水合物法分离混合物技术研究进展

综述了水合物生成法在溶液浓缩和混合气分离两大领域的研究进展。分析表明,水合物法在海水淡化、生物工程、油样分离等溶液分离过程均表现出了一定的应用价值,但仍存在浓缩液夹带、分离效率较低或分离压力高等问题而未能实现工业化应用。针对混合气的分离,与单独水合分离过程相比,包含有水合物生成的吸收-水合和吸附-水合双机制耦合分离技术表现出了气体处理量大、分离效率高、或可实现连续气体分离等优势。但与它们相关的一些基础性问题如水合物浆液的实际流动特性、水合物晶粒与多孔介质之间的作用关系等,需要进一步的研究或确认。在此基础上,对这些分离过程的继续研究给出了参考意见：溶液浓缩分离过程可着眼于开发更有效的水合物生成促进剂或耦合其他分离技术等;混合气分离方面可以在寻找更有效的水合物生成促进剂、明确采用乳液体系分离所得水合物浆液的实际流动特性、揭示采用含水多孔介质分离所得不同相之间的作用机制等方面展开。     

气体水合物快速生成强化技术与方法研究进展

水合物技术可应用于天然气储运、污水处理、海水淡化、混合气体分离、水溶液浓缩以及水合物蓄冷等领域,而该技术成功应用的关键在于如何强化水合物快速生成.本文介绍了水合物的生成机理,综述了气体水合物快速生成强化技术与方法研究进展,分析了各自的优缺点,并对气体水合物快速生成技术进行了展望.     

水合物法分离混合物技术研究进展

综述了水合物生成法在溶液浓缩和混合气分离两大领域的研究进展。分析表明,水合物法在海水淡化、生物工程、油样分离等溶液分离过程均表现出了一定的应用价值,但仍存在浓缩液夹带、分离效率较低或分离压力高等问题而未能实现工业化应用。针对混合气的分离,与单独水合分离过程相比,包含有水合物生成的吸收-水合和吸附-水合双机制耦合分离技术表现出了气体处理量大、分离效率高、或可实现连续气体分离等优势。但与它们相关的一些基础性问题如水合物浆液的实际流动特性、水合物晶粒与多孔介质之间的作用关系等,需要进一步的研究或确认。在此基础上,对这些分离过程的继续研究给出了参考意见:溶液浓缩分离过程可着眼于开发更有效的水合物生成促进剂或耦合其他分离技术等;混合气分离方面可以在寻找更有效的水合物生成促进剂、明确采用乳液体系分离所得水合物浆液的实际流动特性、揭示采用含水多孔介质分离所得不同相之间的作用机制等方面展开。     

水合冷冻法海水淡化研究

试验研究了HCFC-141b在含盐溶液中的水合和分解过程,测定了水合物分解后的盐度变化.结果表明,HCFC-141b在盐水中生成水合物的过程中,盐水的浓度对水合物生成的过冷度有一定影响,浓度太低或太高都对过冷度影响不大,1.0%的氯化钠可以有效减小过冷度.测量水合物分解后的水溶液发现盐度显著降低,用水合物的生成和分解可以达到海水淡化的目的.根据水合物的特点设计了水合物法海水淡化的试验装置,筛选了适用于该方法的水合物工质,其中乙烷为最好的水合物法海水淡化工质.通过计算发现加大气体流量、提高充气压力和改善生成条件可提高淡水产率,当50%的气体参加水合反应则淡水产率可提高到1.25 L·min-1.     

水合物利用技术应用进展

过去的几十年中,对于水合物的研究不单单集中在抑制天然气水合物的生成上,基于水合物的生成利用技术也得到了广泛的研究。基于水合物的生成利用技术是环保和可持续的新技术,利用不同气体生成水合物相平衡条件的差异,可用于气体分离、置换开采。由于水合物具有较高的气体浓度,可用于气体的存储。利用水合物较高的化解潜热,可将其用于蓄冷。本文综述了国内外水合物技术的研究应用现状,分析了水合物技术在气体分离与存储、溶液浓缩分离、蓄冷、二氧化碳（CO₂）置换开采等领域有前景的研究方向。但是其水合反应速率慢、生成压力高、后期分离困难,极大地限制了水合物利用技术的工业应用。展望了水合物技术未来的研究发展方向,开发安全、高效和环保的水合物促进剂,开发高效水合物反应设备,开发连续水合物工艺,以便早日实现工业应用。     

气体水合物生成过程强化方法研究现状

气体水合物因其特殊的物理化学特性,已被气体分离、二氧化碳捕集与封存、海水淡化、气体储运等诸多领域学者广泛研究。但气体水合物生成条件较为苛刻、生成速率及储气能力较商业化应用还有较大差距。本工作从气体水合物生成条件、生成速率、储气能力等角度,分别综述了机械强化、外场作用、添加剂等强化方法对气体水合物生成过程的强化原理、技术特征及其研究现状;综合比较分析了各种强化方法的优势及存在的问题;展望了各强化方法的未来发展方向及其适用领域;特别是针对气体水合物法海水淡化的技术特征和关键问题,提出以外电场强化气体水合物法海水淡化过程的新思路。     

笼形水合物及水合物技术现状及展望

简要介绍了笼形水合物概念及水合物研究史。阐述了水合物的3种晶体结构以及客体分子对晶体结构的影响，讨论了密度、热导率等物性，评述了水合物生成条件和生成机理方面的研究成果。着重介绍了水合物技术在水溶液浓缩和海水淡化、气体混合物分离、气体储运、近临界和超临界萃取、生物蛋白酶提取等主要领域中的应用状况。     

一种从含氢气体分离浓缩氢的新技术——水合物分离技术

引　言由于水合物不仅与石油天然气生产、储藏和运输密切相关 ,而且与环境保护、气候变迁特别是人类未来赖以生存的能源有密切关系 ,对于水合物的研究成为目前国际上的一个热点 .另外 ,由于其特殊的物理化学性质 ,水合物还可以用来开发各种应用技术 ,例如蓄冷、有机水溶液提浓、海水脱盐淡化、重水提浓等[1] .水合物法分离气体混合物技术是在多年水合物相关实验研究[2 ,3] 的基础上提出的一种新技术 ,并在氢气分离提浓方面取得了初步成果 .水合物是小分子物质 (Ｎ2 、ＣＯ2 、ＣＨ4 、Ｃ2 Ｈ6、Ｃ3Ｈ8等 ,称为客体分子 )和水在一定温度和压…     

基于水合物法浓缩低浓度煤层气的研究进展

介绍了我国低浓度煤层气的利用现状,对当前几种浓缩技术进行了对比和分析,认为水合物浓缩低浓度煤层气法具有更广阔的前景。介绍了水合物基本理论,包括其晶体结构、相平衡热力学及生成动力学,阐述了通过强化气体水合物生成来浓缩低浓度煤层气的研究进展,并对水合物法浓缩低浓度煤层气技术进行了总结和展望。     

水合物法分离回收石油化工厂火炬气工艺研究

介绍了4种火炬气回收工艺和水合物法气体分离技术,提出了水合物法分离回收石油化工厂火炬气的新工艺——利用水合物的生成逐一分离、回收其中有价值的组分。对流程的特点和技术可行性进行了分析,指出对于组分复杂的火炬气可采用水合物法分离回收。与传统工艺相比,该工艺具有回收彻底、更节能、更环保等诸多优点。     

离子液体水溶液-气体水合物对CO2的双捕获工艺

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.     

Kinetic investigation of CO2 and N2 clathrate hydrate formation using cyclopentane: Application in desalination

Hydrate-based desalination could be a promising technique for producing fresh water from saline water, as it is an eco-friendly process and suitable for large-scale implementation. To make the hydrate-based desalination technology easily scalable, we looked at using air (or N₂) or CO₂ as a hydrate former, along with cyclopentane (CP). Hydrate former CP helps to reduce the operating conditions, as CP forms hydrate at ambient pressure. However, hydrate formation kinetics due to water-insoluble CP is slow. In this work, the kinetics of hydrate formation in saline water were investigated and compared to identify the utility of CO₂ and N₂ as hydrate formers for desalination work. The addition of CP as a hydrate former should transform the structure of CO₂ hydrate from structure I (sI) to structure II (sII), as CP occupies the large cages (5¹²6⁴) in the gas hydrate. A set of three similar reactors were used for this study to collect data quickly. Furthermore, the triple reactor setup is a unique reactor design mounted on a shaker, and a set of SS-316 balls present inside the horizontal reactor imparts the mixing. Experiments with the CO₂-CP mixture and N₂-CP mixture have been studied in the presence or absence of 3 wt.% NaCl at 274 K and 3 MPa pressure. The gas uptake kinetics, water recovery, and separation efficiency have been investigated.     

Pressure variation due to heat shock of CO2hydrate desserts

CO₂ hydrate desserts are carbonated frozen desserts in which the CO₂ is trapped in a crystalline water‐carbon dioxide structure called a CO₂ clathrate hydrate. The CO₂ concentration of the dessert enables strong perception of carbonation, but CO₂ hydrate dissociation during heat shock can cause high package pressures during storage and distribution. In this work, a model is developed for package pressure as a function of temperature, CO₂ content, package volume, dessert mass, and recipe. The model is validated by comparison with an experimental measurement of the pressure and mass of a CO₂ hydrate dessert subjected to heat shock. It is shown that during heat shock a sealed package can reach pressures greater than the ice‐CO₂ hydrate equilibrium pressure. At pressures above the ice‐CO₂ hydrate equilibrium pressure, the fraction of water crystallized in the dessert can be increased, potentially mitigating heat shock damage. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

水合物法分离低浓度煤层气中的甲烷

向模拟煤层气(13.11vol% CH4+86.89vol% N2)中添加5.8mol%四氢呋喃(THF)?0.03mol%十二烷基硫酸钠(SDS)促进剂溶液分离提纯煤层气,考察了压力、温度、反应时间对气体消耗量、反应速率、分解气中甲烷浓度、甲烷回收率和甲烷分离因子的影响,采用色谱分析法分别测定了CH4在剩余气相和分解气相中的浓度。结果表明,压力增加,CH4回收率增大,CH4分离因子增大,CH4分离效果越好;温度是影响甲烷分离因子的关键因素,温度降低,氮气和甲烷竞争进入水合物晶体中,导致水合物相中甲烷浓度降低;温度升高有利于提高水合物对甲烷的选择性。甲烷回收效率最高可达98.65%,分离因子最大为14.83。随反应时间增加,分解气中CH4浓度升高。     

Sugar cane juice concentration via CO2 gas hydrate formation

Sugar cane juice concentration via evaporation is the traditional method, though the downside in this technique is the product loss due to sucrose inversion. Gas hydrate separation is an emerging technology applied in desalination, carbon capture, and in this study, for concentrating fruit juice by trapping the water in the form of crystalline cages. A 750 cm³ hydrate reactor was used for hydrate formation experiments to concentrate the sugar cane juice, with a sampling of the concentrate to determine the final solids content. Hydrate formation experiments showed the successful concentration of a 0.12 mass fraction feed to approximately 0.56 mass fraction using four batchwise concentration stages. A comparison of the energy usage between the evaporation train as used in sugar factories and a single batch hydrate formation stage, to concentrate a 0.12 mass fraction feed to 0.30 mass fraction showed an energy reduction of approximately 20% for the hydrate method.     

膜分离技术在染料行业中的应用研究进展

介绍了粗制染料的脱盐与浓缩纯化生产的研究进展。膜分离作为一种清洁生产工艺技术,使合成染料的脱盐和浓缩同时进行,从而成功地得到高浓度、低盐的染料产品如活性染料、荧光增白剂和酸性染料等。在膜法治理染料废水方面,介绍了膜分离、预处理/膜分离组合和膜分离/氧化组合等3种工艺及其应用实例,并简要介绍了新型膜材料和膜过程的发展状况。     

利用吸收-水合耦合法从氨弛放气中回收氢气的研究(英文)

In this work, the absorption-hydration hybrid method was used to recover (hydrogen + nitrogen) from (hydrogen + nitrogen + methane + argon) tail gas mixtures of synthetic ammonia plant through hydrate forma-tion/dissociation. A high-pressure reactor with magnetic stirrer was used to study the separation efficiency. The in-fluences of the concentration of anti-agglomerant, temperature, pressure, initial gas-liquid volume ratio, and oil-water volume ratio on the separation efficiency were systematically investigated in the presence of tetrahydro-furan (THF). Anti-agglomerant was used to disperse hydrate particles into the condensate phase for water-in-oil emulsion system. Since nitrogen is the material for ammonia production, the objective production in our separation process is (hydrogen + nitrogen). Our experimental results show that by adopting appropriate operating conditions, high concentration of (hydrogen + nitrogen) can be obtained using the proposed technology based on forming hydrate.     

Progress and trends in hydrate based desalination (HBD) technology: A review

The shortage of freshwater boosts the development of seawater desalination technology. As a novel method, the hydrate based desalination technology has been put forward for decades and achieved considerable development in the past years. This review focuses on the experimental progress at the aspects of the hydrate former choice, formation promotion and ion removal efficiency and conceptive innovation of hydrate separation and energy utilization. It should be noted that gaseous hydrate former with low formation pressure and insoluble liquid hydrate former are worthy for further study. Besides, the water migration caused by propane deserves to be investigated much more deeply for the potential value of wide application. Moreover, the utilization proposal of LNG cold energy brings more possibility of commercial application. In a word, the hydrate based desalination technology is hopefully an environment friendly, low-cost and widely used desalination technology in the near future.