Evaluation on the natural gas hydrate formation process

Gas hydrates have endowed with great potential in gas storage,and rapid formation of gas hydrates is critical to use this novel technology.This work evaluated the natural gas hydrate formation process,which was compared from six parameters,including conversion of water to hydrate,storage capacity,the rate of hydrate formation,space velocity(SV)of hydrate reaction,energy consumption and hydrate removal.The literature was selected by analyzing and comparing these six parameters mentioned above,meanwhile placing emphasis on the three parameters of storage capacity,the rate of hydrate formation and space velocity of hydrate reaction.Through analysis and comparison,four conclusions could be obtained as follows.Firstly,the overall performance of the stirring process and the spraying process were better than other processes after analyzing the six parameters.Secondly,the additive types,the reactor structure and the reactor size had influence on the natural gas hydrate formation process.Thirdly,the energy consumption via reciprocating impact in the hydrate formation process was higher than that via stirring,spraying and static higee.Finally,it was one key for hydrate removal to realize the hydrate industrial production.

EXPERIMENTAL STUDY OF HFC-134a GAS HYDRATE FORMATION PROCESS

Refrigerant gas hydrates have brilliant prospects as cool storage material of air-conditioning system. In this paper, when the ratio of the weight of HFC-134a to that of water is 2. 17%, systematic experiments have been carried out on the formation process of the HFC-134a gas hydrate including of the phase equilibrium, the influence of supercooling degree, and the influence of agitation. The results indicate that the critical decomposition temperature and the critical decomposition pressure of R134a hydrate is 283.4K and 414K respectively, the formation of gas hydrate was promoted with increasing the supercooling degree and the agitation. However, it is desired that the supercooling degree is smaller.Therefore, it is important problem that the study of optimum of supercooling degree for cool storage system.

VISUAL OBSERBATION OF HCFC141b GAS HYDRATE FORMATION/DECOMPOSITION PROCESS OUTSIDE OF A TUBE

In order to design a kind of heat exchanger suitable to the indirect-touched gas hydrate cool storage vessel, a visual observation of HCFC141b gas hydrate formation/decomposition process was presented through a self-designed small-scale visualization apparatus of gas hydrate cool storage. Based on the shooted photos and recorded temperatures, the formation/decomposition process of HCFC141b are described, some characteristics are concluded, and some suggestions of designing heat exchanger are indicated according to the specific characteristics of HCFC141b gas hydrate formation/decomposition process.

Experimental Study on Preparation of Natural Gas Hydrate by Crystallization

In this paper, the saturated solution crystallization method is proposed to promote the formation of hydrate by means of the known similarities between the hydrate formation process and the crystallization process. In this method,adding the second phase crystals was used to replace the spontaneous formation of hydrate crystal nuclei to form hydrate.The effects of saturated Na_2SO_4, MgSO_4, NH_4HCO_3 and CuSO_4 solutions on the formation rates of natural gas hydrate and gas storage capacity were investigated. The results showed that the saturated solution had an influence on the hydrate formation process. Under the given experimental conditions, the saturated Na_2SO_4 solution showed a highest increase in the hydrate formation rate, and the average hydrate formation rate in its presence was 11.8 times higher than that obtained in the deionized water. Moreover, the largest formation rate of gas hydrates observed in the saturated Na_2SO_4 solution was 386 times bigger than that in the deionized water, and the gas storage capacity increased by 10 times. In addition, the average hydrate formation rate in the saturated Mg SO_4 solution was faster than that in water by 20 times. The largest formation rate of gas hydrates in the saturated MgSO_4 solution was 165 times faster than that obtained in the deionized water, and the gas storage capacity increased by 6.2 times. The saturated NH_4HCO_3 and saturated CuSO_4 solutions also influenced the formation process of hydrate. Therefore, the crystallization method of saturated solution can be used to achieve a highefficiency preparation of natural gas hydrates, which provides theoretical guidance for the storage of natural gas in the form of hydrate.

Influences of different types of magnetic fields on HCFC-141b gas hydrate formation processes

In this study, visualizations and experiments are carried out on the influence of static and rotating magnetic fields on the characteristics of HCFC-141b gas hydrate formation, such as crystallization form, formation temperature and induction time. It has been found that a proper rotating magnetic field can considerably improve the low-pressure gas hydrate formation process, especially in increasing the formation temperature and shortening the induction time. The mor- phology of the gas hydrate formation appears rather complex and compact. However, a proper static magnetic field can make the gas hydrate crystal more organized, which will be benefit to heat transfer.

HFC-134a refrigerant gas hydrate formation process and RIN model

In this paper, the macroscopic visualization experiments of HFC-134a refrigerant gas hydrate formation are investigated. According to the macroscopic photos and Mori’s microscopic photos of HFC-134a hydrate formation process, the mechanism of gas hydrate formation is analyzed. A random inducement nucleation model is presented to describe the hydrate formation process. The factors affecting the fractal growth dimension in the model, such as step, branch increment and angle, are discussed.

Analysis of sensitivity to hydrate blockage risk in natural gas gathering pipeline

During the operational process of natural gas gathering and transmission pipelines,the formation of hydrates is highly probable,leading to uncontrolled movement and aggregation of hydrates.The continuous migration and accumulation of hydrates further contribute to the obstruction of natural gas pipelines,resulting in production reduction,shutdowns,and pressure build-ups.Consequently,a cascade of risks is prone to occur.To address this issue,this study focuses on the operational process of natural gas gathering and transmission pipelines,where a comprehensive framework is established.This framework includes theoretical models for pipeline temperature distribution,pipeline pressure distribution,multiphase flow within the pipeline,hydrate blockage,and numerical solution methods.By analyzing the influence of inlet temperature,inlet pressure,and terminal pressure on hydrate formation within the pipeline,the sensitivity patterns of hydrate blockage risks are derived.The research indicates that reducing inlet pressure and terminal pressure could lead to a decreased maximum hydrate formation rate,potentially mitigating pipeline blockage during natural gas transportation.Furthermore,an increase in inlet temperature and terminal pressure,and a decrease in inlet pressure,results in a displacement of the most probable location for hydrate blockage towards the terminal station.However,it is crucial to note that operating under low-pressure conditions significantly elevates energy consumption within the gathering system,contradicting the operational goal of energy efficiency and reduction of energy consumption.Consequently,for high-pressure gathering pipelines,measures such as raising the inlet temperature or employing inhibitors,electrical heat tracing,and thermal insulation should be adopted to prevent hydrate formation during natural gas transportation.Moreover,considering abnormal conditions such as gas well production and pipeline network shutdowns,which could potentially trigger hydrate formation,the installation of methanol injection connectors remains necessary to ensure production safety.

Formation process and fractal growth model of HCFC-141b refrigerant gas hydrate

The microscopic visualization experiment on the formation process of HCFC-141b refrigerant gas hydrate has been investigated, and the morphological photos of hydrate formation process have been obtained. The results show that gas hydrate originally nucleated on the interface of refrigerant HCFC-141b and water under the condition of supercooling, then the hydrate grows continually due to the inducement of formed nucleation and diffusion of refrigerant. The formation of gas hydrate presents an arboreous phenomenon. The fractal dimension of the hydrate formation morphology on different stages was calculated. The calculating results indicate that the initial stage of the hydrate formation belongs to fractal growth, and the dimension is about 1.52. Based on the fractal theory, an RIN-DLA (random inducement nucleation-diffusion limited aggregation) model for the HCFC-141b hydrate growth was developed. The hydrate growth process was simulated with the developed model, and the fractal dimension for the simulated morphology is well compared with that from the experiment.

Experimental Study on the Characteristics of CO_2 Hydrate Formation in Porous Media below Freezing Point

Porous medium has an obvious effect on the formation of carbon dioxide hydrate. In order to study the characteristics of CO2 hydrate formation in porous medium below the freezing point, the experiment of CO2 hydrate formation was conducted in a high-pressure 1.8-L cell in the presence of porous media with a particle size of 380 μm, 500 μm and 700 μm, respectively. The test results showed that the porous medium had an important influence on the process of CO2 hydrate formation below the freezing point. Compared with porous media with a particle size of 500 μm and 700 μm, respectively, the average hydrate formation rate and gas storage capacity of carbon dioxide hydrate in the porous medium with a particle size of 380 μm attained 0.016 14 mol/h and 65.094 L/L, respectively. The results also indicated that, within a certain range of particle sizes, the smaller the particle size of porous medium was, the larger the average hydrate formation rate and the gas storage capacity of CO2 hydrate during the process of hydrate formation would be.

Growth kinetics of hydrate formation from water–hydrocarbon system

Gas hydrates have drawn global attentions in the past decades as potential energy resources.It should be noted that there are a variety of possible applications of hydrate-based technologies,including natural gas storage,gas transportation,separation of gas mixture,and seawater desalination.These applications have been critically challenged by insufficient understanding of hydrate formation kinetics.In this work,the literatures on growth kinetic behaviors of hydrate formation from water-hydrocarbon were systematically reviewed.The hydrate crystal growth,hydrate film growth and macroscopic hydrate formation in water system were reviewed,respectively.Firstly,the hydrate crystal growth was analyzed with respect to different positions,such as gas/liquid interface,liquid–liquid interface and gas–liquid–liquid system.Secondly,experimental and modeling studies on the growth of hydrate film at the interfaces between guest phase and water phase were categorized into two groups of lateral growth and thickening growth considering the differences in growth rates.Thirdly,we summarized the promoters and inhibitors reported(biological or chemical,liquid or solid and hydrophobic or hydrophilic)and analyzed the mechanisms affecting hydrate formation in bulk water system.Knowledge gaps and suggestions for further studies on hydrate formation kinetic behaviors are presented.

压力扰动对丙烷水合物生成过程的影响

气体水合物的快速生成与分解是水合物技术广泛工业化应用的关键,因而进行气体水合物生成过程和生成特性的研究具有重要的意义,但目前关于气体水合物生成过程的研究主要集中在温度梯度、降温速率、温度扰动等方面,而针对压力扰动对气体水合物生成过程影响的研究还较鲜见。为此,进行了压力扰动条件下C3H8水合物的生成实验,研究了压力扰动对C3H8水合物静态生成过程的影响。结果表明:1与无压力扰动的条件相比,压力扰动有效地促进了C3H8水合物的生成过程,提高了C3H8水合物的生成速率和生成量;2在100h的静态水合物生成过程中,压力扰动条件下C3H8水合物的平均生长速率达到了0.052 6mm/h,是无压力扰动条件下C3H8水合物平均生长速率(0.013 2mm/h)的4倍;3静态体系中水合物的生成过程比较困难且水合反应不完全,在压力扰动条件下,0.1MPa的压力差可导致0.4kJ/mol的生成驱动力,可使停滞的水合反应重新开始。

介观孔隙中天然气水合物生成过程模拟

目前,对沉积物中天然气水合物(以下简称水合物)的生成过程研究大部分集中在实验研究以及水合物生成的本征动力学方面,在孔隙尺度方面缺乏对水合物生成过程的全方位考虑。为此,从介观角度出发,结合实验模拟结果,研究了沉积物孔隙中甲烷及二氧化碳水合物的生成过程。首先对甲烷水合物和二氧化碳水合物在沉积物中的生成过程进行了实验模拟(沉积物样品选用南海浅表层沉积物,粒径为60～100目),结果表明:水合物在沉积物孔隙中的生成过程比较平缓,体系温度基本没有大的变化;在初始阶段水合物生成量比较大,随着反应的进行,水合物生成速率逐渐减小。在实验的基础上,以孔隙水中溶解气体的浓度为变量,从介观角度数值模拟了甲烷水合物和二氧化碳水合物在沉积物中的生成过程,并以单个沉积物孔隙空间的水合物生成表征沉积物体系内水合物的生成特性。结论认为:沉积物颗粒堆积孔隙内部的水合物先在沉积物壁面处生成,然后水合物层逐渐加厚,向孔隙中心生长,水合物呈层状生成,最后填满整个沉积物颗粒孔隙;伴随着水合物的生成,沉积物体系孔隙率降低。通过模拟计算得到的水合物转化率与实验结果进行对比,其误差范围介于3%～7%,表明该模型具有较强的可靠性。

混合气体水合物结晶生成过程及其反应速度的实验研究

对混合制冷剂气体水合物HCFC1 41b/HFC1 5 2a在不同外部条件下的结晶生成速度进行了实验研究 ,通过数据分析得到了水合物结晶生成速度和冷却介质温度、扰动速度。

吸水性涂层在霜层生长初期的抑霜

研究吸水性涂层对霜层生长过程的影响,以寻求抑制结霜的有效方法.通过自行设计的试验设备对吸水性涂层表面上霜层生长特性进行试验研究,获取了不同时段霜层的显微图片,采用数字图像处理方法对其分析,与无涂层的铜表面进行对比.结果表明,吸水性涂层使得结霜时间推迟,霜层高度下降,冰晶体分布稀疏.此外霜层生长初期冰晶体的结构发生了变化,晶体呈倒立状,在某个时段内持续这种状态.对列固含率的分析表明,吸水性涂层的表面在初期有些位置冰晶体含量较高,但有些位置则接近于零,这样的霜层在生长初期甚至加强了热传递.最后通过对比不同表面霜层高度随时间的变化规律发现:吸水性涂层在初期抑霜效果最好,随着时间的推移其抑霜能力逐渐下降.

饱和溶液对天然气水合物影响的实验研究

水合物生成速度及储气量严重制约着天然气以水合物形式储运的发展。为提高其生成速度及储气量,采用饱和溶液提供晶种代替水合物晶核自发形成的方式,研究了不同饱和度CuSO_4溶液、MgSO_4溶液及去离子水在8.45MPa,温度分别为3,5,8℃条件下对天然气水合物生成速度及储气量的影响。由结果可知:饱和溶液可以促进天然气水合物生成。相同实验条件下,CuSO_4饱和溶液生成水合物的储气量是去离子水的7倍,MgSO_4饱和溶液生成水合物的储气量是去离子水的7.2倍,水合物在饱和溶液中的生成速度也明显提高。饱和溶液中天然气水合物生成的初始阶段主要受饱和溶液结晶作用影响,降低温度可以改变水合物的平衡压力,影响水合物的平均生成速度,但对水合物初期的生成速度影响不大。

饱和盐溶液对甲烷水合物生成影响的实验研究

甲烷水合物被认为是一种更好的天然气运输和储存的媒介,水合物的快速生成是大规模实施水合物储运天然气技术的基本要求。为了促使水合物更好地适应未来的工业应用,在水合物生成过程中加入一定量的表面活性剂是促进水合物生成的有效手段之一。研究了单一型饱和盐溶液体系、单一型饱和盐溶液加SDS体系和复配型饱和盐溶液加SDS体系在压力为6 MPa,温度为2℃条件下对甲烷水合物生成速率的影响,并得到相应的实验数据。由结果可知,压力为6 MPa,温度为2℃条件下的饱和MgSO_(4)溶液、饱和FeSO_(4)溶液、饱和CuSO_(4)溶液与纯水相比均可大幅降低实验相平衡压强,增加气体消耗量,促进甲烷水合物的生成,且促进效果由弱到强;SDS对水合物的生成产生动力学影响,结果表明SDS缩短了诱导时间,加快了水合物的生成速率,且与饱和盐溶液的促进效果可以累加,两者配合使用可以达到更好的促进效果。

多孔介质水合物中储存二氧化碳的实验研究

为了研究多孔介质中CO_2水合物的生成速率和储气量,利用1.8 L的水合反应釜研究了孔隙为13.8 nm和26.7nm的石英砂中CO_2水合物的生成过程,结果表明:孔径为26.7 nm石英砂中,1 m^3的石英砂可以储存64.4 m^3标准状况的二氧化碳气体,平均生成速率为0.001703 mol/min;孔径为13.8 nm石英砂中,1 m^3的石英砂可以储存118.8m^3标准状况的二氧化碳气体,平均生成速率为0.001803 mol/min;在多孔介质孔径范围为13.8 nm至26.7 nm之间时,粒径越小,储气量越大。

不同体系中丙烷水合物的生成过程

为了解C3H8水合物的生成特性，加快其生成过程，在可视化实验装置上分别研究了在纯水、十二烷基硫酸钠（SDS，浓度1950×10^-6）和十二烷基苯磺酸钠（SDBS，浓度400×10^-6）中c3H8水合物的诱导时间、生成速率等．结果表明，在0．8-1．2℃温度范围内，纯水体系中C3H8水合物的诱导时间最长，SDS体系中C3H8水合物的生成速率最快，达0．0224mm／h．与纯水体系相比，表面活性剂明显缩短了C3H8水合物的诱导时间，提高了其生成速率．

压力扰动促进丙烷水合物生长过程的研究

为了研究气体水合物的快速生成方法,可视化实验研究了压力扰动对丙烷水合物生成过程的促进作用,结合丙烷水合物的生成驱动力计算,分析了静态条件下纯水中丙烷水合物层的厚度、生长速率、水合物生成驱动力等水合反应参数,结果表明:在压差为0.1 MPa的压力扰动下,原本停滞35 h的水合反应重新开始生成水合物,气液界面处水合物层厚度2 h内以0.5 mm/h的速率呈线性增长,2 h后生长速率显著减小,在压力扰动后的175 h内,系统平均生长速率达到0.04 mm/h。