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常见客体分子对笼型水合物晶格常数的影响 被引量:5
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作者 孟庆国 刘昌岭 +4 位作者 李承峰 郝锡荦 胡高伟 孙建业 吴能友 《物理化学学报》 SCIE CAS CSCD 北大核心 2020年第11期64-70,共7页
天然气水合物被认为是未来理想替代能源之一,相关基础与应用研究已成为国内外研究热点。客体分子对水合物晶胞参数的影响规律研究是水合物结构特征研究的重要内容,对理解水合物主客体分子间相互作用、形成分解微观机理及其稳定性变化具... 天然气水合物被认为是未来理想替代能源之一,相关基础与应用研究已成为国内外研究热点。客体分子对水合物晶胞参数的影响规律研究是水合物结构特征研究的重要内容,对理解水合物主客体分子间相互作用、形成分解微观机理及其稳定性变化具有重要意义。为考察不同客体分子对水合物微观结构特征的影响,本文合成了系列水合物样品(甲烷、乙烷、丙烷、异丁烷、二氧化碳、四氢呋喃、甲烷+2,2-二甲基丁烷和甲烷+甲基环己烷),并基于低温X射线衍射技术对样品结构特征进行了分析,探讨了水合物样品晶格常数与客体分子尺寸间的关系。结果表明,(1)低温X射线衍射技术能够有效获取天然气水合物样品的晶格常数及结构类型等特征。(2)甲烷、乙烷、丙烷及异丁烷等烷烃类同系物形成的单一组分水合物样品晶格常数与客体分子的尺寸(范德华直径)呈现正相关关系。同等条件下,分子尺寸越大,相应水合物的晶格常数越大。尺寸较小的甲烷、乙烷生成Ⅰ型结构水合物,而丙烷、异丁烷等相对较大的分子则形成Ⅱ型结构水合物。(3)含氧原子客体分子(如CO_2、THF)水合物样品的结构类型依然受范德华直径的控制,但其晶格常数与客体分子尺寸间的相关性不遵从烷烃类水合物的正相关关系,分析认为该现象是氧原子特殊的电负性致使客体分子与"水笼"间产生异常相互作用所致。(5) H型水合物样品中,大分子与辅助小分子对水合物不同方向晶轴长度影响分别呈现反向趋势特征。与甲烷+2,2-二甲基丁烷水合物样品相比,甲烷+甲基环己烷水合物样品a轴方向长度较短,而c轴方向长度略长。与相同温度下甲烷+2,2-二甲基丁烷水合物样品相比,由小分子氮气辅助形成的H型水合物样品晶胞a轴方向略长,而c轴方向长度较短。 展开更多
关键词 天然气水合物 粉末X射线衍射 结构特征 晶格常数 客体分子尺寸
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Undrained shear strength evaluation for hydrate-bearing sediment overlying strata in the Shenhu area, northern South China Sea 被引量:16
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作者 Yanlong Li Gaowei Hu +3 位作者 Nengyou Wu changling liu Qiang Chen Chen'an Li 《Acta Oceanologica Sinica》 SCIE CAS CSCD 2019年第3期114-123,共10页
The undrained shear strength of shallow strata is a critical parameter for safety design in deep-water operations.In situ piezocone penetration tests(CPTU) and laboratory experiments are performed at Site W18-19 in th... The undrained shear strength of shallow strata is a critical parameter for safety design in deep-water operations.In situ piezocone penetration tests(CPTU) and laboratory experiments are performed at Site W18-19 in the Shenhu area, northern South China Sea, where China's first marine hydrate exploitation operation is due to be located. The validation of the undrained shear strength prediction model based on CPTU parameters. Different laboratory tests, including pocket penetrometer, torvane, miniature vane and unconsolidated undrained triaxial tests, are employed to solve empirical cone coefficients by statistical and mathematical methods. Finally, an optimized model is proposed to describe the longitudinal distribution of undrained shear strength in calcareous clay strata in the Shenhu area. Research results reveal that average empirical cone coefficients based on total cone resistance, effective resistance, and excess-pore pressure are 13.8, 4.2 and 14.4, respectively. The undrained shear strength prediction model shows a good fit with the laboratory results only within specific intervals based on their compaction degree and gas-bearing conditions. The optimized prediction model in piecewise function format can be used to describe the longitudinal distribution of the undrained shear strength for calcareous clay within all depth intervals from the mud-line to the upper boundary of hydrate-bearing sediments(HBS). The optimized prediction result indicates that the effective cone resistance model is suitable for very soft to firm calcareous clays,the excess-pore pressure model can depict the undrained shear strength for firm to very stiff but gas-free clays,while the total cone resistance model is advantageous for evaluating the undrained shear strength for very stiff and gassy clays. The optimized model in piecewise function format can considerably improve the adaptability of empirical models for calcareous clay in the Shenhu area. These results are significant for safety evaluations of proposed hydrate exploitation projects. 展开更多
关键词 PIEZOCONE penetration TEST HYDRATE exploitation TEST UNDRAINED shear strength CALCAREOUS clay Shenhu area South China Sea
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P-T stability conditions of methane hydrate in sediment from South China Sea 被引量:6
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作者 Shicai Sun Yuguang Ye +2 位作者 changling liu Fengkui Xiang Yan Ma 《Journal of Natural Gas Chemistry》 EI CAS CSCD 2011年第5期531-536,共6页
For reasonable assessment and safe exploitation of marine gas hydrate resource, it is important to determine the stability conditions of gas hydrates in marine sediment. In this paper, the seafloor water sample and se... For reasonable assessment and safe exploitation of marine gas hydrate resource, it is important to determine the stability conditions of gas hydrates in marine sediment. In this paper, the seafloor water sample and sediment sample (saturated with pore water) from Shenhu Area of South China Sea were used to synthesize methane hydrates, and the stability conditions of methane hydrates were investigated by multi-step heating dissociation method. Preliminary experimental results show that the dissociation temperature of methane hydrate both in seafloor water and marine sediment, under any given pressure, is depressed by approximately -1.4 K relative to the pure water system. This phenomenon indicates that hydrate stability in marine sediment is mainly affected by pore water ions. 展开更多
关键词 sediment from South China Sea seafloor water methane hydrate stability condition
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Experimental study on geochemical characteristic of methane hydrate formed in porous media 被引量:1
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作者 Qiang Chen changling liu Yuguang Ye 《Journal of Natural Gas Chemistry》 EI CAS CSCD 2009年第2期217-221,共5页
The natural occurrence of methane hydrates in marine sediments has been intensively studied over the past decades, and geochemical charac-teristic of hydrate is one of the most attractive research fields. In this pape... The natural occurrence of methane hydrates in marine sediments has been intensively studied over the past decades, and geochemical charac-teristic of hydrate is one of the most attractive research fields. In this paper, we discussed the geochemical anomaly during hydrate formation in porous media. By doing so, we also investigated the temperature influence on hydrate formation under isobaric condition. It turns out that sub-cooling is an important factor to dominate hydrate formation. Larger subcooling provides more powerful driving force for hydrate formation. During the geochemical anomaly research, six kinds of ions and the total dissolved salt (TDS) were measured before and after the experiment in different porous media. The result is that all kinds of ionic concentration increased after hydrate formation which can be defined as salting out effect mainly affected by gas consumption. But the variation ratio of different ions is not equal. Ca^2+ seems to be the most significantly influenced one, and its variation ratio is up to 80%. Finally, we theoretically made a model to calculate the TDS variation, the result is in good accordance with measured one, especially when gas consumption is large. 展开更多
关键词 hydrate formation porous media SUBCOOLING salting out effect geochemical anomaly
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贻贝仿生增韧自愈合聚天冬酰胺/氧化石墨烯凝胶的制备及性能
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作者 付雁 刘华 +2 位作者 刘长玲 王博 杨洪雨 《高分子材料科学与工程》 EI CAS CSCD 北大核心 2022年第5期94-101,共8页
无论从生物医学到水净化系统,刺激响应和自愈合的新型水凝胶材料凭借其多种协同功能,表现出不同的潜在应用。然而,所得材料往往具有明显的弱点和脆性,力学性能欠佳。在这项工作中,提出了一种新型仿生贻贝足丝的改性多巴胺共轭聚天冬酰胺... 无论从生物医学到水净化系统,刺激响应和自愈合的新型水凝胶材料凭借其多种协同功能,表现出不同的潜在应用。然而,所得材料往往具有明显的弱点和脆性,力学性能欠佳。在这项工作中,提出了一种新型仿生贻贝足丝的改性多巴胺共轭聚天冬酰胺(PHEA-DOPA)与氧化石墨烯(GO)构筑的水凝胶(PHEA-DOPA/GO)。以GO纳米片和硼酸(H_(3)BO_(3))作为交联剂,与PHEA-DOPA的极性官能团相互作用。与不含GO的PHEA-DOPA凝胶相比,含有GO的凝胶的储能模量和损耗模量均增加了10倍、拉伸强度增加了1.5倍。此外,含GO的PHEA-DOPA水凝胶表现出快速和自主的自愈合性质,使得该材料成为生物医学中备受青睐的生物相容性水凝胶。 展开更多
关键词 聚天冬酰胺 氧化石墨烯 水凝胶
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南海珠江口盆地天然气水合物特征
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作者 changling liu Qingguo Meng +1 位作者 Xingliang He 尉建功 《海洋地质》 2017年第3期1-9,共9页
2013年中国在南海珠江口(PRM)盆地东部开展天然气水合物钻探并成功获取天然气水合物样品。我们对其中一块水合物样品进行了实验室分析研究。研究发现水合物样品呈结核状,沉积物主要为粉砂质砂和粘土。拉曼光谱和X射线衍射的结果表明... 2013年中国在南海珠江口(PRM)盆地东部开展天然气水合物钻探并成功获取天然气水合物样品。我们对其中一块水合物样品进行了实验室分析研究。研究发现水合物样品呈结核状,沉积物主要为粉砂质砂和粘土。拉曼光谱和X射线衍射的结果表明,水合物为典型的I型结构(sI),甲烷的大笼和小笼占有率分别为99.5%和91.4%,通过热动力学计算,该样品水合指数为5.90。水合物气体以甲烷气体为主(〉99.9%),含有少量的乙烷(0.04%)和丙烷(0.01%)。同位素分析表明PRM地区水合物中的甲烷气体为典型的生物成因气。 展开更多
关键词 天然气水合物 珠江口(P蹦)盆地 拉曼光谱 气体组成 粒度 南海(SCS)
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Hydrate formation and distribution within unconsolidated sediment:Insights from laboratory electrical resistivity tomography
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作者 Yanlong Li Nengyou Wu +5 位作者 changling liu Qiang Chen Fulong Ning Shuoshi Wang Gaowei Hu Deli Gao 《Acta Oceanologica Sinica》 SCIE CAS CSCD 2022年第9期127-136,共10页
Laboratory visual detection on the hydrate accumulation process provides an effective and low-cost method to uncover hydrate accumulation mechanisms in nature.However,the spatial hydrate distribution and its dynamic e... Laboratory visual detection on the hydrate accumulation process provides an effective and low-cost method to uncover hydrate accumulation mechanisms in nature.However,the spatial hydrate distribution and its dynamic evolutionary behaviors are still not fully understood due to the lack of methods and experimental systems.Toward this goal,we built a two-dimensional electrical resistivity tomography(ERT)apparatus capable of measuring spatial and temporal characteristics of hydrate-bearing porous media.Beach sand(0.05–0.85 mm)was used to form artificial methane hydrate-bearing sediment.The experiments were conducted at 1°C under excess water conditions and the ERT data were acquired and analyzed.This study demonstrates the utility of the ERT method for hydrate mapping in laboratory-scale.The results indicate that the average electrical conductivity decreases nonlinearly with the formation of the hydrate.At some special time-intervals,the average conductivity fluctuates within a certain scope.The plane conductivity fields evolve heterogeneously and the local preferential hydrate-forming positions alternate throughout the experimental duration.We speculate that the combination of hydrate formation itself and salt-removal effect plays a dominant role in the spatial and temporal hydrate distribution,as well as geophysical parameters changing behaviors during hydrate accumulation. 展开更多
关键词 natural gas hydrate electrical resistivity electrical resistivity tomography accumulation mechanism electrical conductivity
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水合物降压分解过程中沉积物孔隙结构动态演化规律 被引量:8
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作者 王代刚 魏伟 +5 位作者 孙静静 彭晖 李承峰 贾春霞 刘昌岭 卢海龙 《科学通报》 EI CAS CSCD 北大核心 2020年第21期2292-2302,共11页
选取两种不同粒径分布的天然海砂样品,在相同实验温度及压力条件下合成甲烷水合物.开展水合物降压分解X-CT微观实验,获取不同时刻的沉积物内部构成图像.对X-CT扫描图像进行阈值分割、三维重建及拓扑等效等处理,建立不同粒径含水合物沉... 选取两种不同粒径分布的天然海砂样品,在相同实验温度及压力条件下合成甲烷水合物.开展水合物降压分解X-CT微观实验,获取不同时刻的沉积物内部构成图像.对X-CT扫描图像进行阈值分割、三维重建及拓扑等效等处理,建立不同粒径含水合物沉积介质不同分解阶段的三维孔隙网络模型,研究水合物降压分解过程中沉积物孔隙结构动态演化规律及其控制机理.研究表明,甲烷水合物微观分布非均质特征显著,分解过程开始于气-水合物接触的位置,分解初期水合物具有孔隙填充、颗粒胶结等多种赋存模式,而分解后期孔隙中主要赋存颗粒胶结型水合物.随着水合物饱和度的减小,不同粒径含水合物沉积物的平均孔喉半径、孔隙度、绝对渗透率以及两相共渗区宽度均不断增大,配位数、形状因子及束缚水饱和度逐渐减小.受水合物分解动力学行为影响,分解前期沉积物平均孔隙半径缓慢降低,水合物饱和度下降至某一临界值(小于0.1)后,平均孔隙半径和绝对渗透率急剧增大.粒径分布越窄,相同水合物饱和度下沉积物平均孔隙及孔喉半径、孔隙度和绝对渗透率越高,但不同粒径沉积介质配位数和形状因子的变化存在交叉点,表明含水合物沉积物微观孔隙结构特征受粒径分布、水合物微观赋存状态及空间分布的协同影响. 展开更多
关键词 甲烷水合物 降压分解 X-CT扫描 孔隙结构 颗粒粒径 网络模型
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CRISPR/dCas-mediated gene activation toolkit development and its application for parthenogenesis induction in maize 被引量:3
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作者 Xiantao Qi Huimin Gao +6 位作者 Renyao Lv Wenbo Mao Jinjie Zhu changling liu Long Mao Xinhai Li Chuanxiao Xie 《Plant Communications》 SCIE CSCD 2023年第2期56-64,共9页
Clustered regularly interspaced short palindromic repeats(CRISPR)-Cas systems can be engineered as programmable transcription factors to either activate(CRISPRa)or inhibit transcription.Apomixis is extremely valuable ... Clustered regularly interspaced short palindromic repeats(CRISPR)-Cas systems can be engineered as programmable transcription factors to either activate(CRISPRa)or inhibit transcription.Apomixis is extremely valuable for the seed industry in breeding clonal seeds with pure genetic backgrounds.We report here a CRISPR/dCas9-based toolkit equippedwith dCas9-VP64 andMS2-p65-HSF1 effectors that may specifically target genes with high activation capability.We explored the application of in vivo CRISPRa targeting of maize BABY BOOM2(ZmBBM2),acting as a fertilization checkpoint,as a means to engineer parthenogenesis.We detected ZmBBM2 transcripts only in egg cells but not in other maternal gametic cells.Activation of ZmBBM2 in egg cells in vivo caused maternal cell-autonomous parthenogenesis to produce haploid seeds.Our work provides a highly specific gene-activation CRISPRa technology for target cells and verifies its application for parthenogenesis induction in maize. 展开更多
关键词 CRISPRa ZmBBM2 egg cell apomixis engineering maternal haploid
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