海底冷泉气体渗漏模拟观测系统设计与开发

由于海底冷泉声探测需要准确的气泡特征信息作为支撑，以真实海底冷泉气泡分布特征为依据，研制了控制精度高、功能全的海底冷泉气体渗漏模拟观测系统。通过模糊PID控制算法对气体流量进行精准控制，相比于常规控制方法流量误差率最高可降低1.5%,可以准确可控地模拟真实环境下的冷泉气泡；通过设计的以太网同步触发器驱动双相机同步拍摄，使拍摄同步误差范围降低1.1 ms,实现了对初始溢出阶段气泡形态的正交同步观测，能够为海底冷泉探测提供数据支持。     

基于SONIC软件的鄂霍次克海浅表陆坡可燃冰勘探研究

运用自主研发设计的SONIC软件,控制深海勘探设备Echo水声探测系统,对位于西北太平洋边缘的鄂霍次克海海底可燃冰甲烷释放情况进行勘探研究。重点对萨哈林岛东面浅表陆坡进行了大规模的水声测扫,通过采集回声信号,应用SONIC软件处理和成像后,实现了海底甲烷气体渗漏点（GF）、冷泉和海床的可视化。在发现甲烷气体渗漏点后,运用SONIC的成像功能,分析冷泉中甲烷气体浓度及形态的变化,运用GPS系统进行实时跟踪与定位,利用重力取样器等采样工具,在多个海域成功采集到了可燃冰岩心样本,并及时进行了分析,得到了该地区可燃冰中的甲烷排放速率和甲烷排放量等数据。另外,通过梳理本次考察的经验,对规范我国可燃冰资源调查方法也会产生积极影响。     

考虑超孔压影响的海底能源土斜坡稳定性数值模拟和评价

水合物分解极易引起海底能源土出现超孔压现象,进而导致能源土变形,引发海底滑坡等地质灾害。本文基于热力学基本理论,并考虑水合物最终分解状态下的相态演变,以及水合物分解过程中海水对甲烷气体的溶解,修正了孔隙气体非逃逸的Grozic超孔压模型,并将修正模型应用到海底能源土斜坡稳定性分析中。研究结果表明：考虑甲烷气体在海水中的溶解,采用修正模型计算的超孔压值相比于原模型减小约26%;水合物分解过程中,相比土体强度参数软化这一不利因素,超孔压积聚对斜坡稳定性影响更为明显,因此在海底能源土斜坡稳定性分析中,必须考虑超孔压积聚这一不利因素。     

SDS促进剂对甲烷水合物蓄冷量的影响

甲烷水合物蓄冷量的确定是甲烷水合物蓄冷降温技术实现工业化的关键。为探究SDS对甲烷水合物蓄冷量的影响,根据Clausius-Clapeyron方程及三参数对应态原理,建立甲烷水合物蓄冷量的计算模型。利用可视化水合物蓄冷实验系统,结合定温压力搜索法测定四组不同SDS浓度体系下甲烷水合物的相平衡条件。依据实验数据和该模型计算得到不同体系、不同相平衡参数下甲烷水合物的蓄冷量。结果表明:甲烷水合物具有较高的蓄冷密度,蓄冷量达40~60 kJ/mol;甲烷水合物的蓄冷量不但与相平衡条件有关,还与SDS的添加浓度有关。相平衡温度越高、SDS添加浓度越高,甲烷气体生成水合物时蓄冷量越低。该研究为甲烷水合物蓄冷降温系统的研制提供了参考。     

甲烷水合固化过程反应热实验研究

为及时将气体水合过程中的反应热传递出去,使水合物稳定快速生成,利用可视化实验系统研究了三种体系甲烷水合物生成过程中的反应热。根据甲烷水合物相平衡数据,结合推导出的反应热计算方程,计算三种实验体系的反应热。结果表明,在表面活性剂的作用下,甲烷水合物的生成速率提高,对应的反应热增多。     

水-气体系生成水合物的缩泡动力学模型

在对海下沉积层中水合物的生成机理、水合物的生成实验现象和已有模型分析的基础上,提出了一种水-气体系水合物生成的缩泡动力学模型,认为溶液中气体首先形成气泡,然后和水反应形成水合物.模型以水合物体积的变化来表示水合物的生成速率,避免了单纯以化学反应过程或结晶过程表达水合物生成速率的缺陷,因此能够准确地表达水合物的生成过程.研究结果表明,在不同初始条件下的计算结果与文献结论一致,不同气体和不同传质系数条件下的计算结果经实验验证正确,甲烷、乙烷及混合气在相同初始条件下,乙烷水合物的层厚度大于甲烷和混合气体水合物的层厚度.在传质系数较大时,水合物的层厚度增加速度也明显较大,因此符合表面活性剂能够加速水合物生成的机理.     

利用多波束水体成像数据进行管道气体泄漏检测

针对当今海底天然气输送管道泄漏事件频频发生的现象,以多波束测深声纳的水体成像数据作为数据来源,设计了一种针对海底天然气管道的泄漏检测方法。该方法主要结合旁瓣抑制和海底底部检测以提高气体泄漏检测的稳定性和可靠性,通过水体成像数据的预处理、形态学处理、最大熵分割及连通区域目标标记等处理流程,得到泄露气体的疑似目标区域。水体成像数据采用真实水池测试数据,通过检测结果可证明该方法能够有效提取泄漏气体的疑似区域,并为之后水体目标检测、识别奠定基础,具有较好的工程应用前景。     

考虑甲烷溶解的天然气水合物分解超孔隙水压力

天然气水合物的分解会生成大量气体和水,在土层渗透性较差的情况下,大量气体无法及时溢出,压力不易传导到外部,使土层的超孔隙水压力迅速增大,有效应力降低,同时水合物分解后其自身与沉积物的胶结作用大幅减小,导致沉积物强度降低,发生大规模变形或失稳,进而引发海底失稳等灾害。基于热力学基本理论,建立了考虑水合物分解产生的甲烷气体部分溶解的超孔隙水压力模型,并对其影响因素进行讨论,最后针对南海工况研究水合物分解对海床稳定性的影响。结果表明,水合物分解产生的超孔隙水压力随着水合物分解先迅速增大后缓慢增长最后趋于稳定;初始饱和度、塑性指数、水深、沉积物埋深、内摩擦角等是影响水合物分解产生的超孔隙水压力的关键影响因素;影响海床稳定性的关键不利因素是超孔隙水压力聚积而非土体强度弱化;生成的甲烷气体二次溶解使超孔隙水压力减小,一定程度上缓解了斜坡的滑动。     

丙烷含量对多组分气体水合物生长速率的影响

为使多组分瓦斯气体迅速固化、储运,利用可视化水合物实验设备,研究了三种多组分气样在0.1 mol/L四氢呋喃(THF)和0.2 mol/L十二烷基硫酸钠(SDS)复配溶液中的水合固化过程,实验获取了水合物生成过程的压力-温度-时间曲线,结合水合物生长速率模型对实验数据进行计算和分析。结果表明:三种气样中随着丙烷含量的提高,生长速率呈增大趋势,在一定程度上可以提高水合物生长速率,抑制水合物中甲烷的含量。     

分子动力学模拟研究ZIF-8颗粒对甲烷水合物形成过程的影响

为了揭示ZIF-8颗粒对甲烷水合物形成过程的微观影响机理,通过分子动力学模拟方法研究了有/无ZIF-8颗粒体系中的甲烷水合物成核及生长过程。结果表明：ZIF-8颗粒的加入会影响甲烷水合物的成核及生长动力学,加速或减缓水合物的成核及生长过程。ZIF-8不同的加入量对水合物形成动力学亦有着不同的影响作用。其中,加入少量的ZIF-8颗粒可在不降低水溶液中甲烷过饱和度的情况下,通过加速甲烷分子在水溶液中的运移及水分子的组装行为,促进水合物前驱体及闭合笼状结构的形成,推动水合物的快速成核及生长。当加入的ZIF-8颗粒达到一定浓度时会在短时间内吸引更多的甲烷分子从水溶液中逃离出来并在其表面聚集成纳米气泡,致使水溶液中的甲烷浓度降低、水合物形成驱动力下降,最终导致水合物的形成过程被明显地抑制。     

First discovery and characterizations of late Cretaceous seep carbonates from Xigaze in Tibet, China

Hydrocarbon seeps,widely occurring in continental margins,have become increasingly focused owing to their close relationships with gas hydrates,strong greenhouse gas methane,and biological resources in extreme environments.Ancient hydrocarbon seeps have already been recognized from Devonian to Quaternary strata worldwide based on seep carbonates or seep-related fossil chemosynthetic assemblages.However,seep-related deposits are rarely found from ancient strata in the mainland China.Here,we report the first discovery of an ancient seep deposit,specifically late Cretaceous seep carbonates from Xigaze in Tibet,China.Xigaze seep carbonates,occurring as nodules,are enclosed in upper Cretaceous turbidite strata in Xigaze forearc basin.These carbonates are composed of authigenic carbonate(56.2% on average),clastic quartz and feldspar(27.3% on average),and clay minerals(chlorite,illite and smectite,16.5% on average).Clotted micrites,peloids and framboid pyrites are frequently observed,all of which are common in modern seep carbonates.The carbonates have negative δ13 C values varying from 27.7‰ to 4.0‰(V-PDB),suggesting that thermogenic methane is the primary carbon source.Ce/Ce* values revised by eliminating La effects show no real Ce anomaly,indicating the carbonates were primarily precipitated in a weak reducing environment.Overall,these features provide unequivocal evidences that the seafloor of Xigaze forearc basin developed hydrocarbon seeps in late Cretaceous.     

Glycerol ether biomarkers and their carbon isotopic compositions in a cold seep carbonate chimney from the Shenhu area,northern South China Sea

At modern cold seeps,the anaerobic oxidation of methane(AOM)is the dominant pathway for methane consumption in marine sediments.AOM,which is mediated by a consortium of methane oxidizing archaea and sulfate reducing bacteria,is proposed to be responsible for authigenic carbonate formation.A methane-derived carbonate chimney was collected from the Shenhu area, northern South China Sea.The membrane lipids and their very low carbon isotopic compositions(?115‰to?104‰)in the Shenhu chimney suggest the presence of an AOM process.Three specific archaeal and bacterial biomarkers were detected,including Ar,DAGE 1f,and monocyclic MDGD.Their strongly depleted??13C values(?115‰to?104‰),which are lower than those of the normal marine lipids in sediments,reveal biogenic methane as their origin.The carbonate deposits exhibiting a chimney structure indicate that a vigorous methane-rich fluid expulsion may have occurred at the seafloor.We propose that the decomposition of gas hydrates at depth is the likely cause of seepage and cold seep carbonate formation in the Shenhu area.     

气体水合物法开发高寒地区湖盐的相平衡预测

中国高寒地区年平均气温为气体水合物的生成提供了天然的温度条件,也为气体水合物法实现高寒地区湖盐的节能开发提供了可能.提出气体水合物法开发高寒地区湖盐的新方法,以van der Waals-Platteeuw模型为基础,结合杜亚和郭天民提出的计算Langmuir常数的三参数方程和计算电解质溶液中水的活度的Pitzer方程,预测饱和NaCl溶液中甲烷水合物、乙烷水合物和丙烷水合物的相平衡条件,对比饱和NaCl溶液凝固点,发现利用环境冷量实现气体水合物法开发湖盐具有实际可行性;与甲烷、乙烷气体相比,丙烷气更适合用于湖盐开发.     

Origin and nature of cold seep in northeastern Dongsha area, South China Sea: Evidence from chimney-like seep carbonates

The occurrence of seep carbonates is one of the characteristic features for cold seep sites at continental margins.The carbonates documented the venting history of methane-rich fluid.Compared to the chemoherm carbonates and carbonate pavements which formed on the sediment-water interface,chimney-like seep carbonates precipitated around fluid conduits below the sediment-water interface therefore better recording information of the past fluid flow and composition.Here the chimney-like seep carbonate samples from the northeastern Dongsha area of the South China Sea were studied to understand the origin and nature of the venting fluids and their potential relationship with gas hydrate deposits underneath the seafloor.Based on the occurrence,morphology,petrology,mineralogy and C-and O-isotope compositions,combined with present and past bottom water temperatures and the timing of methane release events,the oxygen isotopic fractionation between calcite and water were used to estimate the equilibriumδ18O values of the precipitating fluids.Theδ13C values ranging from 56.33‰to 42.70‰V-PDB and thus clearly show that the studied chimneys were mainly derived from biogenic methane oxidation.The calculated equilibriumδ18O values of the precipitating fluids ranged from 1.9‰0.3‰to 0.6‰0.3‰V-SMOW,with an average of 1.4‰0.3‰V-SMOW which is heavier than those of seawater even at the last glacial maximum.It is considered that the formation of chimney-like carbonates was closely related to methane hydrate dissociation in the area.The methane hydrates contributed as much as45.7%of water to the venting fluids.It is suggested that the climate and environmental changes(e.g.sea-level lowering,down-cutting canyons and mass wasting)are the major mechanisms maybe responsible for the destabilization of methane hydrates in the study area.The extensive occurrence of seep carbonates indicates that a large amount of the methane released from methane hydrate dissociation has been effectively captured and sequestered by microbial anaerobic oxidation of methane(AOM)before it escapes into the water column.     

甲烷浓度对瓦斯水合物生长速率的影响

为提高瓦斯水合物生成速率,利用可视化水合物实验设备,研究了四种不同甲烷体积分数的高浓度瓦斯气样在0.3 mol/L四氢呋喃（THF）和0.2 mol/L十二烷基硫酸钠（SDS）复配溶液中水合固化过程,获取了瓦斯水合物生成过程的压力-时间曲线,结合水合物生长速率模型对数据进行计算和分析。结果表明：随着甲烷体积分数的提高,瓦斯水合物生长速率呈增大趋势,最大可达5.40×10~（-6）m~3/min;THF-SDS复配体系在一定程度上提高了瓦斯水合物生长速率,促进了水合物的形成。该研究为应用水合物技术进行瓦斯固化储存提供了参考数据。     

Discovery of seep carbonate nodules as new evidence for gas venting on the northern continental slope of South China Sea

The geotectonic evolution of the northern South China Sea (SCS) is controlled by the Eurasian, the Pa-cific and the Indian-Australian Plates. With regard to its tectonic evolution, the northern margin composed of faulted terraces and basins and deposited …