Results for “Pyrolysis” — Page 49

DOE OSTI2022

Carbon Intensities of Refining Products in Petroleum Refineries with Co-Processed Biofeedstocks

Petroleum refineries increasingly seek to generate fuels with lower carbon intensities (CIs; a measure of life cycle greenhouse gas [GHG] emissions per unit of energy of fuel; well-to-wheel [WTW]) to meet growing demand. Co-processing refers to a process that adds biomass-derived feedstocks to the fossil-based feedstocks of existing petroleum refinery process units. With the use of biofeedstocks, it is expected that co-processed fuels would have lower CIs than their petroleum counterparts without requiring changes in the existing infrastructure for producing, transporting, and using fuels. To quantify the GHG emissions reduction benefits of co-processing, this study uses a linear programming model to simulate petroleum refinery conditions with and without co-processing. The co-processing cases include three biofeedstocks (soy oil, tallow, and used cooking oil or UCO) used as 10 vol.% of the feedstock to a hydrotreater or hydrocracker since these lipid-based feedstocks have favorable properties to be treated in a hydrotreater or hydrocracker. In addition, we considered pyrolysis oil used as 10 vol.% of the feedstock to a fluid catalytic cracking (FCC) unit in the modeled refinery due to its higher oxygen content compared to other lipid-based feedstocks. Life cycle analysis (LCA) using two distinct approaches—process-level energy allocation and a refinery-level marginal approach—has been conducted for each case. The LCA results using process-level allocation show that there are no noticeable changes in emissions or energy use impacts at the facility level. The life cycle GHG emission reductions of co-processing cases are mainly related to the fraction of biogenic carbon embedded in each fuel product. For example, co-processed jet fuels (a mixture of fossil and biogenic fuels) made via hydrotreating or hydrocracking have higher biogenic carbon, which results in jet fuel CI reductions of 3.9%–8.6% compared to the CI of baseline petroleum jet fuels on a WTW basis. However, analysis of co-processed pyrolysis oil in an FCC shows that a higher fraction of biofeedstocks (29%) becomes process emissions (i.e., CO and CO 2 ), mainly due to the oxygenates in pyrolysis oil, and so it generates less renewable fuel than biofeedstocks co-processed via hydrotreating or hydrocracking. Using the refinery-level marginal approach, the changes in energy use and emissions of co-processing cases compared to the petroleum-only baseline case are allocated to the changes in fuel production (assuming renewable fuels). This approach generates the life cycle GHG emission values of co-processed renewable fuels, which are comparable to the CIs of standalone biofuel production pathways. However, as this approach relies on a rough assumption that product yields and emissions from co-processing units on fossil feedstocks remain the same with and without biofeedstock inputs, co-processing cases like FCC pyrolysis oil may generate quite skewed results.

02 PETROLEUM↗

DOE OSTI2025

Microwave-assisted dehydrogenation of fossil fuels using iron-based alumina nanocomposites

Hydrogen is mainly produced via steam reforming of methane and gasification of coal, with enormous CO 2 emissions in both cases. Microwave-assisted thermocatalytic decomposition (pyrolysis) is of interest as a method for hydrogen production from fossil fuels with no CO 2 emissions. For successful implementation of this technology, it is necessary to develop decomposition catalysts that are also good microwave absorbers and can be produced from inexpensive materials via a robust synthetic route. Recently, iron-based alumina nanocomposites, fabricated by solution combustion synthesis (SCS), have shown promising microwave-absorbing and catalytic properties in the pyrolysis of plastics. The reported project explored the feasibilities of improving such catalysts and using them for the microwave-assisted pyrolysis of liquid fossil fuels, viz., diesel fuel, gasoline, and crude oil. The research focused on how SCS parameters affect the material properties and pyrolysis performance.

02 PETROLEUM↗

DOE OSTI2025

1,10-Phenanthroline-Iron Complex-Derived Fe-N-C Electrocatalysts: Enhanced Oxygen Reduction Activity and Stability Through Synthesis Tuning

The development of electrocatalysts composed of earth-abundant elements is essential for advancing the commercial application of Proton Exchange Membrane Fuel Cells (PEMFC). Among these, single-atom electrocatalysts, such as Fe-N-C, show great promise for the oxygen reduction reaction (ORR). This study aims to improve the ORR activity and stability of Fe-N-C electrocatalysts by fine-tuning the straightforward 1,10-phenanthroline-iron complexation synthesis method. Key parameters, including iron-to-phenanthroline ratio, carbon powder surface area, and pyrolysis temperature were systematically varied to evaluate their influence on the resulting electrocatalysts. The findings of this study revealed that the electrocatalysts synthesized with 1,10-phenanthroline (Phen) and high-surface-area Black Pearls (BP) possessed much better ORR activity than electrocatalysts prepared by using Vulcan carbon (lower surface area). Interestingly, electrocatalysts prepared with BP, but with a non-bidentate nitrogen-containing ligand molecule, such as imidazole, showed a much poorer activity, as the resulting material predominantly consisted of inactive structures, such as encapsulated iron nanoparticles and iron oxide, as evidenced by HR-TEM, EXAFS, and XRD. Therefore, the results suggest that only the synergistic combination of the bidentate ligand phenanthroline (Phen) and the high-surface-area carbon support (BP) favored the formation of ORR-active Fe-N-C single-atom species upon pyrolysis. The study also unveiled a significant enhancement in electrocatalyst stability during accelerated durability tests (and air storage) as the pyrolysis temperature was increased from 700 to 1300 °C, albeit at the expense of ORR activity, likely resulting from the generation of iron particles. Pyrolysis at 1050 °C yielded the electrocatalyst with the most favorable balance of activity and stability in rotating disk measurements, while maintaining moderate durability under PEM fuel cell operation. The insights obtained in this study may guide the development of more active efficient and durable electrocatalysts, synthesized via a simple method using earth-abundant elements, for application in PEMFC cathodes.

30 DIRECT ENERGY CONVERSION↗

NASA NTRS1974

Evaluation of the energy transfer in the char zone during ablation. Part 2: In-depth response of ablative composites, volume 1

The decomposition of ablative composites is described along with the transport phenomena of pyrolysis gases which result from the decomposition of these plastics as they flow through the porous char of char-forming ablators. The pyrolysis products are those formed by the thermal degradation of nylon-phenolic resin and silicone elastomer composites. Emphasis is placed on the nature and extent of chemical reactions of the pyrolysis products and the char, along with the energy absorbed by the combined pyrolysis and char zone. Chemical reactions with thermodynamically consistent kinetic data are determined in order to develop a realistic analysis for predicting the thermal performance of ablative heat shields.

Pike, R. W.↗

NASA NTRS1982

Toxicity of thermal degradation products of spacecraft materials

Three polymeric materials were evaluated for relative toxicity of their pyrolysis products to rats by inhalation: Y-7683 (LS 200), Y-7684 (Vonar 3 on Fiberglass), and Y-7685 (Vonar 3 on N W Polyester). Criteria employed for assessing relative toxicity were (1) lethality from in-chamber pyrolysis, (2) lethality from an outside-of-chamber pyrolysis MSTL Procedure, and (3) disruption of trained rats' shock-avoidance performance during sub-lethal exposures to in-chamber pyrolysis of the materials.

Lawrence, W. H.↗

NASA NTRS1985

Role of minerals in the thermal alteration of organic matter. I - Generation of gases and condensates under dry condition

Pyrolysis experiments conducted at 200 and 300 C on kerogen and bitumen from the Monterey formation and on the Green River Formation kerogen with montmorillonite, illite, and calcite added are described. The pyrolysis products are identified and gas and condensate analyses are performed. A catalytic effect is detected in the pyrolysis of kerogen with montmorillonite; however, illite and calcite display no catalytic activity. The increased production of C1-C6 hydrocarbons and the dominance of branched hydrocarbons in the C4-C6 range reveals a catalytic influence. It is observed that the catalysis of montmorillonite is greater during bitumen pyrolysis than for kerogen, and catalysis with minerals affects the production of CO2. It is concluded that a mineral matrix is important in determining the type and amount of gases and condensates forming from organic matter under thermal stress.

Tannenbaum, E.↗

NASA NTRS1987

Elucidation of the organometallic vapor phase epitaxial growth mechanism for InP

A new technique for tracing the organometallic vapor epitaxial growth is reported. The pyrolysis of PH3, alone and in the presence of trimethylindium (TMIn), and of TMIn alone was studied by conducting the epitaxial growth of InP in D2 as the carrier gas, tracing growth reactions by mass spectrometric analysis of the product molecules. The TMIn alone pyrolyzes mostly homogeneously in the gas phase, while the PH3 pyrolysis is completely heterogeneous at the InP surface. Adding TMIn to PH3 results in a dramatic decrease in the pyrolysis temperature. PH3 molecules which interact with TMIn in the gas phase pyrolyze at temperatures as low as 250, and those decomposing without TMIn interaction pyrolyze at temperatures approximately 200 C higher. Similarly, the presence of PH3 lowers the TMIn pyrolysis temperature by at least 50 C. TMIn alone in D2 produces mainly CH3D molecules. For high PH3:TMIn ratios, CH4 is the only carbon-containing reaction product.

Buchan, N. I.↗

NASA NTRS1996

An Experimental Study of Ignition Effects and Flame Growth Over a Thin Solid Fuel in Low-Speed Concurrent Flow Using Drop-Tower Facilities

An experimental study of ignition and flame growth over a thin solid fuel in oxidizer flow speeds from 0 to 10 cm/sec concurrent flow was performed. This study examined the differences between ignition using a resistively heated wire (woven in a sawtooth pattern over the leading edge of the fuel), and a straight resistively heated wire augmented by a chemical ignitor doped onto the leading edge of the fuel. Results showed that the chemical system yielded non-uniform ignition bursts, while the system using only the hotwire gave more uniform ignition. At speeds up to 2.5 cm/sec, the chemical system yielded non-uniform pyrolysis fronts, while the hotwire system gave more uniform pyrolysis fronts. At speeds of 5 cm/sec or greater, both systems gave uniform pyrolysis fronts. The chemically-ignited flames tended to become too dim to see faster than the hotwire-ignited flames, and the flame lengths were observed to be shorter (after the initial burst subsided) for the chemical system for all speeds. Flame and pyrolysis element velocities were measured. Temperature profiles for selected tests were measured using thermocouples at the fuel surface and in the gas phase. Comparisons between the flame element velocities and peak temperatures recorded in these tests with calculated spread rates and peak temperatures from a steady-state model are presented. Agreement was found to be within 20% for most flame elements for nominal velocities of 5 cm/sec and 7.5 cm/sec.

Pettegrew, Richard Dale↗

NASA NTRS2012

Detecting Organic Compounds Released from Iron Oxidizing Bacteria using Sample Analysis at Mars (SAM) Like Instrument Protocols

Mars is a planet of great interest for Astrobiology since its past environmental conditions are thought to have been favourable for the emergence life. At present, the Red Planet is extremely cold and dry and the surface is exposed to intense UV and ionizing radiation, conditions generally considered to be incompatible with life as we know it on Earth. It was proposed that the shallow subsurface of Mars, where temperatures can be above freezing and liquid water can exist on rock surfaces, could harbor chemolithoautotrophic bacteria such as the iron oxidizing microorganism Pseudomonas sp. HerB. The Mars Science Laboratory (MSL) mission will provide the next opportunity to carry out in situ measurements for organic compounds of possible biological origin on Mars. One instrument onboard MSL, called the Sample Analysis at Mars (SAM) instrument suite, will carry out a broad and sensitive search for organic compounds in surface samples using either high temperature pyrolysis or chemical extraction followed by gas chromatography mass spectrometry. We present gas chromatograph mass spectrometer (GC/MS) data on crushed olivine rock powders that have been inoculated with Pseudomonas sp. HerB at different concentrations ranging from approx 10(exp 2) to 10(exp 7) cells per gram. The inoculated olivine samples were heated under helium carrier gas flow at 500 C and the pyrolysis products concentrated using a SAM-like hydrocarbon trap set at -20 C followed by trap heating and analysis by GC/Ms. In addition, the samples were also extracted using a low temperature "one-pot" chemical extraction technique using N-methyl, N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) as the silylating agent prior to GC/MS analysis. We identified several aldehydes, thiols, and alkene nitriles after pyrolysis GC/MS analysis of the bacteria that were not found in the olivine control samples that had not been inoculated with bacteria. The distribution of pyrolysis products extracted from the bacteria was clearly distinct from similar GC/MS analyses of the carbonaceous meteorite Murchison that was dominated by sulfur containing aromatic compounds. A similar comparison, if organic compounds are detected by SAM on Mars, could be useful to help discriminate between meteoritic or biological origins.

Glavin, D. P.↗

NASA NTRS2013

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.

sample analysis at mars↗

NASA NTRS2015

Thermochemical Ablation Analysis of the Orion Heatshield

The Orion Multi-Purpose Crew Vehicle will one day carry astronauts to the Moon and beyond, and Orion's heatshield is a critical component in ensuring their safe return to Earth. The Orion heatshield is the structural component responsible for absorbing the intense heating environment caused by re-entry to Earth's atmosphere. The heatshield is primarily composed of Avcoat, an ablative material that is consumed during the re-entry process. Ablation is primarily characterized by two processes: pyrolysis and recession. The decomposition of in-depth virgin material is known as pyrolysis. Recession occurs when the exposed surface of the heatshield reacts with the surrounding flow. The Orion heatshield design was changed from an individually filled Avcoat honeycomb to a molded block Avcoat design. The molded block Avcoat heatshield relies on an adhesive bond to keep it attached to the capsule. In some locations on the heatshield, the integrity of the adhesive bond cannot be verified. For these locations, a mechanical retention device was proposed. Avcoat ablation was modelled in CHAR and the in-depth virgin material temperatures were used in a Thermal Desktop model of the mechanical retention device. The retention device was analyzed and shown to cause a large increase in the maximum bondline temperature. In order to study the impact of individual ablation modelling parameters on the heatshield sizing process, a Monte Carlo simulation of the sizing process was proposed. The simulation will give the sensitivity of the ablation model to each of its input parameters. As part of the Monte Carlo simulation, statistical uncertainties on material properties were required for Avcoat. Several properties were difficult to acquire uncertainties for: the pyrolysis gas enthalpy, non-dimensional mass loss rate (B´c), and Arrhenius equation parameters. Variability in the elemental composition of Avcoat was used as the basis for determining the statistical uncertainty in pyrolysis gas enthalpy and B´c. A MATLAB program was developed to allow for faster, more accurate and automated computation of Arrhenius reaction parameters. These parameters are required for a material model to be used in the CHAR ablation analysis program. This MATLAB program, along with thermogravimetric analysis (TGA) data, was used to generate uncertainties on the Arrhenius parameters for Avcoat. In addition, the TGA fitting program was developed to provide Arrhenius parameters for the ablation model of the gap filler material, RTV silicone.

Sixel, William↗

NASA NTRSDate not supplied

Benefits of Trash-to-Gas Versus Jettison of Waste Via Trash-Lock for Mars Transit

Human exploration missions to Mars pose difficulties due to the significant waste that will be generated during transit, which will need to be carried along or disposed of in some fashion. Waste removal from the spacecraft decreases the spacecraft’s mass as well as the associated logistic items necessary for storing the waste. A mission propellant analysis was performed to highlight the mass benefits that may be accessed via waste removal. The propellant mass savings were determined for different waste removal rates (2.9 – 11.6 kg/day) with the highest removal rate leading to the greatest propellant savings of 7,785 kg for an 850-day round-trip mission. Due to these benefits, two methods for waste reduction were studied for the 850-day Mars mission: Trash-to-Gas (TtG) and physical jettison via a trash-lock. The trash-to-gas methods considered were combustion, steam reforming, and pyrolysis, which convert waste into ventable gases (e.g., CO2, CO, CH4, etc.). Combustion and steam reforming require a co-reactant (O2 and/or H2O). Therefore, additional processing units or integration with the spacecraft’s environmental control and life support system (ECLSS) are required to facilitate recycle of the pertinent species. In contrast, pyrolysis is a purely thermal degradation process, which can operate as a standalone system; however, a lower percentage of waste is gasified with pyrolysis. The study herein compares standalone TtG (e.g., Advanced Organic Waste Gasifier, Plasma Pyrolysis, etc.), integrated TtG-ECLSS (e.g., Orbital Syngas Commodity Augmentation Reactor, Incineration/Gasification, etc.), and physical jettison. Each system’s mass, volume, power, and cooling requirements were compared via an equivalent system mass (ESM) analysis to ascertain potentially promising technologies that can achieve efficient waste removal while minimizing their own spacecraft load. This study highlights the advantages and disadvantages of the different waste management technologies and provides recommendations on the promising technologies based on the ESM metric and propellant mass savings.

Jettison↗

NASA NTRSDate not supplied

Thermo-Poro-Mechanical Modeling of RTV Intumescence

Room temperature vulcanizing (RTV) silicone is a high-temperature adhesive used as a gap-filler between heatshield tiles in numerous entry missions. Its propensity to intumesce, or swell upon exposure to heat, is a well-known effect that needs to be carefully quantified during design. At tile interfaces of charring ablators, intumescence, combined with differential recession, could cause the gap filler to protrude past the ablator outer mold line, forming a “fence”. Fencing can in turn cause transition to turbulence of the flow wetting the heat shield, leading to augmented surface heating. Recent experiments conducted at the Plasmatron X facility, the high enthalpy wind tunnel of the Center for Hypersonics and Entry Systems Studies, have shown prominent fencing of RTV gap fillers in PICA, under both nitrogen and air plasmas. Similar observations are well known in the arcjet literature. Further experiments under controlled environment, performed using in situ X-ray micro-computed tomography (micro-CT) at the Advanced Light Source (ALS), have shown heating rate-dependent swelling and shrinkage of RTV during pyrolysis. To simulate RTV intumescence, a novel model was introduced in the Porous Materials Analysis Toolbox based on OpenFOAM, PATO, to account for pore-pressure buildup within both closed- and open-pores. The governing equation for the thermo-poro-mechanical response were developed, assuming linear elasticity for the charring silicone. A new multi-pyrolysis model that tracks non-monotonic advancement of material properties with pyrolysis was proposed. This model addresses the limitations of state-of-the-art ablator models to capture the different stages of thermal degradation and coupled thermomechanics. Swelling of RTV was simulated using the new thermo-poro-mechanical model and compared against in situ micro-CT data. Results showed good agreement in intumescence height and temperature profiles at all heating rates, indicating that the key factor contributing to RTV swelling is the internal pressure build-up within closed- and open-pores. As RTV is cured into a soft (rubbery) compound with low-porosity and permeability, initial temperature increase and pyrolysis gas production cause a significant increase of internal pressure, causing a pronounced volume growth. As thermal degradation progresses, rigidization of the silicone occurs due to char hardening which counteract volume shrinkage after gas pressure relief. Overall, our model shows that accounting for changes in properties such porosity, permeability and key thermomechanical coefficients is crucial for capturing the RTV volume change during ablation and enable a predictive capability for heatshield tile interface response. A plan for future calibration of thermomechanical properties evolution during degradation is discussed, as a key next step to close the new model.

RTV↗

NASA NTRSDate not supplied

Thermo-Poro-Mechanical Modeling of RTV Intumescence

Room temperature vulcanizing (RTV) silicone is a high-temperature adhesive used as a gap-filler between heatshield tiles in numerous entry missions. Its propensity to intumesce, or swell upon exposure to heat, is a well-known effect that needs to be carefully quantified during design. At tile interfaces of charring ablators, intumescence, combined with differential recession, could cause the gap filler to protrude past the ablator outer mold line, forming a “fence”. Fencing can in turn cause transition to turbulence of the flow wetting the heat shield, leading to augmented surface heating. Recent experiments conducted at the Plasmatron X facility, the high enthalpy wind tunnel of the Center for Hypersonics and Entry Systems Studies, have shown prominent fencing of RTV gap fillers in PICA, under both nitrogen and air plasmas. Similar observations are well known in the arcjet literature. Further experiments under controlled environment, performed using in situ X-ray micro-computed tomography (micro-CT) at the Advanced Light Source (ALS), have shown heating rate-dependent swelling and shrinkage of RTV during pyrolysis. To simulate RTV intumescence, a novel model was introduced in the Porous Materials Analysis Toolbox based on OpenFOAM, PATO, to account for pore-pressure buildup within both closed- and open-pores. The governing equation for the thermo-poro-mechanical response were developed, assuming linear elasticity for the charring silicone. A new multi-pyrolysis model that tracks non-monotonic advancement of material properties with pyrolysis was proposed. This model addresses the limitations of state-of-the-art ablator models to capture the different stages of thermal degradation and coupled thermomechanics. Swelling of RTV was simulated using the new thermo-poro-mechanical model and compared against in situ micro-CT data. Results showed good agreement in intumescence height and temperature profiles at all heating rates, indicating that the key factor contributing to RTV swelling is the internal pressure build-up within closed- and open-pores. As RTV is cured into a soft (rubbery) compound with low-porosity and permeability, initial temperature increase and pyrolysis gas production cause a significant increase of internal pressure, causing a pronounced volume growth. As thermal degradation progresses, rigidization of the silicone occurs due to char hardening which counteract volume shrinkage after gas pressure relief. Overall, our model shows that accounting for changes in properties such porosity, permeability and key thermomechanical coefficients is crucial for capturing the RTV volume change during ablation and enable a predictive capability for heatshield tile interface response. A plan for future calibration of thermomechanical properties evolution during degradation is discussed, as a key next step to close the new model.

silicone intumescence↗

DOE OSTI2018

Air Pollutant Emissions and Regulatory Implications of a Biorefinery Co-Processing Bio-Oil in a Petroleum Refinery: Preprint

Pyrolysis oil, often referred to as bio-oil when derived from biomass through a fast pyrolysis process, has attracted considerable attention because of the high carbonaceous matter and high heating value compared to the original biomass. Pyrolysis oil provides a viable link between the agriculture/forestry and (petro-) chemical industry. Utilizing existing fossil fuel infrastructure by introducing bio-oil in petroleum refineries to produce renewable hydrocarbon fuels (i.e., repurposing existing assets) is appealing due to its relatively low capital requirement. Our analysis examined the air pollutant emissions for a biorefinery utilizing an ex situ catalytic fast pyrolysis process to produce raw bio-oil, with a design capacity of 2,000 dry metric tons of biomass per day. Such a biorefinery is capable of providing sufficient bio-oil to a 4,200 barrels per day capacity of fluidized catalytic cracking unit if the bio-oil is co-processed at 5% (by volume) feed rate. This research is focused on understanding the potential air pollutant regulatory and permitting implications for a refinery co-processing 5% bio-oil with 95% vacuum gas oil in a fluidized catalytic cracking unit for two scenarios: the first case assumes that an ex situ biorefinery is collocated with a petroleum refinery, and the second one assumes that a petroleum refinery will receive bio-oil from a stand-alone biorefinery. We estimated the potential-to-emit values for 4 biorefinery and FCC sizes and assessed technically feasible emission control options that could help to avoid being subject to prevention of significant deterioration requirements due to petroleum refinery modifications to co-process bio-oil. This research fills gaps and overcomes barriers related to air permitting requirements for co-processing bio-oil in existing refineries for various stakeholders. The insights gained from this analysis can facilitate decision making and help expedite permitting processes for petroleum refineries, which seek opportunities to produce lower carbon fuels in their existing infrastructure.

09 BIOMASS FUELS↗

DOE OSTI2019

Air Pollutant Emissions and Regulatory Implications of a Biorefinery Co-Processing Bio-Oil in a Petroleum Refinery

Pyrolysis oil, often referred to as bio-oil when derived from biomass through a fast pyrolysis process, has attracted considerable attention because of the high carbonaceous matter and high heating value compared to the original biomass. Pyrolysis oil provides a viable link between the agriculture/forestry and (petro-) chemical industry. Utilizing existing fossil fuel infrastructure by introducing bio-oil in petroleum refineries to produce renewable hydrocarbon fuels (i.e., repurposing existing assets) is appealing due to its relatively low capital requirement. Our analysis examined the air pollutant emissions for a biorefinery utilizing an ex situ catalytic fast pyrolysis process to produce raw bio-oil, with a design capacity of 2,000 dry metric tons of biomass per day. Such a biorefinery is capable of providing sufficient bio-oil to a 4,200 barrels per day capacity of fluidized catalytic cracking unit if the bio-oil is co-processed at 5% (by volume) feed rate. This research is focused on understanding the potential air pollutant regulatory and permitting implications for a refinery co-processing 5% bio-oil with 95% vacuum gas oil in a fluidized catalytic cracking unit for two scenarios: the first case assumes that an ex situ biorefinery is collocated with a petroleum refinery, and the second one assumes that a petroleum refinery will receive bio-oil from a stand-alone biorefinery. We estimated the potential-to-emit values for 4 biorefinery and FCC sizes and assessed technically feasible emission control options that could help to avoid being subject to prevention of significant deterioration requirements due to petroleum refinery modifications to co-process bio-oil. This research fills gaps and overcomes barriers related to air permitting requirements for co-processing bio-oil in existing refineries for various stakeholders. The insights gained from this analysis can facilitate decision making and help expedite permitting processes for petroleum refineries, which seek opportunities to produce lower carbon fuels in their existing infrastructure.

09 BIOMASS FUELS↗

DOE OSTI2018

Improved Superconducting Properties of Thick YBa{sub 2}Cu{sub 3}O{sub 7−δ} Film by Adding Amino-Rich Polyethyleneimine in Precursor Solution

Polyethyleneimine (PEI) with an amount of –NH{sub 2} groups used in precursor solution could effectively reduce Cu{sup 2+} volatilization during the pyrolysis process. Thermogravimetric analysis shows that the temperature window of low-temperature pyrolysis for precursor solution with PEI (PEI-YBCO) is widened significantly. The slower pyrolysis process can enrich Cu{sup 2+} and improve critical current density (J{sub c}) of PEI-YBCO films. The highest J{sub c} is 3.03 MA/cm{sup 2} at 77 K when the amount of PEI is 0.5 g/10 mL and the film thickness is 400 nm. Then the thickness increases from 0.4 to 2.0 μm by changing the coating times. The J{sub c} values of PEI-YBCO films decrease gradually with the thickness increase. However, the critical current (I{sub c}) can be up to 197 A/cm (at 77 K, self-field) and J{sub c} can still keep 1.68 MA/cm{sup 2} at 1.2 μm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Promising Hard Carbon Coatings on Cu Substrates: Corrosion and Tribological Performance with Theoretical Aspect

Protecting the surface of metals and alloys against corrosion and wear is of abundant importance owing to their widespread applications. In the present work, we report the improved anticorrosion and tribo-mechanical performance of copper (Cu) by a hard carbon (HC) coating synthesized in different pyrolysis temperature. Structural and surface characterization with roughness measurements was systematically investigated using various techniques. Effect of pyrolysis temperature on the corrosion behavior of coated Cu substrates in 0.6 M NaCl solution was evaluated via electrochemical impedance spectroscopy, potentiodynamic polarization. Pin-on-disk wear test of coated Cu substrate showed the influence of the pyrolysis temperature on the wear resistance performance of the HC coatings. According to the obtained results, it could be concluded that the HC coatings synthesized at 1100 °C revealed an enhanced comprehensive performance, revealing their possible utilization as a protective coating for Cu substrates in chloride environment. Monte Carlo simulations have been utilized to elucidate the interaction between the Cu surface and HC coatings.

36 MATERIALS SCIENCE↗