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Chinese Science Bulletin 2005 Vol. 50 No. 22 2628—2635 cient gas pool are needed. At present, marine source rocks
distributed in the mid-lower part of the superimposed ba-
Oil cracking: An important sins of China are commonly at a higher evolution stage
when a large amount of crude oil has been generated. Thus,
way for highly efficient gen- a series of questions arise: How about the gas generation
eration of gas from marine potential of these high- to over mature kerogens with Ro≥
1.6%? Can these marine source rocks form commercial
source rock kitchen gas pool[1]? What are the real gas sources of the newly
found gas pools of marine origin (e.g. the Hetianhe gas
ZHAO Wenzhi1, WANG Zhaoyun1, pool in Tarim basin, Luojiazhai and Tieshanpo gas pools
ZHANG Shuichang1, WANG Hongjun1 in Sichuan basin)? Does the natural gas originate from the
& WANG Yunpeng2 thermal cracking of the over mature source rocks, from
the early formed oil pool, or from the thermal cracking of
1. Research Institute of Petroleum Exploration & Development, Petro- the disseminated soluble organic matter? What are their
China, Beijing 100083, China;
2. Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, respective contribution ratios? If we can find answers to
Guangzhou 510640, China these questions, the formation mechanism of gas pools of
Correspondence should be addressed to Wang Zhaoyun (email: marine origin and their accumulation ways would be re-
wzy@petrochina.com.cn) vealed, which is helpful for oil and gas exploration.
Abstract The potentials of gas generation by kerogen in 1 Structural variation of kerogens during the hydro-
the late period and by crude oil cracking are closely related carbon generation process and the gas generation po-
to the origin of natural gas in the high- to over mature ma- tential of high- to over mature kerogens
rine area and their exploration perspectives. The carbon
structure of kerogens, with different types and at different Now, solid 13C nuclear magnetic resonance (SNMR)
evolution stages, have been experimentally studied using the technique is the most efficient method for studying the
high magnetic field solid 13C nuclear magnetic resonance material structure[2―5]. In our experiments, five groups of
technique in order to determine the oil and gas potential of samples with different types and at different evolution
kerogens. Results show that the contents of gas potential degrees were collected for structural analysis by the
carbon(GPC) of types I, II, III kerogens at the high- to over
SNMR technique. The geochemical features of the sam-
mature stage are very low, indicating their weak
gas-generating capacity and limited gas production; however, ples and the experimental conditions are presented in Ta-
the content of oil potential carbon(OPC) of the low mature ble 1. Series A in Table 1 are kerogens of Irati oil shales
type I kerogen is much higher, implying that a large amount (Upper Permian) from Parana Basin of Brazil, prepared by
of crude oil generated during the oil-generating period will low-temperature thermal simulation with water at different
be the material for later gas generation by oil cracking. The temperature stages, representing marine type I samples
kinetic experiment of gas generation by crude oil cracking from low mature to mature and high mature stages; Series
shows that, when the temperature is about 160℃(Ro=1.6%), B are kerogens from lacustrine marlite of Shahejie Forma-
the crude oil will start to produce large amounts of gas; the tion (Tertiary) from Bohaiwan basin in China, prepared by
temperature range for major gas generation of crude oil is the same method, representing lacustrine type I kerogens
higher than that of the kerogens, and the gas production is 2
from low mature to high mature stages; Series C are
to 4 times higher than that of kerogens. The natural gas de-
rived from oil cracking (called oil-cracked gas) is much kerogens from fen peat in Germany, standing for type II
abundant in methyl hexamethylene, which is quite different kerogens from low mature to high mature stages; Series D
from the natural gas produced by thermal degradation of are type III kerogens at different evolution stages, which
kerogens (named kerogen degradation gas) at high- to over are also collected from swamp environment in Germany;
mature stage. Series E are marlites deposited in paralic environment of
Keywords: oil-cracked gas, kerogen degradation gas, hydrocar- Carboniferous-Permian sequence in the southern North
bon-generating matrix structure, solid 13C nuclear magnetic reso- China, representing a complete evolution from low mature
nance, oil potential carbon, gas potential carbon. to over mature stages.
DOI:10.1360/982004-522 The SNMR data were collected by the Solid-state 13C
CP/MAS+TOSS (cross polarization, magic angle spinning
The Continental Oil Generation Theory has verified and total side-band suppression) technique on a Bruker
that China is not an oil-poor country. However, will the MSL-400 spectrometer operating at 64 kHz for both 1H
marine sequences be the next exploration field in China as and 13C[6]. The spinning frequency was 4 kHz, the cross
an important substitution for oil and gas exploration in polarization contacting time was 1 ms, the repeat delay
continental basins, and efficiently solve the problem of time was 1.5 s, 1000 k points data were collected and zero
energy shortage in China? To answer this question, accu- was added to 8000k, and the accumulated times was
rate assessment of the natural gas resources and their effi- 2000―5000. The 13C NMR spectra are shown in Fig. 1.
Fig. 1. 13C CP/MAS+TOSS spectra of the analyzed samples (chemical displacement value×106). (a) Kerogens from Irati oil shales; (b)
kerogens from lacustrine marlite; (c) kerogens from fen peat; (d) kerogens from bog peat; (e) kerogens from naturally evolutionary samples.
The sample features are given in Table1.
Chemical displacement values(CDV) varying within matic-structure carbon has almost no change and is pre-
0―90×106 represent carbon functional groups(including served in the residual carbon. Therefore, the fatty-struc-
aroly carbon) of fatty structure in kerogens, whereas CDV ture carbon may be the main contributor of oil and gas.
of carbon functional groups of aromatic structure range The ratio of the carbon content of fatty structure (the inte-
from 90×106 to 170×106, and CDV of carboxyl and gration of the absorption intensity within 0―50×106 and
carbonyl from 165×106 to 220×106. In Fig. 1, for all 165×106―220×106) to that of the total structure (the
samples, the fatty-structure carbon, carboxyl and carbonyl integration of the absorption intensity within 0―220×
carbon gradually decrease during the hydrocarbon gen- 106) is defined as the aliphatic carbon ratio (fal). Further-
eration by kerogen degradation process, but the aro- more, the fatty-structure carbon can be categorized as the
Fig. 2. Comparisons of fal among different types of kerogens and content variations of Coil and Cgas during the hydrocarbon generation proc-
ess. (a) Comparison of fal among different types of kerogens (for sample features, see Fig. 1); (b)―(f) comparison of the content variations of
Coil and Cgas of the same types of kerogen during the hydrocarbon generation process.
Fig. 3. Comparison of oil and gas yields generated by type I and III source rocks derived from low-temperature thermal simulation
experiment with water. Ro values at the corresponding temperature interval are given in the figure). (a) Type I; (b) type III. 1, oil; 2, gas.
Table 2 Physical features and geochemical parameters of crude oil and kerogen obtained by kinetic experiment
Sample Area Depth/m Horizon Physical features and geochemical parameters
density, 20℃ viscosity solidifying fractionation sulphur con-
wax content (%)
Crude oil Lunnan, Tarim 4010 O /g ·cm-3 /mpa.s point/℃ point/℃ tent(%)
0.8573 9.037 30 102 18.15 0.17
Zhangjiakou, TOC(%) Tmax/℃ Ro(%) IH/mg·g−1TOC type
Kerogen outcrop Pt
North China 51.75 430 0.56 419 II1
Fig. 4. Gas yield generated by kerogen and crude oil cracking and their occurring time obtained by the gas generation kinetic experiment. (a)
Gas yield of oil & kerogen; (b) gas generation rate of kerogen; (c) gas generation rate of oil.
oil-cracked gas production of one unit oil is 2―4 times 352(6331): 146―148. [DOI]
higher than that of kerogens , and the gas generation effi- 13. McNeil, R. I., Thermal stability of hydrocarbons: Laboratory crite-
ciency of oil cracking is much higher. Oil-cracked gas is ria and field examples, Energy & Fuels, 1996, 10(2): 60―67.
abundant in methyl hexamethylene, which is quite differ- [DOI]
ent from the composition and isotopes of kerogen degra- 14. Behar, F., Vandenbroucke. M., Experimental determination of the
dation gas. Thus, gas generation by oil cracking is the rate constants of the n-C25 thermal cracking at 120, 400, and 800
main way for marine source rocks. In addition, the forma- bar:implications for high pressure/high temperature prospects, En-
tion of paleo-oil pool and the rapid cracking of crude oil at ergy & Fuel, 1996, 10(12): 932―940. [DOI]
high temperature can make marine source rocks a high 15. Schenk, H. J., Di, P. R, Horsfield, B., The conversion of oil into gas
efficient gas kitchen. in petroleum reservoir, PartⅠ: Comparative kinetic investigation of
Acknowledgments The authors would like to thank Dr. Wang Huitong gas generation from crude oil of lacustrine, marine and fluviodel-
in Experimental Center of the Research Institute of Petroleum Explora-
taic origin by programmed-temperature closed-system pyrolysis,
tion and Development (RIPED) for providing some samples in Table 1
and their geochemical data, and thank Dr. Zhang Guangya and Li Organic Geochemistry, 1997, 26(7-8): 467―481. [DOI]
Hongbo (RIPED) for their help in crude oil sampling in Tarim Basin. The 16. Price, L. C., Thermal stability of hydrocarbons in nature: limits,
NMR, thermal simulation and hydrocarbon generation dynamic experi-
evidence, characteristics, and possible controls, Geochim. Cosmo-
ments were performed in Wuhan Institute of Physics, Chinese Academy
of Sciences (CAS), Beijing Institute of Geology and Geophysics, CAS, chim. Acta, 1993, 57(14): 3261―3280. [DOI]
Guangzhou Institute of Geochemistry (CAS) and Experimental Center of 17. Ungerer, P., Behar, F., Villalba, M. et al., Kinetic modeling of oil
RIPED. This work was supported by the National 973 Natural Gas Pro-
ject (Grant No. 2001CB209100). cracking, Organic Geochemistry, 1988, 13(4-6): 857―868. [DOI]
18. Ungerer, P., State of the art of research in kinetic modeling of oil
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