煤层气水合物定容生成实验研究

为了有效利用与回收直接排放的大量抽放瓦斯,提出了利用水合物技术处理与储运的新方法,根据气体成分确立了水合物生成的温度与压力条件,通过对气体进行初始压力为9.5 MPa的定容法实验,研究了含表面活性剂下水合物生成过程中温度-压力与CH4转化率的变化规律。实验结果表明,水合反应的进行应保持一定的反应驱动力,根据不同温度下反应驱动力进而确定最佳反应条件,同时反应过程中CH4能被有效提取,但要进行高效生产,应进行多级水合分离技术以提高产率。     

干水固化甲烷过程及反应特性研究

利用天然气水合物合成实验系统,采用5%纳米SiO2与纯净水配制的干水和纯甲烷为原料,获得了水合物生成过程中温度、压力、反应速率以及最终的储气密度之间的关系。通过以温度和压力值作为变量进行实验结果表明：在高压条件下,反应温度接近0℃,反应的速率较快,生成的水合物中甲烷含量也较高。在低温条件下,压力接近8 MPa时,干水固化甲烷效果较好。     

元坝高含硫气田水合物实验研究

元坝气田天然气为高含硫过成熟干气,在采集输过程中容易形成水合物,而井筒、集输管线属于水合物形成的高发部位,一旦形成将严重影响正常生产。为此,开展元坝气田长兴组水合物生成及抑制剂实验,结果表明：压力小于20MPa下元坝气田长兴组含硫天然气水合物生成温度随压力增加明显,压力高于20MPa时水合物生成温度增加相对平缓。即在低压情况下水合物形成温度对压力的变化越敏感。天然气水合物生成温度随着甲醇和乙二醇在浓度增加逐步降低,压力较低时水合物生成温度较低,说叫甲醇和乙二醇对水合物生成有明显的抑制作用。     

表面活性剂在瓦斯水合物生成过程中的热力学作用

在实验研究基础上,结合表面活性剂水溶液中瓦斯水合物生成微观机理,提出了表面活性剂改变水合物生成热力学条件物理作用假说,认为表面活性剂胶束对溶于其中的气体分子和吸附于其周围的水分子的束缚作用,相当于降低了体系的温度.利用T40（0.001 mol·L^-1）、T40（0.002 mol·L^-1）、T40/T80（0.001 mol·L^-1）分别组成的3种气 液 煤 水合物反应体系实验测定了水合物生成时的相平衡参数,与同样温度和压力条件下相平衡计算值比较,结果表明,表面活性剂的加入有效地改变了水合物生成的热力学条件.例如,在T40/T80（0.001 mol·L^-1）实验体系中,当压力为22.67 MPa时,水合物生成相平衡温度为22.6℃,比纯水中提高2.1℃.     

表面活性剂对气体水合物生成过程的定量影响

为确定HCFC?141b水合物生成条件下阴离子表面活性剂十二烷基硫酸钠(SDS)和十二烷基苯磺酸钠(SDBS)的临界胶束浓度(CMC),在0~20℃温度下,通过圆环法实验研究了不同浓度表面活性剂溶液体系的表面张力,考察了表面活性剂对溶液体系表面张力的影响机理并通过C3H8水合物的生成过程实验进行了验证,确定了SDS和SDBS的临界胶束浓度. 结果表明,当SDS和SDBS的质量浓度分别低于500?10?6和100?10?6时,表面活性剂降低水表面张力的效果最明显,二者的CMC分别为1950?10?6和400?10?6,表面活性剂能明显缩短水合反应的诱导时间,提高了其平均生成速率.     

SDBS的表面张力对天然气水合物生成的影响

利用德国KRUSS公司生产的界面张力仪K11中的板法测定十二烷基苯磺酸钠在不同温度(5,10,20,30,35℃)和不同浓度下(100,400,800,1200,1600,2000 mg/L)的表面张力,确定有利于天然气水合物合成的最佳浓度为1 200 mg/L,这在工业应用中有着重要的参考价值,同时分析了表面活性剂加速天然气水合物生成的机理。     

番禺35-2气田投产过程井口水合物防治方案研究

番禺35-2气田是我国南海深水天然气田,在投产过程中,当天然气经过水下井口油嘴进行节流时,会产生较大的温降,存在水合物生成风险。针对如何防治投产过程中井口水合物的问题,以A1H井为对象,采用统计热力学模型计算了水合物生成温度、压力条件;以OLGA7.1软件为基础,建立了投产过程仿真模型;分析了投产过程中井口油嘴出口处的压力、温度变化规律,以及在投产的不同阶段水合物的生成风险。针对投产初期存在的水合生成问题,提出了综合采用甲醇、乙二醇作为抑制剂进行水合物防控的方案,并确定了水合物抑制剂的注入浓度和注入速率。     

盐水体系中环戊烷-甲烷水合物的相平衡及分解热

利用可视化水合物相平衡实验装置,采用恒温压力搜索法,测定了284～303K内环戊烷(CP)-甲烷在NaCl溶液中的水合物相平衡数据,并采用Clausius-Clapeyron方程计算了其生成/分解热数据。实验结果表明,CP-甲烷水合物生成条件远低于纯甲烷水合物;采用甲烷辅助气体可使CP在高于其纯水合物四相点的更高温度范围内生成CP-甲烷水合物;CP-甲烷水合物相平衡压力随温度增大而升高;随着NaCl浓度的增大,相平衡压力线性升高,且温度越高,温度和NaCl浓度对相平衡压力的影响越大。CP-甲烷水合物的生成/分解热随着温度的升高而逐渐减小,随NaCl浓度的增加而减小。     

聚苯乙烯磺酸钠作用下Ⅰ型水合物的生成热力学与动力学

通过使用表面活性剂来提升水合物的生成速度和转化率是提高水合物技术经济价值的主要方法。因为泡沫过多不利于生产,低起泡性的聚苯乙烯磺酸钠（PSS）在水合物技术领域具有很好应用的潜力。本文根据对含PSS体系的水合物生成热力学研究,提出了乙烯-PSS溶液体系的热力学模型以定量描述PSS对水合物的热力学影响,该模型可较为准确地预测水合物的热力学临界生成压力：平均相对误差为1.1%,最大相对误差为3.8%。在上述研究基础上,本文研究了在PSS存在的情况下,PSS初始浓度和热力学推动力对Ⅰ型水合物的生成速度、最终转化率（水合物生成结束时的转化率）等参数的影响。结果表明,PSS对Ⅰ型水合物的热力学负面影响很小。PSS使水合物的最终转化率由59.6%±1.9%提升到80%以上,并使水合物的生成速度显著提升。当PSS初始浓度或压力低于特定值时,提高PSS初始浓度或压力可有效提升水合物的生成速度和最终转化率;但PSS初始浓度或压力高于特定值时,提高PSS初始浓度或压力对水合物生成速度和最终转化率的提升效果不再明显。     

CO2-N2-TBAB和CO2-N2-THF体系的水合物平衡生成条件

利用等温压力搜索法测定了CO2-N2-TBAB与CO2-N2-THF体系的水合物平衡生成压力. 实验的压力范围为0.69~14.55 MPa,温度范围为275.75~288.15 K. 结果表明,TBAB与THF均可作为添加剂有效降低气体水合物的平衡生成压力. 在较低的药剂浓度下,CO2-N2-TBAB的水合物平衡生成压力低于CO2-N2-THF体系. 在较高的浓度下,两种体系的水合物平衡生成压力没有明显差别.     

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.     

Influence factors of methane hydrate formation from ice: Temperature,pressure and SDS surfactant

A series of experiments of forming hydrate from ice powders in different conditions have been carried out with constant volume method to evaluate the influence factors such as pressure, temperature, and SDS surfactant. The change of temperature and pressure were collected as a function of elapsed time, which were used to calculate the gas consumption and hydrate saturation during hydrate formation (pVT method). Based on the experimental results and the analysis, it is concluded that: (1) Both initial pressure and temperature have effect on the hydrate formation and temperature plays a more important role in the process; (2) heating and secondary pressurization will promote the gas hydrate formation and enhance the hydrate saturation as a result. Meanwhile, the promotion of heating seems to be more obvious than that of secondary pressurization; (3) different concentrations of SDS surfactant have clearly influence on the saturation of gas hydrate and there is an optimal concentration to promote the hydrate formation.     

Hydrate formation from liquid CO2 in a glass beads bed

CO₂ sequestration in marine sediments as solid hydrates is a potential way to capture and store anthropogenic CO₂. In this study, hydrate formation from liquid CO₂ in marine sediments was simulated in a glass beads bed, and the factors affecting the kinetics of hydrate formation were investigated. The results indicated that the rapid initial hydrate formation with a high driving force always increases the mass transfer resistance, which slows down hydrate growth. The final ratio of water conversion is higher under conditions of low temperature and higher pressure. A smaller particle size is conductive to initial CO₂ hydrate growth, but the water conversion ratio in a bed with larger particles is slightly higher. Compared with other factors, the change in water saturation has an obvious effect on the final water conversion. To inhibit the initial hydrate formation during the injection process, in this paper, a kinetic inhibitor is proposed for pre-injection into marine sediments. This work shows that at a low pressure, a low-concentration inhibitor has an obvious inhibition effect on hydrate growth. However, at a high pressure, it is necessary to increase the concentration of inhibitor to produce an obvious inhibition effect.     

Experimental and Theoretical Investigation of Double Gas Hydrate Formation in the Presence or Absence of Kinetic Inhibitors in a Flow Mini‐Loop Apparatus

Double gas hydrate formation in the presence or absence of kinetic inhibitors in a flow mini‐loop apparatus was investigated. For the prediction of the gas consumption rate during hydrate formation in this system, the rate equation based on the Kashchiev and Firoozabadi model for simple gas hydrate formation in a batch system was developed for double gas hydrate formation in a flow mini‐loop apparatus. To complete the theoretical evaluation of gas hydrate formation through the mini‐loop apparatus in the presence or absence of kinetic hydrate inhibitors (KHI), a laboratory flow mini‐loop apparatus was set up to measure the induction time for hydrate formation and the uptake rate when a gaseous mixture (such as 75 % C1/25 % C3, 25 % C1/75 % C3, 75 % C1/25 % i‐C4, and 25 % C1/75 % i‐C4) is contacted with water containing or not containing dissolved inhibitor under suitable temperature and pressure conditions. In each experiment, a water blend saturated with gas mixture was circulated up to the required pressure. The pressure was maintained at a constant value during the experimental runs by means of a required gas mixture make‐up. The effect of pressure on gas consumption during hydrate formation was investigated in the presence or absence of polyvinylpyrrolidone (PVP) and L ‐tyrosine as kinetic inhibitors at various concentrations. A good agreement was found between the predicted and experimental data in the presence or absence of KHI. The total average absolute deviation percents between the experimental and predicted values of gas consumption were found to be 16.4 and 17.5 % for the double gas hydrate formation in the presence or absence of the kinetic inhibitors, respectively.     

Crystal growth inhibition of tetrahydrofuran hydrate with poly(N-vinyl piperidone) and other poly(N-vinyl lactam) homopolymers

Poly(N-vinyl pyrrolidone) (PVP) containing the 5-ring lactam and poly(N-vinyl caprolactam) (PVCap) containing the 7-ring lactam are well-known kinetic hydrate inhibitors (KHIs). For the first time we have synthesised and studied the performance of poly(N-vinyl piperidone) (PVPip), containing the 6-ring lactam, as a kinetic hydrate inhibitor. In the first part of the study we have investigated the ability of PVPip to inhibit the growth of tetrahydrofuran SII hydrate crystals. The results are compared to those of PVP and PVCap. Various polymer molecular weights have been investigated at varying subcoolings. PVPip shows an intermediate growth inhibition performance compared to PVP and PVCap at similar polymer molecular weights. In addition, the weight percentage concentration of polymer needed to achieve complete THF hydrate crystal growth inhibition increases as the polymer molecular weight decreases.     

Study of the Kinetics and Morphology of Gas Hydrate Formation

The kinetics and morphology of ethane hydrate formation were studied in a batch type reactor at a temperature of ca. 270–280 K, over a pressure range of 8.83–16.67 bar. The results of the experiments revealed that the formation kinetics were dependant on pressure, temperature, degree of supercooling, and stirring rate. Regardless of the saturation state, the primary nucleation always took place in the bulk of the water and the phase transition was always initiated at the surface of the vortex (gas‐water interface). The rate of hydrate formation was observed to increase with an increase in pressure. The effect of stirring rate on nucleation and growth was emphasized in great detail. The experiments were performed at various stirring rates of 110–190 rpm. Higher rates of formation of gas hydrate were recorded at faster stirring rates. The appearance of nuclei and their subsequent growth at the interface, for different stirring rates, was explained by the proposed conceptual model of mass transfer resistances. The patterns of gas consumption rates, with changing rpm, have been visualized as due to a critical level of gas molecules in the immediate vicinity of the growing hydrate particle. Nucleation and decomposition gave a cyclic hysteresis‐like phenomena. It was also observed that a change in pressure had a much greater effect on the rate of decomposition than it did on the formation rate. Morphological studies revealed that the ethane hydrate resembles thread or is cotton‐like in appearance. The rate of gas consumption during nucleation, with different rpm and pressures, and the percentage decomposition at different pressures, were explained precisely for ethane hydrate.     

THF hydrate crystal growth inhibition with small anionic organic compounds and their synergistic properties with the kinetic hydrate inhibitor poly(N-vinylcaprolactam)

Small, cationic tetraalkylammonium ions (particularly for alkyl=butyl or pentyl) are known to inhibit tetrahydrofuran (THF) and natural gas hydrate crystal growth and have been used as synergists for commercial kinetic hydrate inhibitor polymers (KHIs), such as N-vinylcaprolactam polymers, for a number of years. The ability for small, organic anionic molecules to inhibit (THF) hydrate crystal growth and their potential as KHI synergists in blends with poly(N-vinylcaprolactam) have been investigated. Several series of sodium alkyl carboxylates, sulphates and sulphonates were synthesised. It was found that none of these molecules were capable of inhibiting THF hydrate crystal growth as well as the best tetraalkylammonium salts. Alkyl carboxylates appeared to be more effective as inhibitors than the sulphonates or sulphates. The most effective anionic THF hydrate crystal growth inhibitors had butyl or pentyl groups, with alkyl branching at the tail (i.e. iso- rather than n-isomers) being advantageous. Anionic carboxylate molecules, particularly with isopentyl or isobutyl groups, showed some kinetic inhibition synergy with poly(N-vinylcaprolactam) lowering the onset and catastrophic hydrate formation temperatures in high pressure (78 bar) constant cooling experiments with Structure II hydrates by 1–2 °C when dosed at 2500 ppm compared with using 2500 ppm polymer alone. This synergism was however less than the best tetraalkylammonium salts (alkyl=n-butyl or n-pentyl) at the same test conditions. Sodium butyl sulphonate and sodium 4-methylpentanoate did not prevent hydrate agglomeration with 3.6% brine and decane at 25% water cut in stirred sapphire cells when dosed at 20,000 ppm based on the aqueous phase, whereas 10,000–20,000 ppm active material of several commercially available anti-agglomerants gave fine transportable slurries and no hydrate deposits at the same conditions.     

The initial stage of hydrate formation in liquid volume on impurity particles upon contact of gas and water

A concept and appropriate theoretical construction have been proposed to describe initial stage of hydrate layer formation at the interface between water and hydrate-forming gas. The model presented indicates that this stage (or induction period) is accompanied by the dissolution of gas in water, as well as the formation and growth of hydrate in the bulk zone on impurity particles near the contact boundary. An analytical solution was obtained for the characteristic time during which the volume content of the hydrate phase at the contact boundary reaches one and, thus, nuclei form as a film prior to a hydrate layer at the gas–water boundary. This characteristic time is accepted as the induction time. According to the obtained formula, the induction period depends inversely on static pressure and in inverse two-thirds proportion on the number of impurity particles per unit volume of water. The problem of the formation and growth of hydrate at the interface between the hydrate layer and aqueous gas solution has been considered and solved. The temperature fields caused by heat generated during hydrate formation on the contact surface of hydrate massif and gas solution are analyzed.     

撞击流式反应器内水合物法分离沼气中CO2研究

实验考察了撞击流式反应釜内水合物法分离沼气中CO₂的特性。选取纯水和十二烷基硫酸钠（SDS）两个不同的体系，考察了水合物生成过程中压力、温度、撞击强度的影响。实验结果表明在纯水体系和SDS体系下压力的升高均有利于水合物的快速生成，但并不利于沼气中的二氧化碳捕集；实验通过改变撞击流式反应器的撞击强度发现，当撞击强度为0.128时，CO₂分离因子(S.F.)在纯水和SDS两种体系下均达到最大，纯水体系下S.F.的最大值为138.9，SDS体系下S.F.的最大值为64.5；实验结果表明添加剂SDS可以促进水合物的生成，最适宜的浓度为600 mg/L，此时耗气量、CO₂水合率S.Fr.(CO₂)和CH₄水合率S.Fr.(CH₄)达到最大，但SDS对CH₄水合物生成过程的促进作用大于CO₂水合物，反而不利于CO₂的分离，降低CO₂的分离因子。     

降低“固封”对甲烷水合物生成的影响

随着天然气的大量使用,其储存、运输及调峰越来越重要。天然气水合物在常压状态下具有高储存比,适合应用于天然气的储存、运输及调峰过程中。因此,对天然气水合物的生成研究具有重要意义。本文研究了如何大量生成水合物并保证水合物具有较高储气率的方法。在含聚乙烯吡络烷酮[PVP(K90)]的溶液中,改变PVP(K90)的质量分数、搅拌器的转速与搅拌器的类型,研究甲烷水合物生成量与水合物储气率的变化。结果表明,添加一定低质量分数的PVP(K90)和增加搅拌速度,均可以延迟水合物层的"固封"作用,增加水合物的生成量。在PVP(K90)质量分数高于2%时,生成水合物的密封性降低,水合物"固封"作用被破坏,但是水合物储气率较低。采用不同形式的搅拌杆,在旋转过程中形成空心圆柱,破坏水合物层的"固封"作用,搅拌杆附近的甲烷与水合物晶核被输送到溶液底部,增加了水合物的生成量,而且水合物的储气率较高。在水合物生成过程中,存在水合物微粒多次聚结的现象,使甲烷的消耗量迅速增加。