Geochemical study on oil-cracked gases and kerogen-cracked gases (Ⅱ)——Discrimination methods between oil-cracked gases and kerogen-cracked gases

In the processes of discrimination between oil-cracked gases and kerogen-cracked gases,Behar and Pinzgofer et al.'s results were adopted in the former researches,in which the ratio of C2/C3 is basically a constant while the ratio of C1/C2 gradually increases in the course of primary cracking of kerogen. Otherwise in the course of secondary cracking of oil,the ratio of C2/C3 increases rapidly while C1/C2 keeps relatively stable. Our study on analogue experiment shows that,whether it is oil or kerogen,in its process of gas generating by cracking,the ratios of C2/C3,C1/C2 or C1/C3 will all be increased with the growth of thermal conditions. In comparison,the ratio of C2/C3,which is affected by genetic type to some comparatively less extent,mainly responds to the maturity of gases,while the value of C2/C3 is about 2,and that of C2/iC4 is about 10,and the corresponding value of Ro is about 1.5%―1.6%. The influence of gas source on C2/C3 is less than that of gas maturity,otherwise C1/C2(or C1/C3) is obviously affected by cracking matrices. The ratios of C1/C2,C1/C3 of oil-cracked gases are less than that of kerogen-cracked gases,under the condition that the ratios of C2/C3 are similar in value,so are the value of dryness indexes. There exists wide diffidence between this view and the former discrimination method in theory. The analysis of the spot sample indicates that we can apply the above basic view to dealing efficiently with the problem of the discrimination between oil-cracked gas and kerogen-cracked gas.

Geochemical characteristics and exploration significance of ultra-deep Sinian oil and gas from Well Tashen 5,Tarim Basin,NW China

The Well Tashen 5(TS5),drilled and completed at a vertical depth of 9017 m in the Tabei Uplift of the Tarim Basin,NW China,is the deepest well in Asia.It has been producing both oil and gas from the Sinian at a depth of 8780e8840 m,also the deepest in Asia in terms of oil discovery.In this paper,the geochemical characteristics of Sinian oil and gas from the well were investigated and compared with those of Cambrian oil and gas discovered in the same basin.The oil samples,with Pr/Ph ratio of 0.78 and a whole oil carbon isotopic value of31.6‰,have geochemical characteristics similar to those of Ordovician oils from the No.1 fault in the North Shuntuoguole area(also named Shunbei area)and the Middle Cambrian oil from wells Zhongshen 1(ZS1)and Zhongshen 5(ZS5)of Tazhong Uplift.The maturity of light hydrocarbons,diamondoids and aromatic fractions all suggest an approximate maturity of 1.5%e1.7%Ro for the samples.The(4-+3-)methyldiamantane concentration of the samples is 113.5 mg/g,indicating intense cracking with a cracking degree of about 80%,which is consistent with the high bottom hole temperature(179℃).The Sinian gas samples are dry with a dryness coefficient of 0.97.The gas is a mixture of kerogen-cracking gas and oil-cracking gas and has Ro values ranging between 1.5%and 1.7%,and methane carbon isotopic values of41.6‰.Based on the equivalent vitrinite reflectance(R_(eqv)=1.51%e1.61%)and the thermal evolution of source rocks from the Cambrian Yu'ertusi Formation of the same well,it is proposed that the Sinian oil and gas be mainly sourced from the Cambrian Yu'ertusi Formation during the Himalayan period but probably also be joined by hydrocarbon of higher maturity that migrated from other source rocks in deeper formations.The discovery of Sinian oil and gas from Well TS5 suggests that the ancient ultra-deep strata in the northern Tarim Basin have the potential for finding volatile oil or condensate reservoirs.

Effect of Waste Oil-Cracking Catalyst Incorporation on Durability of Mortars

This paper presents research on transport properties and alkali-silica reaction (ASR) susceptibility of mortars containing a pozzolanic waste generated in the fluid catalytic cracking (wFCC) unit by the Portuguese oil-refinery. For this purpose, two series of mortars were prepared by partially replacing cement with 5%, 10% and 15% of wFCC catalyst. The main difference between the two series of mortars is the sand reactivity used in their composition. The results revealed that wFCC catalyst blended cement mortars exhibit an increased resistance against capillary water absorption and chloride migration, as well as a considerable inhibition effect on deleterious ASR expansion. However, under the adopted experimental conditions the incorporation of wFCC catalyst in mortars decreases their carbonation resistance.

Source Rocks for the Giant Puguang Gas Field,Sichuan Basin:Implication for Petroleum Exploration in Marine Sequences in South China

Detailed geochemistry studies were conducted to investigate the origin of solid bitumens and hydrocarbon gases in the giant Puguang gas field. Two types of solid bitumens were recognized： low sulfur content, low reflectance （LSLR） solid bitumens in sandstone reservoirs in the Xujiahe Formation and high sulfur content, high reflectance （HSHR） solid bitumens in the carbonate reservoirs in the Lower Triassic Feixianguan and Upper Permian Changxing formations. Solid bitumens in the Upper Triassic Xujiahe Formation correlate well with extracts from the Upper Triassic to Jurassic nonmarine source rocks in isotopic composition of the saturated and aromatic fractions and biomarker distribution. Solid bitumens in the Feixianguan and Changxing formations are distinctly different from extracts from the Cambrian and Silurian rocks but display reasonable correlation with extracts from the Upper Permian source rocks both in isotopic composition of the saturated and aromatic fractions and in biomarker distribution, suggesting that the Permian especially the Upper Permian Longtan Formation was the main source of solid bitumens in the carbonate reservoirs in the Feixianguan and Changxing formations in the Puguang gas field. Chemical and isotopic composition of natural gases indicates that the majority of hydrocarbon gases originated from sapropelic organic matter and was the products of thermal cracking of accumulated oils. This study indicates that source rock dominated by sapropelic organic matter existed in the Upper Permian and had made major contribution to the giant Puguang gas field, which has important implication for petroleum exploration in marine sequences in South China.

Gas formation mechanism of marine carbonate source rocks in China

By breaking through the conventional ideology on the study of gas-formation mechanism of source rocks which focused on merely the characteristics of source rocks them- selves, and based on the development and distribution characteristics of marine carbonate source rocks in the medium-to-bottom parts of the Chinese superimposed sedimentary basins as well as various processes in the course of gas generation and reservoir forming, the complex hydrocarbon-generating model of carbonates is established. Such a model concerns not only the “three-stage” gas formation characteristics of carbonates, but also the gas generation process due to a thermal cracking of oil and the re-generation process of gas from heated secondary organic matters during the gas-generation and reservoir-forming course. The high-quality hy- drocarbon generating matter of marine carbonate source rocks determined a high gas-oil ratio and tended to form paleo-oil-reservoirs, representing an enrichment process of organic matters. The thermal cracking of oil in palaeo-oil-reservoirs is an important means for the effective forma- tion of gas reservoirs. The secondary organic matters in carbonate reservoirs may regenerate gas after a secondary deep burial, thus becoming an effective gas source.

Origin of natural sulphur-bearing immiscible inclusions and H_(2)S in oolite gas reservoir, Eastern Sichuan

Based on results of microscopic observation and laser Raman analysis about fluid in-clusions,multiple special forms of immiscible inclusions that contain sulphur,liquid hydrocarbon,bi-tumen,etc.were discovered in samples collected from the H_(2)S gas reservoir-containing carbonates in the Lower Triassic Feixianguan Formation in the Jinzhu-Luojia area,Kai County,Sichuan Province.Based on the lithology and burial history of the strata involved as well as measurement results of homogenization temperature of fluid inclusions,bitumen reflectivity,etc.,it is concluded that the H_(2)S in the gas reservoir resulted from the thermal reaction between hydrocarbons in reservoir and CaSO_(4)in the gypsum-bearing dolostone section at the high temperature(140℃―170℃)oil-cracked gas for-mation stage in Late Cretaceous.Thereafter,research on a great number of immiscible inclusions in the reservoir reveals that elemental sulphur resulted from oxidation of part of the earlier-formed H_(2)S and further reaction between sulphates,hydrocarbons and H_(2)S in geological fluids in H_(2)S-bearing gas reservoir at a temperature of 86℃―89℃and a pressure of 340×10^(5)Pa and during the regional uplift stage as characterized by temperature decrease and pressure decrease in Tertiary.Meanwhile,gyp-sum,anhydrite and calcite formed at this stage would trap particles like elemental sulphur and result in a variety of special forms of immiscible inclusions,and these inclusions would contain information concerning the complexity of the fluids in the reservoir and the origin of H_(2)S and natural sulphur in the gas reservoir.

Identification of marine natural gases with different origin sources

Kinetic experiments of gas generation for typical samples of marine gas precursors including low-maturity kerogen,residual kerogen and oil as well as dispersed liquid hydrocarbon(DLH)in source rocks were performed by closed system,and the evolution trends of molecular and isotopic compositions of natural gases from different precursors against the maturity(R0%)at laboratory conditions were analyzed.Several diagrams of gas origin were calibrated by using the experimental data.A diagram based on the ratio of normal and isomerous butane and pentane(i/nC4-i/nC5)was proposed and used to identify the origins of the typical marine natural gases in the Sichuan Basin and the Tarim Basin, China.And the maturities of natural gases were estimated by using the statistical relationships between the gaseous molecular carbon isotopic data and maturities(δ13C-R 0 %)with different origins.The results indicate that the molecular and isotopic compositions of simulated gases from different precursors are different from each other.For example,the dryness index of the oil-cracking gas is the lowest;the dryness indices of gases from DLH and kerogen in closed system are almost the same;and the dryness index of gases from residual kerogen is extremely high,indicating that the kerogen gases are very dry;the contents of non-hydrocarbon gases in kerogen-cracking gases are far higher than those in oil-cracking and DLH-cracking gases.The molecular carbon isotopes of oil-cracking gases are the lightest,those of kerogen in closed system and GLH-cracking gases are the second lightest,and those of cracking gases from residual kerogen are the heaviest.The calibration results indicate that the diagrams of ln(C1/C2)-ln(C2/C3)andδ13C2-δ13C3-ln(C2/C3)can discriminate primary and secondary cracking gases,but cannot be used to identify gas origin sources,while the diagram of i/nC4-i/nC5 can differentiate the gases from different precursors.The application results of these diagrams show that gas mixtures extensively exist in China,which involved the gases from multiple precursors and those from different maturity stages.For example,marine gases in the Sichuan Basin involve the mixture of oil-cracking gases and high-over-maturated kerogen gases,while those in the Tarim Basin involve not only the mixture of gases from multiple precursors,but also those from different maturity gases and post-reservoir alternations such as oxidized degradation and gas intrusion processes.