Low-temperature gas from marine shales: wet gas to dry gas over experimental time

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300° below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100°C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C5, 2% C1) to predominantly light hydrocarbons (56% C1, 8% C5), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results

Thermal modelling of gas generation and retention in the Jurassic organic-rich intervals in the Darquain field, Abadan Plain, SW Iran

The petroleum system with Jurassic source rocks is an important part of the hydrocarbons discovered in the Middle East. Limited studies have been done on the Jurassic intervals in the 26,500 km2 Abadan Plain in south-west Iran, mainly due to the deep burial and a limited number of wells that reach the basal Jurassic successions. The goal of this study was to evaluate the Jurassic organic-rich intervals and shale gas play in the Darquain field using organic geochemistry, organic petrography, biomarker analysis, and basin modelling methods. This study showed that organic-rich zones present in the Jurassic intervals of Darquain field could be sources of conventional and unconventional gas reserves. The organic matter content of samples from the organic-rich zones corresponds to medium-to-high-sulphur kerogen Type II-S marine origin. The biomarker characteristics of organic-rich zones indicate carbonate source rocks that contain marine organic matter. The biomarker results also suggest a marine environment with reducing conditions for the source rocks. The constructed thermal model for four pseudo-wells indicates that, in the kitchen area of the Jurassic gas reserve, methane has been generated in the Sargelu and Neyriz source rocks from Early Cretaceous to recent times and the transformation ratio of organic matter is more than 97%. These organic-rich zones with high initial total organic carbon (TOC) are in the gas maturity stage [1.5–2.2% vitrinite reflectance in oil (Ro)] and could be good unconventional gas reserves and gas source rocks. The model also indicates that there is a huge quantity of retained gas within the Jurassic organic-rich intervals

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAlH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation