Occurrence states and transformation of natural hydrogen mechanism
LI Qiang1,2, MENG Qingqiang1,2, HAN Chao1, ZHOU Yuan3, WU Han1, DAI Shourui1
1. Shandong University of Science and Technology, Shandong Qingdao 266590, China; 2. Petroleum Exploration and Production Research Institute, SINOPEC, Beijing 100083, China; 3. China University of Petroleum (Beijing), Beijing 102206, China
Abstract：As a clean energy source, hydrogen is widely regarded as an effective strategy for replacing fossil fuels and mitigating environmental issues. Based on the domestic and international research on the occurrence state and phase of hydrogen, and combined with the variations in temperature and pressure under geological conditions, the authors concluded the following insights. ① Natural hydrogen is found in free, dissolved, and adsorbed states in earth's shallow layers and in metal hydrides state in earth's deeper layers. The transformation among these states constitutes a pivotal factor influencing the availability of hydrogen resources. ② In geological settings, natural hydrogen predominantly exists in a supercritical state, and it only transitions to a gaseous form near the surface. Further research is warranted to investigate its characteristics. ③ The potential for natural hydrogen development remains largely unrealized. Future research should focus on the accumulation patterns, migration mechanisms, and preservation conditions of hydrogen to thoroughly explore its development potential. Additionally, the transformation processes between different states provides a novel perspective on understanding the earth's hydrogen cycle. The study on the occurrence state and transformation processes of natural hydrogen could provide theory basis for the accumulation patterns of natural hydrogen, and references for further development and exploitation of natural hydrogen.
[1] 韩双彪,唐致远,杨春龙,等.天然气中氢气成因及能源意义[J].天然气地球科学,2021,32(9):1270-1284. Han S B,Tang Z Y,Yang C L,et al.Genesis and energy significance of hydrogen in natural gas[J].Natural Gas Geoscience,2021,32(9):1270-1284. [2] 孟庆强,金之钧,刘文汇,等.天然气中伴生氢气的资源意义及其分布[J].石油实验地质,2014,36(6):712-717,724. Meng Q Q,Jin Z J,Liu W H,et al.Distribution and genesis of hydrogen gas in natural gas[J].Petroleum Geology & Experiment,2014,36(6):712-717,724. [3] 刘全有,吴小奇,孟庆强,等.天然氢气:一种潜在的零碳能源[J].科学通报,2024,69(17):2344-2350. Liu Q Y,Wu X Q,Meng Q Q,et al.Natural hydrogen:A potential carbon-free energy source[J].Chinese Science Bulletin,2024,69(17):2344-2350. [4] Hand E.Hidden hydrogen[J].Science,2023,379(6633):630-636. [5] Zgonnik V.The occurrence and geoscience of natural hydrogen:a comprehensive review[J].Earth-Science Reviews,2020,203:103140. [6] 钟治奇,周文,章威,等.无机成因天然氢气的形成机理与中国天然氢气潜力分析[J/OL].成都理工大学学报:自然科学版,(2024-08-28).http://kns.cnki.net/kcms/detail/51.1634.N.20240828.1012.002.html. Zhong Z Q,Zhou W,Zhang W,et al. The formation mechanism of inorganic-genetic natural hydrogen and the analysis on the potential of natural hydrogen in China[J/OL].Journal of Chengdu University of Technology (Science & Technology Edition),(2024-08-28).http://kns.cnki.net/kcms/detail/51.1634.N.20240828.1012.002.html. [7] Petersen H C.Does natural hydrogen exist?[J].International Journal of Hydrogen Energy,1990,15(1):55. [8] Prinzhofer A,Tahara Cissé C S,Diallo A B.Discovery of a large accumulation of natural hydrogen in Bourakebougou (Mali)[J].International Journal of Hydrogen Energy,2018,43(42):19315-19326. [9] Jin Z J,Zhang P P,Liu R C,et al.Discovery of anomalous hydrogen leakage sites in the Sanshui Basin,South China[J].Science Bulletin,2024,69(9):1217-1220. [10] Herbert E H.Geothermal Hydrogen-1980 Jackling Lecture[R].The American Institute of Mining,Metallurgical,and Petroleum Engineers,1981. [11] Ellis G,Gelman S.A preliminary model of global subsurface natural hydrogen resource potential[C]//Proceedings of GSA Connects 2022 Meeting.Denver,Colorado:GSA,2022:380270. [12] Boreham C J,Edwards D S,Czado K,et al.Hydrogen in Australian natural gas:Occurrences,sources and resources[J].The APPEA Journal,2021,61(1):163. [13] 窦立荣,刘化清,李博,等.全球天然氢气勘探开发利用进展及中国的勘探前景[J].岩性油气藏,2024,36(2):1-14. Dou L R,Liu H Q,Li B,et al.Global natural hydrogen exploration and development situation and prospects in China[J].Lithologic Reservoirs,2024,36(2):1-14. [14] 孟庆强,金之钧,孙冬胜,等.高含量氢气赋存的地质背景及勘探前景[J].石油实验地质,2021,43(2):208-216. Meng Q Q,Jin Z J,Sun D S.Geological background and exploration prospects for the occurrence of high-content hydrogen[J].Petroleum Geology & Experiment,2021,43(2):208-216. [15] 房大任,裴秋明,王海华,等.天然氢气成因与全球氢资源勘探进展[J/OL].成都理工大学学报:自然科学版,(2024-08-14).http://kns.cnki.net/kcms/detail/51.1634.N.20240813.1627.004.html. Fang D R,Pei Q M,Wang H H,et al.Genesis of natural hydrogen and progress in global hydrogen resource exploration[J/OL].Journal of Chengdu University of Technology (Science & Technology Edition),(2024-08-14).http://kns.cnki.net/kcms/detail/51.1634.N.20240813.1627.004.html. [16] 杨文采. 地球内部可能利用的天然氢气[J].科技导报,2024,42(15):7-14. Yang W C.The natural hydrogen inside the Earth[J].Science & Technology Review,2024,42(15):7-14. [17] 刘全有,朱东亚,孟庆强,等.地球多层圈有机-无机相互作用的资源效应[J].天然气地球科学,2024,35(5):741-762. Liu Q Y,Zhu D Y,Meng Q Q,et al.Organic-inorganic interactions in the Earth's multi-spheres and resources effects[J].Natural Gas Geoscience,2024,35(5):741-762. [18] 杨文采,杨午阳,程振炎.中国大陆科学钻探孔区地震反射的标定[J].地球物理学报,2006,49(6):1682-1692. Yang W C,Yang W Y,Cheng Z Y.Calibration of seismic reflectors at the Chinese continental scientific drilling site[J].Chinese Journal of Geophysics,2006,49(6):1682-1692. [19] 杨文采,金振民,于常青.结晶岩中天然气异常的地震响应[J].中国科学 D辑:地球科学,2008,38(9):1057-1067. Yang W C,Jin Z M,Yu C Q.Seismic response to natural gas anomalies in crystalline rocks[J].Science in China Series D:Earth Sciences,2008,51(12):1726-1736. [20] Li Y G,Vo čadlo L,Sun T,et al.The Earth's core as a reservoir of water[J].Nature Geoscience,2020,13(6):453-458. [21] Rumyantsev V N.Hydrogen in the earth's outer core,and its role in the deep earth geodynamics[J].Geodynamics & Tectonophysics,2016,7(1):119-135. [22] Mitrofanov F P,Yakovlev Y N,Ikorsky S V,et al.A change in composition of rocks,mineral phases and trapped gases in the kola super-deep borehole(SD-3) section of the archean complex with depth[C]//Proceedings of Super-Deep Continental Drilling and Deep Geophysical Sounding.Berlin,Heidelberg:Springer,1990:353-363. [23] Faber E,Gerling P,Dumke I.Gaseous hydrocarbons of unknown origin found while drilling[J].Organic Geochemistry,1988,13(4-6):875-879. [24] 李星国. 氢与氢能[M].北京:机械工业出版社,2012. Li X G.Hydrogen and Hydrogen Energy[M].Beijing:Machinery Industry Press,2012. [25] Wiberg N.Lehrbuch der Anorganischen Chemie[M].Berlin,Boston:De Gruyter,2008. [26] 孙学军,康志敏,刘文武.氢分子生物学[M].上海:第二军医大学出版社,2013. Sun X J,Kang Z M,Liu W W.Molecular Hydrogen Biology[M].Shanghai:Second Military Medical University Press,2013. [27] Stolten D,Emonts B.Hydrogen Science and Engineering:Materials,Processes,Systems and Technology[M].Wiley,2016. [28] Leachman J W,Jacobsen R T,Penoncello S G,et al.Fundamental equations of state for parahydrogen,normal hydrogen,and orthohydrogen[J].Journal of Physical and Chemical Reference Data,2009,38(3):721-748. [29] Silvera I F,Cole J W.Metallic hydrogen:The most powerful rocket fuel yet to exist[J].Journal of Physics:Conference Series,2010,215:012194. [30] Young D A.Phase Diagrams of the Elements[M].Berkeley,Calif:University of California Press,1991. [31] Silvera I F.The solid molecular hydrogens in the condensed phase:Fundamentals and static properties[J].Reviews of Modern Physics,1980,52(2):393-452. [32] 魏琪钊,朱如凯,杨智,等.天然氢气藏地质特征、形成分布与资源前景[J].天然气地球科学,2024,35(6):1113-1122. Wei Q Z,Zhu R K,Yang Z,et al.Geological characteristics,formation distribution and resource prospects of natural hydrogen reservoir[J].Natural Gas Geoscience,2024,35(6):1113-1122. [33] Bali E,Audétat A,Keppler H.Water and hydrogen are immiscible in Earth's mantle[J].Nature,2013,495(7440):220-222. [34] Liu J,Hu Q Y,Young Kim D,et al.Hydrogen-bearing iron peroxide and the origin of ultralow-velocity zones[J].Nature,2017,551(7681):494-497. [35] Guélard J,Beaumont V,Rouchon V,et al.Natural H2 in Kansas:deep or shallow origin?[J].Geochemistry,Geophysics,Geosystems,2017,18(5):1841-1865. [36] Maiga O,Deville E,Laval J,et al.Characterization of the spontaneously recharging natural hydrogen reservoirs of Bourakebougou in Mali[J].Scientific Reports,2023,13(1):11876. [37] Truche L,Donzé F V,Goskolli E,et al.A deep reservoir for hydrogen drives intense degassing in the Bulqizё ophiolite[J].Science,2024,383(6683):618-621. [38] Zgonnik V,Beaumont V,Deville E,et al.Evidence for natural molecular hydrogen seepage associated with Carolina bays (surficial,ovoid depressions on the Atlantic Coastal Plain,Province of the USA)[J].Progress in Earth and Planetary Science,2015,2(1):31. [39] 孙龙德,冯子辉,江航,等.松辽盆地富氢天然气地质调查与研究[J].大庆石油地质与开发,2024,43(3):7-16. Sun L D,Feng Z H,Jiang H,et al.Geological survey and study of hydrogen-rich natural gas in Songliao Basin[J].Petroleum Geology & Oilfield Development in Daqing,2024,43(3):7-16. [40] 金之钧,谢方克.中国典型含油气盆地地层压力分布特征[J].石油大学学报:自然科学版,2002,26(6):1-6,16. Jin Z J,Xie F K.Distribution features of formation pressure in typical petroliferous basin of China[J].Journal of China University of Petroleum (Edition of Natural Science),2002,26(6):1-6,16. [41] Giardini A A,Subbarayudu G V,Melton C E.The emission of occluded gas from rocks as a function of stress:its possible use as a tool for predicting earthquakes[J].Geophysical Research Letters,1976,3(6):355-358. [42] Jiang F L,Li G R.Experimental studies of the mechanisms of seismo-geochemical precursors[J].Geophysical Research Letters,1981,8(5):473-476. [43] Zgonnik V,Beaumont V,Larin N,et al.Diffused flow of molecular hydrogen through the Western Hajar mountains,Northern Oman[J].Arabian Journal of Geosciences,2019,12(3):71. [44] Молчанов В И.Генерация Водорода В Литогенезе[M].Наука,1981. [45] Petersilie I A,Sörensen H.Hydrocarbon gases and bituminous substances in rocks from the Ilímaussaq alkaline intrusion,South Greenland:(contribution to the mineralogy of Ilímaussaq No.18)[J].Lithos,1970,3(1):59-76. [46] Соколов В A.Геохимия Природных Газов[M].Москва:Недра,1971. [47] 王永才,孙香荣.河北及邻近地区地下水溶解二氧化碳、氢和氦分布的地震地质特征[J].华北地震科学,1992,10(2):58-66. Wang Y C,Sun X R.Seismogeological features of the dissolved CO2,H2 and He in groundwater in Hebei Province and its adjacent area[J].North China Earthquake Sciences,1992,10(2):58-66. [48] Lin L H,Hall J,Lippmann-Pipke J,et al.Radiolytic H2 in continental crust:Nuclear power for deep subsurface microbial communities[J].Geochemistry,Geophysics,Geosystems,2005,6(7):13. [49] 韩双彪,王缙,黄劼,等.煤岩吸附氢气特征及其地质意义[J].煤炭学报,2024,49(3):1501-1517. Han S B,Wang J,Huang J,et al.Hydrogen adsorption characteristics of coal rock and its geological significance[J].Journal of China Coal Society,2024,49(3):1501-1517. [50] Кононов В И.Геохимия Термальных Вод ОБЛАСТЕЙ Активного Вулканизма (Рифтозых Зон И Островных Дуг)[M].Наука,1983. [51] Hao Y L,Pang Z H,Tian J,et al.Origin and evolution of hydrogen-rich gas discharges from a hot spring in the eastern coastal area of China[J].Chemical Geology,2020,538:119477. [52] Lyon G L,Hulston J R.Carbon and hydrogen isotopic compositions of New Zealand geothermal gases[J].Geochimica et Cosmochimica Acta,1984,48(6):1161-1171. [53] Wang L,Jin Z J,Liu Q Y,et al.The occurrence pattern of natural hydrogen in the Songliao Basin,P.R.China:Insights on natural hydrogen exploration[J].International Journal of Hydrogen Energy,2024,50:261-275. [54] Truche L,Joubert G,Dargent M,et al.Clay minerals trap hydrogen in the Earth's crust:Evidence from the Cigar Lake uranium deposit,Athabasca[J].Earth and Planetary Science Letters,2018,493:186-197. [55] Edge J S.Hydrogen Adsorption and Dynamics in Clay Minerals[D].London:UCL(University College London),2015. [56] Wang L,Cheng J W,Jin Z J,et al.High-pressure hydrogen adsorption in clay minerals:Insights on natural hydrogen exploration[J].Fuel,2023,344:127919. [57] López-Chávez E,Garcia-Quiroz A,Peña-Castañeda Y A,et al.Modeling and simulation of the adsorption and storage of hydrogen in calcite rock oil fields[J].Journal of Molecular Modeling,2020,26(9):248. [58] Muther T,Dahaghi A K.Hydrogen adsorption on calcite mineral surface in the presence of CO2 and CH4:A key factor in hydrogen storage in carbonate rocks[J].International Journal of Hydrogen Energy,2024,58:583-595. [59] Bindi L,Cámara F,Griffin W L,et al.Discovery of the first natural hydride[J].American Mineralogist,2019,104(4):611-614. [60] Yuan L,Steinle-Neumann G.Strong sequestration of hydrogen into the Earth's core during planetary differentiation[J].Geophysical Research Letters,2020,47(15):e2020GL088303. [61] Fuchs K,Kozlovsky Y A,Krivtsov A I,et al.Super-Deep Continental Drilling and Deep Geophysical Sounding[M].Berlin,Heidelberg:Springer,1990. [62] Kerkache H,Hoang H,Cézac P,et al.The solubility of H2 in NaCl brine at high pressures and high temperatures:Molecular simulation study and thermodynamic modeling[J].Journal of Molecular Liquids,2024,400:124497. [63] Akinfiev N N,Diamond L W.Thermodynamic description of aqueous nonelectrolytes at infinite dilution over a wide range of state parameters[J].Geochimica et Cosmochimica Acta,2003,67(4):613-629. [64] Fernández-Prini R,Alvarez J L,Harvey A H.Henry's constants and vapor-liquid distribution constants for gaseous solutes in H2O and D2O at high temperatures[J].Journal of Physical and Chemical Reference Data,2003,32(2):903-916. [65] Li D D,Beyer C,Bauer S.A unified phase equilibrium model for hydrogen solubility and solution density[J].International Journal of Hydrogen Energy,2018,43(1):512-529. [66] Lopez-Lazaro C,Bachaud P,Moretti I,et al.Predicting the phase behavior of hydrogen in NaCl brines by molecular simulation for geological applications[J].BSGF-Earth Sciences Bulletin,2019,190:7. [67] Torín-Ollarves G A,Trusler J P M.Solubility of hydrogen in sodium chloride brine at high pressures[J].Fluid Phase Equilibria,2021,539:113025. [68] Wiebe R.Solubility of hydrogen in water at 250c from 25 to 1000 atmospheres[J].Industrial & Engineering Chemistry,1932,24(7):823-825. [69] Wiebe R,Gaddy V L.The solubility of hydrogen in water at 0,50,75 and 100° from 25 to 1000 atmospheres[J].Journal of the American Chemical Society,1934,56(1):76-79. [70] Morrison T J,Billett F.The salting-out of non-electrolytes.Part II.The effect of variation in non-electrolyte[J].Journal of the Chemical Society (Resumed),1952,3819-3822. [71] Crozier T E,Yamamoto S.Solubility of hydrogen in water,seawater,and NaCl solutions[J].Journal of Chemical and Engineering Data,1974,19(3):242-244. [72] Gordon L I,Cohen Y,Standley D R.The solubility of molecular hydrogen in seawater[J].Deep Sea Research,1977,24(10):937-941. [73] Gillespie P,Wilson G.Vapor-liquid equilibrium data on water-substitute gas components:N2-H2O,H2-H2O,CO-H2O,H2-CO-H2O,and H2S-H2O[R].1980. [74] Alvarez J,Crovetto R,Fernández-Prini R.The Dissolution of N2 and of H2 in water from room temperature to 640 K[J].Berichte der Bunsengesellschaft für physikalische Chemie,1988,92(8):935-940. [75] Kling G,Maurer G.The solubility of hydrogen in water and in 2-aminoethanol at temperatures between 323 K and 423 K and pressures up to 16 MPa[J].The Journal of Chemical Thermodyna-mics,1991,23(6):531-541. [76] Chabab S,Théveneau P,Coquelet C,et al.Measurements and predictive models of high-pressure H2 solubility in brine (H2O+NaCl) for underground hydrogen storage application[J].International Journal of Hydrogen Energy,2020,45(56):32206-32220. [77] Chabab S,Kerkache H,Bouchkira I,et al.Solubility of H2 in water and NaCl brine under subsurface storage conditions:Measurements and thermodynamic modeling[J].International Journal of Hydrogen Energy,2024,50:648-658. [78] Marx D,Nielaba P.Path-integral Monte Carlo techniques for rotational motion in two dimensions:quenched,annealed,and no-spin quantum-statistical averages[J].Physical Review A,1992,45(12):8968-8971. [79] 张峰,冯翠红,张丽鹏,等.物理吸附储氢材料的研究进展[J].硅酸盐通报,2013,32(9):1785-1789,1793. Zhang F,Feng C H,Zhang L P,et al.Study progress on the hydrogen storage material by physical absorption[J].Bulletin of the Chinese Ceramic Society,2013,32(9):1785-1789,1793. [80] Jena P.Materials for hydrogen storage:past,present,and future[J].The Journal of Physical Chemistry Letters,2011,2(3):206-211. [81] Abdulelah H,Keshavarz A,Hoteit H,et al.Hydrogen physisorption in earth-minerals:Insights for hydrogen subsurface storage[J].Journal of Energy Storage,2023,66:107440. [82] Stixrude L,Lithgow-Bertelloni C.Thermodynamics of the Earth's mantle[J].Reviews in Mineralogy and Geochemistry,2010,71(1):465-484. [83] Мелихов В,Лыгин И.Тектонические катастрофы и их место в эволюционном развитии Земли[J].Геофизика,2008(2):11-19. [84] Арчаков Ю.Водородная коррозия стали[J].1985. [85] Буалло Г.Геология Окраин Континентов[M].Мир,1985. [86] 金之钧,王璐.自然界有氢气藏吗?[J].地球科学,2022,47(10):3858-3859. Jin Z J,Wang L.Does hydrogen reservoir exist in nature?[J].Earth Science,2022,47(10):3858-3859. [87] 余琪祥. 自然界中的氢气藏[J].石油知识,2024(3):10-12. Yu Q X.Hydrogen deposits in nature[J].Petroleum Knowledge,2024(3):10-12. [88] 毛宗强. 天然氢开发前景引业界关注[J].中国石化,2024(2):45. Mao Z Q.The development prospect of natural hydrogen has attracted the attention of the industry[J].Sinopec Monthly,2024(2):45. [89] 田黔宁,付刚,刘延明,等.天然氢:不可忽视的无碳新型能源宝藏[J].自然资源科普与文化,2024(1):4-11. Tian Q N,Fu G,Liu Y M,et al. Natural hydrogen:a new carbon-free energy treasure that cannot be ignored[J].Scientific and Cultural Popularization of Natural Resources,2024(1):4-11. [90] Pratt W E.Toward a philosophy of oil-finding[J].AAPG Bulletin,1952,36(12):2231-2236.
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