Investigation of the Methane Adsorption Characteristics of Marine

Feb 8, 2017 - Key Laboratory for Marine Reservoir Evolution and Hydrocarbon Abundance Mechanism, Ministry of Education, China University of...
0 downloads 0 Views 4MB Size
Download PDF
Article pubs.acs.org/EF

Investigation of the Methane Adsorption Characteristics of Marine Shale: A Case Study of Lower Cambrian Qiongzhusi Shale in Eastern Yunnan Province, South China Ang Li, Wenlong Ding,* Xuehui Zhou, Xiangyu Cao, Min Zhang, Fuquan Fu, and En Chen School of Energy Resources, China University of Geosciences, Beijing 100083, China Key Laboratory for Marine Reservoir Evolution and Hydrocarbon Abundance Mechanism, Ministry of Education, China University of Geosciences, Beijing 100083, China Key Laboratory for Shale Gas Exploration and Assessment, Ministry of Land and Resources, China University of Geosciences, Beijing 100083, China ABSTRACT: Marine organic-rich shale in South China has considerable exploration potential, and the shale adsorption capacity has a great impact on the accumulation of shale gas. To study the methane adsorption capacity of marine shale, ten shale samples from the Lower Cambrian Qiongzhusi Formation in eastern Yunnan province were investigated by organic geochemical analysis (total organic carbon content, thermal maturity, and kerogen type), X-ray diffraction (XRD) analysis, field emission scanning electron microscopy (FE-SEM), and low-pressure nitrogen adsorption and methane adsorption experiments. Based on the different adsorption mechanisms of various pores, the Dubinin−Radushkevich and Langmuir−Freundlich models were used to construct a supercritical adsorption model of shale. Combined with this model, the mechanisms and characteristics of shale adsorption under supercritical conditions were analyzed. The maximum absolute methane adsorption capacities of micropores (V1) and mesopores-macropores (V2) were also calculated. Not only have the relationships between organic geochemistry, mineral compositions, pore structure parameters, and maximum absolute methane adsorption capacity (both V1 and V2) been discussed but the impact of moisture on the methane adsorption capacity of shale has also been investigated. The results show that the maximum adsorption capacity of mesopores−macropores is greater than that of micropores. Both V1 and V2 are positively correlated with the TOC content, and V2 is more correlated with the TOC content than V1. High maturity is not conducive to methane adsorption of shale. The maximum absolute methane adsorption amounts of per-unit organic matter have positive correlations with the clay mineral content, but show negative correlations with the quartz content. Different clay minerals have different methane adsorption capacities. Both V1 and V2 increase with increasing specific surface area. V1 has a positive correlation with the micropore volume, but V2 has no apparent relationship with the mesopore−macropore volume. Moreover, shale samples with higher moisture contents have lower methane adsorption capacity. It is anticipated that the results of this study will provide guidance for the adsorption characteristics and influence factors of high maturity marine shale. and (2) a product of increasing kerogen aromaticity.10−12 The organic matter abundance is one of the key factors for shale gas potential. Organic matter is not only the source of hydrocarbon gases but also greatly affects the adsorbed methane amount.13−15 Ross and Bustin16 suggested that shale samples with higher maturity have stronger methane adsorption capacity with similar TOC and moisture contents. However, Chalmers and Bustin17 held the view that the increasing maturity of shale would reduce the TOC content, thus weakening the methane adsorption capacity. In addition, clay minerals contribute differently to adsorbed gas capacity, the amount of which is dependent on clay type.18−20 Shale pores can be divided into three types based on the definition provided by the International Union of Pure and Applied Chemistry (IUPAC): micropores (diameter I/S > kaolinite > chlorite > Illite.20 The clay minerals in shale samples are mainly Illite, I/S, and chlorite. The relationships between different clay minerals and the maximum absolute methane adsorption amounts of perunit organic matter are illustrated in Figure 8. V′1 and V′2 show positive correlations with the Illite and I/S contents, but the chlorite content has no correlation with V′1 and a negative correlation with V′2. Multiple factors, such as moisture, diagenesis, and filling, result in the medium−poor correlations between different clay minerals and methane adsorption capacity.58 In particular, a low content and specific surface area cause an ambiguous correlation or even a negative correlation between chlorite and adsorption capacity. Hence, different degrees of diagenetic evolution also significantly affect the methane adsorption of shale. For some low maturity or organic−lean shale samples, clay minerals are the major contributors to gas adsorption space.7 4.3. Effect of pore structure parameters on methane adsorption capacity. Figure 9 shows the relationships between pore structure parameters and maximum absolute adsorption amount (V1 and V2). The maximum absolute adsorption amounts of micropores and mesopores−macropores are both positively correlated with specific surface area; namely, shale with a greater surface area has stronger adsorption capacity. A similar experimentally determined H

DOI: 10.1021/acs.energyfuels.6b03168 Energy Fuels XXXX, XXX, XXX−XXX

Article

Energy & Fuels

■

moisture content would have a lower methane adsorption capacity, suggesting that moisture has a negative impact on shale adsorption.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Postal address: School of Energy Resources, China University of Geosciences, Beijing 100083, China. Tel.: +86 10 82320629. Fax: +86 10 82326850. ORCID

Wenlong Ding: 0000-0002-5328-7629 Notes

The authors declare no competing financial interest.

■

Figure 10. Relationships between maximum absolute adsorption capacity (V1 and V2) and moisture content.

adsorption capacities of moisture-equilibrated samples were up to 40% lower than those for dry samples. The absorption capacity of pure clay minerals (montmorillonite, Illite, and kaolinite) will be reduced by 80−95% under moist conditions, which implies that moisture is one of the primary factors that influence the adsorbed gas capacity of clay minerals in shale.6,63 Consequently, the high moisture content in shale reservoirs is not conducive to the accumulation of shale gas.

ACKNOWLEDGMENTS This research was supported by the National Natural Science Foundation of China (Project Nos. 41072098 and 41372139) and the Important National Science and Technology Specific Projects of China (Nos. 2016ZX05046-003, 2011ZX05018001-002 and 2011ZX05009-002-205). The authors would like to thank the staff of all of the laboratories that cooperated in performing the tests and analyses. We are also grateful to the reviewers, whose comments improved the quality of this manuscript.

5. CONCLUSION In this paper, the supercritical methane adsorption mechanisms and characteristics of 10 shale samples from the Lower Cambrian Qiongzhusi Formation in eastern Yunnan Province, South China, were investigated using various experiments and methane adsorption models. Moreover, the factors influencing shale adsorption were also discussed. The following conclusions can be drawn: (1) Based on the different adsorption mechanisms of various pore sizes, a supercritical methane adsorption model is proposed to calculate the maximum absolute methane adsorption amounts of micropores (V1) and mesopores− macropores (V2). V2 is greater than V1, indicating that mesopores and macropores in shale greatly contribute to methane adsorption. (2) The two maximum absolute methane adsorption amounts (V1 and V2) are positively correlated with the TOC content with a good fit, suggesting that the organic matter content is the main controlling factor of shale methane adsorption. V2 has a better fit with the TOC content than V1 because the organic matter pores developed in the organic matter and clay aggregate account for a significant proportion in shale. Moreover, excessive maturity would weaken the adsorption ability of shale. (3) A high quartz content is not conducive to shale adsorption, while clay minerals enhance the adsorption ability. Different clay minerals have different methane adsorption capacities, and clay mineral adsorption will be weakened by multiple factors, such as moisture, diagenesis, and filling. (4) V1 increases with increasing micropore specific surface area and micropore volume, while V2 increases with increasing mesopore−macropore specific surface area but exhibits no apparent relationship with the mesopore− macropore volume. Additionally, shale with a higher

(1) Bowker, K. A. Barnett Shale gas production, Fort Worth Basin: Issues and discussion. AAPG Bull. 2007, 91 (4), 523−533. (2) Clarkson, C. R.; Jensen, J. L.; Chipperfield, S. Unconventional gas reservoir evaluation: what do we have to consider? J. Nat. Gas Sci. Eng. 2012, 8, 9−33. (3) Tang, X.; Zhang, J. C.; Wang, X. Z.; Yu, B. S.; Ding, W. L.; Xiong, J. Y.; Yang, Y. T.; Wang, L.; Yang, C. Shale Characteristics in the Southeastern Ordos Basin, China: Implications for Hydrocarbon Accumulation Conditions and the Potential of Continental Shales. Int. J. Coal Geol. 2014, 128−129, 32−46. (4) Curtis, J. B. Fractured shale-gas systems. AAPG Bull. 2002, 86 (11), 1921−1938. (5) Jarvie, D. M.; Hill, R. J.; Ruble, T. E.; Pollastro, R. M. Unconventional shale-gas systems: the Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment. AAPG Bull. 2007, 91, 475−499. (6) Ross, D. J. K.; Bustin, R. M. The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs. Mar. Pet. Geol. 2009, 26, 916−927. (7) Gasparik, M.; Ghanizadeh, A.; Bertier, P.; Gensterblum, Y.; Bouw, S.; Krooss, B. M. High-pressure methane sorption isotherms of black shales from the Netherlands. Energy Fuels 2012, 26, 4995−5004. (8) Rexer, T. F.; Benham, M. J.; Aplin, A. C.; Thomas, K. M. Methane adsorption on shale under simulated geological temperature and pressure conditions. Energy Fuels 2013, 27, 3099−3109. (9) Li, A.; Ding, W. L.; He, J. H.; Dai, P.; Yin, S.; Xie, F. Investigation of pore structure and fractal characteristics of organic-rich shale reservoirs: A case study of Lower Cambrian Qiongzhusi formation in Malong block of eastern Yunnan Province. Mar. Pet. Geol. 2016, 70, 46−57. (10) Chalmers, G. R. L.; Bustin, R. M. Lower Cretaceous gas shales in northeastern British Columbia, Part I: Geological controls on methane sorption capacity. Bull. Can. Pet. Geol. 2008, 56 (1), 1−21. (11) Zhang, T. W.; Ellis, G. S.; Rupple, S. C.; Milliken, K.; Yang, R. Effect of organic matter type and thermal maturity on methane adsorption in shale-gas systems. Org. Geochem. 2012, 47, 120−131. (12) Ji, W. M.; Song, Y.; Jiang, Z. X.; Chen, L.; Li, Z.; Yang, X.; Meng, M. M. Estimation of marine shale methane adsorption capacity based on experimental investigations of lower Silurian Longmaxi

■

I

REFERENCES

DOI: 10.1021/acs.energyfuels.6b03168 Energy Fuels XXXX, XXX, XXX−XXX

Article

Energy & Fuels formantion in the Upper Yangtze Platform, south China. Mar. Pet. Geol. 2015, 68, 94−106. (13) Miceli Romero, A.; Philp, R. P. Organic geochemistry of the Woodford Shale, southeastern Oklahoma: how variable can shales be? AAPG Bull. 2012, 96, 493−517. (14) Hill, R. J.; Zhang, E.; Katz, B. J.; Tang, Y. Modeling of gas generation from the Barnett shale, Fort Worth basin, Texas. AAPG Bull. 2007, 91, 501−521. (15) Rodriguez, N. D.; Paul, P. R. Geochemical characterization of gases from the Mississippian Barnett shale, Fort Worth basin, Texas. AAPG Bull. 2010, 94, 1641−1656. (16) Ross, D. J.; Bustin, R. M. Shale gas potential of the lower Jurassic Gordondale member, northeastern British Columbia, Canada. Bull. Can. Pet. Geol. 2007, 55, 51−75. (17) Chalmers, G. R. L.; Bustin, R. M. Lower Cretaceous gas shales in northeastern British Columbia, Part II: Evaluation of regional potential gas resources. Bull. Can. Pet. Geol. 2008, 56 (1), 22−61. (18) Bustin, R. M.; Clarkson, C. R. Geological controls on coalbed methane reservoir capacity and gas content. Int. J. Coal Geol. 1998, 38, 3−26. (19) Wang, S. B.; Song, Z. G.; Cao, T. T.; Song, X. The methane sorption capacity of Paleozoic shales from the SichuanBasin, China. Mar. Pet. Geol. 2013, 44, 112−119. (20) Ji, L. M.; Zhang, T. W.; Milliken, K. L.; Qu, J. L.; Zhong, X. L. Experimental investigation of main controls to methane adsorption in clay-rich rocks. Appl. Geochem. 2012, 27, 2533−2545. (21) Clarkson, C. R.; Solano, N.; Bustin, R. M.; Bustin, A. M. M.; Chalmers, G. R. L.; He, L.; Melnichenko, Y. B.; Radlinski, A. P.; Blach, T. P. Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion. Fuel 2013, 103, 606−616. (22) Loucks, R. G.; Reed, R. M.; Ruppel, S. C.; Jarvie, D. M. Morphology, genesis, and distribution of nanometer-scale pores in siliceous mudstones of the Mississippian Barnett Shale. J. Sediment. Res. 2009, 79, 848−861. (23) Milliken, K. L.; Rudnicki, M.; Awwiller, D. N.; Zhang, T. Organic matterehosted pore system, Marcellus Formation (Devonian), Pennsylvania. AAPG Bull. 2013, 97 (2), 177−200. (24) Yang, F.; Ning, Z. F.; Zhang, R.; Zhao, H. W.; Krooss, B. M. Investigations on the methane sorption capacity of marine shales from Sichuan Basin, China. Int. J. Coal Geol. 2015, 146, 104−117. (25) Li, A.; Ding, W. L.; Zhang, G. L.; Zhang, M. Q.; Zhang, Z. X.; Yan, B. Z.; Zhou, C. X.; Chen, Z. Z.; Bai, P. Reservoir characteristics of marine shale in the Malong block of eastern Yunnan Province and comparison analysis. Earth Sci. Front. 2016, 23 (2), 176−189. (26) Krooss, B. M.; van Bergen, F.; Gensterblum, Y.; Siemons, N.; Pagnier, H. J. M.; David, P. High pressure CH4 and carbon dioxide adsorption on dry and moisture equilibrated Pennsylvanian coals. Int. J. Coal Geol. 2002, 51, 69−92. (27) Busch, A.; Gensterblum, Y. CBM and CO2-ECBMrelated sorption processes in coal: are view. Int. J. Coal Geol. 2011, 87, 49−71. (28) Gasparik, M.; Bertier, P.; Gensterblum, Y.; Ghanizadeh, A.; Krooss, B. M.; Littke, R. Geological controls on the methane storage capacity in organic-rich shales. Int. J. Coal Geol. 2014, 123, 34−51. (29) Gensterblum, Y.; Busch, A.; Krooss, B. M. Molecular concept and experimental evidence of competitive adsorption of H2O, CO2 and CH4 on organic material. Fuel 2014, 115, 581−588. (30) Tian, H.; Li, T. F.; Zhang, T. W.; Xiao, X. M. Characterization of methane adsorption on ove rmature Lower Silurian−Upper Ordovician shales in Sichuan Basin, southwest China: Experimental results and geological implications. Int. J. Coal Geol. 2016, 156, 36−49. (31) Zhou, L.; Li, M.; Zhou, Y. P. Adsorption measurement and its theoretical analysis of supercritical methane on activated carbon with high surface area. Science in China (Series B) 2000, 30 (1), 49−56. (32) Bouw, S.; Lutgert, J. Shale plays in the Netherlands. Proceedings of the SPE/EAGA European Unconventional Resources Conference and Exhibition USA, 2012.

(33) Crosdale, P. J.; Beamish, B. B.; Valix, M. Coalbed methane sorption related to coal composition. Int. J. Coal Geol. 1998, 35 (1), 147−158. (34) Amankwah, K. A. G.; Schwarz, J. A. A modified approach for estimating pseudo-vapor pressures in the application of the DubininAstakhov equation. Carbon 1995, 33 (9), 1313−1319. (35) Hu, T.; Ma, Z. F.; Yao, H. Q. Study on high pressure adsorption isotherms of supercritical methane. Natural Gas Chemical Industry 2002, 27, 36−40. (36) Reich, R.; Ziegler, W. T.; Rogers, K. A. Adsorption of methane, ethane, and ethylene gases and their binary and ternary mixtures and carbon dioxide on activated carbon at 212−301K and pressure to 35 atm. Ind. Eng. Chem. Process Des. Dev. 1980, 19 (3), 336−344. (37) Guo, T. L.; Zhang, H. R. Formation and enrichment mode of Jiaoshiba shale gas field, Sichuan Basin. Petroleum Exploration and Development 2014, 41 (1), 31−40. (38) Guo, X. S.; Li, Y. P.; Liu, R. B.; Wang, P. B. Characteristics and controlling factors of micro-pore structures of Longmaxi Shale Play in the Jiaoshiba area, Sichuan Basin. Nat. Gas Ind. 2014, 1 (2), 165−171. (39) Wang, R. Y.; Ding, W. L.; Zhang, Y. Q.; Wang, Z.; Wang, X. H.; He, J. H.; Zeng, W. T.; Dai, P. Analysis of developmental characteristics and dominant factors of fractures in Lower Cambrian marine shale reservoirs: A case study of Niutitang formation in Cen’gong block, southern China. J. Pet. Sci. Eng. 2016, 138, 31−49. (40) Chen, J. K.; Zhu, Y. M.; Fu, C. Q.; Tang, X. Characteristics and Significance of Mineral Compositions in Lower Cambrian Qiongzhusi Formation from Eastern Yunnan Province. Coal Technology 2016, 35 (9), 101−103. (41) Dubinin, M. M.; Astakhov, V. A. Development of the concepts of volume filling of micropores in the adsorption of gases and vapors by microporous adsorbents; Izvestiya Akademii Nauk SSSR; Seriya Khimi Cheskaya, 1971; Vol. 1, pp 5−11. (42) Dubinin, M. M. Adsorption in micropores. J. Colloid Interface Sci. 1967, 23 (4), 487−499. (43) Findnegg, G. H. High pressure adsorption of gases on homogeneous surface. In Fundamentals of Adsorption. Proceedings of the Engineering Foundation Conference, Schloss Elmau, Bavaria, West Germany, 1983; pp 207−218. (44) Hou, X. W.; Wang, M.; Liu, Y.; Liu, J. N.; Song, Y. Supercritical adsorption model of gas and its geological significane. Journal of China University of Mining &Technology 2016, 45 (1), 111−118. (45) Ding, W. L.; Zhu, D. W.; Cai, J. J.; Gong, M. L.; Chen, F. Y. Analysis of the Developmental Characteristics and Major Regulating Factors of Fractures in Marine-Continental Transitional Shale-Gas Reservoirs: A Case Study of the Carboniferous-Permian Strata in the Southeastern Ordos Basin, Central China. Mar. Pet. Geol. 2013, 45, 121−133. (46) Cao, Q. Y. Identification of microcomponents and types of kerogen under transmitted light. Pet. Explor. Dev. 1985, 05, 14−23. (47) Yang, F.; Ning, Z. F.; Hu, H. P.; Wang, B.; Peng, K.; Liu, H. Q. Characterization of microscopic pore structures in shale reservoirs. Acta Petrolei Sinica. 2013, 34 (2), 301−311. (48) Zeng, W. T.; Zhang, J. C.; Ding, W. L.; Wang, X. Z.; Zhu, D. W.; Liu, Z. J. The gas content of continental Yanchang shale and it main controlling factors: a case study of Liuping-171 well in Ordos Basin. Nat. Gas Geosci. 2014, 25 (2), 291−301. (49) Cao, T. T.; Song, Z. G.; Wang, S. B.; Xia, J. A comparative study of the specific surface area and pore structure of different shales and their kerogens. Sci. China: Earth Sci. 2015, 58 (4), 510−522. (50) Ji, W. M.; Song, Y.; Jiang, Z. X.; Chen, L.; Wang, P. F.; Liu, Q. X.; Gao, F. L.; Yang, X. Micro-nano pore structure characteristics and its control factors of shale in Longmaxi Formation, southeastern Sichuan Basin. Acta Petrolei Sinica 2016, 37 (2), 182−195. (51) Tian, H.; Zhang, S. C.; Liu, S. B.; Wang, M. Z.; Zhang, H.; Hao, J. Q.; Zheng, Y. P.; Gao, Y. The dual influence of shale composition and pore size on adsorption gas storage mechanism of organic-rich shale. Natural Gas Geoscience 2016, 27 (3), 494−502. (52) Behar, F.; Vandenbroucke, M. Chemical modeling of kerogens. Org. Geochem. 1987, 11, 15−24. J

DOI: 10.1021/acs.energyfuels.6b03168 Energy Fuels XXXX, XXX, XXX−XXX

Article

Energy & Fuels (53) Behar, F.; Kressmann, S.; Rudkiewicz, J. L.; Vandenbroucke, M. Experimentalsimulation in a confined system and kinetic modelling of kerogen and oilcracking. Org. Geochem. 1992, 19, 173−189. (54) Guo, H. J.; Jia, W. L.; Peng, P. A.; Lei, Y. H.; Luo, X. R.; Chen, M.; Wang, X. Z.; Zhang, L. X.; Jiang, C. F. The composition and its impact on the methane sorption of lacustrine shales from the Upper Triassic Yanchang Formation, Ordos Basin. Mar. Pet. Geol. 2014, 57, 509−520. (55) Fu, H. J.; Wang, X. Z.; Zhang, L. X.; Guo, R. M.; Li, Z. T.; Xu, T.; Zhu, X. L.; Xu, W.; Li, Q. Investigation of the factors that control the development of pore structure in lacustrine shale: A case study of block X in the Ordos Basin, China. J. Nat. Gas Sci. Eng. 2015, 26, 1422−1432. (56) Tang, S. H.; Fan, E. P.; Zhang, S. H.; Jiang, W. Reservoir characteristics and gas-bearing capacity of the Lower Palaeozoic marine shales in Northestern Hunan. Earth Sci. Front. 2016, 23 (2), 135−146. (57) Hou, Y. G.; He, S.; Yi, J. Z.; Zhang, B. Q.; Chen, X. H.; Wang, Y.; Zhang, J. K.; Cheng, C. Y. Effect of pore structure on methane sorption capacity of shales. Petroleum Exploration and Development 2014, 41 (2), 272−281. (58) Wang, L.; Chen, Y. Y.; Liu, Y. X. Shale Porous Structural Characteristics of Longmaxi Formation in Pengshui Area of Southeast Sichuan Basin. China Petroleum Exploration 2014, 19 (5), 80−88. (59) Suárez-Ruiz, I.; Tatiana, J.; Fabián, S. G.; Robert, M.; Begoña, R. Porosity development and the influence of pore size on the CH4 adsorption capacity of a shale oil reservoir (Upper Cretaceous) from Colombia. Role of solid bitumen. Int. J. Coal Geol. 2016, 159, 1−17. (60) Li, J.; Li, X. F.; Wang, X. Z.; Li, Y. Y.; Wu, K. L.; Shi, J. T.; Yang, L.; Feng, D.; Zhang, T.; Yu, P. L. Water distribution characteristic and effect on methane adsorption capacity in shale clay. Int. J. Coal Geol. 2016, 159, 135−154. (61) Tan, J. Q.; Weniger, P.; Krooss, B.; Merkel, A.; Horsfield, B.; Zhang, J.; Boreham, C. J.; Graas, V. G.; Tocher, B. A. Shale gas potential of the major marine shale formations in the Upper Yangtze Platform, South China, part II: methane sorption capacity. Fuel 2014, 129, 204−218. (62) Merkel, A.; Fink, R.; Littke, R. High pressure methane sorption characteristics of lacustrine shales from the Midland Valley Basin, Scotland. Fuel 2016, 182, 361−372. (63) Chalmers, G. R. L.; Bustin, R. M. The effects and distribution of moisture in gas shale reservoir systems. AAPG Annual Convention and Exhibition 2010.

K

DOI: 10.1021/acs.energyfuels.6b03168 Energy Fuels XXXX, XXX, XXX−XXX