了CO₂水合物浆的流变特征参数及其流变方程,可为CO₂水合物浆的流动及其应用研究提供理论指导。