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At least 181 records · Page 10

Techno-Economic Analysis for Co-Processing Fast Pyrolysis Liquid in Fossil Refineries

Recent work at the National Renewable Energy Laboratory (NREL) and throughout the bioenergy community has highlighted incentives associated with co-processing bio-intermediates in existing refineries to reduce capital costs associated with renewable fuels and chemicals production and reduce overall risk for emerging biomass conversion technologies. This presentation summarizes the techno-economic analysis results from the NREL-Petrobras collaboration that focused on refinery integration of fast pyrolysis oil through co-processing in the fluid catalytic cracking (FCC) process. The NREL-Petrobras work highlights the economic opportunity for refiners to engage in co-processing for low-carbon products and introduces the risks for refiners based on variability in crude and fossil-product markets. The NREL-Petrobras results also serve as a basis to inform policy design that reduces economic risk for refinery co-processing and repurposing opportunities. The final topics in the presentation highlight experimental capabilities and emerging analysis approaches at NREL and partner laboratories that support the development and commercial deployment of refinery utilization strategies.

bio-fuels↗

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↗

The Development of Catalysts for Upgrading of Pyrolysis Vapor for Refinery Feedstocks and Intermediates: Cooperative Research and Development, CRADA Number CRD-12-00497 (Final Report)

Fast pyrolysis of biomass with vapor phase upgrading (VPU) can produce refinery feedstocks or intermediates that can meet the Department of Energy’s goal of cost-competitive hydrocarbon fuels by 2017. A key technical barrier for this technology is the lack of selective, cost effective catalysts that can produce high yields of fuel-appropriate hydrocarbons from the pyrolysis vapors. In overcoming this barrier, it will be important to engage leading catalyst development companies to devote their resources and expertise to the development of these materials. Thus, we propose a Cooperative Research and Development Agreement (CRADA) between the National Renewable Energy Laboratory (NREL), a world leader in biomass pyrolysis research and Johnson Matthey (JM), a world leader in the production of advanced catalyst materials to develop and test novel catalysts for efficient VPU. Through its Intercat Inc. subsidiary in Savannah, Ga., Johnson Matthey is internationally recognized as a leader in zeolite-based vapor phase upgrading in refinery duties and an emerging developer of biomass conversion technologies. The research and development efforts described in the proposed work will build upon existing collaborations between NREL and JM and play to the strengths of both institutions. NREL will analyze the composition of pyrolysis vapors as an input to catalyst design, screen and test catalysts, characterize the resulting oil and conduct techno-economic analysis. Catalyst samples will be produced and funded by JM. JM will design and synthesize catalysts, characterize fresh and used catalysts and develop catalyst supports needed to achieve commercially meaningful lifetimes. The project will span catalyst development and testing from the fundamental stage using quantum mechanical modeling and chemical reaction analysis to catalyst screening to integrated pilot studies.

09 BIOMASS FUELS↗

Comparative Techno-Economic Analysis of Available Feedstocks for High-Temperature Conversion: Whole Tree Thinnings and Mature Pine Residues

The TEA and LCA impacts of utilizing low-cost feedstocks in a high-temperature conversion process are of great interest. Here, we investigate the conversion cost impacts of two underutilized feedstocks from the commercial pine industry; 13-year-old whole trees, representing trees removed for the purpose of pre-commercial thinning, and 23-year-old pine residues, representing a waste stream produced from the deconstruction of mature trees for other purposes. Experimental fast pyrolysis data for each feedstock was used in tandem with results from supply and preprocessing analyses in order to evaluate the field-to-fuel economics. A low difference in MFSP was found between the conversion costs for the two feedstocks, with residues demonstrating a net benefit of $0.27/GGE compared to the whole tree thinnings, driven primarily by feedstock supply costs. This suggests that both whole tree thinnings and pine residues may be viable feedstock options for CFP conversion. Life cycle inventories were also generated for each case, enabling a field-to-fuel quantification of the cost and carbon cycle associated with each feedstock.

09 BIOMASS FUELS↗

Techno-Economic Analysis and Life Cycle Assessment of Alternative Fuels for Locomotives in the U.S. Freight Rail Sector

Freight rail is more energy-efficient than truck transport over long-haul distances, offering a low-energy and emissions-intensive option for transporting freight. This study evaluates techno-economic analysis and life cycle assessment of seven alternative unblended fuels for freight locomotive engines─biodiesel, renewable diesel (RD), bio-oils, methanol, dimethyl ether (DME), ethanol, and ammonia─across 16 fuel pathways utilizing soybean, corn, woody biomass, renewable hydrogen, and waste sources, e.g., sludge, manure, and industrial CO 2 , and compares these to conventional diesel. The minimum fuel selling price (MFSP) ranged from $\$2.05$ to $\$8.27$ per diesel gallon equivalent (2020 US dollars), with biocrude and RDs produced from hydrothermal liquefaction (HTL) of sludge having the lowest MFSPs due to coproduct credits and avoided waste treatment cost. Life cycle GHG emissions ranged from −41 to 53 g of CO 2 e/MJ. RD from waste via HTL achieves negative emissions by diverting sludge/manure from GHG-intensive conventional management. Few pathways such as biocrude, methanol, and DME require additional control for SO X emissions in the refinery, while ethanol, FT-diesel, and bio-oil require additional control for particulate matter emissions. Bio-oil and RD from sludge have lower marginal abatement cost or MAC (–$\$38$/tonne CO 2 lowest) while methanol and ammonia with renewable hydrogen have higher MAC ($\$490$/tonne CO 2 maximum).

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Co-Processing Fast Pyrolysis Bio-Oils and Hydrothermal Liquefaction Biocrudes in Fluid Catalytic Cracking and Hydroprocessing in Refineries

Co-processing of biogenic feedstocks within the existing petroleum infrastructure represents an opportunity to incorporate large volumes of bio-carbon into transportation fuels. However, upgrading intermediate liquids from biomass and waste to final products efficiently and economically, while minimizing impacts to existing refinery infrastructure, remains a notable barrier to commercialization. The co-processing project, Bio-oil Co-processing with Refinery Streams, aimed to generate foundational knowledge for processing renewable intermediates in petroleum refineries and offer co-processing strategies, as well as develop new methods for biogenic carbon tracking and measurement.

bio-oil↗

Organic Analysis of Catalytic Fischer-Tropsch Synthesis Products and Ordinary Chondrite Meteorites by Stepwise Pyrolysis-GCMS: Organics in the Early Solar Nebula

Abiotic generation of complex organic compounds, in the early solar nebula that formed our solar system, is hypothesized by some to occur via Fischer-Tropsch (FT) synthesis. In its simplest form, FT synthesis involves the low temperature (<300degC) catalytic reaction of hydrogen and carbon monoxide gases to form more complex hydrocarbon compounds, primarily n-alkanes, via reactive nano-particulate iron, nickel, or cobalt, for example. Industrially, this type of synthesis has been utilized in the gas-to-liquid process to convert syngas, produced from coal, natural gas, or biomass, into paraffin waxes that can be cracked to produce liquid diesel fuels. In general, the effect of increasing reaction temperature (>300degC) produces FT products that include lesser amounts of n-alkanes and greater alkene, alcohol, and polycyclic aromatic hydrocarbon (PAH) compounds. We have begun to experimentally investigate FT synthesis in the context of abiotic generation of organic compounds in the early solar nebula. It is generally thought that the early solar nebula included abundant hydrogen and carbon monoxide gases and nano-particulate matter such as iron and metal silicates that could have catalyzed the FT reaction. The effect of FT reaction temperature, catalyst type, and experiment duration on the resulting products is being investigated. These solid organic products are analyzed by thermal-stepwise pyrolysis-GCMS and yield the types and distribution of hydrocarbon compounds released as a function of temperature. We show how the FT products vary by reaction temperature, catalyst type, and experimental duration and compare these products to organic compounds found to be indigenous to ordinary chondrite meteorites. We hypothesize that the origin of organics in some chondritic meteorites, that represent an aggregation of materials from the early solar system, may at least in part be from FT synthesis that occurred in the early solar nebula.

Locke, Darren R.↗

Carbon flowers as electrocatalysts for the reduction of oxygen to hydrogen peroxide

Small-scale and decentralized production of H 2 O 2 via electrochemical reduction of oxygen is of great benefit, especially for sanitization, air and water purification, as well as for a variety of chemical processes. The development of low-cost and high-performance catalysts for this reaction remains a key challenge. Carbon-based materials have drawn substantial research efforts in recent years due to their advantageous properties, such as high chemical stability and high tunability in active sites and morphology. Deeper understanding of structure–activity relationships can guide the design of improved catalysts. We hypothesize that mass transport to active sites is of great importance, and herein we use carbon materials with unique flower-like superstructures to achieve high activity and selectivity for O 2 reduction to H 2 O 2 . The abundance of nitrogen active sites controlled by pyrolysis temperature resulted in high catalytic activity and selectivity for oxygen reduction reaction (ORR). The flower superstructure showed higher performance than the spherical nanoparticles due to greater accessibility to the active sites. Chemical activation improves the catalysts’ performances further, driving the production of H 2 O 2 to a record-setting rate of 816 mmol·g cat -1 ·h -1 using a bulk electrolysis setup. In conclusion, this work demonstrates the development of a highly active catalyst for the sustainable production of H 2 O 2 through rational design and synthetic control. The understanding from this work provides further insight into the design of future carbon-based electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating Diesel/Biofuel Blends Using Artificial Neural Networks and Linear/Nonlinear Equations

Abstract The use of biomass-derived additives in diesel fuel mixtures has the potential to increase the fuel’s efficiency, decrease the formation of particulate matter during its combustion, and retain the fuel’s behavior in cold weather. To this end, identifying compounds that enable these behaviors is paramount. The present work utilizes a series of linear and non-linear equations in series with artificial neural networks to predict the cetane number, yield sooting index, kinematic viscosity, cloud point, and lower heating value of multi-component blends. Property values of pure components are predicted using artificial neural networks trained with existing experimental data, and these predictions and their expected errors are propagated through linear and non-linear equations to obtain property predictions for multi-component blends. Individual component property prediction errors, defined by blind prediction median absolute error, are 4.91 units, 7.84 units, 0.06 cSt, 4.00 °C, and 0.55 MJ/kg for cetane number, yield sooting index, kinematic viscosity, cloud point, and lower heating value respectively. On average, property predictions for blends are shown to be accurate to within 6% of the blends’ experimental values. Further, a multitude of compounds expected to be produced from catalytically upgrading products of fast pyrolysis are evaluated with respect to their behavior in diesel fuel blends.

09 BIOMASS FUELS↗

Small-Scale Engineered High Flexibility Gasifier

This project advances a small-scale gasification unit as the first step in syngas-based hydrogen, chemicals, and synthetic fuels production. This unit is associated with an enhanced flexibility to different carbonaceous feedstocks including different types of coals, biomass, and plastics. The purpose of the project was to demonstrate feasibility and efficiency of coal pyrolysis in an auger reactor (pyrolyzer); supplemental methane and pyrolysis gas conversion into syngas in a proprietary non-catalytic converter; combined performance of pyrolyzer and non-catalytic converter to convert coal into syngas The proposed technology is based on an application of an intermediate speed pyrolysis at the temperature range 400-600°C as the first stage of biomass processing. At an industrial scale, an incorporation of coal pyrolysis into a feeding machine – auger-reactor allows to decrease its capital cost. At a pilot scale, it permits to employ electricity to build a compact device for testing of downstream equipment. The auger-reactor (pyrolyzer) generates pyrolysis gas and char practically from any carbonaceous feedstocks but their compositions and quantities are determined by their types. Pyrolysis gas is converted into syngas (mix of H 2 and CO) in a novel, proprietary hydrogen flame assisted non-catalytic converter which employs O 2 instead of air as an oxidizer. This reactor (converter) allows an easy adjustment to different pyrolysis gas compositions and tolerates a presence of sulfur and nitrogen contaminants. Our technology assumes carbonaceous feedstocks gasification with oxygen to allow the products H 2 , CO or CO 2 to be not diluted in N 2 and ready for the following synthesis of chemicals and fuels. Due to the same reason, it permits a more efficient CO 2 capture for its transport and storage. An implementation of our small-scale gasification process may overcome economic constrains by a flexible acceptance of coal, biomass, and plastics as well as their unsorted mixtures to make syngas for the following production of pure hydrogen, chemical and/or synthetic fuels.

42 ENGINEERING↗

Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels

NREL’s thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient and economical route to completely biogenic pyrolysis-based fuel precursors, potential fuels, and value-added chemicals depending on catalyst choice and process conditions. In this approach, biomass vapors are generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce conditioned vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled with a custom pyrolyzer system designed to produce consistent composition pyrolysis vapors as feed to the DCR. The coupled system is shown below (Figure 1). Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available and laboratory modified zeolite-based catalysts. Upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and micro distillation to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. Measured process parameters identified from technoeconomic process analysis included achieving oil oxygenate contents of 20% or less, carbon-conversion efficiencies of 30% or more, and catalyst coking rates of 10% or less. A proprietary modified zeolite catalyst from Johnson Matthey produced oils that met these requirements. Using the DCR equipped with a proprietary nozzle system, a second approach focused on reducing the carbon intensity of petroleum-derived hydrocarbon fuels by FCC co-processing these CFP oils with petroleum vacuum gas oil (VGO) to produce biogenic carbon containing fuels. The vapor-phase upgrading results demonstrated for the first time the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The co-processing results demonstrated the feasibility of using CFP oils with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

bio-oil↗

Catalytic Layer Makes Aircraft Seats More Fire Retardant

Specially constructed cushion retards fires in aircraft seats through action of catalytic matrix that cracks flammable gaseous decomposition products to less flammable species. Improved cushion contributes substantially to fire safety without adding significantly to weight or to manufacturing cost. In this fire-blocking covering for an aircraft seat cushion, flammable pyrolysis products cracked to less flammable species by catalytic layer covering foam core of cushion. Aluminum foil holds in pyrolysis vapors to promote catalysis and prevent spread of fire by ignition of released vapors.

Parker, John A.↗

BETO 2021 Peer Review - Process Monitoring and Predictions of Biorefinery Performance

Online process monitoring coupled with rapid predictive tools will be essential to refineries of the future to provide real-time feedback and process control on new, renewable feeds and their accompanying processes and products. This project will provide refinery operators with tools to predict product component concentrations in minutes from online, slip stream mass spectra, allowing for rapid detection of off-specification product. We will arrive at a template for predictive tool generation through the development of a specific tool as a starting point -- co-processing of pyrolysis oils and vacuum gas oil over fluid catalytic cracking (FCC) catalysts.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗