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At least 235 records · Page 13

Oxygen production by pyrolysis of lunar regolith

Oxygen was identified as the most important product of initial lunar materials processing efforts. A source of oxygen on the Moon provides an alternative to the costly transport of propellant to the Moon or to low earth orbit. Pyrolysis, or vapor-phase reduction, involves heating a feedstock to temperatures sufficient to decompose the constituent metal oxides and release oxygen. The process relies on the vaporization of metal oxides in the form of reduced suboxides or atomic species. The reduced species must then be condensed without re-oxidizing, yielding oxygen in the gas phase. The feasibility of obtaining oxygen from common lunar minerals was demonstrated using solar furnace experiments. These results are discussed together with chemical equilibrium models which were extended to include the multicomponent oxides used in experiments. For the first time, both experiments and theoretical models dealt with the complex oxides that make up potential lunar feedstocks. Two major conclusions are drawn from this preliminary work. First, unbeneficiated regolith is a suitable feedstock for pyrolysis. Second, the process can operate at moderate temperatures, circa 2000 K, which could be supplied by direct solar or electrical energy. In addition to these advantages in choice of feedstock and energy source, the pyrolysis process requires no chemicals or reagents, making it an attractive process for lunar oxygen production.

Senior, Constance L.↗

Lunar oxygen production by pyrolysis of regolith

Oxygen represents one of the most desirable products of lunar mining and manufacturing. Among the many processes which have been proposed for oxygen production, pyrolysis stands out as one which is uncomplicated and easy to bootstrap. Pyrolysis or vapor-phase reduction involves heating regolith to temperatures sufficient to allow partial decomposition and vaporization. Some metal oxides give up oxygen upon heating, either in the gas phase to form reduced gaseous species or in the condensed phase to form a metallic phase. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2200 K, giving total gas pressures of 0.001 to 0.1 torr. Bulk regolith can be used as a feedstock without beneficiation with concentrated solar radiation supplying most of energy needed. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts.

Senior, Constance L.↗

Analytical pyrolysis experiments of Titan aerosol analogues in preparation for the Cassini Huygens mission

Comparative pyrolysis mass spectrometric data of Titan aerosol analogs, called 'tholins', are presented. The Titan tholins were produced in the laboratory at Cornell by irradiation of simulated Titan atmospheres with high energy electrons in plasma discharge. Mass-spectrometry measurements were performed at FOM of the solid phase of various tholins by Curie-point pyrolysis Gas-Chromatography/Mass-Spectrometry (GCMS) and by temperature resolved in-source Pyrolysis Mass-Spectrometry to reveal the composition and evolution temperature of the dissociation products. The results presented here are used to further define the ACP (Aerosol Collector Pyrolyser)-GCMS experiment and provide a basis for modelling of aerosol composition on Titan and for the iterpretation of Titan atmosphere data from the Huygens probe in the future.

Ehrenfreund, P.↗

Tar Production from Biomass Pyrolysis in a Fluidized Bed Reactor: A Novel Turbulent Multiphase Flow Formulation

A novel multiphase flow model is presented for describing the pyrolysis of biomass in a 'bubbling' fluidized bed reactor. The mixture of biomass and sand in a gaseous flow is conceptualized as a particulate phase composed of two classes interacting with the carrier gaseous flow. The solid biomass is composed of three initial species: cellulose, hemicellulose and lignin. From each of these initial species, two new solid species originate during pyrolysis: an 'active' species and a char, thus totaling seven solid-biomass species. The gas phase is composed of the original carrier gas (steam), tar and gas; the last two species originate from the volumetric pyrolysis reaction. The conservation equations are derived from the Boltzmann equations through ensemble averaging. Stresses in the gaseous phase are the sum of the Newtonian and Reynolds (turbulent) contributions. The particulate phase stresses are the sum of collisional and Reynolds contributions. Heat transfer between phases, and heat transfer between classes in the particulate phase is modeled, the last resulting from collisions between sand and biomass. Closure of the equations must be performed by modeling the Reynolds stresses for both phases. The results of a simplified version (first step) of the model are presented.

Bellan, J.↗

Characterization of exopolymers of aquatic bacteria by pyrolysis-mass spectrometry

Exopolymers from a diverse collection of marine and freshwater bacteria were characterized by pyrolysis-mass spectrometry (Py-MS). Py-MS provides spectra of pyrolysis fragments that are characteristic of the original material. Analysis of the spectra by multivariate statistical techniques (principal component and canonical variate analysis) separated these exopolymers into distinct groups. Py-MS clearly distinguished characteristic fragments, which may be derived from components responsible for functional differences between polymers. The importance of these distinctions and the relevance of pyrolysis information to exopolysaccharide function in aquatic bacteria is discussed.

NASA Program CELSS↗

Method for the determination of lignin content of a sample by flash pyrolysis in an atmosphere of hydrogen or helium and method therefor

The lignin content of wood, paper pulp or other material containing lignin (such as filter paper soaked in black liquor) is more readily determined by flash pyrolysis of the sample at approximately 550.degree. C. in a reducing atmosphere of hydrogen or in an inert atmosphere of helium followed by a rapid analysis of the product gas by a mass spectrometer. The heated pyrolysis unit as fabricated comprises a small platinum cup welded to an electrically-heated stainless steel ribbon with control means for programmed short duration (1.5 sec, approximately) heating and means for continuous flow of hydrogen or helium. The pyrolysis products enter an electron-ionization mode mass spectrometer for spectral evaluation. Lignin content is obtained from certain ratios of integrated ion currents of many mass spectral lines, the ratios being linearly related to the Kappa number of Klason lignin.

Shakkottai, Parthasarathy↗

Effect of the Presence of Chlorates and Perchlorates on the Pyrolysis of Organic Compounds: Implications for Measurements Done with the SAM Experiment Onboard the Curiosity Rover

The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.

Millan, M.↗

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Millan, M.↗

Evaluation of Corrosion Susceptibility of Structural Steels in Biomass Derived Pyrolysis Oil

Biomass derived pyrolysis oil is a promising renewable energy source. Due to the variety of biomass feedstocks, the bio-oils could contain a wide range of organic constituents which would provide unique corrosive environments for structural materials. A preliminary work exposed different classes of steels and stainless steels to selected organic constituents of biomass pyrolysis oils and found that corrosion susceptibility, assessed using electrochemical impedance spectroscopy (EIS), was prominent in the steels with Cr lower than 11 wt.%. Although this result suggests stainless steels will resist corrosion by certain organic constituents, it may not be sufficient to predict the corrosion performance in real bio-oils. Therefore, this study attempted electrochemical measurements on Cr-alloyed steels and stainless steels directly exposed to a biomass derived pyrolysis oil. To overcome the low conductivity of bio-oils, a customized Luggin capillary was designed to minimize the ohmic path in bio-oils. The results of this work will be reported.

Jun, Jiheon↗

Developing a High Value Chemical Coproduct: Bio-Base Insecticides from Catalytic Fast Pyrolysis

Coproduction of biochemicals from the thermochemical conversion of biomass is a strategy to reduce biofuel costs and improve bio-oil quality in an integrated biorefinery. (Challenge) Cost effective separations of coproducts from thermochemical conversion streams remains a challenge largely due to the heterogenous nature and stability of thermochemical conversion streams. (Solution) Bio-based insecticides isolated from catalytic fast pyrolysis (CFP) oils are a viable coproduct that can overcome the oil is more stable, they are a high value product, and they can remain a mixture of components. (Approach) This work focuses on the development of a bio-based insecticide coproduct that is distilled from a catalytic fast pyrolysis bio-oil produced using a platinum on titanium dioxide (Pt/TiO2) catalyst to upgrade pyrolysis vapors.

BIOMASS FUELS↗

Progress on Natural Gas Pyrolysis for Low-Carbon H2 Production

This presentation summarizes the on-going work in NETL's new Natural Gas Decarbonization and H2 Technologies on Pyrolysis. It includes highlights on a modular pyrolysis based process producing H2 and solid carbons, a report documenting market size, drivers, customers for solid carbon products, and new work assessing H2 pyrolysis technologies for large scale H2 production.

Haynes, Daniel↗

Mechanistic insights into the pyrolysis of poly (vinyl chloride)

The accumulation of unmanaged plastic waste in the environment has a devastating impact upon marine life and human health. Catalytic and thermal pyrolysis are promising technologies toward the efficient utilization of plastic waste. Yet, the processing of polymers, such as polyvinyl chloride (PVC), that decompose into corrosive compounds remains a major challenge. In this work, we employ density functional theory (DFT) and thermogravimetric analysis (TGA) to explore the elementary chemical steps that underpin the thermal decomposition of PVC. We determine that the dehydrochlorination reaction (i.e., 1 st stage of thermal decomposition) begins in tertiary chloride defects and propagates via HCl–mediated autocatalysis of internal allylic (IA) chloride groups. The latter groups, when in the vicinity of π–conjugated polymer segments, release HCl in a facile manner. We predict that other compounds, including hydrogen halides and H 2 O could also catalyze PVC’s dehydrochlorination. We suggest that hydrogen halides are the most efficient catalysts for this process, while other compounds like H 2 O may slow down the dehydrochlorination compared to purely HCl-catalyzed process, because of the dilution of the produced HCl. This result is corroborated by TGA experiments. Additionally, we study the thermochemistry and kinetics of polyene chain crosslinking and the formation of aromatics. The former reaction proceeds in parallel with the dehydrochlorination process (i.e., during the 1st stage of thermal decomposition), whilst the latter may occur at high temperatures (i.e., during the 2 nd stage of thermal decomposition). Furthermore, this work contributes to the fundamental understanding of molecular scale phenomena that take place during PVC pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chapter 29 - Pyrolysis of Lignocellulosic Biomass: Oil, Char, and Gas

Biomass pyrolysis is a technology that uses high temperatures to break down biomaterials like wood without completely burning them. Products include char, combustible gas, and vapors; the vapors can be condensed into a liquid with myriad uses. This chapter serves as a primer for the fundamental physics and chemistry involved in biomass pyrolysis, common reactor systems, and some reported uses for the products.

BIOMASS FUELS↗

Optimizing Process Conditions during Catalytic Fast Pyrolysis of Pine with Pt/TiO 2 —Improving the Viability of a Multiple-Fixed-Bed Configuration

Catalytic fast pyrolysis (CFP) has been identified as a promising pathway for the production of renewable fuels and co-products. However, continued technology development is needed to increase process efficiency and reduce process costs. This report builds upon previous research in which a bifunctional metal–acid Pt/TiO 2 catalyst was utilized in a fixed-bed reactor operated with co-fed H 2 to improve product yield and reduce coke generation compared to conventional CFP methods. Here, we report further process optimization, in which we achieved similar CFP oil carbon efficiency (>35%) and CFP oil oxygen content (<20 wt %) to our previous report while reducing catalyst and equipment costs by increasing time-on-stream between regenerations by 40–95% and decreasing required regeneration time by more than a factor of 2. These process improvements were achieved by conducting parameter sweeps to determine optimum conditions for CFP and regeneration with key variables including pyrolysis temperature, catalytic upgrading temperature, hydrogen partial pressure, and regeneration oxygen concentration. Coupled with comprehensive oil analyses, these data provide foundational insight into the deoxygenation and coking chemistries for CFP under realistic process conditions while also advancing the technology through applied engineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting Thermal Excursions During in situ Oxidative Regeneration of Packed Bed Catalytic Fast Pyrolysis Catalyst

Ex situ catalytic fast pyrolysis (CFP) uses a secondary reactor to upgrade biomass pyrolysis vapors to stabilized CFP oils with reduced oxygen content. In one configuration, the secondary reactor is operated as a packed-bed swing reactor system which allows coke-deactivated beds to be decarbonized in situ while other beds remain online for vapor upgrading. In situ decarbonization must be done carefully to avoid irreversible deactivation and/or physical degradation of catalyst pellets. Given that packed bed reactors are well known to have poor heat transfer characteristics, this is a critical issue impacting scaleability and commercial viability of the technology. To predict thermal excursions during regeneration, finite element computational models have been built to assist in scaling up oxidative decarbonization of a Pt/TiO2 CFP catalyst (0.5 mm spheres) from a bench scale packed bed with 100 g of catalyst to a pilot scale packed bed with 2 kg of catalyst and internal cooling tubes. Based on transient measurements of outlet temperature and effluent CO2 concentration, and using an assumed coke profile and activation energy, this paper demonstrates that specific combinations of effective thermal conductivity and wall heat transfer coefficient can fit bench scale oxidative regeneration data equally well. For the upscaled 2 kg bed, four bench-scale “best fit” parameter pairs give different predictions for location and magnitude of thermal excursions, with the maximum computed bed temperature gradients ranging from 30 °C cm-1 to as high as 3000 °C cm-1. The larger the fraction of heat removal by conduction through the cooling tubes, the greater the differences between the parameter pairs. The modelling results presented in this paper cast doubt on the industrial viability of the proposed combination of catalyst, bed and regeneration process, and point to the need for alternate reactor designs. However, there is considerable uncertainly in some of the key model parameters. The reliability of model predictions can be increased by adding more temperature measurements at key bed locations, testing additional variations in process conditions, performing careful bed dissections to determine the true coke profile, and perhaps most importantly, directly measuring the effective thermal conductivity of the catalyst pellets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparing Effects of Feedstock and Run Conditions on Fast Pyrolysis Products Produced at the Pilot Scale: Solids Management from an Operational Perspective

Fast pyrolysis is a promising pathway for mass production of liquid transportable biofuels. The Thermochemical Process Development Unit (TCPDU) pilot plant at NREL is conducting research to support the Bioenergy Technologies Office's 2017 goal of a $3 per gallon biofuel. In preparation for down select of feedstock and run conditions, four different feedstocks were run at three different run conditions. The products produced were characterized extensively. Hot pyrolysis vapors and light gasses were analyzed on a slip stream, and oil and char samples were characterized post run.

09 BIOMASS FUELS↗

From Pyrolysis Oil to Advanced Biographite Anode: Unravelling Biocoke Structural Evolution and Delayed Coking Effects

Catalytic graphitization of biomass-derived carbon offers a promising route to produce biographite as a sustainable alternative to petroleum-based synthetic graphite for lithium-ion battery (LIB) anodes. This study investigates the physicochemical properties of biocokes produced from pyrolysis oil at carbonization temperatures ranging from 150 degrees C to 500 degrees C. Using an iron (Fe) catalyst, graphitization was performed at 1500 degrees C, significantly lower than the ~3000 degrees C required for conventional synthetic graphite. The effects of introducing an intermediate-temperature hold (400 degrees C-600 degrees C) prior to graphitization were evaluated, simulating a "delayed coking" process to enable the coproduction of sustainable aviation fuels (SAFs). Chemical structure evolution during biocoke formation was analyzed, and proposed mechanisms are presented. Biographites produced via the delayed coking pathway exhibited high crystallinity and excellent electrochemical performance in both half-cell and full-cell LIB configurations. The full cells exhibited an initial discharge capacity close to the theoretical capacity of the NMC622 cathode (175 mAh/g at 4.2 V), and high capacity retention (~88%) after 150 cycles. Notably, the graphitic and electrochemical properties remained stable across the range of intermediate hold temperatures. These findings provide a foundation for optimizing temperature parameters in delayed coking systems to enable scalable, integrated production of biographite and SAFs from pyrolysis oil.

09 BIOMASS FUELS↗

Flame stability analysis of flame spray pyrolysis by artificial intelligence

Flame spray pyrolysis (FSP) is a process used to synthesize nanoparticles through the combustion of an atomized precursor solution; this process has applications in catalysts, battery materials, and pigments. Current limitations revolve around understanding how to consistently achieve a stable flame and the reliable production of nanoparticles. Machine learning and artificial intelligence algorithms that detect unstable flame conditions in real time may be a means of streamlining the synthesis process and improving FSP efficiency. In this study, the FSP flame stability is first quantified by analyzing the brightness of the flame's anchor point. This analysis is then used to label data for both unsupervised and supervised machine learning approaches. The unsupervised learning approach allows for autonomous labeling and classification of new data by representing data in a reduced dimensional space and identifying combinations of features that most effectively cluster it. The supervised learning approach, on the other hand, requires human labeling of training and test data but is able to classify multiple objects of interest (such as the burner and pilot flames) within the video feed. The accuracy of each of these techniques is compared against the evaluations of human experts. Both the unsupervised and supervised approaches can track and classify FSP flame conditions in real time to alert users of unstable flame conditions. This research has the potential to autonomously track and manage flame spray pyrolysis as well as other flame technologies by monitoring and classifying the flame stability.

42 ENGINEERING↗