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9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Pilot-Scale CFP Commissioning: Creative Problem Solving and Lessons Learned

We have commissioned a pilot-scale, ex-situ catalytic fast pyrolysis (CFP) reactor system in the Thermal and Catalytic Process Development Unit (TCPDU) at the National Renewable Energy Laboratory. The FCC-style CFP system, including a riser and continuous regeneration, was added to the existing half-ton-per-day biomass fast pyrolysis unit and was designed to run a zeolite-type catalyst. The system is unique due to its scale and catalyst flow control scheme. As the design of this system was informed by early data from a bench-scale reactor, several technical scale-up challenges had to be overcome. Additionally, physical constraints and the complexities of biomass vapors required and inspired creative solutions. This talk will discuss the specific challenges we found and addressed, including an oxygen deficiency in the regenerator and plugging in the exit streams. We explored several options for increasing oxygen availability and selected a cyclone-catalyst return design on the exit line so we could increase air flow through the regenerator. We found that hot gas filtration is essential in any exit streams containing water vapor and trace amounts of catalyst; any combination of catalyst and condensate quickly makes mud that plugs equipment and severely limits run time. Duplicate filters are also required to extend run time. Most of the equipment and solutions were designed and installed by our team of engineers and technicians, working closely together in an iterative process to design, install, operate, then redesign. Collaborations with other national laboratories with computational fluid dynamics expertise helped inform designs and identify creative solutions to these scale-up challenges. Ultimately, data from the reactor system will be used to validate a comprehensive kinetic model of CFP that can be used to better design and inform new systems at various scales.

09 BIOMASS FUELS↗
DOE OSTI2021

Ex Situ Catalytic Fast Pyrolysis of Lignocellulosic Biomass to Hydrocarbon Fuels: 2020 State of Technology

Biomass catalytic fast pyrolysis (CFP) research was funded by the Bioenergy Technologies Office (BETO) of the U.S. Department of Energy (DOE) to enable technical breakthroughs to help reduce the cost of conversion of biomass to liquid hydrocarbon fuels. The key goals were to achieve a mature plant modeled Minimum Fuel Selling Price of $3/GGE, with greater than 60% greenhouse gas (GHG) reduction over petroleum derived gasoline by 2022. Experimental results at NREL and PNNL, along with lifecycle analysis by ANL show that we achieved these goals based on performance at the bench scale. A Pt/TiO2 catalyst was used in a fixed bed reactor for upgrading pyrolysis vapors from an upstream fast pyrolysis reactor (ex-situ configuration) to produce CFP oil with 16.5% oxygen content. Subsequent co-hydrotreating of 10 vol% of CFP oil with 90 vol% straight run diesel (SRD) at the bench scale yielded greater than 95% carbon efficiency for the CFP oil portion of the feed. Light oxygenated coproducts were recovered from the off gases from the CFP process via adsorption and subsequent desorption. Aspen Plus modeling of purification of the desorbed stream using the UNIFAC property method showed that acetone and methyl-ethyl-ketone can be purified to chemicals grade and sold as coproducts to benefit the economics and reduce GHG emissions attributed to the fuel product. Some of the key risks and uncertainties associated with this process, and potential future work are mentioned in this report.

09 BIOMASS FUELS↗
DOE OSTI2022

Co-processing catalytic fast pyrolysis oil in an FCC reactor

Here, studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to a volume fraction of 0.05 with VGO at 521 degrees C and 257 kPa. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elemental analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. The experiments showed that 75%-100% of biocarbon is incorporated into liquid fuels relative to fossil carbon, depending on catalyst and CFPO. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at 24 to 29 $\$$/GJ ($\$$2.90 to $\$$3.50 per gasoline-gallon equivalent; GGE) at a yield of 4.87-7.14 GJ/t(biomass) or 40-58 GGE/t.

09 BIOMASS FUELS↗
DOE OSTI2021

Co-Processing Catalytic Fast Pyrolysis Oil in an FCC Reactor

Studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to 5 vol% with VGO at 521°C and 2.57 bar. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elemental analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. For experiments with E-Cat as catalyst, approximately 70% of biocarbon is incorporated into liquid fuels relative to fossil carbon, while more of the biocarbon is contained in tail gas (as carbon dioxide or olefins) and/or coke. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at $3 to $4 per gasoline-gallon equivalent (GGE) at a yield of 51 GGE per ton of biomass.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2023

Catalytic Upgrading of Pyrolysis Products for the Production of Sustainable Aviation Fuel

The objective of this project is advance the state-of-technology for a catalytic fast pyrolysis (CFP) + hydrotreating (HT) process to produce sustainable aviation fuel and other biogenic products. Our approach focuses on performing integrated experiments using realistic biomass feedstocks and non-noble metal technical catalyst formulations. CFP is performed in an ex-situ configuration using a fluidized bed reactor without co-fed hydrogen. Research advancements over the past two years include establishing benchmark yield structures and compositional data for each step of the biomass-to-SAF process, demonstrating the ability to produce a cycloalkane-rich SAF product that meets key ASTM 4054 guidelines, generating benchmark characterization data for technical catalyst formulations with an emphasis on determining the unique composition and combustion properties of biogenic coke, and establishing bio-oil critical material attributes to mitigate the risk of plugging during down-stream hydroprocessing. Other impacts from this project include generation of broadly enabling scientific knowledge (12 publications/12 presentations since 2021), engagement with industry partners (Johnson Matthey, ExxonMobil, Phillips 66), and identification of a promising pathway to market that addresses emerging demands for biogenic refinery feedstocks.

biomass↗
DOE OSTI2021

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↗
DOE OSTI2022

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 route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated 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 FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

biogenic carbon↗
DOE OSTI2024

Molten-Phase Unsaturation Enhanced Pyrolytic Upcycling of Polyolefins

Fast pyrolysis is a robust deconstruction technology for chemically upcycling waste plastics without losing significant carbon to noncondensable gases. However, fast pyrolysis of polyolefins often produces hydrocarbons with broad molecular weight distributions, mainly waxes, which can also negatively affect the commercial reactor operation and downstream upgrading of the products. We discovered that combining molten-phase thermal treatment with subsequent fast pyrolysis offers a facile method to enhance polyolefin pyrolysis and catalytic upgrading. The molten-phase thermal treatment increased unsaturated C–C bonds in the treated polyolefins. During subsequent pyrolysis, the preheated polyolefins significantly reduced wax range hydrocarbons in the condensable products without an increase in gas formation. Here, the wax yields from pyrolysis of high-density polyethylene (HDPE) preheated to 295 °C and low-density polyethylene (LDPE) preheated to 275 °C were 20.5% and 26.5%, respectively, compared to 38.6% and 46% produced from pyrolyzing untreated polyolefins. When catalytically pyrolyzed using a zeolite catalyst, the preheated polyolefins promoted higher yields of olefins during ex-situ catalytic pyrolysis and higher yields of aromatic hydrocarbons during in-situ catalytic pyrolysis. During ex-situ catalytic pyrolysis, ethylene yields were 23.3% and 24.7% for the preheated HDPE and LDPE compared to 16.7% and 9.3% for untreated HDPE and LDPE, respectively.

Aromatic compounds↗