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At least 919 records · Page 51

Using Separation-Enhanced Isotope Ratio Mass Spectrometry to Enable Increased Renewable Carbon Content in Transportation Fuels (CRADA 525)

Stable isotope ratio measurements of carbon atoms using isotope ratio mass spectrometry (IRMS) can be an effective tool for quantifying biogenic carbon in co-processed fuels, with results approaching the precision and accuracy of accelerator mass spectrometry (AMS). The lower cost of an IRMS may enable deployment to refineries, improving access and analysis turnaround times (≤2 hours), and, by extension, provide data that can allow process optimization to maximize renewable carbon in desired refinery products. This project explored the integration of chemical separation with IRMS analyses to enable highly detailed tracking of biogenic carbon into fuel product streams separated by boiling point range, chemical class, or specific compound. Forty-nine fuels and fuel components of fossil and biogenic origin, spanning gasoline and diesel boiling point ranges, were received from three refiners and were analyzed for their δ 13 C values via IRMS. Results spanned a 13 C range from ca. 10‰ to 44‰ and reflect materials derived from sustainable sources (e.g., C4 or C3 plants, animal-based pathways, syngas) or from fossil-derived fuels. Common ranges are approximately 18‰ to 9‰ and approximately 30‰ to 20‰ for C4 and C3 plants, respectively, and approximately 34‰ to 24‰ and approximately 70‰ to 33‰ for petroleum-derived fuels and methane, respectively. Fuel-like standards were developed and tested using direct-injection elemental analyzer (EA) IRMS for liquid fuels. This method was compared with the published methods, yielding statistically similar results. Four blend curve sets were produced ranging from 0% to 100% of a fuel containing biogenic carbon, focusing on 0% to 10% biogenic carbon. Linear fits were the most applicable for two of the four blend curve sets; however, two sets were found to exhibit slightly quadratic behavior, which was more pronounced in low biogenic blend samples, necessitating second-order fits. The origin of the slight quadratic behavior remains unclear; however, the discussion points to possible interpretations. CanmetENERGY thoroughly characterized a majority of the samples using one- and two-dimensional gas chromatography (GC and GC×GC, respectively) and other analyses. Selected samples were subjected to solid phase extraction (SPE) for saturate, olefin, aromatic, and polar (SOAP) analysis, and the resulting solvent-diluted fractions containing saturates and aromatics were returned to Pacific Northwest National Laboratory (PNNL), where the solvent was removed via evaporation or physical separation using GC techniques. Characterization and separations provided an understanding of saturate and aromatic content, as well as boiling point ranges for each sample and sample fraction. Samples resulting from SPE were examined using EA-IRMS and gas chromatography combustion IRMS (GC-C-IRMS) analyses. Both approaches suggest that the range in values between end-members can be increased by selecting the paraffinic or aromatic fraction of the end-member or by selecting among individual compounds resulting from GC separation of the paraffinic fractions. Considerable work remains to put these approaches into practice and statistically validate the benefit for using a fraction or individual compound over bulk analysis of a sample. However, initial results suggest that separations provide advantages for samples having blend ratios of less than 10% biogenic blendstocks. 13 C results showed statistically similar biofuel blend results to those obtained at PNNL, although additional work is needed to obtain better reproducibility. Select samples were sent to Los Alamos National Laboratory (LANL) for IRMS measurements and Beta Analytics for AMS measurements. This work suggests that IRMS and AMS yield closely comparable results and in some circumstances, IRMS could serve as a surrogate for AMS. While additional work is needed to better resolve statistical advantages for separations and better show the comparable nature of IRMS and AMS in both the biogenic carbon analysis of bulk chemical classes, initial results from this study suggest that these should be pursued in order to proliferate this approach for quantifying biogenic carbon in transportation fuels to the refinery level, thereby potentially enabling process optimization in co-processing scenarios.

09 BIOMASS FUELS↗

Chloride-Induced Stress Corrosion Cracking of Friction Stir-Welded 304L Stainless Steel: Effect of Microstructure and Temperature

Dry storage canisters of used nuclear fuels are fabricated using SUS 304L stainless steel. Chloride-induced stress corrosion cracking (CISCC) is one of the major failure modes of dry storage canisters. The cracked canisters can be repaired by friction stir welding (FSW), a low-heat input ‘solid-phase’ welding process. It is important to evaluate the ClSCC resistance of the friction stir welded material. Stress corrosion cracking (SCC) studies were carried out on mill-annealed base materials and friction stir welded 304L stainless U-bend specimens in 3.5% NaCl + 5 N H2SO4 solution at room temperature and boiling MgCl2 solution at 155 °C. The engineering stress on the outer fiber of the FSW U-bend specimen was ~60% higher than that of the base metal (BM). In spite of the higher stress level of the FSW, both materials (FSW and BM) showed almost similar SCC failure times in the two different test solutions. The SCC occurred in the thermo-mechanically affected zone (TMAZ) of the FSW specimens in the 3.5% NaCl + 5 N H2SO4 solution at room temperature, while the stirred zone (SZ) was relatively crack-free. The failure occurred at the stirred zone when tested in the boiling MgCl2 solution. Hydrogen reduction was the cathodic reaction in the boiling MgCl2 solution, which promoted hydrogen-assisted cracking of the heavily deformed stirred zone. The emergence of the slip step followed by passive film rupture and dissolution of the slip step could be the SCC events in the 3.5% NaCl + 5 N H2SO4 solution at room temperature. However, the slip step height was not sufficient to cause passivity breakdown in the fine-grained SZ. Therefore, the SCC occurred in the partially recrystallized softer TMAZ. Overall, the friction-stirred 304L showed higher tolerance to ClSCC than the 304L base metal.

304L austenitic stainless steel↗

Simplified computer program for the analysis of phase change in liquid face seals

A simplified computer program is presented which allows for the prediction of boiling (phase change) in liquid face seals. The program determines if and when boiling occurs and then calculates the location of the boiling interface, pressure and temperature profiles, and load. The main assumption which allows for a simplified analysis is the assumption of an isothermal gas phase.

Birchak, M.↗

Phase change in liquid face seals

A study is made of boiling (or phase change) in liquid face seals. An appropriate model is set up and approximate solutions obtained. Some practical illustrative examples are given. Major conclusions are that (1) boiling may occur more often than has been suspected particularly when the sealed liquid is near saturation conditions, (2) the temperature variation in a seal clearance region may not be very great and the main reason for boiling is the flashing which occurs as the pressure decreases through the seal clearance, and (3) there are two separate values of the parameter film-thickness/angular-velocity-squared (and associated radii where phase change takes place) which provide the same separating force under a given set of operating conditions. For a given speed seal face excursions about the larger spacing are stable, but excursions about the smaller spacing are unstable, leading to a growth to the larger spacing or a catastrophic collapse.

Hughes, W. F.↗

Phase changes in liquid face seals

Computer program predicts boiling (phase change) in liquid face seals. Program determines if and when boiling occurs, and calculates location of boiling interface, pressure and temperature profiles, and load.

Hughes, W. F.↗

Fuel character effects on the J79 and F101 engine combustion systems

The effects of select fuel property variations on two major engine classifications are summarized. Thirteen refined and blended fuels were used which exhibited significant variations in hydrogen content, aromatic type, initial boiling point, final boiling point, and viscosity. Trends were very similar but the degree of fuel sensitivity was not constant. For both systems the dominant fuel property during high pressure operation was found to be fuel hydrogen content. For operation at low pressure test points the fuel volatility and viscosity became the dominant fuel properties for both systems. Aromatic type and final boiling point did not significantly affect combustion data. Correlations of other fuel properties with these and other performance parameters are presented.

Jackson, T. A.↗

Testing of a high capacity research heat pipe

Tests were performed on a high-capacity channel-wick heat pipe to assess the transport limitations of v-grooves and the effects of boiling. The results showed that transport can vary significantly (less than 50 W) under similar conditions and the continuous boiling was observed at power levels as low as 40 W. In addition, some evidence was found to support the predictions using a groove transport model which shows that transport increases with lower groove densities and longer evaporators. However, due to transport variations, these results were not consistent throughout the program. When a glass fiber wick was installed over the grooves, a relatively low transport level was achieved (80 to 140 W). Based on these results and the identification of some potential causes for them, several design suggestions were recommended for reducing the possibility of boiling and improving groove transport.

Source record↗

Investigation of sources, properties and preparation of distillate test fuels

Distillate test fuel blends were generated for prescribed variations in composition and physical properties. Fuels covering a wide range in properties and composition which would provide a matrix of fuels for possible use in future combustion research programs were identified. Except for tetralin the blending components were all from typical refinery streams. Property variation blends span a boiling range within 150 C to 335 C, freezing point -23 C to -43 C, aromatic content 20 to 50 volume percent, hydrogen content 11.8 to 14.2 mass percent, viscosity 4 and 11 cSt (-20 C), and naphthalenes 8 and 16 volume percent. Composition variation blends were made with two base stocks, one paraffinic and the other napthenic. To each base stock was added each of three aromatic type fuels (alkyl benzenes, tetralin, and naphthalenes) for assigned initial boiling point, final boiling point, and hydrogen content. The hydrogen content was 13.5 mass percent for the paraffinic base stock blends and 12.5 mass percent and 11.5 mass percent for the naphthenic base stock blends. Sample 5-gallon quantities of all blends were prepared and analyzed.

Bowden, J. N.↗

A new hydrodynamic prediction of the peak heat flux from horizontal cylinders in low speed upflow

Flow-boiling data have been obtained for horizontal cylinders in saturated acetone, isopropanol, and water, yielding heat flux vs. wall superheat boiling curves for the organic liquids. A region of low speed upflow is identified in which long cylindrical bubbles break off from the wake with regular frequency. The Strouhal number of bubble breakoff is a function only of the Froude number in any liquid, and the effective wake thickness in all liquids is a function of the density ratio and the Froude number. A low speed flow boiling burnout prediction procedure is presented which yields accurate results in widely dissimilar liquids.

Ungar, E. K.↗

Small scale demand type neon liquefaction plant

Low-temperature measurement of the thermal conductivity of insulating materials is generally made using a boil-off calorimetry technique involving liquid hydrogen (LH2). Liquid neon (LNe) has nearly the same normal boiling point as LH2, but has a much larger heat of vaporization, allowing extended run times. The main drawback of using LNe has been its excessive cost; $170.00 versus $1.50/l for LH2 (1989 prices). A neon liquefaction plant has been designed and constructed to capture, purify, and refrigerate the neon boil-off from calorimetry experiments. Recycling the neon reduces operating costs to approximately $20/l. The system consists of a purification section, a heat exchanger, LNe and LH2 storage dewars, and a fully automated control system. After purification, neon is liquified in the heat exchanger by LH2 flowing countercurrently through stainless steel cooling coils. Hydrogen flow is automatically adjusted to keep the neon at its normal saturation temperature, 27 K. The liquid neon is then stored in a dewar placed directly below the heat exchanger.

Dube, W. P.↗

Design of a pool boiler heat transport system for a 25 kWe advanced Stirling conversion system

The overall operating temperature and efficiency of solar-powered Stirling engines can be improved by adding a heat transport system to more uniformly supply heat to the heater head tubes. One heat transport system with favorable characteristics is an alkali metal pool boiler. An alkali metal pool boiler heat transport system was designed for a 25-kW advanced Stirling conversion system (ASCS). Solar energy concentrated on the absorber dome boils a eutectic mixture of sodium and potassium. The alkali metal vapors condense on the heater head tubes, supplying the Stirling engine with a uniform heat flux at a constant temperature. Boiling stability is achieved with the use of an enhanced boiling surface and noncondensible gas.

Anderson, W. G.↗

A 69 cent look at thermoplastic softening

The objectives are to demonstrate the change in mechanical properties of a thermoplastic polymer when the polymer is heated above the glass transition temperature. The instructor or student can perform this demonstration. In preparation for the demonstration, fill the flask or beaker 3/4 full with water and bring the water to a boil. First observe the initial stiffness of the toothbrush by slightly flexing it. Note that it is fairly stiff and retains its initial shape when the forces are removed. If you were to apply enough force, the toothbrush would break in a somewhat brittle fashion. Now place the toothbrush in the boiling water for 2 minutes. After the 2 minutes are up, remove the toothbrush from the boiling water with the washcloth. At this time, you will be able to bend the toothbrush easily. When it cools it will retain this bent shape. You've just demonstrated heating the polymer above the glass transition temperature, demonstrating thermoplastic softening. Instructor notes are provided.

Vanasupa, Linda S.↗

Response of two-phase droplets to intense electromagnetic radiation

The response of two-phase droplets to intense radiant heating is studied to determine the incident power that is required for causing explosive boiling in the liquid phase. The droplets studied consist of strongly absorbing coal particles dispersed in a weakly absorbing water medium. Experiments are performed by confining droplets (radii of 37, 55, and 80 microns) electrodynamically and irradiating them from two sides with pulsed laser beams. Emphasis is placed on the transition region from accelerated droplet vaporization to droplet superheating and explosive boiling. The time scale observed for explosive boiling is more than 2 orders of magnitude longer than published values for pure liquids. The delayed response is the result of energy transfer limitations between the absorbing solid phase and the surrounding liquid.

Spann, James F.↗

Acoustic Behavior of Vapor Bubbles

In a microgravity environment vapor bubbles generated at a boiling surface tend to remain near it for a long time. This affects the boiling heat transfer and in particular promotes an early transition to the highly inefficient film boiling regime. This paper describes the physical basis underlying attempts to remove the bubbles by means of pressure radiation forces.

Prosperetti, Andrea↗

Design of an Improved Heater Array to Measure Microscale Wall Heat Transfer

An improved array of microscale heaters is being developed to measure the heat transfer coefficient at many points underneath individual bubbles during boiling as a function of space and time. This heater array enables the local heat transfer from a surface during the bubble growth and departure process to be measured with very high temporal and spatial resolution, and should allow better understanding of the boiling heat transfer mechanisms by pin-pointing when and where in the bubble departure cycle large amounts of wall heat transfer occur. Such information can provide much needed data regarding the important heat transfer mechanisms during the bubble departure cycle, and can serve as benchmarks to validate many of the analytical and numerical models used to simulate boiling. The improvements to the heater array include using a silicon-on-quartz substrate to reduce thermal cross-talk between the heaters, decreased space between the heaters, increased pad sizes on the heaters, and progressive heater sizes. Some results using the present heater array are discussed.

Kim, Jungho↗

Preliminary Study of a Piston Pump for Cryogenic Fluids

Preliminary data are presented covering the performance of a low-speed, five-cylinder piston pump designed for handling boiling hydrogen. This pump was designed for a flow of 55 gallons per minute at 240 rpm with a discharge pressure of 135 pounds per square inch. Tests were made using JP-4 fuel, liquid nitrogen, and liquid hydrogen. Pump delivery and endurance characteristics were satisfactory for the range of operation covered. In connection with the foregoing pump development, the cavitation characteristics of a preliminary visual model, glass-cylinder pump and of a simple reciprocating disk were studied. Subcooling of approximately 0.60 F was obtained from the cavitation produced by reciprocating a disk in boiling nitrogen and in boiling water. The subcooling obtained in a similar manner with liquid hydrogen was somewhat less.

Biermann, Arnold E.↗

Multipurpose Thermal Insulation Test Apparatus

A multi-purpose thermal insulation test apparatus is used for testing insulation materials, or other components. The test apparatus is a fluid boil-off calorimeter system for calibrated measurement of the apparent thermal conductivity (k-value) of a specimen material at a fixed vacuum level. The apparatus includes an inner vessel for receiving a fluid with a normal boiling point below ambient temperature, such as liquid nitrogen, enclosed within a vacuum chamber. A cold mass assembly, including the inner vessel and thermal guards, is suspended from the top of the vacuum chamber. Handling tools attach to the cold mass assembly for convenient manipulation of the assembly and for the installation or wrapping of insulation test materials. Liquid nitrogen is typically supplied to the inner vessel using a fill tube with funnel. A single port through the top of the vacuum chamber facilitates both filling and venting. Aerogel composite stacks with reflective films are fastened to the top and the bottom of the inner vessel as thermal guards. The comparative k-value of the insulation material is determined by measuring the boil-off flow rate of gas, the temperature differential across the insulation thickness, and the dimensions (length and diameters) of the test specimen.

Fesmire, James E.↗

Design of Transpiration Cooled Thermal Protection Systems

This study explored three approaches for the utilization of transpiration cooling in thermal protection systems. One model uses an impermeable wall with boiling water heat transfer at the backface (Model I). A second model uses a permeable wall with a boiling water backface and additional heat transfer to the water vapor as it flows in channels toward the exposed surface (Model II). The third model also uses a permeable wall, but maintains a boiling condition at the exposed surface of the material (Model III). The governing equations for the models were developed in non-dimensional form and a comprehensive parametric investigation of the effects of the independent variables on the important dependent variables was performed. In addition, detailed analyses were performed for selected materials to evaluate the practical limitations of the results of the parametric study.

Callens, E. Eugene, Jr.↗