天然烟浸滤液水合物法储甲烷动力学研究

doi:10.11949/0438-1157.20221242

摘要/Abstract

摘要：

水合物法储存天然气被公认为是一种极具潜力的高效储气技术。如何加速水合物生成，又能保证水合促进材料绿色环保，是水合固气技术实用化的关键。本文利用天然烟丝和烟末浸泡滤液在8.0 MPa和274.2 K的实验条件下进行静态水合储甲烷实验，研究甲烷水合物在烟滤液中的生成动力学特性。实验结果表明，水-烟质量比（液固比）为5~100的滤液与表面活性剂溶液性质相似，其表面张力比纯水下降36.7%~47.5%，甲烷水合物在该天然活性溶液中能快速生成。烟丝滤液中活性物含量明显低于烟末滤液，低液固比时，烟丝溶液有更高的水合储气量和储气速率；高液固比时，烟末滤液则表现出更优的水合储气性能，尤其在液固比为50时，烟末滤液中水合物储气量高达118.5 mmol·mol^-1，储气速率达2.98 mmol·mol^-1·min^-1。

关键词: 烟浸滤液, 甲烷储存, 水合物生成, 动力学, 促进

Abstract:

Hydrate storage of natural gas is recognized as a highly efficient gas storage technology with great potential. How to accelerate the formation of hydrates and ensure the environmental protection of hydration-promoting materials are the key to the practical application of hydration storage gas technology. In order to investigate the kinetics of methane hydrate formation in the natural tobacco leaching filtrate, the solutions by filtering tobacco shred/granule-water mixtures were used to store methane in hydrate under 8.0 MPa and 274.2 K. The experimental results showed that the solution with a water-tobacco mass ratio (liquid-solid ratio) of 5—100 had similar properties of surfactant, and its surface tension decreased by 36.7%—47.5% compared with pure water. Methane hydrate could be formed rapidly in active solutions. The content of active substance in tobacco shred leaching filtrate was significantly lower than that in tobacco granule leaching filtrate. When the liquid-solid ratio was low, tobacco shred leaching filtrate could store more gas in hydrate and had higher storage rate. When the liquid-solid ratio was high, tobacco granule leaching filtrate had better gas storage performance. Especially, the methane uptakes in tobacco granule leaching filtrate with liquid-solid ratio of 50 reached 118.5 mmol·mol^-1, and the gas storage rate was up to 2.98 mmol·mol^-1·min^-1.

Key words: tobacco leaching filtrate, methane storage, hydrate formation, kinetics, promotion

中图分类号:

TE 89

胡晗, 杨亮, 李春晓, 刘道平. 天然烟浸滤液水合物法储甲烷动力学研究[J]. 化工学报, 2023, 74(3): 1313-1321.

Han HU, Liang YANG, Chunxiao LI, Daoping LIU. Kinetics of methane storage in the natural tobacco leaching filtrate in the hydrate form[J]. CIESC Journal, 2023, 74(3): 1313-1321.

图/表 11

图1 实验装置

Fig.1 Experimental device

图2 甲烷水合物生长过程中温压变化（RL/S=5）

Fig.2 Temperature and pressure changes during the growth of methane hydrate

图3 RL/S=5时烟溶液中水合物储气量及储气速率

Fig.3 Gas storage capacity and gas storage rate of hydrate in tobacco solution when RL/S=5

图4 不同RL/S烟溶液中储气量及储气速率

Fig.4 Gas storage capacity and gas storage rate in tobacco solutions with different RL/S

表1 水合储气实验结果

Table 1 Experimental results of hydration gas storage

Hydrate system	R_L/S	C_{up, max}/ (mmol·mol^-1)	R_{up, max}/ (mmol·mol^-1·min^-1)	t_in/min
TS solution	5	71.7 (±2.3)	1.16	570
	10	83.4 (±3.0)	1.56	5
	20	—	—	—
	34	—	—	—
	50	—	—	—
	100	—	—	—
TG solution	5	21.1 (±6.1)	—	—
	10	71.9 (±1.9)	1.35	20
	20	85.3 (±2.5)	2.13	50
	34	80.4 (±4.2)	1.57	70
	50	118.5 (±1.9)	2.98	120
	100	—	—	—
deionized water	—	—	—	—

图5 不同RL/S烟溶液中活性物质浓度

Fig.5 Concentration of active substances in different RL/S tabacco solutions

图6 不同RL/S烟溶液中界面张力

Fig.6 Interfacial tension in tobacco solutions with different RL/S

表2 不同液固比条件下烟溶液中溶解物浓度及界面张力

Table 2 Dissolved substance concentration and interfacial tension in tobacco solution under different liquid-solid ratios

Hydrate system	R_L/S	C_AS/%(mass)	IFT/(mN·m^-1)
TS solution	5	3.79 (±0.26)	42.08 (±0.056)
	10	1.34 (±0.09)	43.23 (±0.042)
	20	0.50 (±0.06)	44.73 (±0.053)
TG solution	5	7.47 (±0.38)	38.19 (±0.077)
	10	4.09 (±0.26)	42.17 (±0.074)
	20	2.23 (±0.10)	42.59 (±0.045)
	34	1.22 (±0.09)	43.58 (±0.075)
	50	0.80 (±0.08)	44.20 (±0.090)
	100	0.27 (±0.04)	46.08 (±0.063)
	200	0.12 (±0.01)	43.21 (±0.075)
deionized water	—	0	72.75

图7 不同RL/S烟溶液储气量

Fig.7 Gas storage of tabacco solutions with different RL/S

图8 不同RL/S烟溶液最大储气量及最大储气速率

Fig.8 Maximum gas storage capacity and maximum gas storage rate of tabacco solutions with different RL/S

图9 烟溶液中生成的甲烷水合物

Fig.9 Methane hydrate formed in tabacco solution

参考文献 39

1	Sloan E D. Fundamental principles and applications of natural gas hydrates[J]. Nature, 2003, 426(6964): 353-359.
2	Hao W F, Wang J H, Fan S S, et al. Evaluation and analysis method for natural gas hydrate storage and transportation processes[J]. Energy Conversion and Management, 2008, 49(10): 2546-2553.
3	Kumar R, Linga P, Moudrakovski I, et al. Structure and kinetics of gas hydrates from methane/ethane/propane mixtures relevant to the design of natural gas hydrate storage and transport facilities[J]. AIChE Journal, 2008, 54(8): 2132-2144.
4	Yang L, Fan S S, Wang Y H, et al. Accelerated formation of methane hydrate in aluminum foam[J]. Industrial & Engineering Chemistry Research, 2011, 50(20): 11563-11569.
5	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.
6	Yang M J, Chong Z R, Zheng J N, et al. Advances in nuclear magnetic resonance (NMR) techniques for the investigation of clathrate hydrates[J]. Renewable and Sustainable Energy Reviews, 2017, 74: 1346-1360.
7	Zhao J, Zheng J N, Ma S, et al. Formation and production characteristics of methane hydrates from marine sediments in a core holder[J]. Applied Energy, 2020, 275: 115393.
8	Chong Z R, Yang S H B, Babu P, et al. Review of natural gas hydrates as an energy resource: prospects and challenges[J]. Applied Energy, 2016, 162: 1633-1652.
9	Englezos P, Kalogerakis N, Dholabhai P D, et al. Kinetics of formation of methane and ethane gas hydrates[J]. Chemical Engineering Science, 1987, 42(11): 2647-2658.
10	Hao W F, Wang J Q, Fan S S, et al. Study on methane hydration process in a semi-continuous stirred tank reactor[J]. Energy Conversion and Management, 2007, 48(3): 954-960.
11	Yao S P, Li Y X, Wang W C, et al. Experimental investigation on the microscopic decomposition process of natural gas hydrate particles[J]. Energy & Fuels, 2019, 33(6): 5208-5215.
12	Zhao J F, Wang B, Sum A K. Dynamics of hydrate formation and deposition under pseudo multiphase flow[J]. AIChE Journal, 2017, 63(9): 4136-4146.
13	Mali G A, Chapoy A, Tohidi B. Investigation into the effect of subcooling on the kinetics of hydrate formation[J]. The Journal of Chemical Thermodynamics, 2018, 117: 91-96.
14	Maini B B, Bishoni P R. Experimental investigation of hydrate formation behaviour of a natural gas bubble in a simulated deep sea environment[J]. Chemical Engineering Science, 1981, 36(1): 183-189.
15	Fu W Q, Wang Z Y, Sun B J, et al. A mass transfer model for hydrate formation in bubbly flow considering bubble-bubble interactions and bubble-hydrate particle interactions[J]. International Journal of Heat and Mass Transfer, 2018, 127: 611-621.
16	Tsuji H, Ohmura R, Mori Y H. Forming structure-H hydrates using water spraying in methane gas: effects of chemical species of large-molecule guest substances[J]. Energy & Fuels, 2004, 18(2): 418-424.
17	Zhong Y, Rogers R E. Surfactant effects on gas hydrate formation[J]. Chemical Engineering Science, 2000, 55(19): 4175-4187.
18	Ganji H, Manteghian M, Mofrad H R. Effect of mixed compounds on methane hydrate formation and dissociation rates and storage capacity[J]. Fuel Processing Technology, 2007, 88(9): 891-895.
19	Zhang J S, Lee S Y, Lee J W. Kinetics of methane hydrate formation from SDS solution[J]. Industrial and Engineering Chemistry Research, 2007, 46(19): 6353-6359.
20	Yoslim J, Linga P, Englezos P. Enhanced growth of methane-propane clathrate hydrate crystals with sodium dodecyl sulfate, sodium tetradecyl sulfate, and sodium hexadecyl sulfate surfactants[J]. Journal of Crystal Growth, 2010, 313(1): 68-80.
21	Duan M, Ding Z, Wang H, et al. Evolution of oil/water interface in the presence of SDBS detected by dual polarization interferometry[J]. Applied Surface Science, 2018, 427: 917-926.
22	Zhang C S, Fan S S, Liang D Q, et al. Effect of additives on formation of natural gas hydrate[J]. Fuel, 2004, 83(16): 2115-2121.
23	Zhou L C, Sun Z G, Lu L, et al. Effect of organic phase change material and surfactant on HCFC141b hydrate nucleation in quiescent conditions[J]. Chemical Engineering Science, 2020, 228: 115976.
24	Wang W X, Zeng P Y, Long X Y, et al. Methane storage in tea clathrates[J]. Chemical Communications, 2014, 50(10): 1244-1246.
25	Babakhani S M, Alamdari A. Effect of maize starch on methane hydrate formation/dissociation rates and stability[J]. Journal of Natural Gas Science and Engineering, 2015, 26: 1-5.
26	Sun Q, Chen B, Li Y Y, et al. Promotion effects of mung starch on methane hydrate formation equilibria/rate and gas storage capacity[J]. Fluid Phase Equilibria, 2018, 475: 95-99.
27	Ekta C, Nitish P, Ajay M. Enhanced formation of methane hydrate using a novel synthesized anionic surfactant for application in storage and transportation of natural gas[J]. Journal of Natural Gas Science and Engineering, 2018, 56: 246-257.
28	Yi J, Zhong D L, Yan J, et al. Impacts of the surfactant sulfonated lignin on hydrate based CO₂ capture from a CO₂/CH₄ gas mixture[J]. Energy, 2019, 171: 61-68.
29	黄仙智, 马贵阳, 王平. 鼠李糖脂与多孔介质对天然气水合物生成影响[J]. 天然气化工(C1化学与化工), 2020, 45(6): 42-47.
	Huang X Z, Ma G Y, Wang P. Effects of rhamnolipid and porous media on natural gas hydrate formation[J]. Natural Gas Chemical Industry, 2020, 45(6): 42-47.
30	Trivedi V, Dalvi S V. Enhancing CO₂ hydrate formation: effect of coconut fibers on nucleation kinetics of CO₂ hydrates[J]. Journal of Crystal Growth, 2020, 549: 125865.
31	Mohammadi A, Babakhanpour N, Javidani A M, et al. Corn's dextrin, a novel environmentally friendly promoter of methane hydrate formation[J]. Journal of Molecular Liquids, 2021, 336: 116855.
32	RincóN J, De Lucas A, García M A, et al. Preliminary study on the supercritical carbon dioxide extraction of nicotine from tobacco wastes[J]. Separation Science and Technology, 1998, 33(3): 411-423.
33	郑丹星. 化学工业. 化学热力学教程[M]. 北京: 中国石化出版社, 1995.
	Zheng D X. Chemical Industry. Chemical Thermodynamics[M]. Beijing: China Petrochemical Press, 1995.
34	Banožić M, Babic J, Jokic S. Recent advances in extraction of bioactive compounds from tobacco industrial waste—a review[J]. Industrial Crops and Products, 2020, 144: 112009.
35	Liu Y, Chen B Y, Chen Y L, et al. Methane storage in a hydrated form as promoted by leucines for possible application to natural gas transportation and storage[J]. Energy Technology, 2015, 3(8): 815-819.
36	孙志高, 郭开华, 樊栓狮. 天然气水合物形成促进技术实验研究[J]. 天然气工业, 2004, 24(12): 41-43, 185.
	Sun Z G, Guo K H, Fan S S. Experimental study of promoting natural gas hydrate formation[J]. Natural Gas Industry, 2004, 24(12): 41-43, 185.
37	Vargaftik N B, Volkov B N, Voljak L D. International tables of the surface tension of water[J]. Journal of Physical and Chemical Reference Data, 1983, 12(3): 817-820.
38	Sloan E D, Koh C A. Clathrate Hydrates of Natural Gases[M]. 3rd ed. Boca Raton, FL: CRC Press, 2008.
39	Lee S Y, Zhang J S, Mehta R, et al. Methane hydrate equilibrium and formation kinetics in the presence of an anionic surfactant[J]. The Journal of Physical Chemistry C, 2007, 111(12): 4734-4739.

[1]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[2]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[3]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[4]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[5]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[6]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[7]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[8]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[9]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[10]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[11]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[12]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[13]	何宣志, 何永清, 闻桂叶, 焦凤. 磁液液滴颈部自相似破裂行为[J]. 化工学报, 2023, 74(7): 2889-2897.
[14]	李彬, 徐正虎, 姜爽, 张天永. 双氧水催化氧化法清洁高效合成促进剂CBS[J]. 化工学报, 2023, 74(7): 2919-2925.
[15]	周继鹏, 何文军, 李涛. 异形催化剂上乙烯催化氧化失活动力学反应工程计算[J]. 化工学报, 2023, 74(6): 2416-2426.