天然气水合物分解动力学研究进展Research advances on the dissociation dynamics of natural gas hydrates
郁桂刚,欧文佳,吴翔,宁伏龙,张凌
摘要(Abstract):
天然气水合物是具有巨大开发潜力的清洁能源,但由于开采技术、经济性和环境效应等问题尚未达到商业化开发水准。近年来人们也在探索水合物技术在二氧化碳封存、海水淡化、储能、气体分离等领域中的应用。其中最具挑战性和关键性的问题就是水合物如何随时间形成和分解。概况了水合物分解动力学基础研究,包括水合物分解特性、分解影响因素和分解机理;综述了水合物分解动力学模型研究进展,根据水合物分解控制机制,将现有模型归为4类:热分解模型、本征动力学模型、传质分解模型和综合模型,重点阐述了它们的假设条件、主要认识和局限性,并展望了未来水合物分解动力学研究的改进方向,以期能够加深对水合物分解动力学的理解,促进水合物的开发和利用。
关键词(KeyWords): 气体水合物;分解特性;分解机制;分解动力学模型
基金项目(Foundation): 国家自然科学基金项目(51704266;51874263);; 国家重点研发计划(2018YFE0126400)
作者(Author): 郁桂刚,欧文佳,吴翔,宁伏龙,张凌
DOI: 10.19509/j.cnki.dzkq.tb20210668
参考文献(References):
- [1] Sloan E D,Koh C.Clathrate hydrates of natural gases,thrid edition[M].Boca Raton:CRC Press,2007.
- [2] Sloan E D.Fundamental principles and applications of natural gas hydrates[J].Nature,2003,426:353-359.
- [3] 吴传芝,赵克斌,孙长青,等.天然气水合物开采技术研究进展[J].地质科技情报,2016,35(6):243-250.Wu C Z,Zhao K B,Sun C Q,et al.Research advances of the production techniques for gas hydrate[J].Geological Science and Technology Information,2016,35(6):243-250(in Chinese with English abstract).
- [4] 周守为,陈伟,李清平.深水浅层天然气水合物固态流化绿色开采技术[J].中国海上油气,2014,26(5):1-7.Zhou S W,Chen W,Li Q P.The green solid fluidization development principle of natural gas hydrate stored in shallow layers of deep water[J].China Offshore Oil and Gas,2014,26(5):1-7(in Chinese with English abstract).
- [5] Ma Z W,Zhang P,Bao H S,et al.Review of fundamental properties of CO2 hydrates and CO2 capture and separation using hydration method[J].Renewable and Sustainable Energy Reviews,2016,53:1273-1302.
- [6] 郑智颖,李凤臣,李倩,等.海水淡化技术应用研究及发展现状[J].科学通报,2016,61(21):2344-2370.Zheng Z Y,Li F C,Li Q,et al.State-of-the-art of R&D on seawater desalination technology[J].Chinese Science Bulletin,2016,61(21):2344-2370(in Chinese with English abstract).
- [7] Satoh M,Maekawa T,Okuda Y.Estimation of amount of methane and resources of natural gas hydrates in the world and around Japan[J].The Journal of the Geological Society of Japan,1996,102:959-971.
- [8] Sun Q,Kang Y T.Review on CO2 hydrate formation/dissociation and its cold energy application[J].Renewable and Sustainable Energy Reviews,2016,62:478-494.
- [9] Jeong J H,Cha M,Jang J,et al.Thermodynamic behavior and spectroscopic properties of CO and C3H8 mixed gas hydrates:Implications for hydrate-based gas separation[J].Chemical Engineering Journal,2022,428:132076.
- [10] 刘建辉,李占东,赵佳彬.神狐海域天然气水合物研究新进展[J].矿产与地质,2021,35(3):596-602.Liu J H,Li Z D,Zhao J B.New progress in the study of natural gas hydrate in Shenhu area[J].Mineral Resources and Geology,2021,35(3):596-602(in Chinese with English abstract).
- [11] You K,Flemings P B,Malinverno A,et al.Mechanisms of methane hydrate formation in geological systems[J].Reviews of Geophysics,2019,57(4):1146-1196.
- [12] 宁伏龙,梁金强,吴能友,等.中国天然气水合物赋存特征[J].天然气工业,2020,40(8):1-24.Ning F L,Liang J Q,Wu N Y,et al.Reservoir characteristics of natural gas hydrates in China[J].Natural Gas Industry,2020,40(8):1-24(in Chinese with English abstract).
- [13] 程聪,姜涛,匡增桂,等.天然气水合物系统特征及其对我国水合物勘查的启示[J].地质科技情报,2019,38(4):30-40.Cheng C,Jiang T,Kuang Z G,et al.Characteristics of gas hydrate system and its enlightenment to gas hydrate exploration in China[J].Geological Science and Technology Information,2019,38(4):30-40(in Chinese with English abstract).
- [14] Li Y L,Ning F L,Wu N Y,et al.Protocol for sand control screen design of production wells for clayey silt hydrate reservoirs:A case study[J].Energy Science & Engineering,2020,8(5):1438-1449.
- [15] Sun J X,Ning F L,Lei H W,et al.Wellbore stability analysis during drilling through marine gas hydrate-bearing sediments in Shenhu area:A case study[J].Journal of Petroleum Science and Engineering,2018,170:345-367.
- [16] 宁伏龙,方翔宇,李彦龙,等.天然气水合物开采储层出砂研究进展与思考[J].地质科技通报,2020,39(1):137-148.Ning F L,Fang X Y,Li Y L,et al.Research status and perspective on wellbore sand production from hydrate reservoirs[J].Bulletin of Geological Science and Technology,2020,39(1):137-148(in Chinese with English abstract).
- [17] 孙嘉鑫,张凌,宁伏龙,等.天然气水合物藏增产研究现状与展望[J].石油学报,2021,42(4):523-540.Sun J X,Zhang L,Ning F L,et al.Research status and prospects of increasing production from gas hydrate reservoirs[J].Acta Petrolei Sinica,2021,42(4):523-540(in Chinese with English abstract).
- [18] Bai D S,Zhang D W,Zhang X R,et al.Origin of self-preservation effect for hydrate decomposition:Coupling of mass and heat transfer resistances[J].Scientific Reports,2015,5(1):14599.
- [19] Kawamura T,Ohga K,Higuchi K.Dissociation behavior of pellet-shaped methane-ethane mixed gas hydrate samples[J].Energy & Fuels,2003,17(3):614-618.
- [20] Zhong J R,Sun Y F,Li W Z,et al.Structural transition range of methane-ethane gas hydrates during decomposition below ice point[J].Applied Energy,2019,250:873-881.
- [21] Bishnoi P R,Natarajan V.Formation and decomposition of gas hydrates[J].Fluid Phase Equilibria,1996,117(1/2):168-177.
- [22] Ripmeester J A,Alavi S.Some current challenges in clathrate hydrate science:Nucleation,decomposition and the memory effect[J].Current Opinion in Solid State and Materials Science,2016,20(6):344-351.
- [23] Barbara S,Nobuo M.Statistical study of the memory effect in model natural gas hydrate systems[J].The Journal of Physical Chemistry A,2015,119(44):10784-10790.
- [24] Wu Q,Zhang B Y.Memory effect on the pressure-temperature condition and induction time of gas hydrate nucleation[J].Journal of Natural Gas Chemistry,2010,19(4):446-451.
- [25] 庞维新,陈光进.甲烷水合物分解实验[J].化工学报,2008,59(3):681-686.Pang W X,Chen G J.Dissociation experiment of methane hydrate[J].Journal of Chemical Industry and Engineering,2008,59(3):681-686(in Chinese with English abstract).
- [26] 展静,吴青柏,杨玉忠.冰点以下甲烷水合物分解实验对天然气储运的影响[J].天然气地球科学,2012,23(2):348-352.Zhan J,Wu Q B,Yang Y Z.Effect of methane hydrate dissociation on natural gas storage and transportation[J].Natural Gas Geoscience,2012,23(2):348-352(in Chinese with English abstract).
- [27] Takeya S,Uchida T,Nagao J,et al.Particle size effect of CH4 hydrate for self-preservation[J].Chemical Engineering Science,2005,60(5):1383-1387.
- [28] Kono H O,Narasimhan S,Song F,et al.Synthesis of methane gas hydrate in porous sediments and its dissociation by depressurizing[J].Powder Technology,2002,122(2):239-246.
- [29] 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.
- [30] Chen W Q,Hartman R L.Methane hydrate intrinsic dissociation kinetics measured in a microfluidic system by means of in situ raman spectroscopy[J].Energy & Fuels,2018,32(11):11761-11771.
- [31] Jamaluddin A K M,Kalogerakis N,Bishnoi P R.Modelling of decomposition of a synthetic core of methane gas hydrate by coupling intrinsic kinetics with heat transfer rates[J].The Canadian Journal of Chemical Engineering,1989,67(6):948-954.
- [32] 陈强,业渝光,孟庆国,等.甲烷水合物分解过程模拟实验研究[J].现代地质,2008,22(3):475-479.Chen Q,Ye Y G,Meng Q G,et al.Experimental research of methane hydrate dissociation[J].Geoscience,2008,22(3):475-479(in Chinese with English abstract).
- [33] Pang W X,Xu W Y,Sun C Y,et al.Methane hydrate dissociation experiment in a middle-sized quiescent reactor using thermal method[J].Fuel,2009,88(3):497-503.
- [34] Wang B,Dong H S,Liu Y Z,et al.Evaluation of thermal stimulation on gas production from depressurized methane hydrate deposits[J].Applied Energy,2018,227:710-718.
- [35] 王家生,高钰涯,李清,等.沉积物粒度对水合物形成的制约:来自IODP 311航次证据[J].地球科学进展,2007,22(7):659-665.Wang J S,Gao Y Y,Li Q,et al.Grain size constraint on gas hydrate occurrence:Evidence from sediment size during IODP 311[J].Advances in Earth Science,2007,22(7):659-665(in Chinese with English abstract).
- [36] Fang B,Ning F L,Ou W J,et al.The dynamic behavior of gas hydrate dissociation by heating in tight sandy reservoirs:A molecular dynamics simulation study[J].Fuel,2019,258:116106.
- [37] Anderson R,Llamedo M,Tohidi B,et al.Experimental measurement of methane and carbon dioxide clathrate hydrate equilibria in mesoporous silica[J].The Journal of Physical Chemistry B,2003,107(15):3507-3514.
- [38] Handa Y P,Stupin D Y.Thermodynamic properties and dissociation characteristics of methane and propane hydrates in 70-.ANG.-radius silica gel pores[J].The Journal of Physical Chemistry,1992,96(21):8599-8603.
- [39] 邓帅,胡高伟,卜庆涛.粒径及孔径分布对天然气水合物形成影响的研究进展[J].地质科技情报,2019,38(4):41-52.Deng S,Hu G W,Bu Q T.Research progress on the effects of particle size and pore size distribution on natural gas hydrate formation[J].Geological Science and Technology Information,2019,38(4):41-52(in Chinese with English abstract).
- [40] 徐锋,吴强,朱丽华.甲烷水合物恒压分解动力学研究进展[J].工业安全与环保,2010,36(12):10-12.Xu F,Wu Q,Zhu L H.Study of decomposition kinetics of methane hydrate at constant pressure[J].Industrial Safety and Environmental Protection,2010,36(12):10-12(in Chinese with English abstract).
- [41] Uchida T,Ebinuma T,Ishizaki T.Dissociation condition measurements of methane hydrate in confined small pores of porous glass[J].Journal of Physical Chemistry B,1999,103(18):3659-3662.
- [42] 张郁,蔡晶,李小森,等.南海沉积物中甲烷水合物定压分解特性[J].中国科学:物理学,力学,天文学,2019,49(3):136-143.Zhang Y,Cai J,Li X S,et al.Dissociation behaviors of methane hydrate in marine sediments from South China Sea under constant pressure[J].Scientia Sinica:Physica,Mechanica & Astronomica,2019,49(3):136-143(in Chinese with English abstract).
- [43] Zhao J F,Liu D,Yang M J,et al.Analysis of heat transfer effects on gas production from methane hydrate by depressurization[J].International Journal of Heat and Mass Transfer,2014,77:529-541.
- [44] 杨明军,孙慧茹,陈兵兵,等.水流动强化天然气水合物降压分解研究[J].工程热物理学报,2020,41(2):307-312.Yang M J,Sun H R,Chen B B,et al.The study on natural gas hydrate depressurization dissociation strengthened by water flow process[J].Journal of Engineering Thermophysics,2020,41(2):307-312(in Chinese with English abstract).
- [45] Chen B B,Sun H R,Zhao G J,et al.Experimental observation of methane hydrate dissociation via different depressurization modes under water phase flow[J].Fuel,2021,283:118908.
- [46] Sun H R,Chen B B,Zhao G J,et al.The enhancement effect of water-gas two-phase flow on depressurization process:Important for gas hydrate production[J].Applied Energy,2020,276:115559.
- [47] Yang L,Falenty A,Chaouachi M,et al.Synchrotron X-ray computed microtomography study on gas hydrate decomposition in a sedimentary matrix[J].Geochemistry,Geophysics,Geosystems,2016,17(9):3717-3732.
- [48] Akihiro H,Satoshi T,Evgeny C,et al.Preservation phenomena of methane hydrate in pore spaces[J].Physical Chemistry Chemical Physics:PCCP,2011,13:17449-17452.
- [49] Chaouachi M,Falenty A,Sell K,et al.Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X-ray computed tomographic microscopy[J].Geochemistry,Geophysics,Geosystems,2015,16(6):1711-1722.
- [50] Peng X M,Hu Y F,Yang L Y,et al.Decomposition kinetics for formation of CO2 hydrates in natural silica sands[J].Chinese Journal of Chemical Engineering,2010,18(1):61-65.
- [51] 喻西崇,李刚,李清平,等.沉积物中水合物分解过程影响因素的实验模拟分析[J].中国科学:地球科学,2013,43(3):400-405.Yu X C,Li G,Li Q P,et al.Experimental simulation of gas hydrate decomposition in porous sediment[J].Science China:Earth Sciences,2013,43(3):400-405(in Chinese with English abstract).
- [52] 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.
- [53] 文龙,周雪冰,梁德青.甲烷水合物在天然砂中的分解动力学研究[J].石油化工,2019,48(9):926-931.Wen L,Zhou X B,Liang D Q.Investigation on decomposition kinetics of methane hydrate in natural sand[J].Petrochemical Technology,2019,48(9):926-931(in Chinese with English abstract).
- [54] Wang Y,Feng J C,Li X S,et al.Fluid flow mechanisms and heat transfer characteristics of gas recovery from gas-saturated and water-saturated hydrate reservoirs[J].International Journal of Heat and Mass Transfer,2018,118:1115-1127.
- [55] Li X Y,Li X S,Wang Y,et al.The optimization mechanism for gas hydrate dissociation by depressurization in the sediment with different water saturations and different particle sizes[J].Energy,2021,215:119129.
- [56] Tang L G,Li X S,Feng Z P,et al.Control mechanisms for gas hydrate production by depressurization in different scale hydrate reservoirs[J].Energy & Fuels,2006,21(1):227-233.
- [57] Hong H,Pooladi-Darvish M,Bishnoi P R.Analytical modelling of gas production from hydrates in porous media[J].Journal of Canadian Petroleum Technology,2003,42(11):45-56.
- [58] Zheng R Y,Li S X,Cui G D.Determining the controlling mechanisms of hydrate dissociation front using optimized characteristic time[J].Fuel,2021,298:120805.
- [59] Kamath V A,Holder G D,Angert P F.Three phase interfacial heat transfer during the dissociation of propane hydrates[J].Chemical Engineering Science,1984,39(10):1435-1442.
- [60] Kamath V A,Holder G D.Dissociation heat transfer characteristics of methane hydrates[J].AIChE Journal,1987,33:347-350.
- [61] Selim M S,Sloan E D.Modeling of the dissociation of an in-situ hydrate[C]//Anon.SPE California Regional Meeting.Bakersfield:OnePetro,1985.
- [62] Handa Y.A calorimetric study of naturally occurring gas hydrates[J].Industrial & Engineering Chemistry Research,1988,27(5):872-874.
- [63] Windmeier C,Oellrich L R.Theoretical study of gas hydrate decomposition kinetics-model development[J].The Journal of Physical Chemistry A,2013,117(40):10151-10161.
- [64] Yousif M H,Abass H H,Selim M S,et al.Experimental and theoretical investigation of methane-gas-hydrate dissociation in porous media[J].SPE Reservoir Engineering,1991,6(1):69-76.
- [65] Tsypkin G G.Mathematical model of the dissociation of gas hydrates coexisting with ice in natural reservoirs[J].Fluid Dynamics,1993,28(2):223-229.
- [66] Makogon Y.Hydrates of hydrocarbons[M].USA:Penn Well Publishing Company,1997.
- [67] Clarke M A,Bishnoi P R.Determination of the intrinsic rate of gas hydrate decomposition using particle size analysis[J].Annals of the New York Academy of Sciences,2000,912(1):556-563.
- [68] Goel N,Wiggins M,Shah S.Analytical modeling of gas recovery from in situ hydrates dissociation[J].Journal of Petroleum Science and Engineering,2001,29(2):115-127.
- [69] Sun C Y,Chen G J.Methane hydrate dissociation above 0℃ and below 0℃[J].Fluid Phase Equilibria,2006,242(2):123-128.
- [70] 李娜,奚西峰,何小霞,等.甲烷水合物分解动力学模型[J].天然气地球科学,2006,17(6):880-883.Li N,Xi X F,He X X,et al.Dynamic model for methane hydrate decomposition[J].Natural Gas Geoscience,2006,17(6):880-883(in Chinese with English abstract).
- [71] Vlasov V A.Diffusion model of gas hydrate dissociation into ice and gas:Simulation of the self-preservation effect[J].International Journal of Heat and Mass Transfer,2016,102:631-636.
- [72] Song S F,Shi B H,Yu W C,et al.A new methane hydrate decomposition model considering intrinsic kinetics and mass transfer[J].Chemical Engineering Journal,2019,361:1264-1284.
- [73] Deng X J,Feng J W,Pan S W,et al.An improved model for the migration of fluids caused by hydrate dissociation in porous media[J].Journal of Petroleum Science and Engineering,2020,188:106876.
- [74] Yin Z Y,Chong Z R,Tan H K,et al.Review of gas hydrate dissociation kinetic models for energy recovery[J].Journal of Natural Gas Science and Engineering,2016,35:1362-1387.
- [75] Ullerich J,Selim M S,Sloan E D.Theory and measurement of hydrate dissociation[J].AIChE Journal,1987,33:747-752.
- [76] Selim M S,Sloan E D.Hydrate dissociation in sediment[J].SPE Reservoir Engineering,1990,5(2):245-251.
- [77] Selim M S,Sloan E D.Heat and mass transfer during dissociation of hydrates in porous media[J].AIChE Journal,1989,35:1049-1052.
- [78] Clarke M A,Bishnoi P R.Determination of the intrinsic rate of ethane gas hydrate decomposition[J].Chemical Engineering Science,2000,55(21):4869-4883.
- [79] Clarke M A,Bishnoi P R.Determination of the activation energy and intrinsic rate constant of methane gas hydrate decomposition[J].The Canadian Journal of Chemical Engineering,2001,79(1):143-147.
- [80] Clarke M A,Bishnoi P R.Measuring and modelling the rate of decomposition of gas hydrates formed from mixtures of methane and ethane[J].Chemical Engineering Science,2001,56(16):4715-4724.
- [81] Clarke M A,Bishnoi P R.Determination of the intrinsic rate constant and activation energy of CO2 gas hydrate decomposition using in-situ particle size analysis[J].Chemical Engineering Science,2004,59(14):2983-2993.
- [82] Giraldo C,Clarke M A.Stoichiometric approach toward modeling the decomposition kinetics of gas hydrates formed from mixed gases[J].Energy & Fuels,2013,27(8):4534-4544.
- [83] Windmeier C,Oellrich L R.Theoretical study of gas hydrate decomposition kinetics:Model predictions[J].The Journal of Physical Chemistry A,2013,117(47):12184-12195.
- [84] Takeya S,Ebinuma T,Uchida T,et al.Self-preservation effect and dissociation rates of CH4 hydrate[J].Journal of Crystal Growth,2002,237/239(1/4):379-382.
- [85] Vlasov V A.Diffusion model of gas hydrate dissociation into ice and gas that takes into account the ice microstructure[J].Chemical Engineering Science,2020,215:115443.
- [86] Misyura S Y,Donskoy I G.Dissociation kinetics of methane hydrate and CO2 hydrate for different granular composition[J].Fuel,2020,262:116614.
- [87] 何晓霞,余劲松,马应海,等.甲烷水合物分解的缩粒动力学模型[J].天然气地球科学,2005,16(6):818-821.He X X,Yu J S,Ma Y H,et al.Particle shrinking dynamic model for methane hydrate decomposition[J].Natural Gas Geoscience,2005,16(6):818-821(in Chinese with English abstract).
- [88] 艾志久,王杰.天然气水合物分解的动力学模型研究[J].天然气地球科学,2017,28(3):377-382.Ai Z J,Wang J.Study on kinetic model of natural gas hydrate dissociation[J].Natural Gas Geoscience,2017,28(3):377-382(in Chinese with English abstract).
- [89] 刘犟,阎立军,陈光进,等.活性炭中甲烷水合物的分解动力学[J].化学学报,2002,60(8):1385-1389.Liu J,Yan L J,Cheng G J,et al.Kinetics of methane hydrate dissociation in active carbon[J].Acta Chimica Sinica Chinese Edition,2002,60(8):1385-1389(in Chinese with English abstract).
- [90] 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.
- [91] Nazridoust K,Ahmadi G.Computational modeling of methane hydrate dissociation in a sandstone core[J].Chemical Engineering Science,2007,62(22):6155-6177.
- [92] Chen X Y,Espinoza D N.Surface area controls gas hydrate dissociation kinetics in porous media[J].Fuel,2018,234:358-363.