合成天然气水合物实验研究

天然气水合物(NGH)是天然气与水在低温高压条件下形成的笼形物,亦称可燃冰.在冻土带和海洋中已发现大量天然气水合物,是清洁燃料的后续天然资源,但开采技术尚不成熟.由于1m~3天然气水合物在常温下可释放约164m~3的天然气和0.8m~3的水,因此合成天然气水合物,可实现天然气的固态运输,更便于在天然气汽车上的储存.本文介绍天然气水合物的基本性质及其人工合成研究取得的进展.     

天然气水合物形成的检测

研制的静态水合物试验装置采用可视观察的方法，可以快速确定天然气水合物的形成条件。动态天然气水合物试验装置在利用直接观测来判断水合物形成点的同时，通过监测装置转轮的扭距、试验介质的温度、压力、流速变化，综合判断天然气水合物的形成，此装置可以很好地模拟现场实际的天然气管输工况，实验结果与理论值及实际值差别较小。     

FID/TCD并联气相色谱法测定天然气水合物的气体组成

建立了一种氢火焰离子化检测器（FID）与热导检测器（TCD）并联检测的气相色谱分析技术。该方法一次进样,即可实现天然气水合物中C1~C6、CO2、H2S、O2+N216种气体成分的同时测定。实验优化了色谱柱、升温程序、柱流速、进样口温度、检测器温度、TCD参考气和尾吹气流速等仪器分析参数。在优化条件下,16种气体分子在实验浓度范围内线性关系良好,r2为0.99903~0.99998,方法检出限为0.0003~0.046mol/mol,相对标准偏差（n=6）为1.6%~5.0%。对祁连山冻土区、南海神狐海域、人工合成水合物样品的分析表明,该方法简便实用、灵敏可靠,可满足天然气水合物气体组成的分析要求。     

Initial estimation of hydrate formation temperature of sweet natural gases based on new empirical correlation

Production,processing and transportation of natural gases can be significantly affected by clathrate hydrates.Knowing the gas analysis is crucial to predict the right conditions for hydrate formation.Nevertheless,Katz gas gravity method can be used for initial estimation of hydrate formation temperature (HFT) under the circumstances of indeterminate gas composition.So far several correlations have been proposed for gas gravity method,in which the most accurate and reliable one has belonged to Bahadori and Vuthaluru.The main objective of this study is to present a simple and yet accurate correlation for fast prediction of sweet natural gases HFT based on the fit to Katz gravity chart.By reviewing the error analysis results,one can discover that the new proposed correlation has the best estimation capability among the widely accepted existing correlations within the investigated range.     

天然气吸附储存的进展

天然气作为绿色替代能源,其吸附储存在移动应用方面至关重要,目前广泛关注的3种吸附储存技术存在着各自的优势和劣势。本文综述了多孔碳质吸附剂、金属有机框架吸附剂和吸附天然气水合物的研究进展,总结了天然气吸附性能的主要影响因素和改进途径,介绍了超临界吸附理论和分子模拟预测的相关工作,比较了3种技术的优劣及相关发展趋势。     

Hydrate capture CO2 from shifted synthesis gas,flue gas and sour natural gas or biogas

CO₂ capture by hydrate formation is a novel gas separation technology, by which CO₂ is selectively engaged in the cages of hydrate and is separated with other gases, based on the differences of phase equilibrium for CO₂ and other gases. However, rigorous temperature and pressure, high energy cost and industrialized hydration separator dragged the development of the hydrate based CO₂ capture. In this paper, the key problems in CO₂ capture from the different sources such as shifted synthesis gas, flue gas and sour natural gas or biogas were analyzed. For shifted synthesis gas and flue gas, its high energy consumption is the barrier, and for the sour natural gas or biogas (CO₂/CH₄ system), the bottleneck is how to enhance the selectivity of CO₂ hydration. For these gases, scale-up is the main difficulty. Also, this paper explored the possibility of separating different gases by selective hydrate formation and reviewed the progress of CO₂ separation from shifted synthesis gas, flue gas and sour natural gas or biogas.     

用分子动力学模拟天然气水合物的抑制效应

用分子动力学模拟方法确定了结构H型(SH)天然气水合物的稳定晶体生长面为(001), 系统研究了277 K时三种动力学抑制剂对此晶面的影响. 模拟显示抑制剂中的氧与表面水分子形成氢键, 从而破坏原有的稳定结构, 造成水合物笼型结构坍塌, 达到抑制水合物形成的效果. 比较三种不同动力学抑制剂对SH的抑制效果得出: PVCap＞PEO＞PVP. 在此基础上研究了PVCap对天然气水合物结构I型(SI), 结构II型(SII)和SH三种不同晶型的抑制效应. 模拟发现抑制效果的次序为: SH＞SI＞SII.     

GC–IRMS测定白色块状天然气水合物气体中的碳氢同位素

研究了GC–IRMS联用技术测定烃类气体碳氢稳定同位素的方法。利用气相色谱仪将烃类气体各组分分开,通过高温燃烧/裂解转化为CO2和H2,然后导入MAT–253稳定同位素质谱仪进行测试。用该方法测试的标准甲烷气体碳、氢同位素值和其标定值一致,测定结果的相对标准偏差分别为0.222‰和0.950‰。用该法测定了广东沿海珠江口盆地东部海域首次钻获的高纯度天然气水合物样品所释放的烃类气体碳氢稳定同位素值,其中δ13C为–69.78‰(VPDB),δD为–184.4‰(VSMOW)。GC–IRMS法精确度高,可用范围广,适用于海洋天然气水合物样品所释放烃类气体碳氢同位素的测定。     

A Study on Inhibitors for the Prevention of Hydrate Formation in Gas Transmission Pipeline

Gas Hydrate is usually formed during the transportation and treatment of oil and gas, resulting in the plugging of gas pipeline and equipment. Three thermodynamic calculation formulas are analyzed to deal with this problem. The lowering of the freezing point of the inhibitors AT is used to calculate the formation temperature of natural gas hydrates. This is considered to be a good approach because it is not limited by what kind and what concentration of inhibitors one uses. Besides, the rate of lowering of the freezing point could be easily measured. The result of testing methanol and mono-ethylene glycol in a reactor shows that adding 10% inhibitors to the reactor can prevent the hydrates formation. Kinetic inhibitors are favored in the present research. They are divided into two types, polymer and surface-active agents. Their characteristics, mechanisms, and application prospect are separately discussed. Polymer inhibitors exhibit better efficiency. The result of field application of VC-713 inhibiter is also given in this article. In practice, the combination of thermodynamic inhibitors and kinetic inhibitors gives better result.     

天然气水合物分解热的确定

利用可视化高压流体测试系统研究了6个体系（甲烷、合成天然气、甲烷－环己烷、甲烷－环戊烷、甲烷－甲基环己烷（MCH）、合成天然气－甲基环己烷）水合物的形成条件,根据水合物相平衡数据应用Clausius-Clapeyron方程计算了Ⅰ型、Ⅱ型和H型水合物的分解热,结果表明水合物分解热与填充水合物晶格的气体分子直径有关。     

天然气水合物的导热系数

分析介绍了关于水合物导热系数类玻璃体变化规律的三种模型及其相关测试手段、样品制备方法和测试结果。针对物性和测试手段的特点，笔者指出在制备测试样品的时候就要注意其生成品质。最后对比了国外相关实验结果和本实验室对制冷剂水合物的测量结果。     

气相色谱法分析天然气的组成

摘要：使用一种新型气相色谱仪准确分析天然气的组成。以天然气标准物质为样品,对色谱柱、阀切换时间、柱箱温度控制等方面进行优化,建立了良好的色谱分析条件,利用外标法确定了天然气中各组分的保留时间。在同一最佳色谱分析条件下,标准物质中各组分连续检测两次测定结果的差值不大于0.11%,满足国家标准GB/T 13610-2014的要求,且与标准值相对误差的绝对值小于5%。测定结果组分含量应与所用标准物质浓度的单位保持一致。所建立分析方法准确可靠,适用于天然气的常规分析。     

Measurement and modeling of the effective thermal conductivity for porous methane hydrate samples

The effective thermal conductivities of gas-saturated porous methane hydrates were measured by a single-sided transient plane source (TPS) technique and simulated by a generalized fractal model of porous media that based on self-similarity.The density of porous hydrate,measured by the volume of the sample in the experimental system,was used to evaluate the porosity of methane hydrate samples.The fractal model was based on Sierpinski carpet,a thermal-electrical analogy technique and one-dimensional heat flow assumption.Both the experimental and computational results show the effective thermal conductivity of methane hydrate decreases with the porosity increase.The porosity of 0.3 can reduce the thermal conductivity of the methane hydrate by 25%.By analysis of the experimental data and the simulative result,the optimized thermal conductivity of the zero-porosity methane hydrate is about 0.7 W m-1K-1.     

Phase Diagram of the Xe–H2O System up to 15 kbar

The phase equilibria in the Xe–H2O system have been studied by the DTA technique under hydrostatic pressures up to 15 000 bar in a temperature range from -25 °C to 100 °C. We have shown that the cubic structure I xenon hydrate forming at ambient pressure does not undergo any phase transitions under the conditions studied. The temperature of its decomposition into water solution and gas (fluid) increases from 27 °C at 25 bar to 78.2 °C at 6150 bar. At higher pressures the hydrate decomposes into water solution and solid xenon. In the temperature range from 6800 to 9500 bar the decomposition temperature (79.0–79.5 °C) is practically independent of pressure, while further pressure increase results in a slow decrease to 67 °C at 15 000 bar.     

Gas hydrate fast nucleation from melting ice and quiescent growth along vertical heat transfer tube

Gas hydrates, or clathrate hydrates, are ice-likecrystal, composed of host lattice (cavities) formed byhydrogen-bonded water molecules, and other guestmolecules called guest molecules. The guest mole-cules act with host lattice in weak van der Waals force…     

Depressurization of natural gas hydrates in berea sandstone cores

D. W. Davidsonet al. [7] were among the first to recognize significant deposits of natural gas clathrate hydrates in the Western Hemisphere. This work discusses the recovery of gas from such deposits, through laboratory measurement and modeling of a depressurization scheme. The work provides a determination of the volume of gas produced and the position of the hydrate interface, as a function of time when a hydrate-containing core is depressurized. A moving boundary model is shown to provide a satisfactory fit to hydrate dissociation measurements. Qualitative information is provided concerning hydrate formation in Berea Sandstone cores.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Study on the recovery of hydrogen from refinery (hydrogen + methane) gas mixtures using hydrate technology

A novel technique for separating hydrogen from (H2 CH4) gas mixtures through hydrate formation/dissociation was proposed. In this work, a systematic experimental study was performed on the separation of hydrogen from (H2 CH4) feed mixtures with various hydrogen contents (mole fraction x = 40%-90%). The experimental results showed that the hydrogen content could be enriched to as high as ~94% for various feed mixtures using the proposed hydrate technology under a temperature slightly above 0℃ and a pressure below 5.0 MPa. With the addition of a small amount of suitable additives, the rate of hydrate formation could be increased significantly. Anti-agglomeration was used to disperse hydrate particles into the condensate phase. Instead of preventing hydrate growth (as in the kinetic inhibitor tests), hydrates were allowed to form, but only as small dispersed particles. Anti-agglomeration could keep hydrate particles suspended in a range of condensate types at 1℃ and 5 MPa in the water-in-oil emulsion.