Gaseous hydrocarbons generated during pyrolysis of petroleum source rocks using unconventional grain-size: implications for natural gas composition

Open-system pyrolysis experiments were performed on a suite of immature to marginally mature source rocks to investigate the influence of kerogen type on primary gas composition and the effect of grain size on gas expulsion characteristics. The pyrolysis of rock powders confirmed that hydrogen-rich kerogens yielded wetter gases than did hydrogen-poor kerogens. Gases detected from the pyrolysis of rock chips were drier than those from powders of equivalent samples. This was due to two processes: the retention and secondary cracking of higher molecular weight pyrolysis products and the preferential expulsion of methane from the rock matrix. These two effects, one chemical the other physical, could be distinguished using a novel approach involving multi-step pyrolysis of rock chips followed by on-line crushing of the residues. The enrichment of methane in natural gas attributed, by earlier workers, to be a consequence of fractionation during secondary migration (post-expulsion) has been proven to be real also during expulsion from source rocks at least for pyrolysis conditions.     

Investigation of the fate of nitrogen in Palaeozoic shales of the Central European Basin

Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ¹⁵N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ¹⁵N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N₂ from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N₂ liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.     

Diversified roles of mineral transformation in controlling hydrocarbon generation process,mechanism,and pattern

Organic matter(OM)is intimately associated with minerals in clay-rich mudstones,leading to widespread organic-mineral interaction during hydrocarbon generation in argillaceous source rocks.What we are concerned is the effects of the different mineral properties on hydrocarbon generation process and mechanism during mineral transformation.In this way,pyrolysis experiments with smectite-octadecanoic acid complexes(Sm-OA and Ex-Sm-OA)were conducted to analyze correlation of mineralogy and pyrolysis behaviors.Based on organicmineral interaction,hydrocarbon generation process was divided into three phases.At 200–300℃,collapse of smectite led to desorption of OM,resulting in high yield of resin and slight increase in saturates.Subsequently,enhanced smectite illitization at 350–450
℃was accompanied with large amounts of saturates and a mere gaseous hydrocarbon.Featured by neoformed plagioclase,ankerite,and illite,500
C saw plenty of asphaltene and methane-rich gaseous hydrocarbons,revealing cracking reactions of OM.Noteworthy is that saturated and gaseous hydrocarbons in Ex-Sm-OA were considerably more than that in Sm-OA during second and third phases.Quantitative calculation of hydrogen revealed organic hydrogen provided by cross-linking of OM could not balance hydrogen consumed by cracking reactions,but supply of inorganic hydrogen ensured cracking could readily occur and consequently greatly promoted hydrocarbon generation.Further investigating characteristics of mineralogy and pyrolytic products,as well as effects of solid acidity on hydrocarbon generation,we concluded desorption of OM and decarboxylation promoted by Lewis acid were dominated at 200–300
C,resulting in lowdegree hydrocarbon generation.While high yield of saturated and gaseous hydrocarbons in second and third phases,together with occurrence of ankerite,indicated predominance of decarboxylation and hydrogenation promoted by Lewis and Br?nsted acid,respectively.Variations in organic-mineral interactions indicated(1)the controls of mineral transformation on hydrocarbon generation process and mechanism include desorption,decarboxylation,and hydrogenation reactions;(2)clay minerals acted as reactants evolving together with OM rather than catalysts.These findings are profoundly significant for understanding the hydrocarbon generation mechanisms,organic-inorganic interactions,and carbon cycle.