Effects of U-ore on the chemical and isotopic composition of products of hydrous pyrolysis of organic matter

In order to investigate the impact of U-ore on organic matter maturation and isotopic fractionation,we designed hydrous pyrolysis experiments on Type-II kerogen samples,supposing that the water and water–mineral interaction play a role.U-ore was set as the variable for comparison.Meanwhile,anhydrous pyrolysis under the same conditions was carried out as the control experiments.The determination of liquid products indicates that the presence of water and minerals obviously enhanced the yields of C（15＋） and the amounts of hydrocarbon and nonhydrocarbon gases.Such results may be attributed to waterorganic matter reaction in the high-temperature system,which can provide additional hydrogen and oxygen for the generation of gas and liquid products from organic matter.It is found that δD values of hydrocarbon gases generated in both hydrous pyrolysis experiments are much lower than those in anhydrous pyrolysis.What is more,δD values are lower in the hydrous pyrolysis with uranium ore.Therefore,we can infer that water-derived hydrogen played a significant role during the kerogen thermal evolution and the hydrocarbon generation in our experiments.Isotopic exchange was facilitated by the reversible equilibration between reaction intermediaries with hydrogen under hydrothermal conditions with uranium ore.Carbon isotopic fractionations of hydrocarbon gases were somehow affected by the presence of water and the uranium ore.The increased level of i-C4/n-C4ratios for gas products in hydrous pyrolysis implied the carbocation mechanism for water-kerogen reactions.

Investigation of Hydrous Pyrolysis on Type-Ⅱ Kerogen-bearing Source Rocks from Iran and its Application in Geochemical and Kinetic Analyses of Hydrocarbon Products

Hydrous pyrolysis(HP)practiced on type-Ⅱ kerogen-bearing oil shale samples from the Sargelu Formation in the Ghali-Kuh Area,western Iran,using a specially designed apparatus was performed at different temperatures(250-350℃),with hydrocarbon generation evaluated at each temperature.For comparison,the samples subjected to Rock-Eval pyrolysis before proceeding to HP resulted in T_(max)=418℃,HI=102,and TOC=4.33%,indicating immaturity and hence remarkable hydrocarbon(especially oil)generation potential,making them appropriate for HP.Moreover,the samples were deposited in a low-energy reductive marine environment,with maximum oil and gas generation(739 mg and 348 mg out of50 g of rock sample,respectively)observed at 330℃ and 350℃,respectively.The oil generated at 330℃ was subjected to gas chromatography(GC)and isotopic analyses to assess hydrocarbon quality and composition.The hydrocarbon generation data was devised to estimate kinetic indices of the Arrhenius equation and to investigate the gas-oil ratio(GOR)and overall conversion yield.Based on the producible hydrocarbon quantity and quality,the findings contribute to the economic assessment of oil shales across the study area.The developed kinetic model indicates the history of hydrocarbon generation and organic matter(OM)maturity.

A Comparison Study on the δD Value of Polycyclic Aromatic Hydrocarbons in Hydrous Pyrolysate of Herbaceous Peat with Different Water Medium

To investigate the influence of diagenetic water media on the hydrogen isotopes of individual sedimentary aromatic compounds,a series of hydrous pyrolyses were conducted on herbaceous peat.Polycyclic aromatic hydrocarbons(PAHs)in hydrous pyrolysed samples and their hydrogen isotopic composition characteristics were studied.The aqueous medium demonstrated a significant influence on the hydrogen isotopic composition of the individual PAHs generated during pyrolysis.The results showed that the PAHs formed after pyrolysis in the presence of a saltwater medium with high δD value from a salt lake had a heavy hydrogen isotopic composition.The PAHs formed after pyrolysis in the presence of a fresh water medium with low δD value from a swamp had a light hydrogen isotopic composition.The difference in the average PAHδD value between the two hydrous experiments varied from -174‰ to -109‰,suggesting that the hydrogen isotopic composition of individual sedimentary PAHs can reflect the source of the diagenetic water medium.In addition,a comparative study found that the hydrogen isotopes of PAHs were superior to those of n-alkanes in the same sample for diagenetic water indications.The results indicated that the exchange of water-derived inorganic hydrogen and organic hydrogen was more intensive in freshwater experiments than in saltwater experiments.With an increase in the simulation temperature,the average δD value of PAHs generated in the hydrous simulation experiments showed an increasing trend,reflecting that the δD value of sedimentary PAHs formed with the participation of diagenetic water media was still closely related to the thermal maturity of organic matter.Comparative studies showed that theδD values of different types of organic compounds produced by hydrous pyrolysis of peat were in the order,PAHs>n-alkanes>methane.

Stable carbon isotopes of gaseous alkanes as genetic indicators inferred from laboratory pyrolysis experiments of various marine hydrocarbon source materials from southern China

Using high pressure and geological condition simulation vessels, we conducted hydrous pyrolysis experiments of kerogen, solid bitumen and liquid hydrocarbons in southern China in order to study the processes of gas generation and derive geo- chemical indicators of gas genesis under approximate pressure and temperature. The results indicate that gas generation productivity of different marine material decreased in the ganic matter （solid bitumen and heavy oil）, and kerogen. order of crude oil （light oil and condensate）, dispersed soluble or- Under identical temperature-pressure regimes, pyrolysates derived from kerogen and dispersed soluble organic matter display drastically different geochemical characteristics. For example, the δ13Cc02-δ13C1 values of gaseous products from dispersed soluble organic matter are greater than 20%o, whereas those from kerogen are less than 20%~. The 813C1 values of pyrolysates from different marine hydrocarbon sources generally increase with pyrolysis temperature, but are always lower than those of the source precursors. The δ13C values of ethane and propane in the pyrolysates also increase with increasing pyrolysis temperature, eventually approaching that of their sources, at peak hydro- carbon generation. At high-over mature stages, the δ13C values of ethane and propane are often greater than those of their sources but close to those of coal gases, and thus become ineffective as gas genetic indicators. Ln（CffC3） can clearly distin- guish kerogen degradation gas from oil cracking gas and Ln（CJC2）-（δ13C1-δ13C2） can be an effective indicator for distinguishing oil cracking gas from dispersed soluble organic matter cracking gas.

Hydrocarbon Generation Characteristics of Coal-measure Source Rocks and their Contribution to Natural Gas:A Case Study of Middle and Lower Jurassic Targets from the Southern Junggar Basin Margin

In order to study the hydrocarbon generation(HCGE)characteristics of coal-bearing basins,the coal-measure source rocks of the Middle Jurassic-Lower Jurassic(MLJ)of the piedmont thrust belt in the southern margin of the Junggar Basin in Northwest China are taken as research objects.More than 60 MLJ samples were collected from outcrops and wells.Total organic carbon(TOC),rock pyrolysis(Rock-Eval),organic petrological,vitrinite reflectance(%Ro),and hydrous pyrolysis were performed to analyze the relevant samples.The pyrolysis gases and liquid products were measured,and then the chemical composition,as well as carbon isotopes of the gases,were analyzed.The results indicate that the MLJ source rocks have the capacity for large-scale gas generation.In addition,for coal-measure source rocks,the heavier the carbon isotope of kerogen(δ^(13)C_(kerogen)),the lower the liquid hydrocarbon and hydrocarbon gas yield,and the easier it is to produce non-hydrocarbon gas.It is worth noting that when theδ^(13)C_(kerogen)in organic matter(OM)is relatively heavier,the fractionation of its products may become weaker in the evolutionary process.The vital contribution of the MLJ source rock to natural gas resources in the study area was further confirmed by comparing it with the Jurassic source gas.

Influence of hydrogen fugacity on thermal transformation of sedimentary organic matter:Implications for hydrocarbon generation in the ultra-depth

Hydrocarbon generation from sedimentary organic matter(SOM)with an original net C oxidation state(OS,-1–-2)is a disproportionation reaction involving the transfer of internal(“organic”)hydrogen and producing oxidized C(up to OS=+4)and reduced C(down to OS=-4).The contribution of extrinsic(“inorganic”)hydrogen could lead to an increase of hydrocarbon yields,but mechanisms and potential sources are still unclear,although it is supported by some experimental evidence.In this study,we have analyzed quantitatively the effect of increasing hydrogen fugacity on the hydrocarbon generation behavior of the Cambro-Ordovician Alum shale at 350℃and 40 MPa.Hydrogen fugacity in the experimental system was controlled by the magnetite-hematite(MH)buffer.The experimental data confirm that a more reducing environment will increase overall hydrocarbon yields and depress CO_(2) yields.The elevated hydrogen fugacity was found to correlate with an increase in δ^(13)C isotopic composition of methane and a decrease of δ^(13)C values in CO_(2),ethane and propane.This demonstrates that elevated hydrogen fugacity constrained by water-rock reaction in sedimentary basins can enhance hydrocarbon generation by“hydrocracking”.This mechanism of hydrocarbon generation by organic-inorganic interactions might be ubiquitous in the deeper sections of sedimentary basins(approximately 4–10 km).Thus,it will extend the connotation of the current theory on petroleum generation.The level of hydrogen fugacity,constrained by water-rock reactions,increases with depth and may thus activate over-maturity sedimentary organic matter to produce more hydrocarbons.The end of hydrocarbon generation will thus move to a greater depth than predicted by the traditional theory.It will be correlated to the capacity of the buffer system,which should,in consequence,be taken into account in petroleum exploration,similar to the hydrogen index(HI)of SOM.This extension of the fundamental theory will help to enlarge the area of petroleum exploration to ultra-deep strata in sedimentary basins.