Numerical Investigation into the Gas Production from Hydrate Deposit under Various Thermal Stimulation Modes in a Multi-Well System in Qilian Mountain

The primary objective of this study was to investigate the energy recovery performance of the permafrost hydrate deposit in the Qilian Mountain at site DK-2 using depressurization combined with thermal injection by the approach of numerical simulation. A novel multi-well system with five horizontal wells was applied for large-scale hydrate mining. The external heat is provided by means of water injection, wellbore heating, or the combinations of them through the central horizontal well, while the fluids are extracted outside from the other four production wells under constant depressurization conditions. The injected water can carry the heat into the hydrate deposit with a faster rate by thermal convection regime, while it also raises the local pressure obviously, which results in a strong prohibition effect on hydrate decomposition in the region close to the central well. The water production rate is always controllable when using the multi-well system. No gas seepage is observed in the reservoir due to the resistance of the undissociated hydrate. Compared with hot water injection, the electric heating combined with normal temperature water flooding basically shows the same promotion effect on gas recovery. Although the hydrate regeneration is more severe in the case of pure electric heating, the external heat can be more efficiently assimilated by gas hydrate, and the efficiency of gas production is best compared with the cases involving water injection. Thus, pure wellbore heating without water injection would be more suitable for hydrate development in deposits characterized by low-permeability conditions.     

水流动强化天然气水合物降压分解研究

降压法被认为是最经济可行的天然气水合物开采方法,但开采后期驱动力不足、甚至产生水合物的二次生成,因此其应用受到限制。本文将降压法与水流动结合提升水合物分解驱动力,研究不同降压模式和水流动对天然气水合物分解特性的影响。发现当降压结合水流动时,压降为水合物分解提供初始驱动力,且压降越大水合物分解驱动力越大。同时水流动能够加快传热传质过程,为水合物分解提供额外的驱动力。在快速降压结合水流动模式中,较高背压下水流动为水合物分解提供主要的驱动力;在梯度降压结合水流动模式中,降压和水流动共同为水合物提供分解驱动力,对水合物分解的促进作用更加显著。     

热力法开采地层天然气水合物的热动力评价

本文在推导热力作用下水合物地层温度分布基础上,发展了评价热力法开采天然气水合物的热效率(用于水合物分解的热量与输入总的热量之比)和能量效率(即输出能量与输入能量之比)的模型.模型分析表明,水合物地层热物性参数以及水合物饱和度决定了热力法开采的能量效率.在注入蒸汽开采初始条件下,能量效率可以达到7.0.     

用分子动力学模拟甲烷水合物热激法分解

用分子动力学模拟方法研究甲烷水合物热激法分解，系统地研究注入340 K液态水的结构Ⅰ型甲烷水合物的分解机理.模拟显示水合物表层水分子与高温液态水分子接触获得热能，分子运动激烈，摆脱水分子间的氢键束缚，笼状结构被破坏.甲烷分子获得热能从笼中挣脱，向外体系扩散.热能通过分子碰撞从外层传递给内层水分子，水合物逐层分解.对比注入277K液态水体系模拟结果，得出热激法促进水合物分解. 关键词： 甲烷水合物 分子动力学模拟 热激法     

Molecular dynamics simulation of decomposition and thermal conductivity of methane hydrate in porous media

The hydrate has characteristics of low thermal conductivity and temperature sensitivity. To further analysis the mechanism of thermal conductivity and provide method for the exploitation, transportation and utilization of hydrate, the effect of decomposition and thermal conductivity of methane hydrate in porous media has been studied by using the molecular dynamics simulation. In this study, the simulation is carried out under the condition of temperature 253.15 K-273.15 K and pressure 1 MPa. The results show that the thermal conductivity of methane hydrate increases with the increase of temperature and has a faster growth near freezing. With the addition of porous media, the thermal conductivity of the methane hydrate improves significantly. The methane hydrate-porous media system also has the characteristics of vitreous body.With the decrease of the pore size of the porous media, thermal conductivity of the system increases gradually at the same temperature. It can be ascertained that the porous media of different pore sizes have strengthened the role of the thermal conductivity of hydrates.     

水合物藏降压开采实验及数值模拟

建立了降压法开采水合物藏数学模型,考虑了气-水-水合物-冰相多相渗流、水合物相变及分解动力学过程、冰-水相变、热传导、对流过程、渗透率变化等对于水合物分解的影响。三维水合物藏模拟表明:在开采前期阶段,可采用降压法,但随着储层能量消耗,产气速度下降很快,需转变开采方式。分析了一些主要参数,如孔隙度、渗透率、饱和度、压力等对水合物开采的影响。     

Formation and dissociation of gas hydrate inclusions during migration in water

The paper studies the process of floating a gas hydrate particle in liquid. The typical depths when gas bubble floating is accompanied by gas hydrate formation (or with zero gain of hydrate) were calculated. The low depths were identified when floating occurs with hydrate dissociation. The model assumes that the gas hydrate formation is limited by heat transfer from interface to the surrounding liquid. The model for gas hydrate dissociation assumes the rate governed by thermal conductivity of hydrate particle and by convective heat transfer to surrounding water. The temperature of the gas hydrate surface equals the phase transition temperature at the given water pressure. Comparative analysis of thermal conductivity and convective heat transfer effects on hydrate dissociation rate was performed for different initial radius of the particle.     

Methane combustion in hydrate systems: Water-methane and water-methane-isopropanol

Kinetics of dissociation of synthetic and natural methane gas hydrates, and also double isopropanol-methane hydrate is investigated. Thermal fields of the sample surfaces are measured by means of thermal imaging in combustion of released methane with clathrate dissociation. The dissociation rates of natural hydrate and double hydrate with isopropanol are many times lower than those of synthetic methane hydrate. Methane combustion is accompanied by formation of a thin water film on the powder surface, which has a strong effect on the heat and mass transfer mechanisms. The experiments demonstrated partial self-preservation for methane hydrate and the absence of self-preservation for double isopropanol-methane hydrate. The experimentally observed dissociation rate of double isopropanol-methane hydrate is considerably lower than that of methane hydrate.     

The Carnot Cycle,Reversibility and Entropy

The Carnot cycle and the attendant notions of reversibility and entropy are examined. It is shown how the modern view of these concepts still corresponds to the ideas Clausius laid down in the nineteenth century. As such, they reflect the outmoded idea, current at the time, that heat is motion. It is shown how this view of heat led Clausius to develop the entropy of a body based on the work that could be performed in a reversible process rather than the work that is actually performed in an irreversible process. In consequence, Clausius built into entropy a conflict with energy conservation, which is concerned with actual changes in energy. In this paper, reversibility and irreversibility are investigated by means of a macroscopic formulation of internal mechanisms of damping based on rate equations for the distribution of energy within a gas. It is shown that work processes involving a step change in external pressure, however small, are intrinsically irreversible. However, under idealised conditions of zero damping the gas inside a piston expands and traces out a trajectory through the space of equilibrium states. Therefore, the entropy change due to heat flow from the reservoir matches the entropy change of the equilibrium states. This trajectory can be traced out in reverse as the piston reverses direction, but if the external conditions are adjusted appropriately, the gas can be made to trace out a Carnot cycle in P-V space. The cycle is dynamic as opposed to quasi-static as the piston has kinetic energy equal in difference to the work performed internally and externally.     

驻波型热声制冷机熵产分析

声制冷机是一种新型制冷机,具有无机械运动部件,可靠性高寿命长,采用惰性气体为工质无污染等优点．驻波型热声制冷机的声功泵热效应是不可逆过程,内部不可逆损失导致热声制冷机效率偏低,制约了热声制冷机的发展和应用．本文研究了线性范围内驻波型制冷机换热器和回热器内的可压缩振荡流动与传热过程的熵产,分析了板间距,振荡频率和温度梯度对熵产的影响。     

Density functional theory study of structural stability for gas hydrate

Using the first-principles method based on the density functional theory(DFT),the structures and electronic properties of different gas hydrates(CO_2,CO,CH_4,and H_2) are investigated within the generalized gradient approximation.The structural stability of methane hydrate is studied in this paper.The results show that the carbon dioxide hydrate is more stable than the other three gas hydrates and its binding energy is-2.36 e V,and that the hydrogen hydrate is less stable and the binding energy is-0.36 e V.Water cages experience repulsion from inner gas molecules,which makes the hydrate structure more stable.Comparing the electronic properties of two kinds of water cages,the energy region of the hydrate with methane is low and the peak is close to the left,indicating that the existence of methane increases the stability of the hydrate structure.Comparing the methane molecule in water cages and a single methane molecule,the energy of electron distribution area of the former is low,showing that the filling of methane enhances the stability of hydrate structure.     

Modeling the properties of methane + ethane (Propane) binary hydrates,depending on the composition of gas phase state in equilibrium with hydrate

The properties of methane + ethane and methane + propane hydrates of cubic structures sI and sII are theoretically investigated. It is shown that the composition of the formed binary hydrate strongly depends on the percentage of a heavier guest in gas phase. For instance, for a 1% molar ethane concentration in gas phase, even at a low pressure, ethane occupies 60% large cavities in the hydrate sII, and as the pressure grows to 100 atm, it occupies 80% large cavities at a low temperature. The tendency remains the same at a temperature of higher than the ice melting point, but the methane concentration in the hydrate decreases to 30%. In the structure sI, the influence of the component composition of the gas mixture on that of the formed hydrate is less evident. However, in this case, calculation showed also that for a 1% molar ethane concentration in gas phase, ethane molecules occupy from 8 to 10% large hydrate cavities, depending on the pressure. This work is concerned with modeling phase transitions between cubic structures sI and sII of methane + ethane binary hydrates in view of incomplete occupation of cavities in the hydrate by guest molecules. For an ethane concentration under 2% in the gas mixture, the structure sII becomes more thermodynamically stable than the structure sI. However, as the ethane concentration grows to 20% in the equilibrium ice-gas-hydrate and to 40% in the equilibrium water-gas-hydrate, the structure sI becomes more thermodynamically stable. Hence, for low ethane concentrations in a gas mixture, the structure sI can be formed only as a metastable phase. Phase equilibria of methane hydrate sI and mixed methane + propane hydrate sII are considered, depending on the gas phase composition. Similar results are obtained for this equilibrium; this can evidence simultaneous formation of hydrates sI and sII at low propane concentrations.     

Theoretical investigation of the possibility of using multicomponent (N2-O2-CH4-Y2O) clathrate hydrates for methane recovery from mine gas

Phase equilibria in a multicomponent ice-gas mixture-hydrate system are investigated for a mixture of nitrogen, oxygen, and methane, depending on the gas phase composition, pressure, and temperature. Equilibrium compositions of the formed hydrates are found, depending on the gas mixture composition. Calculations show that with increasing concentration ofmethane in gas phase the pressure of hydrate formation gradually decreases. It is shown that this pressure at considerable methane concentrations approximately corresponds to partial pressure of methane in the gas phase. Conditions of hydrate formation are calculated in the range of temperatures from 258 to 273 K, at pressures from 1 to 350 atm. The obtained results are in agreement with the known experimental data for hydrates of pure gases-nitrogen, oxygen, and methane.     

甲烷水合物形成促进技术实验研究

实验研究了液态烃(环戊烷和甲基环己烷)对甲烷水合物形成条件的影响,测试结果表明液态烃降低了甲烷水合物的形成压力,并改变了形成水合物的结构。实验研究了促进剂(液态烃和表面活性剂)对水合物形成诱导时间和生长过程的影响,结果表明液态烃和表面活性剂降低了水合物形成的诱导时间,提高了水合物形成速度;而且表面活性剂提高了水合物形成过程中的耗气量,并改变了水合物形成机理。     

非平衡热力学中传热过程熵产表达式的修正

熵产是非平衡热力学中的核心物理量,传统上表示为广义力(驱动力)与广义流的乘积.这种表达存在两方面缺陷:一是广义力与广义流的拆分具有任意性;更重要的是,以其计算热波传递时熵产可以为负值,从而违反热力学第二定律.本文基于热质理论分析表明,传热过程的熵产实质上是由热质流体的热质能耗散引起的,所以熵产中的力不是驱动力而是阻力,并且具有力的量纲.由此提出的熵产修正表达式,不仅在计算热波传递过程中熵产恒为正值,与扩展不可逆热力学中的熵产表达式一致,而且不存在力和流拆分的任意性.     

热波传递过程中的熵产分析

傅里叶导热定律导出的温度演化方程将得出无限大的热扰动传播速率。为了克服这个问题,一些修正导热模型被提出,可以得到双曲型温度方程,保证有限的热波传播速率。但是,新的传热模型得出的温度演化将使现有的不可逆热力学中熵产不能保持正定。拓展不可逆热力学通过修正熵以及熵产的表达式,使双曲导热也能得到正定的熵产率。热质理论用力学的概...     

Molecular dynamics study on the dissociation of methane hydrate via inorganic salts

Hydrate plugging is a hidden threat to the safe exploitation of oil and gas. Inorganic salts are widely used as thermodynamic inhibitors to effectively prevent the hydrate formation. This study uses a molecular dynamics method to explore the mechanism of the hydrate dissociation via inorganic salts on the micro-scale. We simulated the dissociating process of methane hydrate under different concentration series of NaCl, KCl and CaCl₂ solutions at 273 K, and analysed the changes of ionic structure, transport parameters and kinetic energy in the system of inorganic salt/hydrate. The simulation results successfully revealed the step-by-step dissociation of hydrate, and the differences in dissociation rates among the different inhibitors. The energy needed for hydrate dissociation alters for different inorganic solutions; the energy reaches maximum when KCl is the inhibitor, and lowest when the concentration of CaCl₂ exceeds 30% w/w. We calculated the coordination numbers of all components, including oxygen atoms, cations and anions, and also their diffusion coefficients; analysed the effects of the three inorganic salts on the simulated hydrate structure and its transport; in addition, investigated the mechanism of hydrate dissociation via inorganic salts.     

TheH theorem and irreversible thermodynamics

Following a method first introduced by Prigogine, theH theorem is written as the law of increase of entropy for a slightly inhomogeneous gas. It is shown that the local rate of entropy production for such a gas is simply a homogeneous quadratic form of the generalized forces associated with the various irreversible processes with coefficients possessing all the properties of the phenomenological coefficients of irreversible thermodynamics. The local rate of entropy production is explicitly evaluated for a simple monatomic gas and is compared with the corresponding expression of irreversible thermodynamics.     

Performance Analysis and Optimization for Irreversible Combined Carnot Heat Engine Working with Ideal Quantum Gases

An irreversible combined Carnot cycle model using ideal quantum gases as a working medium was studied by using finite-time thermodynamics. The combined cycle consisted of two Carnot sub-cycles in a cascade mode. Considering thermal resistance, internal irreversibility, and heat leakage losses, the power output and thermal efficiency of the irreversible combined Carnot cycle were derived by utilizing the quantum gas state equation. The temperature effect of the working medium on power output and thermal efficiency is analyzed by numerical method, the optimal relationship between power output and thermal efficiency is solved by the Euler-Lagrange equation, and the effects of different working mediums on the optimal power and thermal efficiency performance are also focused. The results show that there is a set of working medium temperatures that makes the power output of the combined cycle be maximum. When there is no heat leakage loss in the combined cycle, all the characteristic curves of optimal power versus thermal efficiency are parabolic-like ones, and the internal irreversibility makes both power output and efficiency decrease. When there is heat leakage loss in the combined cycle, all the characteristic curves of optimal power versus thermal efficiency are loop-shaped ones, and the heat leakage loss only affects the thermal efficiency of the combined Carnot cycle. Comparing the power output of combined heat engines with four types of working mediums, the two-stage combined Carnot cycle using ideal Fermi-Bose gas as working medium obtains the highest power output.     

强迫耗散系统的有序结构和系统的发展(Ⅰ)，最小熵产生原理和有序结构

一个系统的发展总是由不可逆热力过程和非线性动力过程所驱动.将大气动力学方程组同考虑了动能变化的Gibbs关系结合起来构建的熵平衡方程，才能更好地描述大气系统的不可逆热力过程和非线性动力过程.至今非平衡态热力学仅利用Onsager线性唯象关系证明了最小熵产生原理.利用新建立的熵平衡方程和大气动力学方程的性质证明，最小熵产生原理在热力学线性区和非线性区都是普遍成立的.且当热量输送平衡、水汽输送平衡和动量输送平衡时，系统达到不可逆过程最弱的最小熵产生热力学状态.当系统又是动力平衡且无平流时，这种最小熵产生态就是 关键词： 非线性热力学 熵产生 最小熵产生原理 有序结构