水合物利用技术应用进展

doi:10.16085/j.issn.1000-6613.2020-0614

摘要/Abstract

摘要：

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。

关键词: 水合物, 气体分离, 溶液浓缩分离, 气体储存, 蓄冷, 置换开采

Abstract:

In the past few decades, research on hydrates has not only focused on inhibiting the formation of natural gas hydrates. Utilization technologies based on hydrate formation have also been extensively studied. Hydrate-based utilization technology is a new environmentally-friendly and sustainable technology. It can be used for gas separation and replacement by taking advantage of the differences in the equilibrium conditions. Due to high storage capacity, it can be used for gas storage. With high latent heat, it can be used for cold storage. The current status of application of hydrate technology was summarized, and the promising research directions of hydrate technology in the fields of gas separation and storage, solution concentration, cold storage, and replacement was analyzed. However, the slow hydration reaction rate, high generation pressure, and difficulty in separation at a later stage have greatly limited the industrial application of hydrate utilization technology. The future research and development directions of hydrate technology were prospected, including the development of safe, efficient and environmentally-friendly hydrate promoters, the development of high-efficiency hydrate reaction equipment, the development of continuous hydrate processes, and the conduct of a large number of pilot experiments.

Key words: hydrate, gas separation, solution concentration, gas storage, cold storage, CH₄-CO₂ replacement

中图分类号:

TQ028.8

薛倩, 王晓霖, 李遵照, 刘名瑞, 赵巍. 水合物利用技术应用进展[J]. 化工进展, 2021, 40(2): 722-735.

Qian XUE, Xiaolin WANG, Zunzhao LI, Mingrui LIU, Wei ZHAO. Research progresses in hydrate based technologies and processes[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 722-735.

图/表 9

图1 水合物的晶体结构示意图

表1 不同气体在0℃时生成水合物所需压力

气体	生成压力/MPa
H₂	200
N₂	16.3
O₂	11.1
CO₂	1.22
C₂H₄	0.55
C₂H₆	0.53
C₃H₈	0.17
H₂S	0.09

图2 水合物法联合化学吸收法的CO2气体分离工艺流程

表2 海水淡化常用的水合剂

水合剂	特点
气体
CH₄	易于分离，无毒，但需要较高的生成压力
CO₂	易于分离，无毒，生成压力较大
C₃H₈	易于分离，操作条件适中，易燃
液体
HCFC-R141b	在高温下可生成水合物，对臭氧层有破坏作用
CP	溶解度低，与水不互溶，常压下生成水合物
二元水合物
CP+CO₂	提高了相平衡温度、生成速率，盐的去除率较高，但需要进一步分离
CP+CH₄	生成压力较低，溶解度小，水合物固体密度小于海水
CO₂+R141b	价格便宜，脱盐率高，但需要进一步分离
CO₂+C₃H₈	生成压力较低

图3 基于水合物脱盐研究进展

表3 几种浓缩技术的对比分析

方法	能耗/ $k J ? k g 水 - 1$
蒸发技术	180~2160
冷冻浓缩	936~1800
水合物浓缩技术	252~360

表3 几种浓缩技术的对比分析

方法	能耗/ $k J ? k g 水 - 1$
蒸发技术	180~2160
冷冻浓缩	936~1800
水合物浓缩技术	252~360

图4 水合物法储存天然气的工艺流程

表4 不同促进剂的比较

储氢方法	优缺点	促进剂	反应条件	储氢量(质量分数) /%
纯氢水合物
sⅡ型	储能密度大，生成条件苛刻	无	300MPa，249K	5.3
液相促进剂
sⅡ型	生成条件温和储氢量低	THF、CP、环己酮、呋喃、四氢噻吩	10~70MPa，255~280K	0.1~4
sⅥ型	储氢量大稳定性高	叔丁胺	13.8MPa，250K	0.7
sH型	储氢量比sⅡ型的储氢量高，生成条件较纯氢气水合物的生成条件温和	甲基叔丁基醚、2,2,3-三甲基丁烷、甲基环己烷、1,1-二甲基环己烷	60~100MPa，269~275K	0.85~1.05
半笼型	生成条件更加温和，储氢量更低	TBAB、TBAF、TBAC和四丁基溴化磷、四丁基氢硼化铵	13~70MPa，253~294K	0.009~1.35
气体促进剂水合物
sⅡ型	生成条件温和，提升了总热值和储能密度	CH₄、C₂H₆和C₃H₈等	0.4~70MPa，263~281K	0.31~0.33
sⅠ型	氢气可以占据多个笼，不稳定	CO₂、CH₄等	8~60MPa，253~263K	0.02~0.31

表5 不同蓄冷方式的比较[77-79]

冷能储存介质	相变温度/℃	相变潜热/kJ·kg^-1	换热性能	投资	COP(制冷系数)	蓄冷温度/℃	供冷温度/℃
水	0~10		好	<0.6	1	4~6	1~4
冰	0	334	较好	1^①	0.6~0.7	-6~-3	1~3
共晶盐	8~12	153~253	一般	1.3~2	0.92~0.95	-2~4	9~10
气体水合物	5~12	200~500	好	1.2~1.5	0.89~1	0~8	9~12

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