喷雾反应器中甲烷水合物生长动力学模型

提出了喷雾反应器中甲烷水合物的形成机理,并引入传质对水合反应影响的有效因子等参数,得到了喷雾法生成水合物的改进动力学方程.通过实验验证,实验数据与模型计算数据基本吻合,平均误差为4.63%.方程回归得出甲烷水合物表观活化能(Ea)为54.25 kJ/mol,根据文献结果,说明喷雾反应器中甲烷水合物生长过程由表面反应所控制.     

Experimental Study of Methane Hydrate Decomposition Kinetics

Experimental investigations of methane hydrate dissociation kinetics were performed. The test rig consists of a stirred reactor equipped with particle size analysis. The observed dissociation rates were found to be about one order of magnitude faster than previously reported by others. A mass transfer control of the dissociation process is proposed to dominate in the proximity of a dispersed hydrate‐liquid interface. The results are relevant for the design of processes employing dispersed gas hydrates in chemical engineering and the production of natural gas from dispersed deposits.     

甲烷水合物生成和分解的实验研究

利用水合物法实现对天然气的工业储运,需要提高水合物的储气量并解决水合物的分解速度问题。为此,文章研究了在十二烷基硫酸钠(SDS)体系中,甲烷水合物的储气量和在冰点以下的常压分解规律。研究发现,SDS浓度为650 mg/L时甲烷水合物储气量达到最高值,约为170 V/V。分解温度为268.2~272.2 K区域内,甲烷水合物的分解速率随温度的降低而降低;在268.2 K时,甲烷水合物分解速率最低。     

Static Formation and Dissociation of Methane+Methylcyclohexane Hydrate for Gas Hydrate Production and Regasification

The formation and decomposition of methane+methylcyclohexane (MCH) hydrate in a static batch reactor, which was also designed as a high‐pressure microwave reactor, were investigated. The addition of 300 ppm sodium dodecyl sulfate (SDS) provides continuous formation of CH₄+MCH hydrate under static conditions. Increasing the initial pressure within the narrow range of 2.7 to 4.6 MPa at 274 K enhances the formation rate by even several times. The gas storage capacity can be largely improved with partial coexisting of sI CH₄ hydrate. Unlike a stirred formation, an increase of nonaqueous MCH inhibits the static formation of sH hydrate. The following regasification by 2.45 GHz microwave heating indicates that the dissociation is rate‐controlled by the parallel connection of efficient internal heating and conventional external heating. The multiphase convection characterized by osmotic dehydration and driven by intensified regasification is considered as the dominant mechanism affecting the quiescent dissociation.     

A型分子筛对甲烷水合物生成的影响

The porous medium has an important effect on hydrate formation. In this paper, the formation process and the gas storage capacity of the methane hydrate were investigated with A-type zeolite and Sodium Dodecyl Sulfate (SDS) existing in the system. The results show that A-type zeolite can influence methane hydrate formation. At the temperature of 273.5 K and pressure of 8.3 MPa, the distilled water with A-type zeolite can form methane hydrate with gaseous methane in 12 hours. The formation process of the system with A-type zeolite was quite steady and the amount of A-type zeolite can influence the gas storage capacity significantly. The adding of A-type zeolite with 0.067 g•(g water)－1 into 2×10－3 g•g－1 SDS-water solution can increase the gas storage capacity, and the maxi-mum increase rate was 31%. Simultaneously the promotion effect on hydrate formation of 3A-type zeolite is much more obvious than that of 5A-type zeolite when the water adding amounts are 0.033 g•g－1 and 0.067 g•g－1 at the experimental conditions.     

煤层气水合物技术在储运中的应用

对煤层气和水在一定条件下生成结晶状物质（NGH）从而使得煤层气以固态方式储运进行了研究。结果表明：NGH制备和储存条件温和，分解技术难度不大。与传统储运技术相比，应用NGH技术储运煤层气密度高、费用低，而且安全可靠，在煤层气储运和矿井瓦斯处理等方面都具有很高的应用价值。     

Kinetic Modeling of Methane Hydrate Formation in the Presence of Low‐Dosage Water‐Soluble Ionic Liquids

The kinetic and thermodynamic effects of three typical low‐dosage imidazolium‐based ionic liquids (ILs) on methane hydrate formation and dissociation were investigated, considering the anion nature and subcooling and/or overpressure driving forces. Isochoric hydrate formation and dissociation data were obtained by the modified slow step‐heating method. ILs proved to have a dual effect on both formation and dissociation of methane hydrate including thermodynamic and kinetic inhibition. Kinetic modeling of methane hydrate inhibition by low‐dosage ILs was performed. Kinetic analysis showed that IL inhibitors mainly cause a delay in the nucleation or hydrate growth step. The related inhibition mechanism was resolved regarding the ionic nature and electrostatic interactions of ILs with water molecules. Two binomial exponential kinetic relations were derived and used for simple methane hydrate formation in the presence of ILs as kinetic hydrate inhibitors. The proposed relations can serve for a quick estimation of the nature, extent, strength, and effectiveness of ILs on various gas hydrates.     

天然气水合物动力学抑制剂的合成及评价

随着全球不可再生资源(石油、天然气、煤)的消耗不断增大,人们迫切想发现和利用新型能源来解决危机。天然气水合物是一种由天然气与水在一定条件下形成的可燃的、非化学计量的、笼型结晶化合物,由于其形状外观与冰类似,又俗称"可燃冰",被誉为21世纪的新能源[1]。但是天然气水合物的形成严重影响了石油天然气工业中开采、输送、储运,特别是堵塞管道,降低了采收率。本文通过对天然气水合物的结构研究,合成了一种高效的天然气水合物动力学抑制剂,并对各种实验因素分析,模拟天然气水合物的评价方法,与PVP和VC-713进行试验对比,得出实验的较优配比。     

天然气水合物生成与相平衡曲线的试验分析

通过改变动力学抑制剂、过冷度、搅拌,借助生成实验装置,分析天然气水合物的生成效果,比较以上三个条件下的天然气水合物的生成速度和生成量,进而得出以上三个变量的对天然气水合物生成效果的贡献。结果表明:增加搅拌在天然气水合物生成过程中起主要作用,其次是过冷度以及动力学抑制剂。通过对水合物生成以及分解过程中压力-温度曲线的拟合,放缓反应釜内温度的升幅,可以得到更长更精确的拟合曲线。     

静止悬垂水滴形成甲烷水合物的生长动力学

在273.35～277.15 K,4.86～6.65 MPa条件下开展了静止悬垂水滴形成甲烷水合物的可视化实验,提出了气-液平衡时水滴表面CH_4气体溶解度的计算方法以及描述水滴表面水合物膜生长的动力学模型,预测了悬垂水滴形成甲烷水合物的生长时间。结果表明,悬垂水滴转化为水合物颗粒的时间随着系统压力的升高而缩短,随着系统温度的降低而减小。水滴越小,反应时间越短。水滴尺寸和CH_4的扩散阻力对水合反应的影响比系统压力、温度的影响大得多。CH_4在水合物膜中的扩散阻力是影响悬垂水滴转化为水合物的主要因素,进行喷雾反应釜设计时,须尽量消除扩散阻力的影响,加快气体水合物的合成速率。     

水合肼还原硝化棉动力学模型研究

为了处理过期的废药以达到资源回收再利用的目的,安全、环保的水合肼还原法成为废药处理的发展方向之一.通过化学动力学定律结合紫外光谱分析,研究了水合肼还原过期废药硝化纤维素(硝化棉)的动力学,为今后处理废弃发射药提供理论模型.实验采用的水合肼浓度为10、8、6、4g·L-1,温度选择30～90℃,通过硝化纤维素在水合肼溶液...     

Methane Hydrate Formation and Dissociation in the presence of Bentonite Clay Suspension

The present work reports the effect of bentonite clay on methane hydrate formation and dissociation in synthetic seawater of salinity 3.55 % of total dissolved salts. Extensive observations of pressure‐temperature equilibrium during formation and decomposition of methane hydrate under different conditions have been made. It is observed that phase equilibrium conditions of hydrate are affected on changing the concentration of bentonite clay in synthetic seawater. Induction time for hydrate nucleation has been measured under different concentrations of clay and subcooling conditions. The presence of bentonite clay in synthetic seawater reduces the induction time of hydrate formation. Enthalpy of hydrate dissociation is calculated by Clausius‐Clapeyron equation using measured phase equilibrium data. The amount of gas consumed during hydrate formation has been calculated using real gas equation. It is found that a larger amount of gas is consumed upon addition of bentonite clay in synthetic seawater.     

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.     

基于凝胶干水的水合物储甲烷实验研究

利用搅拌器通过高速剪切的方法制备了疏水性气相二氧化硅(HB-630):结冷胶:水的质量比为1:2:17的凝胶干水,用显微镜观察了其微观形貌,并用高压水合物反应装置对其进行了储甲烷实验研究。显微观察发现,凝胶干水粒径范围为10～150(?)m。储甲烷实验表明,在压力为7.98 MPa、温度为0.8℃左右甲烷能在6 min内与凝胶干水作用快速生成水合物,并且2 h内储甲烷量达到100(V/V),大大提高了水合物储甲烷速率和短时间内的储气量。通过5次循环储甲烷实验发现,凝胶干水储甲烷量随着循环次数的增加而降低。     

次氯酸钙对水合物中甲烷储气量的影响

1 INTRODUCTION At present,natural gas accounts for 3% of the total energy consumption in China.It will go up to 5% in 2005 and 8% in 2010. Natural gas storage is a subject of great interest to many industries and particularly to transportation.Compressed natural gas,liquefied natural gas and adsorbed natural gas are techniques widely used.The possibility of developing a convenient storage system based on hydrate has been explored for about ten years around the world[1-5].Gudmundsson[1] has focused on the storage and transportation of gas as hydrate at atmospheric pressure since 1990.Khokhar[2] used 1,3-dimethylcyclohexane and polyvinyl-pyrrolidone as additives to lower hydrate formation pressure. Saito[3] surveyed the effects of tetrahydrofuran and acetone.Rogers[3] used sodium dodecyl sulfate as accelerator to natural gas hydrate formation. In this work,the effects of calcium hypochlorite on hydrate formation are investigated.The data show that it can lower the degree of supercooling and enhance the relative cage occupancy.     

油包水乳化液滴形成甲烷水合物的动力学特性研究

针对油气输运管线中天然气水合物堵塞问题,重点研究了油包水乳化液滴形成气体水合物的动力学特性。根据原油的甲烷溶解能力经验模型,预测了油包水乳化液(35%(V)水和65%(V)白油)中油-液两相区的甲烷饱和溶解度,优化了乳化液滴的水合反应动力学模型,并且对单个乳化液滴在不同压力和不同液滴尺寸条件的水合物结晶过程进行了数值模拟。研究结果表明,水合物在白油-水乳化体系的结晶生长过程是一个缩核过程,甲烷消耗量和反应速率随着液滴半径的增大而增大,但是水合物转化率随着液滴半径的增大而减小;压力越高,水合物转化时间越短,该结果对揭示油包水乳化液滴的水合结晶机理以及油气输运管线水合物抑制技术的发展具有重要意义。     

Kinetic Study on CO2 Reforming of Methane

The kinetics of CO2 reforming of methane has been studied at 976－1033K on a commercial NiO/CaO/Al2O3 catalyst in a packed-bed continuous reactor. The reaction was carried out at atmospheric pressure and CO2/CH4 ratio ＞ 2. The Hougen-Watson rate models were fitted to experimental data assuming the disso ciative adsorption of methane as the rate-determining step. The reaction rate showed an effective reaction order of about unity for CH4. The apparent activity energy was found to be 104 kJ·mol-1. Therefore the kinetic reaction parameters were determined and a possible reaction mechanism was proposed.     

Kinetic Study of Nickel Oxide Reduction by Methane

The reduction of the nickel oxide, NiO, by methane was investigated in this work. The thermogravimetric technique was used for the determination of kinetic parameters for the reaction. The reaction was carried out in the temperature range of 600–725 °C, at atmospheric pressure with porous pellets prepared from nickel oxide powder with a mean particle size of 0.026 μm. The conversion‐time data have been interpreted by using the grain model. Complete conversion can be achieved in 11 min at 725 °C, which is shorter than the time required by carbon, i.e., ca. 120 min at 1000 °C. This faster reduction in comparison with carbonthermal reduction is attributed to the high carbon activity in methane. For the first order reaction with respect to methane concentration, the activation energy is found to be 63.9 kcal/g mol.     

甲烷水蒸汽催化转化的动力学模型

在常压下使用内循环式无梯度反应器研究了Z102镍催化剂上甲烷水蒸汽催化转化反应的动力学。实验条件如下:反应温度500—700℃,H_2O/CH_4=2.5—4.5（克分子比）,甲烷空速为2000—10000ml/h·g-cat。根据实验结果的分析,作者认为在反应过程中一氧化碳和二氧化碳是同时生成的,即甲烷水蒸汽催化转化反应可用平行反应模型来表示。所得到的一氧化碳及二氧化碳的生成速度方程分别为: rco=k,p_(CH_4)~(0.8)及 rco_2=k_2p_(CH_4)~(0.8) p_(H_2O)~(1.5)反应速度常数k_1及k_2与温度的关系均符合阿累尼乌斯方程。一些研究者认为在通常的操作条件下,甲烷水蒸汽催化转化反应过程中,水煤气变换反应很快就达到平衡,我们的实验数据计算证明这个见解是不妥的。     

电解质及醇类对天然气水合物相平衡影响机理分析

天然气水合物作为潜力巨大的清洁资源,同时对天然气运输管道会产生堵塞,影响运输。开展天然气水合物相平衡的研究,对天然气水合物的开发及天然气的运输有重要的意义。总结了电解质及醇类对水分子间氢键形成和天然气水合物相平衡的影响相关研究成果,在天然气水合物生成机理的基础上,运用氢键理论分析电解质及醇类对天然气水合物相平衡的影响。此外,推测电场与磁场及微波对水合物的形成也有产生一定的影响。