Nucleation of methane hydrate and ice in emulsions of water in crude oils and decane under non-isothermal conditions

Achievable supercooling for the formation of methane hydrate from water emulsions was studied in seven different crude oils and in decane. The experiments were performed under constant rate cooling from + 20 to-15 °C and a pressure of methane of 12 MPa. It was demonstrated that the shapes and positions of the resulting survival curves depend on the density, viscosity and dispersive power of oil samples used in the experiments, as well as on the degree of oil oxidation. In addition, results of the experiments on ice freezing under the same emulsions are presented. The results obtained in the work allowed us to discuss the possibility and features of primary and secondary nucleation of the hydrate and ice in the systems under consideration.     

甲烷水合物在纯水和抑制剂体系中的生成动力学

Kinetic data of methane hydrate formation in the presence of pure water,brines with single salt and mixed salts,and aqueous solutions of ethylene glycol(EG) and salt EG were measured.A new kinetic model of hydrate formation for the methane water systems was developed based on a four-step formation mechanism and reaction kinetic approach.The proposed kinetic model predicts the kinetic behavior of methane hydrate formation in pure water with good accuracy.The feasibility of extending the kenetic model of salt(s) and EG containing systems was explored.     

孔隙尺寸、盐度和气体组分对水合物相平衡的影响(英文)

An experimental device was set up to study the hydrate formation conditions. Effects of pore size, salinity, and gas composition on the formation and dissociation of hydrates were investigated. The result indicates that the induction time for the formation of hydrates in porous media is shorter than that in pure water. The decrease in pore size, by decreasing the size of glass beads, increases the equilibrium pressure when the salinity and temperature are kept constant. In addition, higher salinity causes higher equilibrium pressure when the pore size and temperature are kept constant. It is found that the effects of pore size and salinity on the hydrate equilibrium are quite different. At lower methane concentration, the hydrate equilibrium is achieved at lower pressure and higher temperature.     

流动体系中的水合物成核诱导期研究

The appearance of turbidity due to large numbers of critical size hydrate nuclei may significantly affect the outgoing light intensity and the flow resistance in the pipe loop. The induction period of hydrate formation was determined by analyzing the experimental data——either based on the shading ratio data of laser detector or based on the pressure drop data of the flow system. The induction period of CC12F2 (R12) in pure water and that of CH4 in (tetrahydrofuran ＋ water) systems were then measured with the above two methods. Experimental data show that the induction period depends on the driving force exponentially. Flow rate also has a significant influence on the hydrate nucleation. A new induction period model taking the driving force and liquid flow rate into account was proposed. And it is successfully applied to the calculation of the induction period, which is in good agreement with the experimental data obtained in this study.     

CH4、CO2及CH4+C2H6+C3H8在纯水、SDS水溶液和含石英砂体系中水合物相平衡条件的测定

Phase equilibrium conditions of gas hydrate in several systems were measured by the step-heating method using the cylindrical transparent sapphire cell device. The experimental data for pure CH4 or CO2 + deionized water systems showed good agreement with those in the literatures. This kind of method was then applied to CH4/CO2 + sodium dodecyl sulfate (SDS) aqueous solution, CH4/CO2 + SDS aqueous solution + silica sand, and (CH4 + C2H6 + C3H8) gas mixture + SDS aqueous solution systems, where SDS was added to increase the hydrate formation rate without evident influence on the equilibrium conditions. The feasibility and reliability of the step-heating method, especially for porous media systems and gas mixtures systems were determined. The experimental data for CO2 + silica sand data shows that the equilibrium pressure will change significantly when the particle size of silica sand is less than 96 μm. The formation equilibrium pressure was also measured by the reformation of hydrate.     

STUDY FOR NATURAL GAS HYDRATE CONVERSED FROM ICE

Natural gas hydrates are crystalline clathrate compounds composed of water and gases of small molecular diameters that can be used for storage and transport of natural gas as a novel method. In the paper a series of experiments of aspects and kinetics for hydrate formed from natural gas and ice were carried out on the industrial small scale production apparatus. The experimental results show that formation conditions of hydrate conversed from ice are independent of induction time, and bigger degrees of supersaturation and supercooling improved the driving force and advanced the hydrate formation. Superpressure is also favorable for ice particle conversion to hydrate. In addition, it was found there have an optimal reaction time during hydrate formation.     

Review on application of nanoparticles for EOR purposes: A critical review of the opportunities and challenges

Nanoparticles have already gained attentions for their countless potential applications in enhanced oil recovery.Nano-sized particles would help to recover trapped oil by several mechanisms including interfacial tension reduction, impulsive emulsion formation and wettability alteration of porous media. The presence of dispersed nanoparticles in injected fluids would enhance the recovery process through their movement towards oil–water interface. This would cause the interfacial tension to be reduced. In this research, the effects of different types of nanoparticles and different nanoparticle concentrations on EOR processes were investigated. Different flooding experiments were investigated to reveal enhancing oil recovery mechanisms. The results showed that nanoparticles have the ability to reduce the IFT as well as contact angle, making the solid surface to more water wet. As nanoparticle concentration increases more trapped oil was produced mainly due to wettability alteration to water wet and IFT reduction. However, pore blockage was also observed due to adsorption of nanoparticles, a phenomenon which caused the injection pressure to increase. Nonetheless, such higher injection pressure could displace some trapped oil in the small pore channels out of the model. The investigated results gave a clear indication that the EOR potential of nanoparticle fluid is significant.     

Oil–water pre-separation with a novel axial hydrocyclone

A novel hydrocyclone with guide vanes, named as axial hydrocyclone(AHC), is designed to tackle the problem of oil–water separation faced by most mature oilfields. Optimal design of the AHC is carried out by using numerical methods. The effects of guide vanes, cone angle, tapered angle and overflow pipe on the oil–water separation are discussed in this paper. The results show that a double swirling flow is generated in the tapered section where oil–water separation occurs. Both the cylindrical and the tapered section have important influences on AHC performance. On the basis of single factor results, response surface methodology is employed to optimize the AHC design. The experimental results indicate that the novel AHC has an excellent performance for the oil–water separation.     

油性微乳液的循环气升式反应器的流体力学和传质性能研究简

This study reports an experimental investigation on hydrodynamics and mass transfer characteristics in a 15.6x10-3 m3 external loop airlift reactor for oil-in-water micro-emulsions with oil to water volume ratio （φ） rang- ing from 3% to 7% （by volume）. For comparative purposes, experiments were also carried out with water. Increase in φ of micro-emulsion systems results in an increment in the gas holdup and a decrease in the volumetric gas-liquid oxygen transfer coefficient and liquid circulation velocity, attributed to the escalation in the viscosity of mi- cro-emulsions. The gas holdup and volumetric mass transfer coefficient for micro-emulsion systems are signifi- cantly higher than that of water system. Two correlations are developed to predict the gas holdup and oxygen trans- fer coefficient     

油水体系内水合物的生成:温度、压力和搅拌速率影响

水合物在管道内的生成对流动安全保障构成了极大威胁。为研究水合物在油水体系内的生成特性,本文以天然气、柴油、水为实验介质,在高压可视反应釜内开展了一系列不同温度、压力和搅拌速率的水合物生成实验。根据测试实验中温度、压力的变化趋势,首先分析了两种不同实验步骤下水合物的生成过程。然后,基于从反应釜可视窗处观察到的实验现象,研究了温度、压力和搅拌速率对水合物生成和分布位置、水合物生成形态及水合物形态演化过程的影响。实验中,可以观察到水合物的聚集、沉积和壁面膜生长现象。同时,实验还研究了温度、压力和搅拌转速对诱导时间、壁面水合物膜生长速率及气体消耗速率等水合物生成动力学参数的影响。本文研究成果可为油气管道水合物防治技术的发展提供理论支持。     

Experimental study of hydrate formation in oil–water systems using a high-pressure visual autoclave

To investigate the characteristics of hydrate formation in oil–water systems, a high-pressure visual autoclave equipped with visual windows was used where a series of hydrate formation experiments were performed from natural gas + diesel oil + water systems at different water cuts (30 and 70%), rotation rates (100, 200, 300 r/min) and thermodynamic conditions (temperature, pressure). According to the temperature and pressure profiles in test experiments, the processes of hydrate formation under two kinds of experimental procedures were analyzed first. Then, based on the experimental phenomenon observed through the visual windows, hydrate morphologies and hydrate morphological evolvements throughout the experiments were mainly investigated. In experiments, the growth and annealing of hydrate films on the wall, the agglomeration and deposition of hydrate coated water droplets, flocculent-like hydrate deposition with water trapped in and the Pickering effect of hydrates were identified. Simultaneously, based on the experimental data of thermodynamic parameters, the kinetics of hydrate formation was studied by calculating the variations of hydrate film area and gas consumption in different experiments. In addition, the influences of temperature, pressure, and rotation rate on hydrate morphologies, hydrate morphological evolvements, and hydrate formation kinetics were also focused on.     

Bimodal model for predicting the emulsion-hydrate mixture viscosity in high water cut systems

For many production operations, particularly deepwater fields, those requiring long tiebacks, water flooded and mature reservoirs (where water cuts can be very high), the traditional techniques to prevent hydrate problem may not be economical and/or logistically practical. Thus the industry needs improved techniques to tackle flow assurance problems for such challenging conditions.Preventing hydrate agglomeration and transportation of hydrate slurry could be a new solution. The rheological behaviour of hydrate slurry has mainly been investigated in low water cut systems where water is the limiting factor. In high water cut systems, hydrate former components are the limiting factor and therefore the rheological behaviour of hydrate slurry has to be study in water–oil emulsion and this has a significant role on the viscosity of the system.In this communication, a model to predict the viscosity of water–oil emulsion in the presence of hydrate particles in high water cut systems using the concept for a bimodal mixture is proposed. In the model, water–oil emulsion and hydrate particles in the liquid continuous phase are treated separately as unimodal models. In addition, a modification has been applied to the Mills (1985) model to calculate the viscosity of unimodal hydrate suspensions. The model has been validated using experimental data for high water cut systems (above 50%) in the presence of different anti-agglomerant (AA) concentrations. The predictions of the proposed model are in good agreement with experimental data for both oil-in-water and water-in-oil hydrate mixtures.     

利用吸收-水合耦合法从氨弛放气中回收氢气的研究(英文)

In this work, the absorption-hydration hybrid method was used to recover (hydrogen + nitrogen) from (hydrogen + nitrogen + methane + argon) tail gas mixtures of synthetic ammonia plant through hydrate forma-tion/dissociation. A high-pressure reactor with magnetic stirrer was used to study the separation efficiency. The in-fluences of the concentration of anti-agglomerant, temperature, pressure, initial gas-liquid volume ratio, and oil-water volume ratio on the separation efficiency were systematically investigated in the presence of tetrahydro-furan (THF). Anti-agglomerant was used to disperse hydrate particles into the condensate phase for water-in-oil emulsion system. Since nitrogen is the material for ammonia production, the objective production in our separation process is (hydrogen + nitrogen). Our experimental results show that by adopting appropriate operating conditions, high concentration of (hydrogen + nitrogen) can be obtained using the proposed technology based on forming hydrate.     

盐对气体水合物防聚剂作用的影响

利用可视化高压磁力反应釜研究无机盐对4种不同类型的水合物防聚剂的影响,结果表明:和纯水体系相比,不含盐的防聚剂增加了甲烷水合物的生成速率以及其生成量,促进了甲烷水合物的生成,而含盐的防聚剂却降低了水合物的生成速率及其生成量,明显地抑制了水合物的生成。另外,盐能增强防聚剂的防聚性能,随着盐浓度的增加,其作用效果逐渐增强,并讨论了盐效应的机理。在工业应用中防聚剂可以和盐混合起来使用,添加的较优浓度为5%～8%(m/m)。     

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。     

油气管道水合物堵塞机理研究进展

国内外对油气管道水合物堵塞机理的实验研究虽然较多,但一直缺少系统的总结归纳。本文根据水合物堵塞实验开展条件的不同,首先将油气管输体系分为油基体系、水基体系（纯水体系及水主导体系）、气主导体系和部分分散体系。文章分析表明,管道水合物堵塞机理众多,具体包括水合物的聚集和沉积、水合物大量聚集阻塞管道流通截面及油水相分离等。其中,水合物的聚集和沉积是油基体系水合物堵塞的主要机理,水合物颗粒的着床沉积是纯水体系水合物堵塞的主要机理,水合物大量聚集阻塞管道流通截面则是气主导体系水合物堵塞的主要机理。水主导体系和部分分散体系的水合物堵塞机理,目前尚无统一定论,有待进一步深入研究。文章指出对环状流液滴分布、油水分散状态、乳状液稳定性及未乳化自由水层等的量化研究则是未来水合物堵塞机理的研究重点。     

A water droplet size distribution dependent modeling of hydrate formation in water/oil emulsion

Experimental data on chord length distributions and growth rate during methane hydrate formation in water‐in‐oil emulsions were obtained in a high pressure stirring reactor using focused beam reflectance measurement and particle video microscope. The experiments were carried out at 274.2 K for 10–30% water cuts and agitation rates ranging from 200 to 500 rpm initially at 7.72 MPa. Rapid growth was accompanied by gradually decrease in rate. Free water was observed to become depleted during rapid growth while some water remained encapsulated inside hydrate layers constituting a mass transfer barrier. The apparent kinetic constants of methane hydrate formation and free‐water fractions were determined using a newly developed kinetic model independent of the dissolution rate at the gas–oil interface. It was illustrated that continued growth depends on distribution and transfer of water in oil‐dominated systems. This perception accords with observations of hydrate film growth on suspended water droplet in oil and clarifies transfer limits in kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1010–1023, 2017     

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.     

Experimental determination of methane hydrate dissociation curve up to 55 MPa by using a small amount of surfactant as hydrate promoter

Methane hydrate equilibrium has been studied upon continuous heating of the water-hydrate-gas system within the temperature range of 275-300 K. This temperature range corresponds to equilibrium pressures of 3.15-55 MPa. The hydrate formation/dissociation experiments were carried out in a high-pressure reactor under isochoric conditions and with no agitation. A small amount of surfactant (0.02 wt% sodium dodecyl sulfate, SDS) was added to water to promote hydrate formation. It was demonstrated that SDS did not have any influence on the gas hydrate equilibrium, but increased drastically both the hydrate formation rate and the amount of water converted into hydrate, when compared with the experiments without surfactant. To understand and clarify the influence of SDS on hydrate formation, macroscopic observations of hydrate growth were carried out using gas propane as hydrate former in a fully transparent reactor. We observed that 10^-3 wt% SDS (230 times less than the Critical Micellar Concentration of SDS) were sufficient to prevent hydrate particles from agglomerating and forming a rigid hydrate film at the liquid-gas interface. In the presence of SDS, hydrates grew mainly on the reactor walls as a porous structure, which sucked the solution due to capillary forces. Hydrates grew with a high rate until about 97 wt% of the water present in the reactor was transformed into hydrate.Our data on methane hydrate equilibrium both confirm already published literature data and complement them within the pressure range of 20-55 MPa.