C3H8 synergistic flue gas (CO2+N2) replacement of CH4 hydrate

Guo Jinyuan; Chen Xiao; Gui Xia

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C₃H₈ synergistic flue gas (CO₂+N₂) replacement of CH₄ hydrate

Updated：2026-05-14

- C₃H₈ synergistic flue gas (CO₂+N₂) replacement of CH₄ hydrate
- Chinese Journal of Chemical Engineering Vol. 90, Issue 2, Pages: 18-32(2026)
- Affiliations：
  
  College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
- Author bio：
  
  Corresponding author. E-mail address: guixia@njtech.edu.cn (X. Gui).
- Funds：
- DOI：
  CLC：
- Received：03 July 2025，
  
  Revised：2025-08-16，
  
  Accepted：12 September 2025，
  
  Online First：19 November 2025，
  
  Published：2026-02
- Accepted：
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Guo Jinyuan, Chen Xiao, Gui Xia. C₃H₈ synergistic flue gas (CO₂+N₂) replacement of CH₄ hydrate[J]. Chinese Journal of Chemical Engineering, 2026, 90(2): 18-32.
DOI：

Guo Jinyuan, Chen Xiao, Gui Xia. C₃H₈ synergistic flue gas (CO₂+N₂) replacement of CH₄ hydrate[J]. Chinese Journal of Chemical Engineering, 2026, 90(2): 18-32. DOI：

摘要

Abstract

There are bottleneck problems in the binary replacement process of flue gas (CO

)

such as the decreased stability of the sediment layer of hydrates after replacement and the decline in replacement efficiency. This paper innovatively proposes a pathway for the replacement of natural gas hydrates by flue gas with the synergistic effect of C

. The study reveals that doping a trace amount of C

(approximately 2% (mol)) can increase the dissociation enthalpy value of flue gas hydrates by nearly 20 kJ·mol

-1

. The crystal structure of the hydrates significantly transforms from the sI type to the sII type

which promotes the occupation of N

molecules in the small cages (with an increase of about 5%). This leads to a reduction of the phase equilibrium conditions by 15% to 25% through molecular scale pressure sharing. C

and N

have a synergistic effect on the re

covery of CH

hydrates. Compared with the flue gas without C

doping

the flue gas doped with 3.5% C

can increase the CH

recovery rate by approximately 4.5% and the N

sequestration rate by about 5%

while maintaining a high CO

sequestration rate. Since it is a surface reaction

doping an excessive amount of C

(more than 5%) does not significantly improve the CH

recovery rate. This study provides a new option for the design of engineering schemes and processes for the replacement-based exploitation of natural gas hydrates.

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Keywords

references

E.D. Sloan Jr., Fundamental principles and applications of natural gas hydrates, Nature 426 (6964) (2003) 353—359.

S. Merey, C. Sinayuc, Investigation of gas hydrate potential of the black sea and modelling of gas production from a hypothetical class 1 methane hydrate reservoir in the Black Sea conditions, J. Nat. Gas Sci. Eng. 29(2016)66—79.

K.A. Kvenvolden, Gas hydrates: geological perspective and global change, Rev. Geophys. 31(2)(1993)173—187.

Y.F. Makogon, S.A. Holditch, T.Y. Makogon, Natural gas-hydrates: a potential energy source for the 21st Century, J. Petrol. Sci. Eng. 56(1—3)(2007)14—31.

K.A. Kvenvolden, Methane hydrate: a major reservoir of carbon in the shallow geosphere? Chem. Geol. 71 (1—3)(1988) 41—51.

D.W. Davidson, Y.P. Handa, C.I. Ratcliffe, J.S. Tse, B.M. Powell, The ability of small molecules to form clathrate hydrates of structure II, Nature 311(1984) 142—143.

G.D. Holder, Clathrate hydrates of natural gases. Chemical Industries Series, CRC Press, New York,1998.

E. Berecz, M. Balláné Achs, Gas Hydrates, Elsevier, Amsterdam,1983.

T. Uchida, T. Hirano, T. Ebinuma, H. Narita, K. Gohara, S. Mae, R. Matsumoto, Raman spectroscopic determination of hydration number of methane hydrates, AlChE. J. 45 (12) (1999) 2641—2645.

L.J. Sun, H.S. Dong, Y. Lu, L.X. Zhang, L. Yang, J.F. Zhao, Y.C. Song, A hydratebased zero liquid discharge method for high-concentration organic wastewater: resource recovery and water reclamation, NPJ Clean Water 6 (2023) 49.

H.S. Dong, L.X. Zhang, Z. Ling, J.F. Zhao, Y.C. Song, The controlling factors and ion exclusion mechanism of hydrate-based pollutant removal, ACS Sustainable Chem. Eng. 7 (8) (2019) 7932—7940.

E.D. Sloan, Clathrate hydrates of natural gases, in: Revised and Expanded, second ed., CRC Press, Boca Raton,1998.

E.D. Sloan Jr., C.A. Koh, Clathrate Hydrates of Natural Gases, third ed., CRC Press, Boca Raton,2008.

C.A. Koh, E. Dendy Sloan, A.K. Sum, D.T. Wu, Fundamentals and applications of gas hydrates, Annu. Rev. Chem. Biomol. Eng. 2(2011)237—257.

X.S. Li, Y. Zhang, G. Li, Z.Y. Chen, H.J. Wu, Experimental investigation into the production behavior of methane hydrate in porous sediment by depressur-ization with a novel three-dimensional cubic hydrate simulator, Energy Fuels 25(10) (2011)4497—4505.

X.S. Li, B. Yang, G. Li, B. Li, Numerical simulation of gas production from natural gas hydrate using a single horizontal well by depressurization in Qilian mountain permafrost, Ind. Eng. Chem. Res. 51(11)(2012)4424—4432.

S.H. Tabatabaie, M. Pooladi-Darvish, Hydrate decomposition and its material balance in a volumetric tilted hydrate-capped gas reservoir by method of depressurization, SPE Reservoir Eval. Eng. 15 (4)(2012)410—422.

C. Cranganu, In-situ thermal stimulation of gas hydrates, J. Petrol. Sci. Eng. 65 (1—2)(2009)76—80.

G.C. Fitzgerald, M.J. Castaldi, Y. Zhou, Large scale reactor details and results for the formation and decomposition of methane hydrates via thermal stimulation dissociation, J. Petrol. Sci. Eng. 94 (2012)19—27.

G.C. Fitzgerald, M.J. Castaldi, Thermal stimulation based methane production from hydrate bearing quartz sediment, Ind. Eng. Chem. Res. 52 (19) (2013) 6571—6581.

V. Chandrasekharan Nair, D. Mech, P. Gupta, J.S. Sangwai, Polymer flooding in artificial hydrate bearing sediments for methane gas recovery, Energy Fuels 32(6)(2018)6657—6668.

G. Li, D.M. Wu, X.S. Li, Y. Zhang, Q.N. Lv, Y. Wang, Experimental investigation into the production behavior of methane hydrate under methanol injection in quartz sand, Energy Fuels 31(5)(2017)5411—5418.

Q. Yuan, C.Y. Sun, X. Yang, P.C. Ma, Z.W. Ma, Q.P. Li, G.J. Chen, Gas production from methane-hydrate-bearing sands by ethylene glycol injection using a three-dimensional reactor, Energy Fuels 25(7) (2011)3108—3115.

T. Ebinuma, Method for Dumping and Disposing of Carbon Dioxide Gas and Apparatus Therefor, US Pat.,1993. US5261490A.

M. Ota, Y. Abe, M. Watanabe, R.L. Smith, H. Inomata, Methane recovery from methane hydrate using pressurized CO 2 , Fluid Phase Equilib. 228 (2005) 553—559.

Y.L. Ding, H.Q. Wang, C.G. Xu, X.S. Li, The effect of CO 2 partial pressure on CH 4 recovery in CH 4 -CO 2 swap with simulated IGCC syngas, Energies 13 (5) (2020) 1017.

X.M. Zhang, S.L. Zhang, S.Q. Yin, G .Y. He, J.P. Li, Q.B. Wu, Research progress of the kinetics on natural gas hydrate replacement by CO 2 -containing mixed gas: a review, J. Nat. Gas Sci. Eng. 108 (2022) 104837.

Y. Park, D.Y. Kim, J.W. Lee, D.G. Huh, K.P. Park, J. Lee, H.E. Lee, Sequestering carbon dioxide into complex structures of naturally occurring gas hydrates, Proc. Natl. Acad. Sci. USA 103(34)(2006)12690—12694.

Y.F. Sun, J.R. Zhong, R. Li, T. Zhu, X.Y. Cao, G.J. Chen, X.H. Wang, L.Y. Yang, C.Y. Sun, Natural gas hydrate exploitation by CO 2 /H 2 continuous Injection-production mode, Appl. Energy 226 (2018) 10—21.

M. Ota, K. Morohashi, Y. Abe, M. Watanabe, H. Inomata, Replacement of CH 4 in the hydrate by use of liquid CO 2 , Energy Convers. Manag. 46 (11—12) (2005) 1680—1691.

Y.J. Seo, S. Park, H. Kang, Y.H. Ahn, D. Lim, S.J. Kim, J. Lee, J.Y. Lee, T. Ahn, Y. Seo, H.E. Lee, Isostructural and cage-specific replacement occurring in sII hydrate with external CO 2 /N2 gas and its implications for natural gas production and CO 2 storage, Appl. Energy 178 (2016) 579—586.

A.M. Gambelli, A. Presciutti, F. Rossi, Review on the characteristics and advantages related to the use of flue-gas as CO 2 /N2 mixture for gas hydrate production, Fluid Phase Equilib. 541 (2021) 113077.

Y.S. Yu, X.W. Zhang, J.W. Liu, Y. Lee, X.S. Li, Natural gas hydrate resources and hydrate technologies: a review and analysis of the associated energy and global warming challenges, Energy Environ. Sci. 14 (11)(2021)5611—5668.

A.A.A. Majid, C.A. Koh, Self-preservation phenomenon in gas hydrates and its application for energy storage. Intra- and Intermolecular Interactions Between Non-covalently Bonded Species, Elsevier, 2021, pp. 67—285.

N. Li, J.Y. Kan, C.Y. Sun, G.J. Chen, Hydrate formation from liquid CO 2 in a glass beads bed, Chin. J. Chem. Eng. 43 (2022)185—191.

W.L. Mao, C.A. Koh, E.D. Sloan, Clathrate hydrates under pressure, Phys. Today 60(10)(2007)42—47.

L.W. Diamond, Salinity of multivolatile fluid inclusions determined from clathrate hydrate stability, Geochem. Cosmochim. Acta 58 (1)(1994)19—41.

Y.T. Seo, H.E. Lee, Structure and guest distribution of the mixed carbon dioxide and nitrogen hydrates as revealed by X-ray diffraction and 13 C NMR spectroscopy, J. Phys. Chem. B 108 (2) (2004) 530—534.

C.A. Koh, R.E. Westacott, W. Zhang, K. Hirachand, J.L. Creek, A.K. Soper, Mechanisms of gas hydrate formation and inhibition, Fluid Phase Equilib. 194 (2002)143—151.

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