Pore pressure built-up in hydrate-bearing sediments during phase transition: A poromechanical approach

Due to the density contrast between the hydrate and methane gas,the pore pressure is accumulated in the sediment during the decomposition process of methane hydrate.This accumulation of pore pressure decreases the magnitude of effective stress,further triggering potential geological disasters such as landslide.This paper establishes a theoretical framework to investigate the evolution of fluid pressure in the hydrate-bearing sediments during the decomposition process.This model consists of two parts:an unsaturated thermo-poromechanical constitutive law as well as a phase equilibrium equation.Compared with the existing studies,the present work incorporates the effect of pore volume change into the pressure built-up model.In addition,the capillary effect is considered,which plays a nontrivial role in fine-grained sediments.Based on this model,the evolution of fluid pressure is investigated in undrained conditions.It is shown that four mechanisms mainly contribute to the pressure built-up:the density contrast between decomposing hydrate and producing fluid,the variation of pore volume,the compaction of hydrate due to variation of capillary pressure,and the thermal deformation of pore constituents induced by temperature change.Among these mechanisms,the density contrast dominates the pore pressure accumulation.Under the combined effect of these contributions,the evolution of fluid pressure exhibits a strong nonlinearity during the decomposition process and can reach up to dozens of mega Pascal.Nevertheless,this high-level pressure built-up results in a significant tensile strain,yielding potential fracturing of the sediment.

In situ High-pressure NMR Observations on the Formation and Dissociation of Methane Hydrate

A home-made static NMR cell with pressure up to 10 MPa was employed to observe the formation and dissociation processes of methane hydrate by in situ ^1H and ^13C NMR spectroscopies. Methane hydrate can be formed or decomposed in the temperature range of -5 to -13℃ at pressures between 4.0 and 7.0 MPa. The higher methane pressure, the formation or dissociation temperature of methane hydrate was higher. In situ ^1H NMR experiments indicated that the critical size of the hydrate clusters is crucial for the formation of methane hydrate.

Pressure Tight Piston Corer—A New Approach on Gas Hydrate Investigation

A pressure tight sediment sampling technology, which can be introduced into the modification of the piston corer to accommodate the investigation of gas hydrate, is put forward. In this paper, the three basic rules of the technology are analyzed in detail: specimen transferring rule, seal self-tightening rule and semi-active pressure holding rule. Based on these, the structure of the pressure tight piston corer is put forward and its working principle is analyzed. Finally, a pressure tight sediment sampler, to which the same technology is applied, is researched through experiments. Results show that the sampler based on the above-mentioned theory has a good ability in sampling and in -situ pressure holding.

Research on Pressure Tight Sampling Technique of Deep-Sea Shallow Sediment—A New Approach to Gas Hydrate Investigation

Analyzed and calculated are pressure changes and body deformation of the sample inside of the corer in the process of sampling of deep-sea shallow sediment with a non-piston corer for gas hydrate investigation, Two conclusions are drawn： （1） the stress increments associated with the corer through the sampling process do not affect the stabilization of the gas hydrate; （2） the body deformation of the sample is serious and the ＂incremental filling ratio＂ （IFR） is less than unit, For taking samples with in-situ pressure and structure, combining with the design theories of the pressure tight corer, we have designed a kind of piston corer, named the gas hydrate pressure tight piston corer, Several tests on the sea have been conducted. Test results indicate that the piston corer has a good ability of taking sediment samples on the seafloor and maintaining their original in-situ pressure, meeting the requirement of exploration of gas hydrate in deep-sea shallow sediment layers.

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.

Pore capillary pressure and saturation of methane hydrate bearing sediments

To better understand the relationship between the pore capillary pressure and hydrate saturation in sediments, a new method was proposed. First, the phase equilibria of methane hydrate in fine-grained silica sands were measured. As to the equilibrium data, the pore capillary pressure and saturation of methane hydrate were calculated. The results showed that the phase equilibria of methane hydrates in fine-grained silica sands changed due to the depressed activity of pore water caused by the surface group and negatively charged characteristic of silica particles as well as the capillary pressure in small pores together. The capillary pressure increased with the increase of methane hydrate saturation due to the decrease of the available pore space. However, the capillary-saturation relationship could not yet be described quantitatively because of the stochastic habit of hydrate growth.

Structural stability of methane hydrate at high pressures

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil ceils. The diffraction data for types II （slI） and H （sH） were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sl methane hydrate transforms to the sll phase at 120 MPa, and then to the sH phase at 600 MPa. The slI methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII （Pn3m）. The results highlight the role of guest （CH4）-host （H2O） interactions in the stabilization of the hydrate structures under pressure.

A study of hydrate plug formation in a subsea natural gas pipeline using a novel high-pressure flow loop

The natural gas pipeline from Platform QKI8-1 in the southwest of Bohai Bay to the onshore processing facility is a subsea wet gas pipeline exposed to high pressure and low temperature for a long distance. Blockages in the pipeline occur occasionally. To maintain the natural gas flow in the pipeline, we proposed a method for analyzing blockages and ascribed them to the hydrate formation and agglomeration. A new high-pressure flow loop was developed to investigate hydrate plug formation and hydrate particle size, using a mixture of diesel oil, water, and natural gas as experimental fluids. The influences of pressure and initial flow rate were also studied. Experimental results indicated that when the flow rate was below 850 kg/h, gas hydrates would form and then plug the pipeline, even at a low water content （10%） of a water/oil emulsion. Furthermore, some practical suggestions were made for daily management of the subsea pipeline.

Decomposition Kinetics for Formation of CO_2 Hydrates in Natural Silica Sands

The decomposition kinetics for formation of CO2 hydrates in 90 cm 3wet natural silica sands were studied systematically using the depressurization method at the temperatures ranging from 273.2 to 277.2 K and the pressures from 0.5 to 1.0 MPa.The effects of temperature,pressure,particle diameter,porosity,and salinity of formation water on the decomposition kinetics were investigated.The results show that the dissociation percentage increases as temperature increases or as the initial decomposition pressure decreases.An increase in porosity or a decrease in particle diameter of silica sands accelerates the decomposition.Increasing the salinity of the formation water gives rise to a faster decomposition.However,a combination of the present results with the observations in literature reveals that the effect of the coexisting ionic solute depends on its chemical structure.

Research and application of thermal insulation effect of natural gas hydrate freezing corer based on the wireline-coring principle

Natural gas hydrate(NGH)holds great promise as a source of clean energy.It is critical for acquiring the largest possible in situ NGH core for NGH eigen features and resource assessment.However,the existing NGH coring technology has limitations,such as temperature increments,limited coring diameters,low coring rates,and complex coring structures.Therefore,this study designs and proposes an NGH freezing coring(NGHFC)method and verifies the freezing and coring capacities of the NGHFC method in laboratories and experimental wells.Results suggest that NGHFC shows good freezing and heat-retention properties.A freezing core heat transfer model is developed.According to the actual air temperature and operating time,the optimum initial temperature of the cold source can be determined using this model.The average coring rate of NGHFC can reach 77.86%.The research results will provide a new idea of coring gas hydrates.

A Preliminary Study on Hydrate Anti-agglomerant Applied in Multiphase Flow Pipeline

When new types of hydrate chemical inhibitor （such as hydrate anti-agglomerant） are used in offshore fields, some difficulties will be encountered in the pipe transportation processing design. In view of these difficulties, a horizontal flow experiment pipe loop of transparent polypropylene pipe （25.4 mm inner diameter, 20 m long） was constructed, and some experiments were conducted. The working fluids were the mixed paraffin hydrocarbons, water and condensate oil mixtures obtained from offshore oil field. Analyzing the experimental results and adopting relevant theories of liquid-solid two-phase flow, the computational method of hydrate slurry transportation in pipe was developed. For the operating conditions of a certain multiphase pipeline, by using OLGA software, this method can be used to calculate pressure drop of the multiphase flow pipelines using anti-agglomerant, which can provide support for hydrate anti-agglomerant application.

Meso-level simulation of gas hydrate dissociation in low-permeability sediments

This paper presents a meso-level simulation of gas hydrate dissociation in low-permeability marine sediments. Interstitial pores are defined to describe fluid flow and particle movement. The proposed model couples multiphase fluid flow with particle movement to simulate the thermodynamics of gas hydrate dissociation triggered by sharp temperature rises. Hydrates respond quickly to temperature rise in low-permeability sediments. Dissociation causes pore pressure to rise rapidly to equilibrium then steadily increase above equilibrium pressure. Lower permeability sediment builds up greater excess pore pressure as the dissipation of pore pressure is constrained.

Laboratory measurement of longitudinal wave velocity of artificial gas hydrate under different temperatures and pressures

The longitudinal wave velocity and attenuation measurements of artificial gas hydrate samples at a low temperature are reported. And the temperature and pressure dependence of longitudinal wave velocity is also investigated. In order to understand the acoustic properties of gas hydrate, the pure ice, the pure tetrahydrofuran (THF), the pure gas hydrate samples and sand sediment containing gas hydrate are measured at a low temperature between 0°C and ?15°C. For the pure ice, the pure THF and the pure gas hydrate samples, whose density is 898 kg/m3, 895 kg/m3 and 475 kg/m3, the velocity of longitudinal wave is respectively 3574 m/s, 3428 m/s and 2439 m/s. For synthesized and compacted samples, the velocity of synthesized samples is lower than that of compacted samples. The velocities increase when the densities of the samples increase, while the attenuation decreases. Under the condition of low temperature, the results show that the velocity is slightly affected by the temperature. The results also show that wave velocities increase with the increase of piston pressures. For example, the velocity of one sample increases from 3049 up to 3337 m/s and the other increases from 2315 up to 2995 m/s. But wave velocity decreases from 3800 to 3546 m/s when the temperature increases from ?15°C to 5°C and changes significantly close to the melting point. Formation conditions of the two samples are the same but with different conversion ratios of water. The results of the experiment are important for exploration of the gas hydrate resources and development of acoustic techniques.

Fractal-like Kinetic Characteristics of Coalbed Methane Hydrate Dissociation at Normal Pressure

Surface modality of coalbed methane hydrate and fractal-like kinetic characteristics of the hydrate dissociation at normal pressure have been studied by using fractal geometry theory. The results show that the surface modality of coalbed methane hydrate has fractal characteristic, and the dissociation kinetics of coalbed methane hydrate is fractal-like. Moreover, a new kinetic model for coalbed methane hydrate dissociation was proposed, and its reliability was validated.

水合物开采模拟超重力试验装置的研发及应用

天然气水合物是突破世界能源瓶颈的重要潜在能源,广泛分布于深海沉积物和陆域永冻土。水合物赋存在高压低温环境下,储层厚度达数十至百米,大尺度储层重力场显著影响其开采时的液气渗流、储层变形和传热过程,进而影响开采产气效率且可能诱发工程灾变。研发了一套能够在超重力场下模拟大尺度水合物储层长历时开采演变过程的离心模型试验装置,主要由高压釜系统、水合物制备模块、水压力控制模块、水合物开采模块、监测与响应模块组成。该装置能够在100g超重力下伺服调控高压釜内气液压力和温度环境,在模型尺度上有效再现水合物储层应力、温度和荷载条件。在系统介绍装置研发思路和技术特色的基础上,通过100g下水合物储层模型降压分解试验探析了原位等效重力场下储层不同深度处孔压演化规律及开采产气特性,再现了Nankai海槽原位试采产气速率峰值模式,为揭示水合物储层开采相变多相多场耦合机制和灾变防控提供了新的研究手段。

熟化银精矿氧压强化酸浸行为研究

考虑到浮选银精矿极具回收价值及现有处理工艺存在不足,本文提出了浓硫酸熟化-氧压酸浸的工艺路线。首先,以湿法炼锌过程产出的浮选银精矿为对象,利用浓硫酸的强氧化性破坏浮选残留有机药剂矿物包裹体;其次,利用加压湿法冶金独特的技术优势,氧化溶解低价金属硫化物;最后,重点研究了工艺过程原理及氧压酸浸过程中Zn、Cu、In的浸出行为及浸出渣中物相演变规律。研究结果表明:银精矿颗粒表面残留浮选药剂的P—O、—OH极性基团被浓硫酸氧化破坏,避免产生水化膜及矿物包裹体,促进有价元素的高效浸出;在高温氧化性条件和Fe^(3+)/Fe^(2+)变价离子对的助浸作用下,银精矿物相组成由闪锌矿(Zn S)、锌铁尖晶石(Zn Fe_(2)O_(4))、雌黄铁矿(FeS)、氯化亚铜(Cu Cl)为主,转变为以单质硫(S8)、铁矾(MeFe_(3)(SO_(4))_(2)(OH)_(6),Me:1/2Pb、Na、K)为主,并残留少量的闪锌矿(Zn S);适当提高反应温度和初始质量浓度可促进Zn、Cu、In的浸出,但温度过高会加剧铟铁共沉淀问题,降低锌、铟的浸出率,而质量浓度过高会降低氧气对Zn S及Fe^(2+)的氧化能力,抑制银精矿的溶解;延长反应时间、提高液固比均有利于银精矿的解离浸出;增大氧分压可以加强Fe^(3+)的氧化能力,促进对Zn S及ZnxFe(1-x)S的氧化作用,有利于银精矿的溶解。在反应温度为155℃、初始质量浓度为160 g/L、反应时间为180 min、氧分压为0.8 MPa、液固比为7 m L/g的氧压酸浸条件下,银精矿中Zn、Cu、In的浸出率分别为94.84%、98.36%和91.13%,浸出渣中铅、银的富集率分别达2.88%和7754 g/t。

井研地区筇竹寺组页岩储层水平井钻井井壁稳定性评价

川西南井研区块筇竹寺组页岩气具有良好的开发前景,但由于对其岩矿组分、力学性质、水化特征等认识程度较低,钻井井壁稳定性认识不清,导致出现掉块、阻卡等复杂情况。为了充分认识该区寒武系筇竹寺组地层的井壁稳定性,明确粉砂质页岩水化作用及其对坍塌压力的影响规律,在岩石力学实验的基础上,研究不同钻井液浸泡时间对岩石力学参数的影响规律,建立考虑水化作用的井壁稳定性预测模型,分析不同井斜方位下坍塌压力的差异。研究结果表明:筇竹寺组伊蒙混层含量高,具有一定膨胀性,水化作用后导致岩石强度降低,对井壁稳定性有较大影响;不同钻井液体系对井壁稳定性的影响有差异,总体上油基钻井液更有利于井壁稳定;考虑了水化作用的井壁稳定预测模型更加符合实际,以此为依据,通过优化钻井液设计可以有效降低井壁失稳风险,提高钻井时效。

深井固井水泥浆凝固阶段的传压效率时变规律

随着油气井向深层超深层发展,地质条件愈加复杂,开采难度越来越大,尤其是高温高压、窄压力窗口地层是固井工程面临的突出难题。深层超深层压力敏感地层固井过程中,精确控制水泥浆柱压力是保障固井安全与水泥环层间封隔质量的关键。为探究凝固阶段水泥浆的失重规律和传压能力,建立了固井水泥浆静液柱压力评价装置和水泥浆传压效率评价方法,结合微量热仪和超声波静胶凝强度仪,测试了水泥浆水化过程不同厚度水泥浆的水化速率和静胶凝强度,最后分析了水泥浆失重和传压效率的时变规律。研究结果表明:①沉降稳定性良好的水泥浆体系,凝固阶段可根据其水化进程将失重分为水化诱导期的平稳阶段和水化加速期的快速降低阶段;②在水化诱导期内,悬浮分散结构的水泥浆静胶凝强度缓慢发展,其失重速率随厚度降低而加快,遵循胶凝悬挂理论,且该阶段液态水泥浆可高效、快速传递顶部压力,传压效率超过95%;③在水化加速期内,水泥浆变为凝胶网架结构,水化产物增强凝胶网架的强度及其与外界面胶结强度,转移固相重力和上部加压值至外界面,降低水泥浆静液柱压力和传压效率,最终使水泥浆丧失传压能力。结论认为,该规律认识可为压力敏感地层固井憋压候凝工艺的高效实施提供实验和理论支撑,为深层超深层油气的高效开发奠定坚实基础。

煤中超临界CO_(2)解吸滞后机理及其对地质封存启示

将CO_(2)注入不可采煤层地质封存既是降低温室气体效应最理想选择之一,也是煤炭工业降低CO_(2)排放、实现低碳化可持续发展的必由之路,然而,煤层CO_(2)地质封存悬而未决的关键问题是:“注入煤层中的CO_(2)到底能否长期停留而安全封存?”。鉴于此,在弄清煤体CO_(2)解吸滞后规律的基础上,揭示超临界CO_(2)解吸滞后机理,建立煤层CO_(2)地质封存量化模型,探讨利用解吸滞后实现煤层CO_(2)长期安全封存。研究表明:煤中超临界态CO_(2)解吸滞后程度大于亚临界态CO_(2),在超临界阶段,吸附与解吸等温线形成近似“平行线”的稳定滞后特征;解吸滞后的本质原因是煤中微纳米级亲水性孔隙形成弯液面、产生强大毛细压力、渗吸液态水、截断并固定超临界CO_(2)流体、最终形成了CO_(2)残余封存,例如,煤中直径40~10 nm圆柱形无机孔隙可产生7.30~29.12 MPa毛细压力,足以封堵超临界态CO_(2);以九里山煤样解吸等温线数据为例,采用基于煤层CO_(2)解吸滞后的地质封存量化模型,评估出900~1500 m深部二1煤层封存总量稳定在35~37 m^(3)/t,其中,吸附封存约占80%,残余封存约占15%,而结构封存仅占5%;解吸滞后启示应尽可能采取措施提高煤层残余封存CO_(2)比例,原因是毛细堵塞的残余封存CO_(2)较围岩密封的游离和吸附CO_(2)更安全且没有泄露风险,煤层灰分、水分、孔隙尺寸和形貌等物性参数是影响残余封存效率的主要因素。