水合物法提纯低浓度煤层气的研究进展

doi:10.16085/j.issn.1000-6613.2020-1344

摘要/Abstract

摘要：

开发利用低浓度煤层气资源，对于缓解我国能源紧缺、消费结构不合理等问题具有重要意义。本文介绍了我国低浓度煤层气的利用现状，通过比较和分析几种煤层气提纯技术的优缺点，认为水合物法提纯技术具有很大潜力。水合物法提纯低浓度煤层气技术具有环保、安全、储气率高、原料简单等优点，同时仍需解决降低水合物生成条件、缩短水合物诱导时间、提高CH₄回收率等关键问题。重点概括了低浓度煤层气水合物热力学和动力学基本理论的发展以及水合法提纯低浓度煤层气技术的机理研究。从表面活性剂、新型耦合技术及水合反应器三个方面分别阐述了水合物法提纯低浓度煤层气技术的研究进展。最后，展望了水合物法提纯低浓度煤层气技术的工业化前景，提出了以下具体研究方向：探寻优质的添加剂组合并结合多级分离的方法对低浓度煤层气进行提纯，进一步探究水合法同其他煤层气提纯法相耦合的技术，优化反应器结构以及完善经济评价体系来促进其工业化进程。

关键词: 低浓度煤层气, 水合物, 表面活性剂, 反应器

Abstract:

The development and utilization of low concentration coal-bed methane (LCCBM) resources are of great significance to alleviating energy shortage and irrational consumption structure in China. The present situation of utilization of LCCBM is introduced. Through comparing and analyzing the advantages and disadvantages of several purification technologies of CBM, hydrate purification technology is considered to have great potential. The method of hydrate purification of LCCBM has the advantages of environmental protection, safety, high gas storage rate and simple raw materials, etc. At the same time, key problems such as reducing hydrate formation conditions, shortening the hydrate induction time and improving the recovery rate of CH₄ still need to be solved. The development of the basic theory of thermodynamics and kinetics of LCCBM hydrate and the mechanism research of the technology of purifying LCCBM by hydration are summarized. The research progress of LCCBM purification technology by hydrate method is described in three aspects: surfactants, new coupling technology and hydration reactor. Finally, the industrialization of LCCBM purification technology by hydrate method is prospected, and the following specific research directions are proposed: exploring the high-quality additive combination and combining it with multi-stage separation methods to purify LCCBM, further exploring the technology of coupling the hydration method with other CBM purification methods, optimizing the reactor structure and improving the economic evaluation system, so as to promote its industrialization process.

Key words: low-concentration coal-bed methane, hydrate, surfactant, reactor

中图分类号:

TQ546.5

邵伟强, 梁海峰, 张锡彦, 张华. 水合物法提纯低浓度煤层气的研究进展[J]. 化工进展, 2021, 40(6): 3143-3150.

SHAO Weiqiang, LIANG Haifeng, ZHANG Xiyan, ZHANG Hua. Research progress of purification of low-concentration coal-bed methane via hydrate method[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3143-3150.

图/表 1

参考文献 47

1	BIBLER C J, MARSHALL J S, PILCHER R C. Status of worldwide coal mine methane emissions and use[J]. Int. J. Coal Geol., 1998, 35(1/2/3/4): 283-310.
2	朱耀剑, 梁海峰, 车雯, 等. 基于水合物法浓缩低浓度煤层气的研究进展[J]. 现代化工, 2013, 33(11): 31-35.
	ZHU Y J, LIANG H F, CHE W, et al. Progress of condensation of low-concentration coal-bed methane based on hydrate-based[J]. Modern Chemical Industry, 2013, 33(11):31-35.
3	JIANG K, ZHOU S Y, CHEN X K, et al. Research status and progress of hydrate gas separation technology[J]. Nature Gas Chemical Industry, 2018, 43(3): 121-126.
4	孙栋军. 水合物法提纯低浓度煤层气的实验研究[D]. 重庆: 重庆大学, 2015.
	SUN D J. Experimental study on the purification of low-concentration coal mine gas using gas hydrate formation[D]. Chongqing: Chongqing University, 2015.
5	WAALS J H VAN DER. Clathrate solutions[J]. Adv. Chem. Phys., 1959, 2: 1-58.
6	PARRISH W R, PRAUSNITZ J M. Dissociation pressures of gas hydrates formed by gas mixtures[J]. Industrial & Engineering Chemistry Process Design & Development, 1972, 11(1): 26-35.
7	DU Y, GUO T M. Prediction of hydrate formation for systems containing methanol[J]. Chemical Engineering Science, 1990, 45(4): 893-900.
8	CHEN G J, GUO T M. Thermodynamic modeling of hydrate formation based on new concepts[J]. Fluid Phase Equilibria, 1996, 122(1/2): 43-65.
9	梁海峰, 朱耀剑, 赵阳升, 等. 水逸度模型预测THF添加剂体系下气体水合物相平衡[J]. 化工进展, 2016, 35(3): 700-705.
	LIANG H F, ZHU Y J, ZHAO Y S, et al. Phase equilibrium study of gas mixtures hydrate formation with additives THF based on water fugacity model[J]. Chemical Industry and Engineering Progress, 2016, 35(3): 700-705.
10	朱耀剑. 水合物法分离低浓度煤层气热力学模型研究[D]. 太原: 太原理工大学, 2014.
	ZHU Y J. Thermodynamic model study of hydrate formation for low-concentration coal-bed methane[D]. Taiyuan: Taiyuan University of Technology, 2014.
11	郭迎, 梁海峰, 关钰, 等. 季铵盐对煤层气水合物相平衡条件的影响[J]. 过程工程学报, 2017, 17(4): 874-878.
	GUO Y, LIANG H F, GUAN Y, et al. Effect of quaternary ammonium salts on phase equilibrium condition of coal mine methane gas hydrate[J]. Journal of Process Engineering, 2017,17(4): 874-878.
12	ALADKO L, DYADIN Y A, RODIONOVA T V, et al. Clathrate hydrates of tetrabutylammonium and tetra-isoamyl-ammonium halides[J]. Journal of Structural Chemistry, 2002, 43(6): 990-994.
13	SHI L L, LIANG D Q, et al. Phase equilibria of double semi-clathrate hydrates formed with tetra-amyl-ammonium bromide plus CH₄, CO₂, or N₂[J]. Journal of Chemical & Engineering Data, 2015, 60(9): 2749-2755.
14	王山榕. 多孔介质内水合物成核诱导时间与生长动力学研究[D]. 大连: 大连理工大学, 2019.
	WANG S R. Studies on nucleation induction time and growth kinetics of hydrate formation in porous media[D]. Dalian: Dalian University of Technology, 2019.
15	王山榕, 刘卫国, 杨明军, 等. 多孔介质内甲烷水合物生成动力学研究[J]. 热科学与技术, 2019, 18(3): 173-178.
	WANG S R, LIU W G, SUN M J, et al. Kinetics of methane hydrate formation in porous media[J]. Journal of Thermal Science and Technology, 2019, 18(3): 173-178.
16	芦文浩, 梁海峰, 王帅,等. 环状化合物-甲烷水合物稳定性的分子模拟[J]. 天然气化工(C1化学与化工), 2019, 44(1): 61-65, 70.
	LU W H, LIANG H F, WANG S, et al. Molecular simulation of the stability of ring compounds-methane clathrate hydrate[J]. Natural Gas Chemical Industry, 2019, 44(1): 61-65, 70.
17	贾菊, 梁海峰, 郭栋,等. 环状促进剂对煤层气水合物稳定性的影响[J]. 现代化工, 2020, 40(S1): 211-215.
	JIA J, LIANG H F, GUO D, et al. Impact of ring accelerator on stability of coalbed methane hydrate[J]. Modern Chemical Industry, 2020, 40(S1): 211-215.
18	董巧北. 有序纳米空间内水合物法强化煤层气N₂/CH₄分离[D]. 天津: 天津大学, 2015.
	DONG Q B. Studies on hydrate separation of N₂/CH₄ in ordered nano-space[D]. Tianjing: Tianjing University, 2015.
19	ZHONG D L, Wang W C, ZOU Z L, et al. Investigation on methane recovery from low-concentration coal mine gas by tetra- n -butyl ammonium chloride semi-clathrate hydrate formation[J]. Applied Energy, 2018, 227(1): 686-693.
20	YAN J, LU Y Y, ZHONG D L, et al. Enhanced methane recovery from low-concentration coalbed methane by gas hydrate formation in graphite nanofluids[J]. Energy, 2019, 180: 728-736.
21	曾大龙, 王传磊, 唐建峰, 等. 水合物法气体分离添加剂研究进展[J]. 油气储运, 2013, 32(2): 115-120.
	ZENG D L, WANG C L, TANG J F, et al. Progress in research of gas separation additives of hydrate[J]. Gas Storage and Transportation, 2013, 32(2): 115-120.
22	DASHTI H, YEW L Z, LOU X. Recent advances in gas hydrate-based CO₂ capture[J]. Journal of Natural Gas Science and Engineering, 2015, 23:195-207.
23	赵建忠, 赵阳升, 石定贤. THF溶液水合物技术提纯含氧煤层气的实验[J]. 煤炭学报, 2008, 33(12): 1419-1424.
	ZHAO J Z, ZHAO Y S, SHI D X. Experiment on methane concentration from oxygen containing coal bed gas by THF solution hydrate formation[J]. Journal of China Coal Society, 2008, 33(12): 1419-1424.
24	ZHANG B, WU Q. Thermodynamic promotion of tetrahydrofuran on methane separation from low-concentration coal mine methane based on hydrate[J]. Energy & Fuels, 2010, 24(4): 2530-2535.
25	ZHONG D L, YE Y, YANG C, et al. Experimental investigation of methane separation from low-concentration coal mine gas (CH₄/N₂/O₂) by tetra-n-butyl ammonium bromide semi-clathrate hydrate crystallization[J]. Industrial & Engineering Chemistry Research, 2012, 51(45): 14806-14813.
26	钟栋梁, 何双毅, 严瑾, 等. 低甲烷浓度煤层气的水合物法提纯实验[J]. 天然气工业, 2014, 34(8): 123-128.
	ZHONG D L, HE S Y, YAN J, et al. An experimental study of using hydrate formation to enhance the methane recovery of low-concentration coal bed methane [J]. Nature Gas Industry, 2014, 34(8): 123-128.
27	ZHONG D L, DING K, YAN J, et al. Influence of cyclopentane and SDS on methane separation from coal mine gas by hydrate crystallization[J]. Energy & Fuels, 2013, 27(12): 7252-7258.
28	吕秋楠, 李小森, 李刚, 等. 水合物法分离低浓度煤层气中的甲烷[J]. 过程工程学报, 2019, 19(6): 1129-1134.
	LYU Q N, LI X S, LI G, et al. Separation of methane from low concentration coal bed methane by hydrate-based process[J]. The Chinese Journal of Process Engineering, 2019, 19(6): 1129-1134.
29	CAI J, XU C G, CHEN Z Y, et al. Recovery of methane from coal-bed methane gas mixture via hydrate-based methane separation method by adding anionic surfactants[J]. Energy Sources Part A: Recovery, Utilization & Environmental Effects, 2018, 40(9): 11019-1026.
30	ZHANG Q, WU Q, ZHANG H, et al. Effect of montmorillonite on hydrate-based methane separation from mine gas[J]. Journal of Central South University, 2018, 25(1): 38-50.
31	KUMAR A, VELUSWAMY H P, KUMAR R, et al. Kinetic promotion of mixed methane-THF hydrate by additives: opportune to energy storage[J]. Energy Procedia, 2019, 158: 5287-5292.
32	SUN Q, CHEN B, LI Y, et al. Enhanced separation of coal bed methane via bio-clathrates formation[J]. Fuel, 2019, 243: 10-14.
33	KIM N-J, S-S PARK. Study on methane hydrate formation using ultrasonic waves[J]. Journal of Industrial & Engineering Chemistry, 2013, 19(5): 1668-1672.
34	FAKHARIAN H, GANJI H, NADERI FAR A, et al. Potato starch as methane hydrate promoter[J]. Fuel, 2012, 94: 356-360.
35	杨西萍, 刘煌, 李赟. 水合物法分离混合物技术研究进展[J]. 化工学报, 2017, 68(3): 831-840.
	YANG X P, LIU H, LI Y. Research progress of separation technology based on hydrate formation[J]. CIESC Journal, 2017, 68(3): 831-840.
36	ZHONG D L, DING K, LU Y Y, et al. Methane recovery from coal mine gas using hydrate formation in water-in-oil emulsions [J]. Applied Energy, 2016, 162: 1619-1626.
37	丁坤. 气体水合物法分离煤层气及IGCC燃气的热力学与动力学特性研究[D]. 重庆: 重庆大学, 2018.
	DING K. Study on the thermodynamic and kinetic characteristics of hydrate based gas separation for coal mine gas and IGCC gas[D]. Chongqing: Chongqing University, 2018.
38	FAN S S, YANG L, WANG Y H, et al. Rapid and high capacity methane storage in clathrate hydrates using surfactant dry solution[J]. Chemical Engineering Science, 2014, 106: 53-59.
39	ZHONG D L, SUN D J, LU Y Y, et al. Adsorption–hydrate hybrid process for methane separation from a CH₄/N₂/O₂ gas mixture using pulverized coal particles[J]. Industrial & Engineering Chemistry Research, 2014, 53(40): 15738-15746.
40	苏向东. 多孔介质+THF+TBAB体系煤层气水合物生成实验及理论研究[D]. 太原: 太原理工大学, 2016.
	SU X D. Experiment and theoretical research for formation of coal-bed methane hydrate in porous media +THF+TBAB system[D]. Taiyuan: Taiyuan University of Technology, 2016.
41	LI J B, ZHONG D L, YAN J. Improving gas hydrate-based CH₄ separation from low-concentration coalbed methane by graphene oxide nanofluids[J]. Journal of Natural Gas Science and Engineering, 2020, 76: 103212.
42	ZHONG D L, LU Y Y, SUN D J, et al. Performance evaluation of methane separation from coal mine gas by gas hydrate formation in a stirred reactor and in a fixed bed of silica sand[J]. Fuel, 2015, 143: 586-594.
43	陈广印, 孙强, 郭绪强, 等. 水合物法连续分离煤层气实验研究[J]. 高校化学工程学报, 2013, 27(4): 561-566.
	CHEN G Y, SUN Q, GUO X Q, et al. Experimental study on the continuous separation process of coal bed methane via forming hydrate[J]. Journal of Chemical Engineering of Chinese Universities, 2013, 27(4): 561-566.
44	孙兆虎, 程逵炜, 吴剑峰. 利用水合物法回收低浓度煤层气中甲烷的方法及装置: CN103160351A[P]. 2013-06-19.
	SUN Z H, CHENG K W, WU J F. Method and device used for utilizing hydrate method to recover methane in low concentration coal bed gas: CN103160351A[P]. 2013-06-19.
45	LUCIA B, CASTELLANI B, ROSSI F, et al. Experimental investigations on scaled-up methane hydrate production with surfactant promotion: energy considerations[J]. Journal of Petroleum Science & Engineering, 2014, 120: 187-193.
46	XIAO P, YANG X M, SUN C Y, et al. Enhancing methane hydrate formation in bulk water using vertical reciprocating impact[J]. Chemical Engineering Journal, 2018, 336: 649-658.
47	白净, 李凌乾, 刘风莉, 等. 机械扰动强化气体水合物快速生成研究进展[J]. 化工进展, 2018, 37(1): 60-67.
	BAI J, LI L Q, LIU F L, et al. Progress of rapid formation of gas hydrate by mechanical disturbance[J]. Chemical Industry and Engineering Progress, 2018, 37(1): 60-67.

LCCBM的提纯技术	原理	分析
变压吸附法	利用固体吸附剂对LCCBM中CH₄的选择性吸附作用来提纯LCCBM中的CH₄	技术较成熟、能耗低、工艺流程简单、操作灵活，但是对于吸附剂研制的技术要求很高
低温精馏法	利用LCCBM中CH₄和N₂两种气体沸点之间的差异，将混合气液化后进行分离	技术较为成熟，产品中CH₄的纯度高、回收率高，但操作条件要求高、设备投资大、危险系数也较高
膜分离法	利用CH₄和N₂在压力的推动下，通过溶解、扩散及脱附等步骤产生CH₄和N₂透过膜的传递速率不同来实现提纯	分离效率高、设备简单、能耗低、操作简单、可持续运行，但是膜选择性低、成本高、力学性能差
水合物法	利用气体与水在低温高压条件下形成水合物时CH₄优先于N₂包埋在水合物空腔中，从而实现混合气体的分离	技术安全、高效、节能、压力损失小、工业试验流程短，但是往往面临着分离效率不高、产品纯度较低等缺陷

LCCBM的提纯技术	原理	分析
变压吸附法	利用固体吸附剂对LCCBM中CH₄的选择性吸附作用来提纯LCCBM中的CH₄	技术较成熟、能耗低、工艺流程简单、操作灵活，但是对于吸附剂研制的技术要求很高
低温精馏法	利用LCCBM中CH₄和N₂两种气体沸点之间的差异，将混合气液化后进行分离	技术较为成熟，产品中CH₄的纯度高、回收率高，但操作条件要求高、设备投资大、危险系数也较高
膜分离法	利用CH₄和N₂在压力的推动下，通过溶解、扩散及脱附等步骤产生CH₄和N₂透过膜的传递速率不同来实现提纯	分离效率高、设备简单、能耗低、操作简单、可持续运行，但是膜选择性低、成本高、力学性能差
水合物法	利用气体与水在低温高压条件下形成水合物时CH₄优先于N₂包埋在水合物空腔中，从而实现混合气体的分离	技术安全、高效、节能、压力损失小、工业试验流程短，但是往往面临着分离效率不高、产品纯度较低等缺陷

[1]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[2]	赵景超, 谭明. 表面活性剂对电渗析减量化工业含盐废水的影响[J]. 化工进展, 2023, 42(S1): 529-535.
[3]	盛维武, 程永攀, 陈强, 李小婷, 魏嘉, 李琳鸽, 陈险峰. 微气泡和微液滴双强化脱硫反应器操作分析[J]. 化工进展, 2023, 42(S1): 142-147.
[4]	黄益平, 李婷, 郑龙云, 戚傲, 陈政霖, 史天昊, 张新宇, 郭凯, 胡猛, 倪泽雨, 刘辉, 夏苗, 主凯, 刘春江. 三级环流反应器中气液流动与传质规律[J]. 化工进展, 2023, 42(S1): 175-188.
[5]	刘炫麟, 王驿凯, 戴苏洲, 殷勇高. 热泵中氨基甲酸铵分解反应特性及反应器结构优化[J]. 化工进展, 2023, 42(9): 4522-4530.
[6]	罗成, 范晓勇, 朱永红, 田丰, 崔楼伟, 杜崇鹏, 王飞利, 李冬, 郑化安. 中低温煤焦油加氢反应器不同分配器中液体分布的CFD模拟[J]. 化工进展, 2023, 42(9): 4538-4549.
[7]	王谨航, 何勇, 史伶俐, 龙臻, 梁德青. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.
[8]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[9]	李由, 吴越, 钟禹, 林琦璇, 任俊莉. 酸性熔盐水合物预处理麦秆高效制备木糖及其对酶解效率的影响[J]. 化工进展, 2023, 42(9): 4974-4983.
[10]	邓建, 王凯, 骆广生. 面向硝基化学品安全生产的绝热连续微反应技术发展及思考[J]. 化工进展, 2023, 42(8): 3923-3925.
[11]	李洞, 王倩倩, 张亮, 李俊, 付乾, 朱恂, 廖强. 非水系纳米流体热再生液流电池串联堆性能特性[J]. 化工进展, 2023, 42(8): 4238-4246.
[12]	尹新宇, 皮丕辉, 文秀芳, 钱宇. 特殊浸润性材料在防治油气管道中水合物成核与聚集的应用[J]. 化工进展, 2023, 42(8): 4076-4092.
[13]	张凯, 吕秋楠, 李刚, 李小森, 莫家媚. 南海海泥中甲烷水合物的形貌及赋存特性[J]. 化工进展, 2023, 42(7): 3865-3874.
[14]	鲁少杰, 刘佳, 冀芊竹, 李萍, 韩月阳, 陶敏, 梁文俊. 硅藻土基复合填料制备及滴滤塔去除二甲苯的性能[J]. 化工进展, 2023, 42(7): 3884-3892.
[15]	王松松, 刘培乔, 陶长元, 王运东, 陈恩之, 苗迎彬, 赵风轩, 刘作华. 工业物联网技术在搅拌反应器领域的应用[J]. 化工进展, 2023, 42(7): 3331-3339.