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Hideki Tanaka Takuma Yagasaki Masakazu Matsumoto 《American Institute of Chemical Engineers》2021,67(3):e17009
An elaborated statistical mechanical theory on clathrate hydrates is applied to exploration of their phase equilibria and dissociation enthalpies. The experimental dissociation pressures of methane, ethane, acetylene, and propane hydrates are well recovered by the method we have proposed. We estimate water/hydrate and hydrate/guest two-phase coexisting conditions in the temperature, pressure, and composition space in addition to three-phase equilibrium conditions. It is shown that the occupancy of guest molecules and the two-phase boundaries in the phase diagram vary depending sensitively on its size. Enthalpy components arising from the host and guest interactions are separately calculated from the temperature dependence of the corresponding free energy values. This enables to evaluate the dissociation enthalpy at any stable and metastable thermodynamic state taking account of the phase transition in the coexisting phase such as melting of ice, notably that along the three-phase equilibrium line. 相似文献
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Capture of CO2 by hydrate is one of the attractive technologies for reducing greenhouse effect.The primary challenges are the large energy consumption,low hydrate formation rate and separation efficiency.This work presents a new method for capture of CO2 from simulated flue gasCO2(16.60%,by mole) /N2 binary mixture by formation of cyclopentane(CP) hydrates at initial temperature of 8.1°C with the feed pressures from 2.49 to 3.95 MPa.The effect of cyclopentane and cyclopentane/water emulsion on the hydrate formation rate and CO2 separation efficiency was studied in a 1000 ml stirred reactor.The results showed the hydrate formation rate could be increased remarkably with cyclopentane/water emulsion.CO2 could be enriched to 43.97%(by mole) and 35.29%(by mole) from simulated flue gas with cyclopentane and cyclopentane/water(O/W) emulsion,respectively,by one stage hydrate separation under low feed pressure.CO2 separation factor with cyclopentane was 6.18,higher than that with cyclopentane/water emulsion(4.01) ,in the range of the feed pressure.The results demonstrated that cyclopentane/water emulsion is a good additive for efficient hydrate capture of CO2. 相似文献
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设计了以离子液体[APMIM]Br水溶液吸收-生成水合物捕获CO2工艺流程,并利用CO2在该离子水溶液中的溶解度数据和在其中生成CO2水合物的相平衡实验数据进行物料衡算. 考察了水含量、压力和液气流量比对气体吸收-水合物生成的CO2双重捕获效果的影响,对比了气体水合物与离子液体水溶液捕获CO2的能力. 结果表明,在较高压力和水含量条件下,水合物捕获CO2的效应强于离子液体溶液;较低压力下离子液体溶液吸收CO2起主要作用. 与纯水合物法相比,双捕获工艺具有一定优势,且突破了单纯水合物脱碳的压力和CO2含量要求高的局限性. 当原料气中CO2低于65%(j)时,系统的脱碳效率低于40%,对于CO2含量较低的气体,其CO2的脱除性能回归至单纯离子液体溶液体系. 相似文献
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In this work, CO2 capture was experimentally investigated by forming tetra-n-butyl ammonium bromide (TBAB) semiclathrate in a new system of TBAB + graphite nanofluids. The experiments were carried out at 3.5 MPa and 277.15 K. Compared to the TBAB solution and the TBAB + sodium dodecyl sulphate (SDS) solution, it was found that the system of TBAB + graphite nanofluids was preferable for CO2 capture, and 0.2 wt.% graphite nanoparticles (GNP) was an optimal concentration for the enhancement of hydrate growth in TBAB + graphite nanofluids. At this GNP concentration, CO2 consumption gained at 0.29 mol% TBAB is greater than that acquired at 0.62 and 2.57 mol% TBAB. CO2 consumption obtained in TBAB + graphite nanofluids is larger than other systems containing GNP. Moreover, the morphologies of TBAB + CO2 semiclathrate formed in TBAB solution, TBAB + SDS solution, and TBAB + graphite nanofluids were presented, and the mechanism of CO2 capture using TBAB semiclathrate formation in graphite nanofluids was presented. Therefore, it is an efficient way to capture CO2 by forming TBAB semiclathrate in graphite nanofluids. 相似文献
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目前实验室模拟开采天然气水合物(NGH)的最主要的方法为外激法,通过注热、降压等方式使水合物分解释放出甲烷(CH4),外激法最大的问题在于水合物的分解容易造成地层结构变化,导致地质斜坡灾害。利用二氧化碳(CO2)在水合物相中置换开采CH4,由于置换过程发生在水合物相中,不改变水合物相结构,因此可以降低地质灾害风险。本文全面介绍了利用CO2在水合物相从NGH中置换CH4的研究进展,从置换可行性、动力学模型、模拟研究、实验研究等方面对当前的研究进行了综述,并为进一步发展置换法开采CH4技术指出了方向。 相似文献
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目前对水合物稳定性的研究主要以实验为主,水合物的晶穴占有率和客体分子的比例难以人为控制,本文采用分子动力学(MD)模拟方法,在正则系综(NVT)模拟条件下,研究了温度为263.15K、273.15K及晶穴占有率为100%、66.7%、33.3%、0时,客体分子甲烷、四氢呋喃对Ⅱ型水合物稳定性的影响,发现较低的温度、较高的晶穴占有率和适宜的客体分子均有利于保持Ⅱ型水合物晶体结构的稳定;晶穴占有率对晶体稳定性的影响大于客体分子种类对晶体稳定性的影响;在一定范围内温度的变化对于已经处于稳定状态的晶体的稳定性影响不大;提出了提高天然气水合物稳定性、降低储存温度与压力的方法,为水合物法储存运输天然气提供参考。 相似文献
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Chungang Xu Xiaosen Li Kefeng Yan Xuke Ruan Zhaoyang Chen Zhiming Xia 《中国化学工程学报》2019,27(9):1998-2013
Natural gas hydrate (NGH) is considered as an alternative energy resource in the future as it is proven to contain about 2 times carbon resources of those contained in the fossil energy on Earth. Gas hydrate technology is a new technology which can be extensively used in methane production from NGH, gas separation and purification, gas transportation, sea-water desalination, pipeline safety and phase change energy storage, etc. Since the 1980s, the gas hydrate technology has become a research hotspot worldwide because of its relatively economic and environmental friendly characteristics. China is a big energy consuming country with coal as a dominant energy. With the development of the society, energy shortage and environmental pollution are becoming great obstacles to the progress of the country. Therefore, in order to ensure the sustainable development of the society, it is of great significance to develop and utilize NGH and vigorously develop the gas hydrate technology. In this paper, the research advances in hydrate-based processes in China are comprehensively reviewed from different aspects, mainly including gas separation and purification, hydrate formation inhibition, sea-water desalination and methane exploitation from NGH by CH4-CO2 replacement. We are trying to show the relevant research in China, and at the same time, summarize the characteristics of the research and put forward the corresponding problems in a technical way. 相似文献
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Yangmin Kuang Lunxiang Zhang Yongchen Song Lei Yang Jiafei Zhao 《American Institute of Chemical Engineers》2020,66(4):e16859
Quantitatively characterizing the seepage features is critical important for multi-fluid flow in gas hydrate accumulations; however, limited researches concern water permeability during hydrate phase transition. In this work, nuclear magnetic resonance (NMR) measurement is employed to observe the in situ formation and dissociation of tetrahydrofuran (THF) hydrate in porous media. Results indicate that the relative free water and bound water consumption during hydrate phase transition can affect the seepage features of sediments. In addition, we investigate the growth habits of THF hydrate in quartz glass sand and find the growth pattern of the hydrate transforms from suspension to cementation when its saturation exceeds approximately 35%. The Tokyo model shows that the hydrate are heterogeneous distribution of pore-filling and likely to evolve in larger pores; The findings clearly show that NMR is an efficient and direct technique for investigating the seepage characteristics during hydrate phase transition as well as pore fluid distribution in sediments. 相似文献
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Sub‐seabed geological storage of CO2 in the form of gas hydrate is attractive because clathrate hydrate stably exists at low temperature and high pressure, even if a fault occurs by diastrophism like a big earthquake. For the effective design of the storage system it is necessary to model the formation of CO2‐hydrate. Here, it is assumed that the formation of gas hydrate on the interface between gas and water consists of two stages: gas diffusion through the CO2‐hydrate film and consequent CO2‐hydrate formation on the interface, between film and water. Also proposed is the presence of a fresh reaction interface, which is part of the interface between the gas and aqueous phases and not covered with CO2‐hydrate. Parameters necessary to model the hydrate formation in sand sediment are derived by comparing the results of the present numerical simulations and the measurements in the literature. 相似文献
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天然气水合物因其储量巨大、清洁无污染而成为未来最具潜力的清洁能源之一,CO2置换法可实现天然气水合物的安全开采和温室气体的地层封存。然而,多孔介质中CO2-CH4水合物的置换过程存在反应周期长、速率慢、效率低等特点,已成为制约天然气水合物高效开采的瓶颈问题。本文全面综述了多孔介质体系中CO2-CH4水合物的置换特性,分析了CO2-CH4水合物的置换机理及其动力学过程。在此基础上,详述了不同因素对多孔介质中CO2-CH4水合物置换效率的影响规律及强化机理,包括热刺激、置换压力、小分子气体、化学添加剂等的作用机理及其规律。最后指出了多孔介质体系中CO2-CH4水合物置换过程强化技术存在的不足和未来的发展方向。对多孔介质体系中CO2-CH4水合物置换过程的强化机理及其动力学机制的认识仍需进一步研究。 相似文献
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Study on the microscopic structure of clathrate hydrate has made significant progress in the past decades. This review aims to summarize the state of the art of the experimental characterization of guest molecular occupancy in clathrate hydrate cages, which is an important area of the microscopic structures. The characterizing method and features of different guest molecular, such as hydrocarbon, carbon dioxide, hydrogen and inhibitor/promoter, in different hydrate cages have been extensively reviewed. A comprehensive use of advanced technologies such as X-ray diffraction, Raman spectroscopy and nuclear magnetic resonance may provide better understanding on the compositions and microscopic mechanisms of clathrate hydrate. 相似文献
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对烟道气CO2回收改造项目的背景、技术方案的比较与选定、改造工艺路线及特点进行了总体介绍。改造的总体方案是用改良MEA脱碳法从燃气快装锅炉的烟道气中回收3 000 m3/h(标态)CO2作为尿素、甲醇和碳酸二甲酯生产装置的补充原料气。 相似文献
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为了明确玉米棒颗粒与四氢呋喃(THF)对整体煤气化联合循环(IGCC)合成气气体水合物生成的协同作用,在温度276.15K、初始压力为6.0MPa的静态反应条件下,通过实验研究了玉米棒颗粒+THF溶液体系中气体水合物的生成动力学过程,并确定了不同THF浓度溶液条件下水合物的生成诱导时间、气体消耗量、CO2分离效率及水合物的晶体结构。实验结果表明:玉米棒的存在会延长实验的稳定时间,且其压降幅度相较于不含玉米棒颗粒的体系更高;无论是否含玉米棒颗粒,诱导时间均在180s以内,且随着THF浓度上升到摩尔分数4.0%和5.6%,二者的诱导时间变得非常接近;玉米棒颗粒存在时,THF溶液的浓度越大,气体消耗量达到最终气体消耗量90%的时间则越短,且在相同THF浓度下,其所获得的气体消耗量和CO2分离效率普遍比纯THF溶液体系高,这意味着玉米棒颗粒的存在提高了THF溶液对CO2的分离效果。同时,微观结构分析表明无论是否含有玉米棒颗粒,THF溶液体系中所生成的IGCC合成气气体水合物的结构均为sⅡ型,纯水体系中生成的IGCC合成气气体水合... 相似文献
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通过并流共沉淀法制备了Au/-Fe2O3催化剂,考察了金负载量及焙烧温度对Au/-Fe2O3催化剂的物化结构及其选择性氧化富氢气体中CO催化性能的影响。研究结果表明,金负载量和焙烧温度对催化剂的性能均有较大影响,金负载量为1.5%(wt),低温焙烧(200~400℃)时制得的Au/-Fe2O3催化剂对CO选择性氧化反应具有很好的催化活性和选择性,其中金负载量为1.5%(wt)、300℃焙烧的Au/-Fe2O3催化剂,在40℃时对富氢气体中CO的转化率达到100%,选择性为 66%,该催化剂连续反应120h催化活性没有明显下降。XRD、BET和TEM分析结果表明,催化剂的性能与单质Au的粒径有关,粒径越小,催化活性越高。 相似文献