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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Center for Efficiency in Sustainable Energy Systems

The main goal of the Center for Efficiency in Sustainable Energy Systems is to produce a methodology that evaluates a variety of energy systems. Task I. Improved Energy Efficiency for Industrial Processes: This task, completed in partnership with area manufacturers, analyzes the operation of complex manufacturing facilities to provide flexibilities that allow them to improve active-mode power efficiency, lower standby-mode power consumption, and use low cost energy resources to control energy costs in meeting their economic incentives; (2) Identify devices for the efficient transformation of instantaneous or continuous power to different devices and sections of industrial plants; and (3) use these manufacturing sites to demonstrate and validate general principles of power management. Task II. Analysis of a solid oxide fuel cell operating on landfill gas: This task consists of: (1) analysis of a typical landfill gas; (2) establishment of a comprehensive design of the fuel cell system (including the SOFC stack and BOP), including durability analysis; (3) development of suitable reforming methods and catalysts that are tailored to the specific SOFC system concept; and (4) SOFC stack fabrication with testing to demonstrate the salient operational characteristics of the stack, including an analysis of the overall energy conversion efficiency of the system. Task III. Demonstration of an urban wind turbine system: This task consists of (1) design and construction of two side-by-side wind turbine systems on the YSU campus, integrated through power control systems with grid power; (2) preliminary testing of aerodynamic control effectors (provided by a small business partner) to demonstrate improved power control, and evaluation of the system performance, including economic estimates of viability in an urban environment; and (3) computational analysis of the wind turbine system as an enabling activity for development of smart rotor blades that contain integrated sensor/actuator/controller modules to enhance energy capture and reduce aerodynamic loading and noise by way of virtual aerodynamic shaping. Accomplishments: Task I. Improved Energy Efficiency for Industrial Processes: We organized an energy management training session held on February 22, 2011, which was advertised through a regional manufacturing association to provide wide-ranging notification. Over two dozen companies were represented a the seminar, ranging from heavy manufacturing businesses with $5,000,000 per year energy expenses, to small, light manufacturing facilities. Task 2. Landfill Fuel Cell Power Generation Solid Oxide Fuel Cells (SOFCs) were constructed and evaluated as a means of obtaining electrical energy from landfill gas. Analysis of landfill gas. Attempts at collecting gas samples at the landfill and evaluating them on campus were still unsuccessful. Even a Teflon® sample bag would lose its H2S content. Evaluation of Gas Clean-up We consider this a confirmation of the CO2 effect on the solubility of H2S in water making much less sulfide available for the photocatalyst. It also means that another method should be employed to clean up landfill gas. Nonetheless, composition of impurities in landfill gas was reduced sufficiently to allow successful operation of the test fuel cell. Comparison to a PEM fuel cell system. If a PEMFC were to be operated with landfill gas as the fuel, the gas would have to be treated for sulfur removal, and then processed in a reformer large enough to drive the equilibrium far toward the products, so that negligible CO would flow into the fuel cell. Analysis of a fuel cell running on landfill gas. Using a Gow-Mac gas chromatograph with a thermal conductivity detector, unambiguous determination of CO can be made, at least as a primary constituent Task 3: Task 3 Plasma Controlled Turbine Blades Wind Turbine Selection. After carefully reviewing the various model available in the market the team selected the ARE 110 (2.5kW). The ARE 110 provides a very long life with little maintenance due to their relatively low rotational speeds (low RPM). The turbines large swept area (10.2ms2/110sq.ft), high-efficiency blades, purpose built alternator, and optimized power electronics ensure maximum energy capture from a wide range of wind speeds. Two wind turbines were installed side-by-side at the Melnick Hall site to compare their performance. Evaluate and Optimize Aerodynamically Enhanced Turbine Blades Due to delays in the installation of the wind turbines, no actual data was obtained within the contract period. At this time, the turbines are installed and operational at YSU with standard blades. We are in contact with Orbital Research and in discussion as to how best the required data can be obtained.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2015

Solute concentrations influence microbial methanogenesis in coal-bearing strata of the Cherokee basin, USA

In this study, microorganisms have contributed significantly to subsurface energy resources by converting organic matter in hydrocarbon reservoirs into methane, the main component of natural gas. In this study, we consider environmental controls on microbial populations in coal-bearing strata of the Cherokee basin, an unconventional natural gas resource in southeast Kansas, USA. Pennsylvanian-age strata in the basin contain numerous thin (0.4–1.1 m) coalbeds with marginal thermal maturities (0.5–0.7% R o ) that are interbedded with shale and sandstone. We collected gas, water, and microbe samples from 16 commercial coalbed methane wells for geochemical and microbiological analysis. The water samples were Na–Cl type with total dissolved solids (TDS) content ranging from 34.9 to 91.3 g L –1 . Gas dryness values [C 1 /(C 2 + C 3 )] averaged 2640 and carbon and hydrogen isotope ratios of methane differed from those of carbon dioxide and water, respectively, by an average of 65 and 183‰. These values are thought to be consistent with gas that formed primarily by hydrogenotrophic methanogenesis. Results from cultivation assays and taxonomic analysis of 16S rRNA genes agree with the geochemical results. Cultivable methanogens were present in every sample tested, methanogen sequences dominate the archaeal community in each sample (avg 91%), and few archaeal sequences (avg 4.2%) were classified within Methanosarcinales , an order of methanogens known to contain methylotrophic methanogens. Although hydrogenotrophs appear dominant, geochemical and microbial analyses both indicate that the proportion of methane generated by acetoclastic methanogens increases with the solute content of formation water, a trend that is contrary to existing conceptual models. Consistent with this trend, beta diversity analyses show that archaeal diversity significantly correlates with formation water solute content. In contrast, bacterial diversity more strongly correlates with location than solute content, possibly as a result of spatial variation in the thermal maturity of the coalbeds.

03 NATURAL GAS↗
DOE OSTI2018

Elemental mapping and geochemical characterization of gas producing shales by laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) has been used for the analysis of hydrocarbon bearing shale samples. Shale samples taken from a Marcellus gas well at depths ranging from 7498 to 7551 ft (2285.4–2301.5 m) were analyzed by LIBS using an 81 × 81 grid pattern covering an 8 × 8 mm area. The data collected from these experiments were used to construct 2D elemental maps for each sample including the hydrocarbon forming elements C and H. Results show that the spatial elemental composition of the shale varies due to the matrix of the rock, and as a function of the sample depth. The accuracy of the analysis was confirmed by analyzing a shale sample of known elemental concentrations and obtaining a good agreement between analyzed and reference values. It has been shown that LIBS can be used to determine elemental composition variations in hydrocarbon bearing shales in a laboratory setting. In conclusion, extending this capability into wellbores will enable producers to rapidly target resources with greater accuracy.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2010

Hydrothermal Liquefaction of Biomass

Hydrothermal liquefaction technology is describes in its relationship to fast pyrolysis of biomass. The scope of work at PNNL is discussed and some intial results are presented. HydroThermal Liquefaction (HTL), called high-pressure liquefaction in earlier years, is an alternative process for conversion of biomass into liquid products. Some experts consider it to be pyrolysis in solvent phase. It is typically performed at about 350 C and 200 atm pressure such that the water carrier for biomass slurry is maintained in a liquid phase, i.e. below super-critical conditions. In some applications catalysts and/or reducing gases have been added to the system with the expectation of producing higher yields of higher quality products. Slurry agents ('carriers') evaluated have included water, various hydrocarbon oils and recycled bio-oil. High-pressure pumping of biomass slurry has been a major limitation in the process development. Process research in this field faded away in the 1990s except for the HydroThermal Upgrading (HTU) effort in the Netherlands, but has new resurgence with other renewable fuels in light of the increased oil prices and climate change concerns. Research restarted at Pacific Northwest National Laboratory (PNNL) in 2007 with a project, 'HydroThermal Liquefaction of Agricultural and Biorefinery Residues' with partners Archer-Daniels-Midland Company and ConocoPhillips. Through bench-scale experimentation in a continuous-flow system this project investigated the bio-oil yield and quality that could be achieved from a range of biomass feedstocks and derivatives. The project was completed earlier this year with the issuance of the final report. HydroThermal Liquefaction research continues within the National Advanced Biofuels Consortium with the effort focused at PNNL. The bench-scale reactor is being used for conversion of lignocellulosic biomass including pine forest residue and corn stover. A complementary project is an international collaboration with Canada to investigate kelp (seaweed) as a biomass feedstock. The collaborative project includes process testing of the kelp in HydroThermal Liquefaction in the bench-scale unit at PNNL. HydroThermal Liquefaction at PNNL is performed in the hydrothermal processing bench-scale reactor system. Slurries of biomass are prepared in the laboratory from whole ground biomass materials. Both wet processing and dry processing mills can be used, but the wet milling to final slurry is accomplished in a stirred ball mill filled with angle-cut stainless steel shot. The PNNL HTL system, as shown in the figure, is a continuous-flow system including a 1-litre stirred tank preheater/reactor, which can be connected to a 1-litre tubular reactor. The product is filtered at high-pressure to remove mineral precipitate before it is collected in the two high-pressure collectors, which allow the liquid products to be collected batchwise and recovered alternately from the process flow. The filter can be intermittently back-flushed as needed during the run to maintain operation. By-product gas is vented out the wet test meter for volume measurement and samples are collected for gas chromatography compositional analysis. The bio-oil product is analyzed for elemental content in order to calculate mass and elemental balances around the experiments. Detailed chemical analysis is performed by gas chromatography-mass spectrometry and 13-C nuclear magnetic resonance is used to evaluate functional group types in the bio-oil. Sufficient product is produced to allow subsequent catalytic hydroprocessing to produce liquid hydrocarbon fuels. The product bio-oil from hydrothermal liquefaction is typically a more viscous product compared to fast pyrolysis bio-oil. There are several reasons for this difference. The HTL bio-oil contains a lower level of oxygen because of more extensive secondary reaction of the pyrolysis products. There are less amounts of the many light oxygenates derived from the carbohydrate structures as they have been further reacted to phenolic Aldol condensation products. The bio-oil is more hydrophobic because of the lower oxygen content and resulting lower polarity and therefore has a lower amount of dissolved water. Without the light oxygenates acting as solvents along with the water, the bio-oil product is much more viscous. Related results are that the bio-oil is less dense and has a higher energy content. These differences in properties led to the earlier held belief that the HTL bio-oils could be upgraded by catalytic hydroprocessing in a manner more similar to simple petroleum hydrotreating. Some initial results from the HydroThermal Liquefaction of kelp are shown in Table 1. The experiments were performed with kelp slurries of 5-13 wt.% dry solids in water. Oil yields from kelp are low at 24% on ash-free basis but up to 41% calculated on a carbon basis. The bulk of the rest of the carbon ends up dissolved in the water stream.

02 PETROLEUM↗
DOE OSTI2023

Analysis of gas storage and transport in Eagle Ford shale using pressure pulse decay measurements with He, Kr and CO 2

Detailed characterization of gas transport and storage in low-permeability and organic-rich shales is associated with an array of challenges due to the complex morphology of the pore space, representing a broad range of pore sizes, combined with the heterogeneous fabric of the shale matrix. These factors, and their interplay during gas transport and sorption, complicate a) the analysis of shale samples at the laboratory scale (~ up to a ft. In length), and b) the prediction of natural gas production and carbon sequestration potential at larger scales. Here, in this work, tandem experiments with inert (helium – He) and adsorbing (krypton - Kr and carbon dioxide - CO 2 ) gases were performed and analyzed to develop an efficient workflow for characterizing and modeling transport and sorption at the laboratory scale. In particular, pressure pulse-decay (PPD) measurements were conducted on an Eagle Ford shale core sample at room temperature using He, Kr, and CO 2 . PPD measurements with He (a non-sorbing gas) were employed to probe the overall porosity, including natural fractures, microcracks, mesopores, and micropores. A triple-porosity model (TPM) was adopted to interpret the gas transport in the shale sample: The pore space is represented by three interacting continua, including macropores (larger fractures), mesopores (including microcracks), and micropores. To facilitate the application of the TPM, a modified analytical approach is introduced to extract effective transport parameters (in terms of the characteristic time for transport at relevant porosity levels) directly from the PPD measurements with He. To validate the modeling approach, model parameters extracted from two He PPD measurements are demonstrated to provide excellent agreement with a 3rd He PPD measurement performed at a higher pressure. The effective transport parameters, extracted from the He experiments, were subsequently converted for application to the Kr and CO 2 PPD experiments, by accounting for relevant transport modes and differences in fluid properties. Excess adsorption isotherms were extracted from the equilibrium pressures of the Kr and CO 2 PPD experiments using the He pore volume as a baseline. These adsorption isotherms were then integrated into the TPM to predict combined gas transport and sorption for Kr and CO 2 , with transport coefficients translated from the He measurements. The predictions for Kr and CO 2 are demonstrated to be in excellent agreement with the experimental observations. This, in turn, demonstrates that the proposed analytical approach provides for an effective characterization of mass transfer rates in shales, that can be applied directly in a TPM representation of mass transfer and sorption.

58 GEOSCIENCES↗
DOE OSTI2014

The contribution of lubricant to the formation of particulate matter with reactivity controlled compression ignition in light-duty diesel engines

Reactivity controlled compression ignition (RCCI) has been shown in single- and multi-cylinder engine research to achieve high thermal efficiencies with ultra-low NO X and soot emissions. The nature of the particulate matter (PM) produced by RCCI operation has been shown in recent research to be different than that of conventional diesel combustion and even diesel low-temperature combustion. Previous research has shown that the PM from RCCI operation contains a large amount of organic material that is volatile and semi-volatile. However, it is unclear if the organic compounds are stemming from fuel or lubricant oil. The PM emissions from dual-fuel RCCI were investigated in this study using two engine platforms, with an emphasis on the potential contribution of lubricant. Both engine platforms used the same base General Motors (GM) 1.9-L diesel engine geometry. The first study was conducted on a single-cylinder research engine with primary reference fuels (PRFs), n-heptane, and iso-octane. The second study was conducted on a four-cylinder GM 1.9-L ZDTH engine which was modified with a port fuel injection (PFI) system while maintaining the stock direct injection fuel system. Multi-cylinder RCCI experiments were run with PFI gasoline and direct injection of 2-ethylhexyl nitrate (EHN) mixed with gasoline at 5 % EHN by volume. In addition, comparison cases of conventional diesel combustion (CDC) were performed. Particulate size distributions were measured, and PM filter samples were collected for analysis of lube oil components. Triplicate PM filter samples (i.e., three individual filter samples) for both gas chromatography-mass spectroscopy (GC-MS; organic) analysis and X-ray fluorescence (XRF; metals) were obtained at each operating point and queued for analysis of both organic species and lubricant metals. Here, the results give a clear indication that lubricants do not contribute significantly to the formation of RCCI PM.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2019

On-Line Monitoring and Real-Time Characterization of Low Level Waste and Off-Gas Condensate Samples using Raman Spectroscopy - 19274

The demand for Hanford waste property analysis is expected to significantly increase as the U.S. Department of Energy River Protection Project progresses toward transferring waste to the Hanford Waste Treatment and Immobilization Plant. The analysis of waste includes chemical, radionuclide, and physical property characterizations, with the goal of achieving safe/informed transfer and processing. Waste sampling followed by offline laboratory analysis is the current baseline analytical approach. The addition of field-deployed/in situ instruments has the potential to provide improvements and benefits over offline analysis in the areas of 1) Worker Safety: by reducing the need for sampling and thereby reducing the need for worker interaction with waste during sample handling; 2) Operational Efficiency: by reducing analysis turnaround times and offsetting demand on analytical laboratories; and 3) Accuracy: continuous analysis of a flowing waste stream allows cumulative results to be produced for the batch, which is more representative than discrete samples of batch properties. This paper describes the development and application of an online monitor to provide chemical characterizations; specifically, Raman spectroscopy is utilized to identify and quantify tank components. Accurate quantification is achieved through the use of chemometric analysis, which can be configured to provide real-time analysis in field deployment settings. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Hydrogen Extremely Low Probability of Rupture Version 1

SAND2024-08511O The Hydrogen Extremely Low Probability of Rupture (HELPR) software toolkit provides probabilistic fracture assessments of natural gas infrastructure for transporting hydrogen. Using probabilistic sampling and sensitivity analysis—along with engineering fatigue and fracture mechanics— the software develops models that can predict structural integrity measures for natural gas pipelines under stress. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Schroeder, Benjamin↗
DOE OSTI2016

Determination of elemental composition of shale rocks by laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) is used for elemental characterization of outcrop samples from the Marcellus Shale. Powdered samples were pressed to form pellets and used for LIBS analysis. Partial least squares regression (PLS-R) and univariate calibration curves were used for quantification of analytes. The matrix effect is substantially reduced using the partial least squares calibration method. Predicted results with LIBS are compared to ICP-OES results for Si, Al, Ti, Mg, and Ca. As for C, its results are compared to those obtained by a carbon analyzer. Relative errors of the LIBS measurements are in the range of 1.7 to 12.6%. The limits of detection (LODs) obtained for Si, Al, Ti, Mg and Ca are 60.9, 33.0, 15.6, 4.2 and 0.03 ppm, respectively. An LOD of 0.4 wt.% was obtained for carbon. Finally, this study shows that the LIBS method can provide a rapid analysis of shale samples and can potentially benefit depleted gas shale carbon storage research.

58 GEOSCIENCES↗
DOE OSTI2018

On-Line Monitoring and Real-Time Characterization of Low Level Waste and Off-Gas Condensate Samples using Raman Spectroscopy

The demand for Hanford waste property analysis is expected to significantly increase as the U.S. Department of Energy River Protection Project progresses toward transferring waste to the Hanford Waste Treatment and Immobilization Plant. The analysis of waste includes chemical, radionuclide, and physical property characterizations, with the goal of achieving safe/informed transfer and processing. Waste sampling followed by offline laboratory analysis is the current baseline analytical approach. The addition of field-deployed/in situ instruments has the potential to provide improvements and benefits over offline analysis in the areas of 1) Worker Safety: by reducing the need for sampling and thereby reducing the need for worker interaction with waste during sample handling; 2) Operational Efficiency: by reducing analysis turnaround times and offsetting demand on analytical laboratories; and 3) Accuracy: continuous analysis of a flowing waste stream allows cumulative results to be produced for the batch, which is likely to be more representative than discrete samples of batch properties. This paper describes the development and application of an online monitor to provide chemical characterizations; specifically, Raman spectroscopy is utilized to identify and quantify tank components. Accurate quantification is achieved through the use of chemometric analysis, which can be configured to provide real-time analysis in field deployment settings.

Lines, Amanda M.↗
DOE OSTI2021

X-ray diffraction, differential scanning calorimetry and evolved gas analysis of aged plutonium tetrafluoride (PuF4)

A 30 year-old PuF4 sample consisting of brown powder (PuF4-b) and pink granules (PuF4-p) was analyzed. X-ray difraction shows the bulk is comprised of three compounds: PuF4, PuO2, and PuF4·1.6H2O. Broadening of PuF4 XRD peaks suggests possible a-damage. After annealing at 650 °C, crystalline PuF4 and PuO2 remain. Thermogravimetric analysis and diferential scanning calorimetry—with simultaneous evolved gas analysis—of the separated PuF4-p and PuF4-b components reveal a distinct sequence of reactions. Dehydration occurs between~90 and 300 °C. Exothermic annealing of the a-damage occurs in two stages: at 350–355 °C and at 555–558 °C. Hydrofuoric acid, fuorine and helium desorb during the frst exotherm. Above 700 °C, PuF4 reacts with PuO2, resulting in oxygen release and mass loss.

PuF4, dsc, differential scanning calorimetry, plut↗
DOE OSTI2023

Investigation of desorption of hydrogen gas from polymer matrix using thermal desorption analysis and finite element modeling

Polymer materials are used widely as sealing materials and liners in hydrogen storage and transportation infrastructure. During operating conditions, polymers are exposed to high pressure hydrogen gas periodically. When in contact, the hydrogen gas diffuses through the polymer material with ease due to its smaller sized molecules compared to the polymer molecules. In the event of rapid decompression of outside hydrogen gas, the hydrogen molecules within the polymer diffuse out. This process is known as the desorption of polymer and can cause blisters or cracking causing permanent damage to the polymer. Here, we used a combined experimental and modeling approach to investigate the desorption of the hydrogen gas in the polymer. Thermal desorption analysis (TDA) experiments were performed on the polymer sample exposed to the high-pressure hydrogen gas to measure the diffusion coefficient and equilibrium hydrogen concentration. Experiments also provided the quantity of hydrogen within the polymer during the desorption process which followed Fick’s law. However, for higher pressurization values, some anomaly was observed in the quantity of hydrogen remaining in the polymer sample. A continuum mechanics based coupled diffusion–deformation-damage model was deployed to simulate the gas desorption process in the material using the finite element method to understand its effect on the material. It was found that the anomaly in TDA results were due to the blister formation on the polymer surface which resulted in longer hydrogen retention. Simulations also showed that blister formation can be affected by multiple parameters such as the addition of filler particles, and pre-existing cavity size.

36 MATERIALS SCIENCE↗
DOE OSTI2011

June 2011 Natural Gas and Produced Water Sampling at the Gasbuggy, New Mexico, Site

Annual natural gas and produced water monitoring was conducted for gas wells adjacent to Section 36, where the Gasbuggy test was conducted, in accordance with the draft Long-Term Surveillance and Maintenance Plan for the Gasbuggy Site, Rio Arriba County, New Mexico. Sampling and analysis were conducted as specified in the Sampling and Analysis Plan for U.S. Department of Energy Office of Legacy Management Sites (LMS/PLN/S04351, continually updated). Natural gas samples were collected for tritium and carbon-14 analyses. Produced water samples were collected and analyzed for tritium, gamma-emitting radionuclides (by high-resolution gamma spectrometry), gross alpha, and gross beta. A duplicate produced water sample was collected from well 30-039-21743. Produced water samples were not collected at locations 30-039-30161 and 30-039-21744 because of the lack of water. Samples were not collected from location 30-039-29988 because the well was shut-in.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Co-registered Topographical, Band Excitation Nanomechanical, and Mass Spectral Imaging Using a Combined Atomic Force Microscopy/Mass Spectrometry Platform

The advancement of a hybrid atomic force microscopy/mass spectrometry imaging platform demonstrating for the first time co-registered topographical, band excitation nanomechanical, and mass spectral imaging of a surface using a single instrument is reported. The mass spectrometry-based chemical imaging component of the system utilized nanothermal analysis probes for pyrolytic surface sampling followed by atmospheric pressure chemical ionization of the gas phase species produced with subsequent mass analysis. We discuss the basic instrumental setup and operation and the multimodal imaging capability and utility are demonstrated using a phase separated polystyrene/poly(2-vinylpyridine) polymer blend thin film. The topography and band excitation images showed that the valley and plateau regions of the thin film surface were comprised primarily of one of the two polymers in the blend with the mass spectral chemical image used to definitively identify the polymers at the different locations. Data point pixel size for the topography (390 nm x 390 nm), band excitation (781 nm x 781 nm), mass spectrometry (690 nm x 500 nm) images was comparable and submicrometer in all three cases, but the data voxel size for each of the three images was dramatically different. The topography image was uniquely a surface measurement, whereas the band excitation image included information from an estimated 10 nm deep into the sample and the mass spectral image from 110-140 nm in depth. Moreover, because of this dramatic sampling depth variance, some differences in the band excitation and mass spectrometry chemical images were observed and were interpreted to indicate the presence of a buried interface in the sample. The spatial resolution of the mass spectral image was estimated to be between 1.5 m 2.6 m, based on the ability to distinguish surface features in that image that were also observed in the other images.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Characterization of Tight Gas Reservoir Pore Structure Using USANS/SANS and Gas Adsorption Analysis

Small-angle and ultra-small-angle neutron scattering (SANS and USANS) measurements were performed on samples from the Triassic Montney tight gas reservoir in Western Canada in order to determine the applicability of these techniques for characterizing the full pore size spectrum and to gain insight into the nature of the pore structure and its control on permeability. The subject tight gas reservoir consists of a finely laminated siltstone sequence; extensive cementation and moderate clay content are the primary causes of low permeability. SANS/USANS experiments run at ambient pressure and temperature conditions on lithologically-diverse sub-samples of three core plugs demonstrated that a broad pore size distribution could be interpreted from the data. Two interpretation methods were used to evaluate total porosity, pore size distribution and surface area and the results were compared to independent estimates derived from helium porosimetry (connected porosity) and low-pressure N{sub 2} and CO{sub 2} adsorption (accessible surface area and pore size distribution). The pore structure of the three samples as interpreted from SANS/USANS is fairly uniform, with small differences in the small-pore range (< 2000 {angstrom}), possibly related to differences in degree of cementation, and mineralogy, in particular clay content. Total porosity interpreted from USANS/SANS is similar to (but systematically higher than) helium porosities measured on the whole core plug. Both methods were used to estimate the percentage of open porosity expressed here as a ratio of connected porosity, as established from helium adsorption, to the total porosity, as estimated from SANS/USANS techniques. Open porosity appears to control permeability (determined using pressure and pulse-decay techniques), with the highest permeability sample also having the highest percentage of open porosity. Surface area, as calculated from low-pressure N{sub 2} and CO{sub 2} adsorption, is significantly less than surface area estimates from SANS/USANS, which is due in part to limited accessibility of the gases to all pores. The similarity between N{sub 2} and CO{sub 2}-accessible surface area suggests an absence of microporosity in these samples, which is in agreement with SANS analysis. A core gamma ray profile run on the same core from which the core plug samples were taken correlates to profile permeability measurements run on the slabbed core. This correlation is related to clay content, which possibly controls the percentage of open porosity. Continued study of these effects will prove useful in log-core calibration efforts for tight gas.

03 NATURAL GAS↗
DOE OSTI2014

Setup for in situ investigation of gases and gas/solid interfaces by soft x-ray emission and absorption spectroscopy

We present a novel gas cell designed to study the electronic structure of gases and gas/solid interfaces using soft x-ray emission and absorption spectroscopies. In this cell, the sample gas is separated from the vacuum of the analysis chamber by a thin window membrane, allowing in situ measurements under atmospheric pressure. The temperature of the gas can be regulated from room temperature up to approximately 600 °C. To avoid beam damage, a constant mass flow can be maintained to continuously refresh the gaseous sample. Furthermore, the gas cell provides space for solid-state samples, allowing to study the gas/solid interface for surface catalytic reactions at elevated temperatures. To demonstrate the capabilities of the cell, we have investigated a TiO{sub 2} sample behind a mixture of N{sub 2} and He gas at atmospheric pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Analysis of liquid petroleum using a laser-induced breakdown spectroscopy instrument

Here, a prototype analyzer for the direct LIBS analysis of nebulized liquid samples was developed and tested, particularly for the analysis of petroleum, organic solvents and aqueous solutions. The LIBS analyzer requires about 750 µl of liquid sample, 1 liter of N 2 gas, and 10 s of the analysis time to record 100 spectra. The limits of detection in oil and solvent are as low as 0.01–0.04 ppm for Li, Mg, and Cu. They increase for the difficult elements, such as Pb and Hg (7-10 ppm), Cl (250 ppm), and S (~0.7%). The relative standard deviation of measuring 100 ppm vanadium in oil and solvent was 1.5%. The LIBS detection limits and repeatability are better than required by the standard method ASTM D5185 for the analysis of lubricating oils in ICP-OES. Several petroleum samples were analyzed by LIBS and the quantitative results for V, Ni, and Fe compared to the ICP-OES data. Light crude oils can be nebulized and analyzed directly. Medium crude oils require minimal dilution at least 1:1, otherwise errors of determination become large. Presumably, utilization of the internal standard and chemometrics can be useful to correct for the matrix effects. In addition to the trace element analysis, the LIBS prototype demonstrated ability to measure the hydrogen-to-carbon ratio in organic liquid samples. Several unidentified features were observed in the carbon spectrum. Their possible origin is discussed.

02 PETROLEUM↗
DOE OSTI2018

DOE/DOT Crude Oil Characterization Research Study, Task 2 Test Report on Evaluating Crude Oil Sampling and Analysis Methods, Revision 1 - Winter Sampling

The Crude Oil Characterization Research Study is designed to evaluate whether crude oils currently transported in North America, including those produced from “tight” formations, exhibit physical or chemical properties that are distinct from conventional crudes, and how these properties associate with combustion hazards that may be realized during transportation and handling. The current report presents results from Task 2, investigating which commercially available methods can accurately and reproducibly collect and analyze crude oils for vapor pressure and composition, including dissolved gases. This issue, Revision 1 – Winter Sampling, incorporates additional seasonal data and compositional analysis results that have become available since publication of a prior report, SAND2017-12482, released in December 2017. Both reports compare performance of commercially available methods to that of a well-established mobile laboratory system that currently serves as the baseline instrument system for the U.S. Strategic Petroleum Reserve Crude Oil Vapor Pressure Program. The experimental matrix evaluates the performance of selected methods for (i) capturing, transporting, and delivering hydrocarbon fluid samples from the field to the analysis laboratory, coupled with (ii) analyzing for properties related to composition and volatility of the oil, including vapor pressure, gas-oil ratio, and dissolved gases and light hydrocarbons. Several combinations of sample capture and analysis were observed to perform well in both summer and winter sampling environments, though conditions apply that need to be considered carefully for given applications. Methods that perform well from Task 2 will then be utilized in subsequent Task 3 (combustion studies) and Task 4 (compositional analyses of multiple crude types), to be addressed in subsequent reports.

02 PETROLEUM↗