多孔材料中甲烷水合物生成的传热数值模拟研究

doi:10.11949/0438-1157.20220512

摘要/Abstract

摘要：

水合物储运(NGH)是近几年发展起来的天然气储运技术，已具备实现工业化的潜力。但水合物的生长是传质传热控制的反应，因此在放大实验中存在诸多不确定因素。针对该问题，对水合物反应器中多孔材料内甲烷水合物生成传热过程建立了基于化学反应动力学和多孔材料内传质传热的甲烷水合物生成传热数学模型，可用于计算反应器内水合物生成分布和热量分布，指导水合反应器的设计和优化。通过模拟与实验数据对比验证了该模型的可靠性，并对使用了不同热导率填料的水合反应过程进行数值模拟。结果显示，模拟值与实验值的绝对平均相对误差小于6%，生成传热模型准确性高；在水合反应过程中，热量传递是影响水合物生成速率的关键因素之一。导热不良时，易在水合物生成中心部分形成局部过热，对水合物生长造成热抑制。在进行水合物生成放大实验时，应特别注意反应器内部的热量控制。

关键词: 水合物, 数值模拟, 传热, 水合物生成, 多孔材料

Abstract:

Hydrate storage and transportation (NGH) is a natural gas storage and transportation technology developed in recent years and has the potential to realize industrialization. However, the growth of hydrate is a reaction controlled by mass and heat transfer, so there are many uncertain factors in the scale-up experiment. Based on the chemical reaction kinetic and the mass and heat transfer in porous materials, a mathematical model of methane hydrate formation and heat transfer is established in hydrate reactor for the formation and heat transfer process in porous materials, which can be used to predict the hydrate formation and heat distribution in the reactor and guide the design and optimization of hydration reactor. The reliability of the model was verified by comparing with experimental data, and the hydrate reaction process in porous materials with different thermal conductivity was numerically simulated. The results show that the AARD between the simulated value and the experimental value is less than 6%, and the heat transfer model is highly accurate. Heat transfer is one of the key factors affecting the hydrate formation rate during hydrate reaction. When the heat conduction is poor, it is easy to form local overheating in the hydrate formation center, resulting in thermal inhibition of hydrate formation. When performing scale-up experiments on hydrate formation, special attention should be paid to thermal control inside the reactor.

Key words: hydrate, numerical simulation, heat transfer, hydrate formation, porous materials

中图分类号:

TE 82

郎雪梅, 姚柳眉, 樊栓狮, 李刚, 王燕鸿. 多孔材料中甲烷水合物生成的传热数值模拟研究[J]. 化工学报, 2022, 73(9): 3851-3860.

Xuemei LANG, Liumei YAO, Shuanshi FAN, Gang LI, Yanhong WANG. Numerical simulation of methane hydrate formation and heat transfer in porous materials[J]. CIESC Journal, 2022, 73(9): 3851-3860.

图/表 12

图1 物理模型

Fig.1 Physical model

图2 模型网格划分

Fig.2 Grid system of model

表1 模拟运行参数

Table 1 Operating parameters of the simulation

编号	多孔材料种类	工作压力/MPa	壁面温度/K	孔隙率	热导率/ (W/(m·K))
①	聚氨酯泡沫PU	7.70	273.15	0.9778	0.039
②	泡沫铝AF	8.39	273.15	0.7278	237.00

图3 甲烷水合物生成动力学[15-16]

Fig.3 Kinetic of methane hydrate formation[15-16]

图4 模拟数据与实验数据比较

Fig.4 Comparison of simulation data and experimental data

图5 聚氨酯泡沫PU内z=0平面甲烷水合物体积分数随时间的变化

Fig.5 Methane hydrate volume fraction at z=0 plane with time variation in PU foam system

图6 聚氨酯泡沫PU内z=0平面甲烷水合物温度随时间的变化

Fig.6 Methane hydrate temperature at z=0 plane with time variation in PU foam system

图7 泡沫铝AF内z=0平面甲烷水合物体积分数随时间的变化

Fig.7 Methane hydrate volume fraction at z=0 plane with time variation in AF foam system

图8 泡沫铝AF内z=0平面甲烷水合物温度随时间的变化

Fig.8 Methane hydrate temperature at z=0 plane with time variation in AF foam system

图9 水合反应中心的水合物、气、水饱和度和介质表观热导率随时间的变化

Fig.9 Plot of Sh, Sg, Swand λa of hydration reaction center with time

图10 聚氨酯泡沫PU和泡沫铝AF体系内水合物温度计算值取点位置

Fig.10 The point of hydrate temperature in PU and AF porous materials system

图11 不同高度甲烷水合物温度随时间的变化

Fig.11 Methane hydrate temperature variation with time at different heights

参考文献 36

1	Exxonmobil. The outlook for energy: a view to 2040[R]. the United States: ExxonMobil, 2014.
2	He T B, Chong Z R, Zheng J J, et al. LNG cold energy utilization: prospects and challenges[J]. Energy, 2019, 170: 557-568.
3	朱琳琳, 皇甫立霞, 郭开华. 液化天然气航运安全标准的现状及最新进展[J]. 化工学报, 2018, 69(S2): 1-8.
	Zhu L L, Huangfu L X, Guo K H, et al. Current status and recent progress of LNG navigation safety standards[J]. CIESC Journal, 2018, 69(S2): 1-8.
4	Veluswamy H P, Wong A J H, Babu P, et al. Rapid methane hydrate formation to develop a cost effective large scale energy storage system[J]. Chemical Engineering Journal, 2016, 290: 161-173.
5	Fan S S, Wang Y, Wang Y H, et al. Design and optimization of offshore ship-based natural gas storage technologies in the South China Sea[J]. Energy Conversion and Management, 2021, 239: 114218.
6	郎雪梅, 樊栓狮, 王燕鸿, 等. 笼型水合物为能源化工带来新机遇[J]. 化工进展, 2021, 40(9): 4703-4710.
	Lang X M, Fan S S, Wang Y H, et al. Opportunities for energy and chemical engineering through clathrate hydrates[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4703-4710.
7	Deng Z X, Wang Y H, Yu C, et al. Promoting methane hydrate formation with expanded graphite additives: application to solidified natural gas storage[J]. Fuel, 2021, 299: 120867.
8	裴俊华, 杨亮, 汪鑫, 等. 泡沫铜强化甲烷水合物生成动力学实验研究[J]. 化工学报, 2021, 72(11): 5751-5760.
	Pei J H, Yang L, Wang X, et al. Experimental study on kinetics of methane hydrate formation enhanced by copper foam[J]. CIESC Journal, 2021, 72(11): 5751-5760.
9	Sloan E D, Koh C A. Clathrate Hydrates of Natural Gases [M]. Florida: CRC Press, 2007.
10	Xie Y, Zheng T, Zhong J R, et al. Experimental research on self-preservation effect of methane hydrate in porous sediments[J]. Applied Energy, 2020, 268: 115008.
11	Wang S L, Xu J, Fan S S, et al. Atmospheric preservation of CH₄ hydrate above ice point: a potential application for high-density natural gas storage under moderate conditions[J]. Fuel, 2021, 293: 120482.
12	Bhattacharjee G, Veluswamy H P, Kumar A, et al. Stability analysis of methane hydrates for gas storage application[J]. Chemical Engineering Journal, 2021, 415: 128927.
13	Kanda H. Economic study on natural gas transportation with natural gas hydrate (NGH) pellets[J]. International Gas Union World Gas Conference Papers, 2006, 4: 1990-2000.
14	Ke W, Svartaas T M, Chen D Y. A review of gas hydrate nucleation theories and growth models[J]. Journal of Natural Gas Science and Engineering, 2019, 61: 169-196.
15	Fan S S, Yang L, Lang X M, et al. Kinetics and thermal analysis of methane hydrate formation in aluminum foam[J]. Chemical Engineering Science, 2012, 82: 185-193.
16	黄怡. 碳纳米管、聚氨酯泡沫和新型干水对甲烷水合物生成的强化作用[D]. 广州: 华南理工大学, 2016.
	Huang Y. Effects of MWCNT, PU foam and new dry water on methane hydrate formation[D]. Guangzhou: South China University of Technology, 2016.
17	Esmaeilzadeh F, Zeighami M E, Kaljahi J F. 1-D mathematical modeling of hydrate decomposition in porous media by depressurization and thermal stimulation[J]. Journal of Porous Media, 2011, 14(1): 1-16.
18	Li P, Zhang X H, Lu X B. Three-dimensional Eulerian modeling of gas-liquid-solid flow with gas hydrate dissociation in a vertical pipe[J]. Chemical Engineering Science, 2019, 196: 145-165.
19	Song G C, Li Y X, Wang W C, et al. Hydrate agglomeration modeling and pipeline hydrate slurry flow behavior simulation[J]. Chinese Journal of Chemical Engineering, 2019, 27(1): 32-43.
20	Neto E T. A mechanistic computational fluid dynamic CFD model to predict hydrate formation in offshore pipelines[C]//SPE Annual Technical Conference and Exhibition. Dubai, UAE: SPE, 2016: 184491.
21	Song R, Sun S Y, Liu J J, et al. Numerical modeling on hydrate formation and evaluating the influencing factors of its heterogeneity in core-scale sandy sediment[J]. Journal of Natural Gas Science and Engineering, 2021, 90: 103945.
22	Chou I M, Sharma A, Burruss R C, et al. Transformations in methane hydrates[J]. Proceedings of the National Academy of Sciences of the United States of America, 2000, 97(25): 13484-13487.
23	Kumar A, Veluswamy H P, Linga P, et al. Molecular level investigations and stability analysis of mixed methane-tetrahydrofuran hydrates: implications to energy storage[J]. Fuel, 2019, 236: 1505-1511.
24	Vysniauskas A, Bishnoi P R. A kinetic study of methane hydrate formation[J]. Chemical Engineering Science, 1983, 38(7): 1061-1072.
25	郝天翔. 应用FLUENT数值模拟天然气水合物开采过程[D]. 长春: 吉林大学, 2015.
	Hao T X. Numerical simulation of exploiting gas hydrate processes based on FLUENT software[D]. Changchun: Jilin University, 2015.
26	Waite W F, Santamarina J C, Cortes D D, et al. Physical properties of hydrate-bearing sediments[J]. Reviews of Geophysics, 2009, 47(4): RG4003.
27	Yin Z Y, Khurana M, Tan H K, et al. A review of gas hydrate growth kinetic models[J]. Chemical Engineering Journal, 2018, 342: 9-29.
28	Fluent A. ANSYS FLUENT 14.5 Theory Guide[M]. The United States: Canonsburg, 2012.
29	孙长宇, 陈光进, 郭天民, 等. 甲烷水合物分解动力学[J]. 化工学报, 2002, 53(9): 899-903.
	Sun C Y, Chen G J, Guo T M, et al. Kinetics of methane hydrate decomposition[J]. Journal of Chemical Industry and Engineering (China), 2002, 53(9): 899-903.
30	辛亚男, 张建文, 张淑珍, 等. 螺旋内槽管内天然气-水-表面活性剂体系的水合物生成动力学计算[J]. 化工学报, 2018, 69(6): 2463-2473.
	Xin Y N, Zhang J W, Zhang S Z, et al. Modelling hydrate formation kinetics of natural gas-water-surfactant system in internal spiral-grooved tube[J]. CIESC Journal, 2018, 69(6): 2463-2473.
31	Kim H C, Bishnoi P R, Heidemann R A, et al. Kinetics of methane hydrate decomposition[J]. Chemical Engineering Science, 1987, 42(7): 1645-1653.
32	Ji C, Ahmadi G, Smith D H. Natural gas production from hydrate decomposition by depressurization[J]. Chemical Engineering Science, 2001, 56(20): 5801-5814.
33	Sun X F, Mohanty K K. Kinetic simulation of methane hydrate formation and dissociation in porous media[J]. Chemical Engineering Science, 2006, 61(11): 3476-3495.
34	Amyx J W, Bass D, Whiting R. Petroleum Reservoir Engineering: Physical Properties[M]. New York: McGraw-Hill, 1960.
35	Kleinberg R L, Flaum C, Griffin D D, et al. Deep sea NMR: methane hydrate growth habit in porous media and its relationship to hydraulic permeability, deposit accumulation, and submarine slope stability[J]. Journal of Geophysical Research: Solid Earth, 2003, 108(B10): 2508.
36	Hinz D. A 4-phase flow model for methane production from an unconsolidated hydrate reservoir[D]. Illinois: Illinois Institute of Technology, 2019.

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