Natural Gas Samples Research Articles

CFD Research on Natural Gas Sampling in a Horizontal Pipeline

Accurately determining if the sample parameters from a natural gas pipeline’s sampling system reflect the fluid characteristics of the main pipe has been a significant industry concern for many years. In this paper, samples of natural gas in a horizontal pipeline are investigated. CFD is used in this work and the turbulence is considered in the simulation. Firstly, the critical diameter for particles affected by gravity within such pipeline is determined. And then, the effects of the operation pressure and velocity of sampling branches on sample parameters, and the influence of particle density on these sample parameters, are analyzed. Finally, four different structures of sample branches for natural gas in a horizontal pipeline are compared. It is found that 100 μm is the critical diameter at which particles are affected by gravity; the operating pressure of the sampling branch has a significant impact on the particle mass concentration. The particle density has little impact on the sampling system. Overall, the design of the sampling branches does not cause significant sampling errors. This study provides guidance for optimal sampling in existing natural gas pipelines and enables effective monitoring of particle impurity content and properties in natural gas.

Impacts of CO2-CH4 Mixed Gas on Property of Formation Oil from the Bohai Oilfield

Mechanism analysis and technical scheme optimization on CO2 displacement and CO2 storage are based on the high-pressure physical properties of CO2-added formation oil. Oil and natural gas samples from the BZ25-1 block in the Bohai oilfield were used to conduct high-pressure physical property experiments to explore the impacts of CO2-CH4 mixed gas on the properties of formation oil. After injecting different amounts of mixed gas, the saturated pressure was measured by constant mass expansion test, the viscosity was measured by falling ball method, the expansion coefficient was measured by gas injection expansion test, and the gas–oil ratio and volume coefficient were obtained by single degassing test. The results show that with gas injection, the saturation pressure and dissolved gas–oil ratio of formation oil increase, the volume coefficient and expansion factor go up, while the oil viscosity reduces. With the increase in gas addition, the properties of formation oil continue to improve, but the increase in improvement becomes flat. With the increase in pressure, the amount of dissolved gas in the formation oil will also increase. High-purity CO2 is more helpful to change the properties of formation oil, while the gas mixed with CH4 is more beneficial to elevate the formation energy. For the BZ 25-1 block, the gas injection amount of about 80 mol% is appropriate and the CO2 purity of 60% can well balance the oil properties improvement and the formation pressure elevation.

Helium Geochemical Characteristics and Favorable Zones in the Tarim Basin: Implications for Helium Exploration

Helium is an irreplaceable ore resource for many applications, such as nuclear magnetic resonance, aviation, semiconductors, and nuclear energy. Extracting helium in a free state from natural gas is currently the only economical approach at the industrial level. In this study, we compiled geochemical data of 719 natural gas samples from 36 oil and gas fields in the Tarim basin that include experimental results and previously reported data. Helium is of primarily crustal origin in the Tarim Basin according to helium isotope characteristics (not exceeding 0.1 Ra), except in the Ake gas field that has not more than 7% of mantle helium. Helium concentrations in diverse tectonic units vary considerably. Oil-type gas, on the whole, has a higher helium concentration relative to coal-type gas. Abundant helium flux, a favorable fault system between the source-reservoir system, no strong charging of gaseous hydrocarbons, and the good sealing capacity are important factors that control the formation of helium-rich gas fields. Considering both the helium concentration and natural gas reserves, helium-rich gas fields located in the Southwest Depression and Tabei Uplift can be regarded as the major favorable zones of further deployment for helium extraction.

Downstream natural gas composition across U.S. and Canada: implications for indoor methane leaks and hazardous air pollutant exposures

Previous research has shown that natural gas (NG) leaks from residential appliances are common, affecting greenhouse gas emission inventories and indoor air quality. To study these implications, we collected and analyzed 587 unburned NG samples from 481 residences over 17 North American cities for hydrocarbons, hazardous air pollutants, and organosulfur odorants. Nearly all (97% of) gas samples contained benzene (between-city mean: 2335 ppbv [95% CI: 2104, 2607]) with substantial variability between cities. Vancouver, Los Angeles, Calgary, and Denver had at least 2x higher mean benzene concentrations than other cities sampled, with Vancouver exhibiting a nearly 50x greater mean benzene level than the lowest-concentration city (Boston). We estimate that current U.S. and Canadian emissions inventories are missing an additional 25 000 [95% CI: 19 000, 34 000] and 4000 [95% CI: 3700, 5200] lbs benzene yr−1 through downstream NG leakage, respectively. Concentrations of odorants added for leak detection varied substantially across cities, indicating a lack of standardization. Houston, for instance, had 5x higher mean tert-butyl mercaptan levels than Toronto. Using these odorant measurements, we found that methane emissions as high as 0.0080–0.28 g h−1 and indoor benzene enhancements 0.0096–0.11 ppbv could go undetected by persons with an average sense of smell, with large uncertainties driven by smelling sensitivity, gas composition, and household conditions. We also observed larger leaks (>10 ppm ambient methane) in ∼4% of surveyed homes, confirming that indoor leakage occurs at varying degrees despite the presence of odorants. Overall, our results illustrate the importance of downstream NG composition to understand potential emissions, exposures, and odor-mediated leak detection levels. Given methane’s global warming potency, benzene’s toxicity, and wide variation in smelling abilities, our findings highlight the deficiencies regarding the sole reliance on odorization to alert and protect all occupants from indoor leaks.

Unrecognized extensive charge of microbial gas in the Junggar basin

Different from the Qaidam basin with about 320 billion m3 microbial gas, only limited microbial gases were found from the Junggar basin with similarly abundant type III kerogen. To determine whether microbial gases have not yet identified, natural gas samples from the Carboniferous to Cretaceous in the Junggar basin have been analyzed for chemical and stable isotope compositions. The results reveal some of the gases from the Mahu sag, Zhongguai, Luliang and Wu-Xia areas in the basin may have mixed with microbial gas leading to straight ethane to butane trends with a “dogleg” light methane in the Chung’s plot. Primary microbial gas from degradation of immature sedimentary organic matter is found to occur in the Mahu sag and secondary microbial gas from biodegradation of oils and propane occurred in the Zhongguai, Luliang and Beisantai areas where the associated oils were biodegraded to produce calcites with δ13C values from + 22.10‰ to + 22.16‰ or propane was biodegraded leading to its 13C enrichment. Microbial CH4 in the Mahu sag is most likely to have migrated up from the Lower Wuerhe Formation coal-bearing strata by the end of the Triassic, and secondary microbial gas in Zhongguai and Beisantan uplifts may have generated after the reservoirs were uplifted during the period of the Middle and Late Jurassic. This study suggests widespread distribution of microbial gas and shows the potential to find large microbial gas accumulation in the basin.

Contribution of abiotic methane polymerization of C2+ hydrocarbons in highly mature natural gas reservoirs

The formation and evolution of thermogenic gases were investigated using a combination of intermolecular and intramolecular isotope analyses of 32 natural gas samples collected from the Sichuan and Tarim basins (China) and the Arkoma Basin (USA). Three evolution stages (I–III) were identified: In stage I, hydrocarbon gases are produced through thermal decomposition of organic matter, and kinetic isotope effects in C–C bond breakage control their isotopic distributions; In stage II, C2–C5 hydrocarbons crack with increasing thermal maturity, with their formation and decomposition tending toward thermodynamic equilibrium, and at the end of this stage, the intermolecular and intramolecular isotopic compositions of gaseous hydrocarbons are in thermodynamic equilibrium; A remarkable feature of stage III is the surface-catalyzed abiotic polymerization of methane, which provides a critical origin of C2+ hydrocarbons in this stages and leads to isotopic anomalies in C2+ hydrocarbons, including the reversal of δ13C distributions of C1–C3 and the reverse evolution trend of SP value of propane (i.e., tending to be positive). The contribution of C2+ hydrocarbons from the abiotic polymerization of methane can be determined based on a two-end member model. C2+ hydrocarbons in the Changning shale gases are all generated from abiotic methane polymerization, and the contribution ratio in the Weiyuan shale gases is about 85 %, while, the contribution of C2+ hydrocarbons in dry gases from the Tarim Basin formed by this way is no more than 55 %. High methane abundance, high temperature, and abundant catalyst are beneficial to abiotic methane polymerization.

Stability Analysis of Feed Gas Based on Pressure using Gas Chromatography at PT Badak NGL

As one of the LNG processing companies in Indonesia, Badak NGL plays an important role in product QA and QC. Laboratory and Environment Control PT Badak NGL obtained ISO 17025 as a testing and calibration laboratory. In clause 7.7 of ISO 17025, stated that each laboratory is required to improve competence, one of which is by holding interlaboratory meetings. Currently, PT Badak NGL is participating in the implementation of the Inter Laboratory Meeting (ILM) in East Kalimantan. In the implementation of the ILM 112th and 113th in 2022, several laboratories provide outlier results in natural gas sample testing. Various factors affect the results of natural gas sample testing, one of them is the sample pressure. This research aims to determine the minimum pressure limit in testing feed gas samples. The test is carried out by designing a series of two cylinders to test the repeatability value. The sampling process is based on GPA 2166 and the measurement of repeatability values is based on GPA 2261. This method is effective for determining the limit of repeatability values as a reference for the minimum sample pressure before being injected into Gas Chromatography.

Geochemistry of Liquid Hydrocarbons and Natural Gases Combined with 1D Basin Modeling of the Oligocene Shale Source Rock System in the Offshore Nile Delta, Egypt.

The current study aims to integrate the geochemical characteristics of the Oligocene shale source rock system, oil, condensate, and natural gas samples in the Oligocene sandstone reservoirs from three exploration wells located in the offshore Nile Delta, East Mediterranean Sea, using organic geochemistry and a 1D basin modeling scheme. The Tineh shales exhibit total organic carbon values ranging between 0.90 and 1.89 wt %, along with hydrogen index values in the range of 54-240 mg hydrocarbon/g rock. The geochemical characterization suggests that the shale intervals of the Oligocene Tineh Formation contain type II-III and type III kerogens and, thereby, could be regarded as promising oil- and gas-prone source rocks with high contributions of gas generation potential. The study also reconstructs the 1D thermal and burial history models, showing that the Oligocene Tineh source rock system is in the main oil and wet gas generation phases from the late Miocene to the present time. The simulated basin models reveal the transformation (TR) of 10-50% kerogen to oil during the late Miocene-early Pliocene period and that the Oligocene Tineh source rock system has larger oil generation and expulsion competency, with a TR value of up to 65% during the early Pliocene-Pleistocene time period. The thermogenic gas was also formed during this time and continued to the present day. This study also investigated the presence of oil and condensate in the Oligocene sandstone reservoir samples and revealed that they were generated from mature source rock, ranging from moderately to highly mature stages. This source rock unit was deposited in fluvial to fluvial-deltaic environments under oxic mixed organic conditions and accumulated during the Tertiary time, as evidenced by the presence of the oleanane biomarker dating indicator. The molecular and isotope compositions of natural gases revealed that most of the natural gases in the Oligocene sandstone reservoir are mainly thermogenic methane gases that were generated from mainly mixed organic matter. The thermogenic methane gases were formed mainly from secondary cracking of oil and gas, with small contributions of primary kerogen cracking. The properties of natural gases together with oil and condensate in the Oligocene reservoir rocks suggest that most of the thermogenic methane gases and associated liquid hydrocarbons are derived primarily from the Oligocene shale source rock system and formed by primary kerogen cracking and secondary oil and oil/gas cracking in different thermal maturity stages. Therefore, the Oligocene Tineh Formation can be regarded as self-source generation and self-reservoir rock; hence, an intensive oil exploration and production program can be recommended whenever the Tineh source rock system is is well developed and deeply buried.

The coupling action of helium and nitrogen enrichment and its significance

Helium, a critical rare strategic resource primarily sourced from natural gas, is currently a subject of intense research regarding its enrichment processes within gas reservoirs. Investigating the enrichment of helium is urgent and vital for advancing helium exploration. This study involved the collection of natural gas samples from the Qaidam, Sichuan, and Junggar basins for helium and nitrogen content testing and analysis. The findings were combined with studies on natural gas fractions and helium content in local and international major helium-rich fields. The investigation revealed a strong correlation between helium content and nitrogen presence in helium-rich fields, a phenomenon that also extends to some helium-poor fields. Accordingly, this study proposes a coupling relationship between helium and nitrogen, suggesting that both elements are simultaneously enriched in natural gas. Furthermore, both are associated with groundwater and may share a common origin in source rocks. This proposed coupling relationship holds the potential to unveil the mystery of helium enrichment, offering a new perspective for the exploration of helium-rich resources and providing a foundational framework for helium enrichment theory.

Geochemical characteristics and genesis of the Ordovician sub-salt natural gas in the Ordos Basin, China

A significant amount of natural gas resources has been discovered in the Ordovician reservoirs under a thick layer of gypsum-salt strata as a result of ongoing research into deep natural gas in China’s Ordos Basin, however, the genetic type and source of the Ordovician sub-salt natural gas remain contentious. These limits understanding how the geochemical properties of the natural gas in Ordos Basin have evolved and how to best guide future exploration and development. Based on the components, carbon and hydrogen isotopic ratios of natural gas from the latest exploration wells, combined with the geological background, this study systematically analyzed the genetic types and sources of sub-salt natural gas of the central and eastern Ordos Basin. The results show that the Ordovician natural gas is mainly composed of hydrocarbon gases with low content of heavy hydrocarbons and dryness (CCH4/CCH4+) above 0.95, belonging to typical dry gas. Non-hydrocarbon gases mainly include N2 and CO2, and some natural gas samples contained H2S. The Ordovician sub-salt natural gas is primarily a self-generating and self-preserving oil-cracking gas with relatively high maturity (Ro ranging from 1.5% to 2.1%) mixed with coal-derived gas generated from upper-Paleozoic coal with relatively low maturity (Ro ranging from 1.1% to 1.5%). Due to the dual-source hydrocarbon supply, the Ordovician sub-salt reservoirs provide favorable gas accumulation conditions and development prospects. This study offers a reasonable explanation for the anomalous geochemical characteristics of the Ordovician sub-salt reservoirs in the Ordos Basin, and also may serve as a guide for future exploration of natural gas in the carbonate gypsum-salt sedimentary system in other basins.

PAS-based analysis of natural gas samples.

Photoacoustic spectroscopy (PAS) is well known for the detection of short-chain hydrocarbons, such as methane, ethane and propane, in the ppm (parts per million) or ppb (parts per billion) range. However, in the production process of natural gas and its combustion in gas-fired devices the composition, especially the concentrations of the main alkanes, plays a decisive role. Gas chromatography (GC) is considered the gold standard for natural gas analysis. We present a method to analyze natural gas samples by PAS. Furthermore, we describe a method to prepare storage gas samples, which are usually under atmospheric pressure, for PAS analysis. All measurements are validated by means of GC. The investigation allows conclusions to be drawn to what extent PAS is suitable for the investigation of natural gas samples.

Gas source of the Middle Jurassic Shaximiao Formation in the Zhongjiang large gas field of Western Sichuan Depression: Constraints from geochemical characteristics of light hydrocarbons

The Zhongjiang gas field is a typical large gas field in terrigenous strata of the Western Sichuan Depression. It remains debatable which member of the Upper Triassic Xujiahe Formation served as the source rocks and how significant the member contributed to the gas accumulations in the Zhongjiang gas field. In this study, we analyzed the essential characteristics of the Lower Jurassic source rocks and the geochemical features of light hydrocarbons in natural gas from the 2nd (T3x2) and 4th members (T3x4) of the Upper Triassic Xujiahe Formation (T3x), as well as the Middle Jurassic Shaximiao (J2s) and Qianfoya (J2q) formations. Based on this, we explored the sources of the natural gas in the Zhongjiang gas field and determined the natural gas migration patterns and their effects on the properties of light hydrocarbons in the natural gas. The results indicate that the Lower Jurassic lacustrine source rocks of the Zhongjiang gas field contain humic organic matter, with vitrinite reflectance (Ro) values ranging from 0.86% to 0.98%. Samples meeting the criterion for effective source rocks [total organic carbon (TOC) content ≥0.75%] exhibited an average TOC content of merely 1.02%, suggesting significantly lower hydrocarbon generation potential than source rocks in the underlying T3x, which show higher thermal maturity and TOC contents. For natural gas samples from T3x2, T3x4, J2s, and J2q reservoirs, their C5–7 iso-alkane content was significantly higher than their n-alkane content, and their methylcyclohexane (MCH) index ranged from 59.0% to 77.3%, indicating the predominance of methylcyclohexane in C7 light hydrocarbons. As indicated by the origin identification and gas-source correlation based on the geochemical features of light hydrocarbons, the natural gas in the Zhongjiang gas field is typical coal-derived gas. The gas from the primary pay zone of the Shaximiao Formation, with significantly high K1, (P2 + N2)/C7, and P3/C7 values, predominantly originated from the 5th member of the T3x and migrated in the free phase, with a small amount possibly sourced from the Lower Jurassic source rocks. The dissolution and adsorption during gas migration led to a decrease in the aromatic content in C6–7 light hydrocarbons and an increase in the iso-heptane values. Therefore, their effects must be considered when determining the gas origin and thermal maturity based on the aromatic content in C6–7 light hydrocarbons and iso-heptane values.

Deciphering the origin and secondary alteration of deep natural gas in the Tarim basin through paired methane clumped isotopes

The Tarim Basin is one of the most complex, ancient, and petroliferous deep craton basins in the world. Multiple sets of source rocks, stages of tectonism, and episodes of hydrocarbon generation and accumulation complicate the formation and evolutionary processes of hydrocarbons in the basin, especially for the deeply buried petroleum system at >6000 m depth. Paired clumped isotopes (Δ13CH3D and Δ12CH2D2) allow the investigation of methane isotopic bond ordering, elucidating the methane generation mechanism and its post-generation processes, which can complement studies of the molecular and conventional stable isotopic compositions of gas hydrocarbons in constraining the origin and source of natural gas. This study focused on methane clumped isotopes, and chemical and conventional stable isotopic compositions of natural gas samples from four typical oil and gas regions of the Tarim Basin. Results indicate that these gases are thermogenic gases with relatively high stable isotopic δ values (i.e., −46.1‰ < δ13C–CH4 < −25.9‰, −184‰ < δD-CH4 < −140‰). Most exhibit equilibrium methane clumped isotope signatures at temperatures of 128–257 °C, consistent with the main oil-window to gas-window region. The clumped isotope apparent temperature of equilibrated methane was used to determine its formation temperature, which was applied for gas–source correlations and thermal maturity assessments of the natural gases based on the results of previous basin modeling. The clumped isotope compositions of two gas samples from the Keshen area of the basin are characterized by significant deficits in Δ12CH2D2 values but with similar Δ13CH3D values to those of other equilibrated gases there, indicating the possibility of methane bond re-ordering at high temperatures (>300 °C) exceeding the methane “closure temperature”. Non-equilibrium gases in the Tabei area yielded a plausible Δ13CH3D apparent temperature (<160 °C) with a pronounced deficit in Δ12CH2D2 values, possibly owing to irreversible chemical kinetic processes in thermal cracking of organic matter at early thermal maturity (Ro < 1.5‰) or mixing between thermogenic gases generated at two distinct temperatures (i.e., ∼200 °C and ∼120 °C). Equilibrium clumped isotope signatures also rule out the possible effects of secondary alteration on natural gases in the Hetianhe area that were previously considered in conventional isotope studies. Such findings demonstrate that methane clumped isotopes provide independent and effective indicators of gas–source correlations in deep basins while also elucidating secondary processes that are often under- or over-estimated in conventional stable isotope studies.

Combining methane clumped and bulk isotopes, temporal variations in molecular and isotopic composition, and hydrochemical and geological proxies to understand methane's origin in the Ronda peridotite massifs (Spain)

In serpentinised peridotite and ultramafic rock systems, methane (CH4) origin is frequently considered abiotic, but variable microbial and thermogenic components can also exist. Typically, the origin of CH4 is studied using bulk, 13C/12C and 2H/H isotopic composition, molecular gas composition, occasionally radiocarbon (14C), microbiology and geological context. Recent advances in CH4-clumped isotope methods have yielded novel insights into the formation of CH4: nonetheless, their interpretation in natural gas samples is often uncertain and requires additional research. Here, we study the origin of the gas released in hyperalkaline (pH > 10) springs in the Ronda Peridotite Massifs (southern Spain), combining bulk and clumped CH4 isotopes with molecular gas composition, hydrochemical (Total Organic Carbon and Platinum Group Elements in water), geothermal and geo-structural data. Five springs analysed in 2014 have been re-examined for changes in gas chemistry over time, and three newly discovered gas-bearing springs are analysed for the first time. Regardless of whether springs have microbial or abiotic isotopic fingerprints, we find that bulk CH4 isotopes are fairly stable over a seven-year period. This suggests that the CH4 source(s) or postgenetic processes (such as oxidation and diffusion) have not undergone significant temporal changes. Major variations in H2 and CH4 concentrations in certain springs may be the result of changes in gas pressure and migration intensity. Paired CH4 clumped isotopes (Δ12CH2D2 - Δ13CH3D) were analysed in two bubbling springs, where the presence of CH4 can be interpreted as non-microbial based on 13C enrichment, absence of 14C, and the presence of ethane and propane. However, these isotopes are in disequilibrium, which prevents the quantification of the gas formation temperature. Within the Δ12CH2D2 - Δ13CH3D diagram, the data lie within both the microbialgenic zone, suggested by previous authors, and the abiotic zone that results combining data from laboratory gas synthesis and other natural gas samples. Therefore, attributing a microbial origin to CH4 based only on clumped isotopes is less definite than previously assumed. The amount of Total Organic Carbon appears to be correlated with the origin of CH4, as it is higher in 13C-depleted CH4 samples and lower in 13C-enriched samples. Palladium (Pd) and Rhodium (Rh) dissolved in water (the more soluble Platinum Group Elements) can be a proxy for the chromitite ore deposits contained in plagioclase tectonite layers throughout the investigated area, which may act as catalysts for abiotic CO2 hydrogenation. Clumped isotope disequilibrium and the reported absence of diffuse CH4-bearing fluid inclusions in the peridotites appear to rule out high temperature gas genesis in post-magmatic inclusions. These observations, along with the moderate temperatures at the base of the peridotite massifs and the consistent occurrence of gas along tectonic contacts between serpentinised (H2-bearing) peridotite and carbon-bearing rocks, are compatible with the theory of low-temperature CO2 hydrogenation.

Origin, Migration, and Characterization of Gas in the Xinglongtai Area, Liaohe Subbasin (Northeast China): Insight from Geochemical Evidence and Basin Modeling

Buried hill zones in the rift basins have a significant impact on the enrichment of natural gas resources, and this is of great significance for exploration and development. This study aims to unravel the origins, migration, and dynamic accumulation process of natural gas in the Xinglongtai structural belt, Liaohe Subbasin. A comprehensive geological and geochemical analysis was performed on source rocks and natural gas samples from various geological structures within the Xinglongtai structural belt. Moreover, basin modeling techniques were employed to trace the genesis and migration of natural gas, offering an in-depth understanding of the dynamic process of accumulation. We identified the Fourth Mbr (Es4) and Third Mbr (Es3) of the Shahejie Fm as the main source rocks in the Qingshui and Chenjia Sags. The Es4, primarily Shallow Lacustrine Mudstones, contributed mainly type II organic matter, while the Es3, consisting of Nearshore Subaqueous Fan and Deep Lacustrine Mudstones, contributed mainly type III and type II organic matter, respectively. Two distinct hydrocarbon accumulation systems were observed, one inside and one outside the buried hills. The system outside the buried hill is governed by a complex fault system within the lacustrine basin, resulting in dual-source directions, dual-source rock types, two migration phases, and late-stage accumulation. In contrast, the system within the buried hill primarily involves reservoirs nested in the basement, exhibiting dual-source directions, dual-source rock types, a single migration phase, and early-stage charging. The understanding of this interplay, alongside dynamic simulation of generation, migration, and accumulation, can provide valuable insights for predicting natural gas distribution and accumulation patterns in terrestrial faulted lacustrine basins. This knowledge can guide more effective exploration and development strategies for natural gas.

Chemical and Carbon Isotope Composition Proves Effective as Gas Diagnostic Tool

_ This article, written by JPT Technology Editor Chris Carpenter, contains highlights of paper SPE 209992, “Gas Chemical and Carbon Isotope Composition as a Diagnostic Tool for Energy,” by Zainab Almubarak, SPE, Mohammad Alrowaie, and Feng Lu, Saudi Aramco, et al. The paper has not been peer reviewed. _ Chemical and carbon isotopic compositions of produced gases are useful tools to monitor gas production and to assess their origin, thermal maturity, and migration. In the complete paper, the authors present different geochemical approaches to assess the origin of gases and thermal maturity and to evaluate the effect of adsorption on shale gas during production. Introduction Carbon isotope type curves constructed for compounds from methane through n-pentane can be used to group gases into distinct families and correlate them to their source rocks. Large variations in carbon isotope ratios exist among the natural gas compounds, which are caused by isotopic fractionation between the sedimentary organic matter (kerogen) and each individual hydrocarbon compound. During the generation of hydrocarbons from kerogen, cracking of 12C-12C bonds requires slightly less energy than 13C-12C bonds. Thus, hydrocarbons will be enriched in 12C relative to the kerogen. Methane, which contains only one carbon atom, shows the greatest fractionation and will have the most negative δ13C value (most enriched in 12C). Ethane through pentane show progressively less fractionation (less negative δ13C values), with the latter usually having a δ13C value close to that of kerogen (and associated oil). The magnitude of the fractionation effect will vary depending on the type of kerogen (i.e., Type I, II, IIS, or III), the temperature during hydrocarbon generation, and the adsorption/desorption effect. Thus, gases generated from different source rocks often have distinctive carbon isotope type curves. In shale gas (unconventional reservoirs), two different types of gases coexist—free gas and adsorbed gas. Free gas occurs in natural fractures and matrix pores, whereas adsorbed gas is noted on the surface of pores. During the early stages of production, free gas accounts for most produced gas. The adsorbed gas starts in mid-late stages but maintains high and stable production. In this study, the authors use carbon isotopic compositions of light hydrocarbons (C1–C5) to assess origin and thermal maturity and to compare different gases derived from unconventional reservoirs. Moreover, carbon isotopes are used to assess migration paths and to monitor gas production in unconventional shale gas reservoirs. The gas samples were collected periodically from the same interval to monitor any isotope variation and evaluate the effect of gas adsorption. Methods Pressurized samples of natural gas were collected from conventional and unconventional reservoirs through production tests, drillstem tests, or downhole samplers and analyzed for chemical composition. For the conventional study, a total of 13 gas samples were collected from different reservoirs (A, B, C, D, and J): four gas samples from Reservoir A, two gas samples from Reservoir B, three gas samples from Reservoir C, three gas samples from Reservoir D, and one gas sample from Reservoir J. Gases derived from Reservoirs A, B, and J are younger and shallower than gases derived from Reservoirs C and D (older and deeper). For the unconventional study, seven gas samples were collected periodically from the same shale interval (Reservoir W) from the same well (Well Y) on different dates to monitor any isotope variation.

Determination of intermolecular and intramolecular isotopic compositions of low-abundance gaseous hydrocarbons using an online hydrocarbon gas concentration method

The stable isotopic composition of natural gas can be used to identify its origin and source. However, low concentrations of gaseous hydrocarbons in high-mature natural and shale gases hinder accurate determination of their compound- and position-specific isotopic compositions. In this study, an online C2+ hydrocarbon gas concentration system combined with gas chromatography–isotope ratio mass spectrometry (GC–IRMS) or gas chromatography–pyrolysis–gas chromatography–isotope ratio mass spectrometry (GC–Py–GC–IRMS) was developed to determine compound- and position-specific isotopic compositions of low-abundance gaseous hydrocarbons. The lower limit of the gas concentration required for isotope ratio determination using the online concentration system is 0.001% (0.003%) for compound-specific carbon (hydrogen) isotopes and 0.005% for position-specific carbon isotopes and is thus applicable to most natural gas samples. The online concentration technique does not cause significant isotopic fractionation effects, and the combination with GC–IRMS and GC–Py–GC–IRMS can accurately and precisely determine the compound-specific δ13C and δD values of low-content C2+ gaseous hydrocarbons and the position-specific δ13C values (δ13Ca, δ13Cb, and SP values) of propane in low-content propane samples, respectively. The application of our method to two natural gas samples from the Ordos and Sichuan basins further confirms that the online concentration method allows simple and rapid determination of the compound- and position-specific isotopic compositions of low-abundance gaseous hydrocarbons.

Portable chemical detection platform for on-site monitoring of odorant levels in natural gas

The adequate odorization of natural gas is critical to identify gas leaks and to reduce accidents. To ensure odorization, natural gas utility companies collect samples to be processed at core facilities or a trained human technician smells a diluted natural gas sample. In this work, we report a detection platform that addresses the lack of mobile solutions capable of providing quantitative analysis of mercaptans, a class of compounds used to odorize natural gas. Detailed description of the platform hardware and software components is provided. Designed to be portable, the platform hardware facilitates extraction of mercaptans from natural gas, separation of individual mercaptan species, and quantification of odorant concentration, with results reported at point-of-sampling. The software was developed to accommodate skilled users as well as minimally trained operators. Detection and quantification of six commonly used mercaptan compounds (ethyl mercaptan, dimethyl sulfide, n-propylmercaptan, isopropyl mercaptan, tert‑butyl mercaptan, and tetrahydrothiophene) at typical odorizing concentrations of 0.1–5 ppm was performed using the device. We demonstrate the potential of this technology to ensure natural gas odorizing concentrations throughout distribution systems.

Identifying gas mixtures based on acoustic relaxation spectroscopy and attention recurrent neural network

Qualitative and quantitative detection of the composition of gaseous mixtures remains challenging in acoustic gas sensing. Traditional feature-based methods attempt to extract local features from complex numerical models, but tend to ignore crucial information owing to the lack of a global view. Deep learning can achieve competitive performance in acquiring information. This study proposes an attention recurrent gas detection (ARGD) neural network for gas sensing based on acoustic relaxation spectroscopy. This model combines a bidirectional gated recurrent unit to extract gas information and an attention module to determine the crucial features. The processed features were input into a double-task network for simultaneous prediction of the types of gas and their respective concentrations. Samples of natural gas involving CO2, CH4, and N2 were identified with six acoustic sensor pairs. The simulated and experimental results demonstrate the effectiveness and robustness of the proposed model. A classification accuracy of up to 99% was achieved, with the root mean squared error declining to 0.67%. The combination of deep learning and acoustic relaxation spectroscopy provides new ideas for further research of acoustic gas detection.

Experimental analysis and performance of refinery fuel gas on lean and rich fuel–air premixed combustion

Refinery fuel gas (RFG) is a blend of gas streams produced as by-products in various refinery processes. Large amounts of RFG are burning around the clock in the air with thermal energy waste and adverse effects on the environment. The present work investigates experimentally the performance of different compositions of RFG from lean to rich fuel–air premixed combustion, with focus on an efficient and low-emission combustion for its heat recovery. Radiant and porous media burners are the combustion technologies used. For the radiant burner, fuel compositions are propane and ethane with an average ethane ratio of 5%, 10%, and 15% (E05, E10, E15 respectively), which are contrasted with pure propane and liquefied petroleum gas (LPG). The pure gases fluxes are fixed as 1 and 2 m3/h for low and high flame configurations, respectively. The lean fuel–air flames investigated are stable for all ethane ratios with low carbon monoxide (CO) and nitrate oxides (NOx) emissions. Maximum temperature is given by pure propane flame (besides LPG), followed by E05, E10 and E15, for both flame configurations. Then, the radiation heat flux of ethane mixtures exhibits a reduction in comparison with LPG. For the porous media burner, lean and rich fuel–air mixture composed by natural gas (NG, 97% methane) and representative flue samples of 55% (C1) and 70% (C2) methane concentration are tested. The C1 and C2 flue samples present high combustion temperatures, showing a positive swap from NG. The NG rich-fuel combustion exposes high hydrogen conversion (27%) at high equivalence ratio (ϕ=1.8). Finally, for both burners lean fuel–air premixed combustion shows high combustion efficiencies, 74.8% with E05 and 80.7% with C1 flue sample.