Bacterial biomarkers thermally released from dissolved organic matter
Greenwood, P.F.; Leenheer, J.A.; McIntyre, C.; Berwick, L.; Franzmann, P.D.
2006-01-01
Hopane biomarker products were detected using microscale sealed vessel (MSSV) pyrolysis gas chromatography-mass spectrometry (GC-MS) analysis of dissolved organic matter from natural aquatic systems colonised by bacterial populations. MSSV pyrolysis can reduce the polyhydroxylated alkyl side chain of bacteriohopanepolyols, yielding saturated hopane products which are more amenable to GC-MS detection than their functionalised precursors. This example demonstrates how the thermal conditions of MSSV pyrolysis can reduce the biologically-inherited structural functionality of naturally occurring organic matter such that additional structural fragments can be detected using GC methods. This approach complements traditional analytical pyrolysis methods by providing additional speciation information useful for establishing the structures and source inputs of recent or extant organic material. ?? 2006.
Synthesis of Bio-aromatics from Black Liquors Using Catalytic Pyrolysis
2018-01-01
Bio-aromatics (benzene, toluene, xylenes, BTX) were prepared by the catalytic pyrolysis of six different black liquors using both in situ and ex situ approaches. A wide range of catalysts was screened and conditions were optimized in microscale reactors. Up to 7 wt % of BTX, based on the organic fraction of the black liquors, was obtained for both the in situ and ex situ pyrolysis (T = 500–600 °C) using a Ga-modified H-ZSM-5 catalyst. The in situ catalytic pyrolysis of black liquors from hardwood paper mills afforded slightly higher yields of aromatics/BTX than softwood black liquors, a trend that could be confirmed by the results obtained in the ex situ catalytic pyrolysis. An almost full deoxygenation of the lignin and carbohydrate fraction was achieved and both organic fractions were converted to a broad range of (substituted) aromatics. The zeolite catalyst used was remarkably stable and even after 100 experiments in batch mode with intermittent oxidative catalyst regeneration, the yields and selectivity toward BTX remained similar. The ex situ pyrolysis of black liquor has potential for large-scale implementation in a paper mill without disturbing the paper production process. PMID:29607268
Modeling & processing of ceramic and polymer precursor ceramic matrix composite materials
NASA Astrophysics Data System (ADS)
Wang, Xiaolin
Synthesis and processing of novel materials with various advanced approaches have attracted much attention of engineers and scientists for the past thirty years. Many advanced materials display a number of exceptional properties and can be produced with different novel processing techniques. For example, AlN is a promising candidate for electronic, optical and opto-electronic applications due to its high thermal conductivity, high electrical resistivity, high acoustic wave velocity and large band gap. Large bulk AlN crystal can be produced by sublimation of AlN powder. Novel nonostructured multicomponent refractory metal-based ceramics (carbides, borides and nitrides) show a lot of exceptional mechanical, thermal and chemical properties, and can be easily produced by pyrolysis of suitable preceramic precursors mixed with metal particles. The objective of this work is to study sublimation and synthesis of AlN powder, and synthesis of SiC-based metal ceramics. For AlN sublimation crystal growth, we will focus on modeling the processes in the powder source that affect significantly the sublimation growth as a whole. To understand the powder porosity evolution and vapor transport during powder sublimation, the interplay between vapor transport and powder sublimation will be studied. A physics-based computational model will be developed considering powder sublimation and porosity evolution. Based on the proposed model, the effect of a central hole in the powder on the sublimation rate is studied and the result is compared to the case of powder without a hole. The effect of hole size on the sublimation rate will be studied. The effects of initial porosity, particle size and driving force on the sublimation rate are also studied. Moreover, the optimal growth condition for large diameter crystal quality and high growth rate will be determined. For synthesis of SiC-based metal ceramics, we will focus on developing a multi-scale process model to describe the dynamic behavior of filler particle reaction, microstructure evolution, at the microscale as well as transient fluid flow, heat transfer, and species transport at the macroscale. The model comprises of (i) a microscale model and (ii) a macroscale transport model, and aims to provide optimal conditions for the fabrication process of the ceramics. The porous media macroscale model for SiC-based metal-ceramic materials processing will be developed to understand the thermal polymer pyrolysis, chemical reaction of active fillers and transport phenomena in the porous media. The macroscale model will include heat and mass transfer, curing, pyrolysis, chemical reaction and crystallization in a mixture of preceramic polymers and submicron/nano-sized metal particles of uranium, zirconium, niobium, or hafnium. The effects of heating rate, sample size, size and volume ratio of the metal particles on the reaction rate and product uniformity will be studied. The microscale model will be developed for modeling the synthesis of SiC matrix and metal particles. The macroscale model provides thermal boundary conditions to the microscale model. The microscale model applies to repetitive units in the porous structure and describes mass transport, composition changes and motion of metal particles. The unit-cell is the representation unit of the source material, and it consists of several metal particles, SiC matrix and other components produced from the synthesis process. The reactions between different components, the microstructure evolution of the product will be considered. The effects of heating rate and metal particle size on species uniformity and microstructure are investigated.
Wu, Zhiqiang; Wang, Shuzhong; Luo, Zhengyuan; Chen, Lin; Meng, Haiyu; Zhao, Jun
2017-07-01
In this paper, the influence of cellulose on the physicochemical properties and the gasification reactivity of co-pyrolysis char was investigated. A specific surface area analyzer and an X-ray diffraction system were used to characterize the pore structure and the micro-crystalline structure of char. Fractal theory and deconvolution method were applied to quantitatively investigate the influence of cellulose on the structure of co-pyrolysis char. The results indicate that the improvements in the pore structure due to the presence of cellulose are more pronounced in the case of anthracite char with respect to bituminous char. Cellulose promotes the ordering of micro-scale structure and the uniformity of both anthracite and bituminous char, while the negative synergetic effect was observed during gasification of co-pyrolysis char. The exponential relationships between fractal dimension and specific surface area were determined, along with the relations between the gasification reactivity index and the microcrystalline structure parameter. Copyright © 2017 Elsevier Ltd. All rights reserved.
Microscale Titration in Schools Titration Competition.
ERIC Educational Resources Information Center
Clark, Michael J.
1998-01-01
Reviews the requirements of the National Titration Competition and describes how a team in a local competition used the technique. Compares microscale titration to conventional titration. Outlines the benefits of employing microscale techniques. (DDR)
Tienpont, Bart; David, Frank; Pereira, Alberto; Sandra, Pat
2011-11-18
A new generic pyrolysis unit (PyroVial) is presented. Pyrolysis is carried out in a 2 mL autosampler vial placed in a XYZ robot for automated pyrolysis as well as for pre- and post-pyrolysis treatment of the sample. Analysis of the volatiles is performed by headspace analysis while the semi- and non-volatiles are extracted from the pyrolysate with an organic solvent. The features of the PyroVial are such that all chromatographic techniques can be applied. The pyrolysis unit is discussed in terms of its technical features and its performance is illustrated with applications including conventional pyrolysis, in situ and post-pyrolysis derivatization, reaction pyrolysis and catalytic cracking. Copyright © 2011 Elsevier B.V. All rights reserved.
Experimental Study and Numerical Modeling of Gas Flow in Microchannels and Micronozzles
2005-12-01
built and used to study gas flows in microscale. Gas velocity measurements in microscale were conducted using both Laser Induced Fluorescence...velocity measurements in microscale were conducted using both Laser Induced Fluorescence technique (LIF) in conjunction with Image Correlation...micronozzles, several velocity measurement techniques have been used, such as laser doppler anemometry (LDA), particle image velocimetry (PIV), molecular
Gunduz, Sema; Akman, Suleyman
2015-04-01
Sulphur was determined in various vegetables via molecular absorption of carbon monosulphide (CS) at 258.056 nm using a solid sampling high resolution continuum source electrothermal atomic absorption spectrometer (SS HR-CS ETAAS). Samples were dried, ground and directly introduced into the ruthenium coated graphite furnace as 0.05 to 0.50mg. All determinations were performed using palladium+citric acid modifier and applying a pyrolysis temperature of 1000 °C and a volatilisation temperature of 2400 °C. The results were in good agreement with certified sulphur concentrations of various vegetal CRM samples applying linear calibration technique prepared from thioacetamide. The limit of detection and characteristic mass of the method were 7.5 and 8.7 ng of S, respectively. The concentrations of S in various spinach, leek, lettuce, radish, Brussels sprouts, zucchini and chard samples were determined. It was showed that distribution of sulphur in CRM and grinded food samples were homogeneous even in micro-scale. Copyright © 2014 Elsevier Ltd. All rights reserved.
Aligned carbon nanotubes patterned photolithographically by silver
NASA Astrophysics Data System (ADS)
Huang, Shaoming; Mau, Albert H. W.
2003-02-01
Selective growth of aligned carbon nanotubes (CNTs) by pyrolysis of iron (II) phthalocyanine (FePc) on quartz substrate patterned photolithographically by metallic silver has been demonstrated. Micro/nanopattern of aligned CNTs can be achieved by using a photomask with features on a microscale. With convenient use of simple high-contract black and white films as a photomask, aligned nanotubes patterned with 20 μm resolution in large scale can be fabricated. This practical fabrication of aligned CNTs on patterned conducting substrate could be applied to various device applications of CNTs.
Nichkova, Mikaela; Dosev, Dosi; Perron, Richard; Gee, Shirley J; Hammock, Bruce D; Kennedy, Ian M
2006-02-01
Lanthanide oxide nanoparticles are promising luminescent probes in bioanalysis, because of their unique spectral properties, photostability, and low-cost synthesis. We report for the first time the application of europium-doped gadolinium oxide (Eu:Gd2O3) nanoparticles to the optical imaging of antibody micropatterns. The nanoparticles were synthesized by spray pyrolysis and coated with antibody (IgG) molecules by physical adsorption. Our experiments showed that the Eu:Gd2O3 is a good biocompatible solid support for antibody immobilization. The antibodies (anti-rabbit IgG) immobilized on the nanoparticles had excellent biological activity in the specific recognition reaction with rabbit IgG patterned in line strips (10 micromx10 microm) on a glass substrate by use of a micro-contact printing technique. The specific immunoreaction was confirmed by two independent microscopic techniques-fluorescence and scanning electron microscopy (SEM). Both microscopic images revealed that the nanoparticles were organized into designated structures as defined by the microcontact printing process with negligible non-specific binding. The nanoparticles can be used as fluorescent markers in a variety of immunosensing applications in a microscale format.
Recent progress on biomass co-pyrolysis conversion into high-quality bio-oil.
Hassan, H; Lim, J K; Hameed, B H
2016-12-01
Co-pyrolysis of biomass with abundantly available materials could be an economical method for production of bio-fuels. However, elimination of oxygenated compounds poses a considerable challenge. Catalytic co-pyrolysis is another potential technique for upgrading bio-oils for application as liquid fuels in standard engines. This technique promotes the production of high-quality bio-oil through acid catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize research progress on co-pyrolysis and catalytic co-pyrolysis, as well as their benefits on enhancement of bio-oils derived from biomass. This review focuses on the potential of plastic wastes and coal materials as co-feed in co-pyrolysis to produce valuable liquid fuel. This paper also proposes future directions for using this technique to obtain high yields of bio-oils. Copyright © 2016 Elsevier Ltd. All rights reserved.
Accelerated design of bioconversion processes using automated microscale processing techniques.
Lye, Gary J; Ayazi-Shamlou, Parviz; Baganz, Frank; Dalby, Paul A; Woodley, John M
2003-01-01
Microscale processing techniques are rapidly emerging as a means to increase the speed of bioprocess design and reduce material requirements. Automation of these techniques can reduce labour intensity and enable a wider range of process variables to be examined. This article examines recent research on various individual microscale unit operations including microbial fermentation, bioconversion and product recovery techniques. It also explores the potential of automated whole process sequences operated in microwell formats. The power of the whole process approach is illustrated by reference to a particular bioconversion, namely the Baeyer-Villiger oxidation of bicyclo[3.2.0]hept-2-en-6-one for the production of optically pure lactones.
NASA Astrophysics Data System (ADS)
Haupt, Sue Ellen; Kosovic, Branko; Shaw, William
2017-04-01
The purpose of the US DOE's Mesoscale-Microscale Coupling (MMC) Project is to develop, verify, and validate physical models and modeling techniques that bridge the most important atmospheric scales that determine wind plant performance and reliability. As part of DOE's Atmosphere to Electrons (A2e) program, the MMC project seeks to create a new predictive numerical simulation capability that is able to represent the full range of atmospheric flow conditions impacting wind plant performance. The recent focus of MMC has been on nonstationary conditions over flat terrain. These nonstationary cases are critical for wind energy and represent a primary need for mesoscale meteorological forcing of the microscale models. The MMC team modeled two types of non-stationary cases: 1) diurnal cycles in which the daytime convective boundary layer collapses with the setting of the sun when the surface heat flux changes from positive to negative, passing through a brief period of neutral stability before becoming stable, with smaller scale turbulence and the potential for low level jet (LLJ) formation; and 2) frontal passage as an example of a synoptic weather event that may cause relatively rapid changes in wind speed and direction. The team compared and contrasted two primary techniques for non-stationary forcing of the microscale by the mesoscale model. The first is to use the tendencies from the mesoscale model to directly force the microscale mode. The second method is to couple not only the microscale domain's internal forcing parameters, but also its lateral boundaries, to a mesoscale simulation. While the boundary coupled approach provides the greatest generality, since the mesoscale flow information providing the lateral boundary information for the microscale domain contains no explicit turbulence information, the approach requires methods to accelerate turbulence production at the microscale domain's inflow boundaries. Forefront assessment strategies, including comparing spectra and cospectra, were used to assess the techniques. Testing methods to initialize turbulence at the microscale was also accomplished.
NASA Astrophysics Data System (ADS)
Ji, Xiaoyu; Cheng, Hiu Yan; Grede, Alex J.; Molina, Alex; Talreja, Disha; Mohney, Suzanne E.; Giebink, Noel C.; Badding, John V.; Gopalan, Venkatraman
2018-04-01
Conformally coating textured, high surface area substrates with high quality semiconductors is challenging. Here, we show that a high pressure chemical vapor deposition process can be employed to conformally coat the individual fibers of several types of flexible fabrics (cotton, carbon, steel) with electronically or optoelectronically active materials. The high pressure (˜30 MPa) significantly increases the deposition rate at low temperatures. As a result, it becomes possible to deposit technologically important hydrogenated amorphous silicon (a-Si:H) from silane by a simple and very practical pyrolysis process without the use of plasma, photochemical, hot-wire, or other forms of activation. By confining gas phase reactions in microscale reactors, we show that the formation of undesired particles is inhibited within the microscale spaces between the individual wires in the fabric structures. Such a conformal coating approach enables the direct fabrication of hydrogenated amorphous silicon-based Schottky junction devices on a stainless steel fabric functioning as a solar fabric.
Flash Vacuum Pyrolysis: Techniques and Reactions.
Wentrup, Curt
2017-11-20
Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation, and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave, and millimeterwave spectroscopies, gas-phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution-spray and falling-solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Towards microscale electrohydrodynamic three-dimensional printing
NASA Astrophysics Data System (ADS)
He, Jiankang; Xu, Fangyuan; Cao, Yi; Liu, Yaxiong; Li, Dichen
2016-02-01
It is challenging for the existing three-dimensional (3D) printing techniques to fabricate high-resolution 3D microstructures with low costs and high efficiency. In this work we present a solvent-based electrohydrodynamic 3D printing technique that allows fabrication of microscale structures like single walls, crossed walls, lattice and concentric circles. Process parameters were optimized to deposit tiny 3D patterns with a wall width smaller than 10 μm and a high aspect ratio of about 60. Tight bonding among neighbour layers could be achieved with a smooth lateral surface. In comparison with the existing microscale 3D printing techniques, the presented method is low-cost, highly efficient and applicable to multiple polymers. It is envisioned that this simple microscale 3D printing strategy might provide an alternative and innovative way for application in MEMS, biosensor and flexible electronics.
Small-scale hydrous pyrolysis of macromolecular material in meteorites
NASA Astrophysics Data System (ADS)
Sephton, M. A.; Pillinger, C. T.; Gilmour, I.
1998-12-01
The hydrous pyrolysis method, usually performed on several hundred grams of terrestrial rock sample, has been scaled down to accommodate less than two grams of meteorite sample. This technique makes full use of the high yields associated with hydrous pyrolysis experiments and permits the investigation of the meteorite macromolecular material, the major organic component in carbonaceous meteorites. The hydrous pyrolysis procedure transforms the high molecular weight macromolecular material into low molecular weight fragments. The released entities can then be extracted with supercritical fluid extraction. In contrast to the parent structure, the pyrolysis products are amenable for analysis by gas chromatography-based techniques. When subjected to hydrous pyrolysis, two carbonaceous chondrites (Orgueil and Cold Bokkeveld) released generally similar products, which consisted of abundant volatile aromatic and alkyl-substituted aromatic compounds. These results revealed the ability of small-scale hydrous pyrolysis to dissect extraterrestrial macromolecular material and thereby reveal its organic constitution.
McAdams, Harley; AlQuraishi, Mohammed
2015-04-21
Techniques for determining values for a metric of microscale interactions include determining a mesoscale metric for a plurality of mesoscale interaction types, wherein a value of the mesoscale metric for each mesoscale interaction type is based on a corresponding function of values of the microscale metric for the plurality of the microscale interaction types. A plurality of observations that indicate the values of the mesoscale metric are determined for the plurality of mesoscale interaction types. Values of the microscale metric are determined for the plurality of microscale interaction types based on the plurality of observations and the corresponding functions and compressed sensing.
Ozbek, Nil; Akman, Suleyman
2016-11-15
This study describes the applicability of solid sampling technique for the determination of fluorine in various baby foods via molecular absorption of calcium monofluoride generated in a graphite furnace of high-resolution continuum source atomic absorption spectrometry. Fluorine was determined at CaF wavelength, 606.440nm in a graphite tube applying a pyrolysis temperature of 1000°C and a molecule forming temperature of 2200°C. The limit of detection and characteristic mass of the method were 0.20ng and 0.17ng of fluorine, respectively. The fluorine concentrations determined in standard reference sample (bush branches and leaves) were in good agreement with the certified values. By applying the optimized parameters, the concentration of fluorine in various baby foods were determined. The fluorine concentrations were ranged from
Mattonai, Marco; Ribechini, Erika
2018-08-09
Reactive pyrolysis is a technique that provides mechanistic information by performing pyrolysis of the substrate in a sealed glass capsule at elevated temperature and pressure for relatively long time. This technique has already shown great potential for the analysis of biomass, favouring the formation of only the most thermostable compounds. In this work, both fast and reactive pyrolysis with on-line gas chromatography-mass spectrometry analysis (Py-GC/MS) are used to study fructose, inulin and Jerusalem artichoke tubers (Heliantus tuberosus). Interesting differences were found between the two systems, and became even more evident as the reaction time was increased. The most striking result was the formation of di-fructose dianhydrides (DFAs), a class of compounds with interesting biological activities. DFAs were obtained in high yields from reactive pyrolysis, but not from fast pyrolysis. Hypotheses on the pyrolysis mechanisms were made based upon the composition of the pyrolysates. This work describes for the first time the behaviour of fructans under reactive pyrolysis. Copyright © 2018 Elsevier B.V. All rights reserved.
Demonstrating Microscale Gas Reactions Using Disposable Plastic Syringes
ERIC Educational Resources Information Center
Goodwin, Alan
2011-01-01
This article provides an example of a teacher's learning, since the author only became aware of the microscale technique described very late in his professional career. The technique provides a convenient method of preparing and manipulating gases on a very small scale and a relatively safe means of demonstrating reactions that would be very…
Waste-to-Energy Plant Environmental Assessment, Dyess Air Force Base, Texas
2011-09-01
pyrolysis can be defined as “ gasification minus oxygen.” Pyrolysis is the technique of heating organic matter ( biomass ) between 480 and 1,470 °F in the...provider using one of four alternative technologies: 1) gasification ; 2) pyrolysis; 3) plasma gasification /pyrolysis and 4) incineration. Under this...the solicitation to build a WTE plant based on one of the following alternative technologies: I) gasification ; 2) pyrolysis; 3) plasma gasification
Pore-Scale X-ray Micro-CT Imaging and Analysis of Oil Shales
NASA Astrophysics Data System (ADS)
Saif, T.
2015-12-01
The pore structure and the connectivity of the pore space during the pyrolysis of oil shales are important characteristics which determine hydrocarbon flow behaviour and ultimate recovery. We study the effect of temperature on the evolution of pore space and subsequent permeability on five oil shale samples: (1) Vernal Utah United States, (2) El Lajjun Al Karak Jordan, (3) Gladstone Queensland Australia (4) Fushun China and (5) Kimmerdige United Kingdom. Oil Shale cores of 5mm in diameter were pyrolized at 300, 400 and 500 °C. 3D imaging of 5mm diameter core samples was performed at 1μm voxel resolution using X-ray micro computed tomography (CT) and the evolution of the pore structures were characterized. The experimental results indicate that the thermal decomposition of kerogen at high temperatures is a major factor causing micro-scale changes in the internal structure of oil shales. At the early stage of pyrolysis, micron-scale heterogeneous pores were formed and with a further increase in temperature, the pores expanded and became interconnected by fractures. Permeability for each oil shale sample at each temperature was computed by simulation directly on the image voxels and by pore network extraction and simulation. Future work will investigate different samples and pursue insitu micro-CT imaging of oil shale pyrolysis to characterize the time evolution of the pore space.
Experimental Investigation and Aspen Plus Simulation of the MSW Pyrolysis Process
NASA Astrophysics Data System (ADS)
Ansah, Emmanuel
Municipal solid waste (MSW) is a potential feedstock for producing transportation fuels because it is readily available using an existing collection/transportation infrastructure and fees are provided by the suppliers or government agencies to treat MSW. North Carolina with a population of 9.4 millions generates 3.629 million metric tons of MSW each year, which contains about 113,396,356 TJs of energy. The average moisture content of MSW samples is 44.3% on a wet basis. About 77% of the dry MSW mass is combustible components including paper, organics, textile and plastics. The average heating values of MSW were 9.7, 17.5, and 22.7 MJ/kg on a wet basis, dry basis and dry combustible basis, respectively. The MSW generated in North Carolina can produce 7.619 million barrels of crude bio-oil or around 4% of total petroleum consumption in North Carolina. MSW can be thermally pyrolyzed into bio-oil in the absence of oxygen or air at a temperature of 500°C or above. As bio-oil can be easily stored and transported, compared to bulky MSW, landfill gas and electricity, pyrolysis offers significant logistical and economic advantages over landfilling and other thermal conversion processes such as combustion and gasification. Crude bio-oils produced from the pyrolysis of MSW can be further refined to transportation fuels in existing petroleum refinery facilities. The objective of this research is to analyze the technical and economic feasibility of pyrolyzing MSW into liquid transportation fuels. A combined thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) instrument, which can serve as a micro-scale pyrolysis reactor, was used to simultaneously determine the degradation characteristics of MSW during pyrolysis. An ASPEN Plus-based mathematical model was further developed to analyze the technical and economic feasibility of pyrolysing of MSW into liquid transportation fuels in fixed bed reactors at varying operating conditions
Bio-based barium alginate film: Preparation, flame retardancy and thermal degradation behavior.
Liu, Yun; Zhang, Chuan-Jie; Zhao, Jin-Chao; Guo, Yi; Zhu, Ping; Wang, De-Yi
2016-03-30
A bio-based barium alginate film was prepared via a facile ionic exchange and casting approach. Its flammability, thermal degradation and pyrolysis behaviors, thermal degradation mechanism were studied systemically by limiting oxygen index (LOI), vertical burning (UL-94), microscale combustion calorimetry (MCC), thermogravimetric analysis (TGA) coupled with Fourier transform infrared analysis (FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). It showed that barium alginate film had much higher LOI value (52.0%) than that of sodium alginate film (24.5%). Moreover, barium alginate film passed the UL-94 V-0 rating, while the sodium alginate film showed no classification. Importantly, peak of heat release rate (PHRR) of barium alginate film in MCC test was much lower than that of sodium alginate film, suggested that introduction of barium ion into alginate film significantly decreased release of combustible gases. TG-FTIR and Py-GC-MS results indicated that barium alginate produced much less flammable products than that of sodium alginate in whole thermal degradation procedure. Finally, a possible degradation mechanism of barium alginate had been proposed. Copyright © 2015 Elsevier Ltd. All rights reserved.
Analysis of Low-Pressure Gas-Phase Pyrolytic Reactions by Mass Spectrometric Techniques,
1989-01-01
temperatures and pressures known only as a polymeric substance, is similarly obtained in high purity by heating the polymer to its melting point (105-110’ C...filaments for Curie- point pyrolysis’ J.Anal.Appl.Pyrolysis. 5 (1983) 1-7 (with Helge Egsgaard) 4) ’Heterogeneous catalysis in gas phase reactions studied...by Curie- point pyrolysis. Gas phase pyrolysis of methyl dithio- acetat’ J.Anal.Appl.Pyrolysis. 5 (1983) 257-259 (with Helge Egsgaard) 5) ’Continuous
Muradov, Nazim; Fidalgo, Beatriz; Gujar, Amit C; T-Raissi, Ali
2010-11-01
The aim of this work was to conduct the experimental study of pyrolysis of fast-growing aquatic biomass -Lemna minor (commonly known as duckweed) with the emphasis on the characterization of main products of pyrolysis. The yields of pyrolysis gas, pyrolytic oil (bio-oil) and char were determined as a function of pyrolysis temperature and the sweep gas (Ar) flow rate. Thermogravimetric/differential thermogravimetric (TG/DTG) analyses of duckweed samples in inert (helium gas) and oxidative (air) atmosphere revealed differences in the TG/DTG patterns obtained for duckweed and typical plant biomass. The bio-oil samples produced by duckweed pyrolysis at different reaction conditions were analyzed using GC-MS technique. It was found that pyrolysis temperature had minor effect on the bio-oil product slate, but exerted major influence on the relative quantities of the individual pyrolysis products obtained. While, the residence time of the pyrolysis vapors had negligible effect on the yield and composition of the duckweed pyrolysis products. Copyright 2010 Elsevier Ltd. All rights reserved.
Generation of functional structures by laser pyrolysis of polysilazane
NASA Astrophysics Data System (ADS)
Krauss, Hans-Joachim; Otto, Andreas
2002-06-01
The pyrolysis of polysilazanes by laser power represents an innovative technique for the generation of ceramic-like coatings and structures. The dissolved polysilazanes can be easily applied by painting techniques such as dipping or spraying. In the following pyrolysis the polysilazane layer transforms into an amorphous ceramic-like coating. The laser power is absorbed in the precursor layer, which leads to the latter's ceramization without damaging the substrate by thermal load. While plane laser pyrolysis creates a protective coating, selective pyrolysis creates a raised and adherent ceramic-like structure that remains after the unexposed polymer layer has been removed. The flexibility of a writing laser system in conjunction with a suitable handling system makes it possible to inscribe any kind of 2D structure on nearly any complexly shaped part. Some of the chemical, magnetic, and electrical structure properties can be adjusted by the pyrolysis parameters and special types of filler particles. Especially the possibility to control electric conductivity should make it possible to create structure dielectric films or planar resistors, inductors or capacitors, which are basically written on the surface of the part. Because of their ceramic nature of the structures are resistant against high temperatures and corrosive media. Thus, this new additive structuring technique could finally strike a new path in creating corrosion resistant high- temperature sensors and control systems.
USDA-ARS?s Scientific Manuscript database
Catalytic fast pyrolysis of biomass with ZSM-5 type zeolites is a commonly considered in situ upgrading technique for the production of partially deoxygenated bio-oils. The acidity and structure of ZSM-5 catalysts favor the production of aromatic hydrocarbons from oxygenates present in the pyrolysis...
Synthesis of carbon nanomaterials from different pyrolysis techniques: a review
NASA Astrophysics Data System (ADS)
Umer Zahid, Muhammad; Pervaiz, Erum; Hussain, Arshad; Shahzad, Muhammad Imran; Niazi, Muhammad Bilal Khan
2018-05-01
In the current age, the significance of carbon-based nanomaterials for many applications has made the efforts for the facile synthesis methods from abundantly available wastes in a cost-effective way. Pyrolysis in a broad spectrum is commonly employed for the synthesis of carbon nanostructures by thermally treating the organic waste. The mechanism of growth of the nanoparticles determines the functional distribution of nanoparticles based on the growing size, medium, and physio-chemical properties. Carbon nanomaterial’s growth is a complicated process which is profoundly influenced by temperature, catalyst, and type of precursor. Nowadays, significant progress has been made in improving nanomaterial’s growth techniques, opening new paths for commercial production of carbon-based nanomaterials. The most promising are the methods involving hydrocarbon-rich organic waste as the feed source. In this review, synthesis of carbon-based nanomaterials, specifically carbon nanotubes (CNTs), Carbon nanofibers (CNFs) and Graphene (G) are discussed by different pyrolysis techniques. Furthermore, the review explores recent advancements made in the context of pyrolysis.
A generalized methodology to characterize composite materials for pyrolysis models
NASA Astrophysics Data System (ADS)
McKinnon, Mark B.
The predictive capabilities of computational fire models have improved in recent years such that models have become an integral part of many research efforts. Models improve the understanding of the fire risk of materials and may decrease the number of expensive experiments required to assess the fire hazard of a specific material or designed space. A critical component of a predictive fire model is the pyrolysis sub-model that provides a mathematical representation of the rate of gaseous fuel production from condensed phase fuels given a heat flux incident to the material surface. The modern, comprehensive pyrolysis sub-models that are common today require the definition of many model parameters to accurately represent the physical description of materials that are ubiquitous in the built environment. Coupled with the increase in the number of parameters required to accurately represent the pyrolysis of materials is the increasing prevalence in the built environment of engineered composite materials that have never been measured or modeled. The motivation behind this project is to develop a systematic, generalized methodology to determine the requisite parameters to generate pyrolysis models with predictive capabilities for layered composite materials that are common in industrial and commercial applications. This methodology has been applied to four common composites in this work that exhibit a range of material structures and component materials. The methodology utilizes a multi-scale experimental approach in which each test is designed to isolate and determine a specific subset of the parameters required to define a material in the model. Data collected in simultaneous thermogravimetry and differential scanning calorimetry experiments were analyzed to determine the reaction kinetics, thermodynamic properties, and energetics of decomposition for each component of the composite. Data collected in microscale combustion calorimetry experiments were analyzed to determine the heats of complete combustion of the volatiles produced in each reaction. Inverse analyses were conducted on sample temperature data collected in bench-scale tests to determine the thermal transport parameters of each component through degradation. Simulations of quasi-one-dimensional bench-scale gasification tests generated from the resultant models using the ThermaKin modeling environment were compared to experimental data to independently validate the models.
Microfabricated cylindrical ion trap
Blain, Matthew G.
2005-03-22
A microscale cylindrical ion trap, having an inner radius of order one micron, can be fabricated using surface micromachining techniques and materials known to the integrated circuits manufacturing and microelectromechanical systems industries. Micromachining methods enable batch fabrication, reduced manufacturing costs, dimensional and positional precision, and monolithic integration of massive arrays of ion traps with microscale ion generation and detection devices. Massive arraying enables the microscale cylindrical ion trap to retain the resolution, sensitivity, and mass range advantages necessary for high chemical selectivity. The microscale CIT has a reduced ion mean free path, allowing operation at higher pressures with less expensive and less bulky vacuum pumping system, and with lower battery power than conventional- and miniature-sized ion traps. The reduced electrode voltage enables integration of the microscale cylindrical ion trap with on-chip integrated circuit-based rf operation and detection electronics (i.e., cell phone electronics). Therefore, the full performance advantages of microscale cylindrical ion traps can be realized in truly field portable, handheld microanalysis systems.
NASA Technical Reports Server (NTRS)
Socki, Richard A.; Fu, Qi; Niles, Paul B.
2010-01-01
We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.
NASA Technical Reports Server (NTRS)
He, Qun; Hallinan, Kevin
1996-01-01
The goal of this paper is to present details of the development of a new three-dimensional velocity field measurement technique which can be used to provide more insight into the dynamics of thin evaporating liquid films (not limited to just low heat inputs for the heat transfer) and which also could prove useful for the study of spreading and wetting phenomena and other microscale flows.
Yeung, Edward S.; Chang, Yu-chen
1999-06-29
The present invention provides a laser-induced vaporization and ionization interface for directly coupling microscale separation processes to a mass spectrometer. Vaporization and ionization of the separated analytes are facilitated by the addition of a light-absorbing component to the separation buffer or solvent.
Yeung, E.S.; Chang, Y.C.
1999-06-29
The present invention provides a laser-induced vaporization and ionization interface for directly coupling microscale separation processes to a mass spectrometer. Vaporization and ionization of the separated analytes are facilitated by the addition of a light-absorbing component to the separation buffer or solvent. 8 figs.
Thermal and catalytic slow pyrolysis of Calophyllum inophyllum fruit shell.
Alagu, R M; Sundaram, E Ganapathy; Natarajan, E
2015-10-01
Pyrolysis of Calophyllum inophyllum shell was performed in a fixed bed pyrolyser to produce pyrolytic oil. Both thermal (without catalysts) and catalytic pyrolysis process were conducted to investigate the effect of catalysts on pyrolysis yield and pyrolysis oil characteristics. The yield of pyrolytic oil through thermal pyrolysis was maximum (41% wt) at 425 °C for particle size of 1.18 mm and heating rate of 40 °C/min. In catalytic pyrolysis the pyrolytic oil yield was maximum (45% wt) with both zeolite and kaolin catalysts followed by Al2O3 catalyst (44% wt). The functional groups and chemical components present in the pyrolytic oil are identified by Fourier Transform Infrared Spectroscopy (FT-IR) and Gas Chromatography-Mass Spectrometry (GC-MS) techniques. This study found that C. inophyllum shell is a potential new green energy source and that the catalytic pyrolysis process using zeolite catalyst improves the calorific value and acidity of the pyrolytic oil. Copyright © 2015 Elsevier Ltd. All rights reserved.
Bach, Quang-Vu; Chen, Wei-Hsin
2017-12-01
Pyrolysis is a promising route for biofuels production from microalgae at moderate temperatures (400-600°C) in an inert atmosphere. Depending on the operating conditions, pyrolysis can produce biochar and/or bio-oil. In practice, knowledge for thermal decomposition characteristics and kinetics of microalgae during pyrolysis is essential for pyrolyzer design and pyrolysis optimization. Recently, the pyrolysis kinetics of microalgae has become a crucial topic and received increasing interest from researchers. Thermogravimetric analysis (TGA) has been employed as a proven technique for studying microalgae pyrolysis in a kinetic control regime. In addition, a number of kinetic models have been applied to process the TGA data for kinetic evaluation and parameters estimation. This paper aims to provide a state-of-the art review on recent research activities in pyrolysis characteristics and kinetics of various microalgae. Common kinetic models predicting the thermal degradation of microalgae are examined and their pros and cons are illustrated. Copyright © 2017 Elsevier Ltd. All rights reserved.
Analytical pyrolysis mass spectrometry: new vistas opened by temperature-resolved in-source PYMS
NASA Astrophysics Data System (ADS)
Boon, Jaap J.
1992-09-01
Analytical pyrolysis mass spectrometry (PYMS) is introduced and its applications to the analysis of synthetic polymers, biopolymers, biomacromolecular systems and geomacromolecules are critically reviewed. Analytical pyrolysis inside the ionisation chamber of a mass spectrometer, i.e. in-source PYMS, gives a complete inventory of the pyrolysis products evolved from a solid sample. The temperature-resolved nature of the experiment gives a good insight into the temperature dependence of the volatilisation and pyrolytic dissociation processes. Chemical ionisation techniques appear to be especially suitable for the analysis of oligomeric fragments released in early stages of the pyrolysis of polymer systems. Large oligomeric fragments were observed for linear polymers such as cellulose (pentadecamer), polyhydroxyoctanoic acid (tridecamer) and polyhydroxybutyric acid (heneicosamer). New in-source PYMS data are presented on artists' paints, the plant polysaccharides cellulose and xyloglucan, several microbial polyhydroxyalkanoates, wood and enzyme-digested wood, biodegraded roots and a fossil cuticle of Miocene age. On-line and off-line pyrolysis chromatography mass spectrometric approaches are also discussed. New data presented on high temperature gas chromatography--mass spectrometry of deuterio-reduced permethylated pyrolysates of cellulose lead to a better understanding of polysaccharide dissociation mechanisms. Pyrolysis as an on-line sample pretreatment method for organic macromolecules in combination with MS techniques is a very challenging field of mass spectrometry. Pyrolytic dissociation and desorption is not at all a chaotic process but proceeds according to very specific mechanisms.
NASA Astrophysics Data System (ADS)
Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping
2018-02-01
A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.
Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping
2018-01-01
A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994
Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping
2018-01-01
A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.
Method for Hot Real-Time Analysis of Pyrolysis Vapors at Pilot Scale
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pomeroy, Marc D
Pyrolysis oils contain more than 400 compounds, up to 60% of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during quenching and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition before condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors at the pilot scale, many challenges must be overcome.
Characterization of exopolymers of aquatic bacteria by pyrolysis-mass spectrometry
NASA Technical Reports Server (NTRS)
Ford, T.; Sacco, E.; Black, J.; Kelley, T.; Goodacre, R.; Berkeley, R. C.; Mitchell, R.
1991-01-01
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.
Behavior of sulfur during coal pyrolysis
Shao, D.; Hutchinson, E.J.; Heidbrink, J.; Pan, W.-P.; Chou, C.-L.
1994-01-01
The behavior of sulfur in Illinois coals during pyrolysis was evaluated by thermogravimetry/ Fourier transform-infrared spectroscopy (TG/FT-IR) techniques. SO2, COS, and H2S were major gaseous sulfur-containing products observed during coal pyrolysis. The release rates of the gaseous sulfur species showed several peaks within the temperature ranges, which were due to the emission of different forms of sulfur in coal. ?? 1994.
Understanding the fast pyrolysis of lignin.
Patwardhan, Pushkaraj R; Brown, Robert C; Shanks, Brent H
2011-11-18
In the present study, pyrolysis of corn stover lignin was investigated by using a micro-pyrolyzer coupled with a GC-MS/FID (FID=flame ionization detector). The system has pyrolysis-vapor residence times of 15-20 ms, thus providing a regime of minimal secondary reactions. The primary pyrolysis product distribution obtained from lignin is reported. Over 84 % mass balance and almost complete closure on carbon balance is achieved. In another set of experiments, the pyrolysis vapors emerging from the micro-pyrolyzer are condensed to obtain lignin-derived bio-oil. The chemical composition of the bio-oil is analyzed by using GC-MS and gel permeation chromatography techniques. The comparison between results of two sets of experiments indicates that monomeric compounds are the primary pyrolysis products of lignin, which recombine after primary pyrolysis to produce oligomeric compounds. Further, the effect of minerals (NaCl, KCl, MgCl(2), and CaCl(2)) and temperature on the primary pyrolysis product distribution is investigated. The study provides insights into the fundamental mechanisms of lignin pyrolysis and a basis for developing more descriptive models of biomass pyrolysis. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis
Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; ...
2016-09-05
Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less
Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.
Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less
González-Pérez, José A; Jiménez-Morillo, Nicasio T; de la Rosa, José M; Almendros, Gonzalo; González-Vila, Francisco J
2016-02-01
Pyrolysis-compound specific isotopic analysis (Py-CSIA: Py-GC-(FID)-C-IRMS) is a relatively novel technique that allows on-line quantification of stable isotope proportions in chromatographically separated products released by pyrolysis. Validation of the Py-CSIA technique is compulsory for molecular traceability in basic and applied research. In this work, commercial sucrose from C4 (sugarcane) and C3 (sugarbeet) photosystem plants and admixtures were studied using analytical pyrolysis (Py-GC/MS), bulk δ(13)C IRMS and δ(13)C Py-CSIA. Major pyrolysis compounds were furfural (F), furfural-5-hydroxymethyl (HMF) and levoglucosan (LV). Bulk and main pyrolysis compound δ(13)C (‰) values were dependent on plant origin: C3 (F, -24.65 ± 0.89; HMF, -22.07 ± 0.41‰; LV, -21.74 ± 0.17‰) and C4 (F, -14.35 ± 0.89‰; HMF, -11.22 ± 0.54‰; LV, -11.44 ± 1.26‰). Significant regressions were obtained for δ(13)C of bulk and pyrolysis compounds in C3 and C4 admixtures. Furfural (F) was found (13)C depleted with respect to bulk and HMF and LV, indicating the incorporation of the light carbon atom in position 6 of carbohydrates in the furan ring after pyrolysis. This is the first detailed report on the δ(13)C signature of major pyrolytically generated carbohydrate-derived molecules. The information provided by Py-CSIA is valuable for identifying source marker compounds of use in food science/fraud detection or in environmental research. © 2015 Society of Chemical Industry.
Washington's "free" 300-station microscale weather network
Thomas Blackburn
1977-01-01
This article is intended to encourage those planning to conduct meso- or microscale weather studies to supplement their sophisticated observing techniques and equipment- with low-cost observations taken by volunteers. Such observations can often show high benefits per unit costs in expanding the geographical area of study, increasing the density of observations, or in...
Economic assessment of flash co-pyrolysis of short rotation coppice and biopolymer waste streams.
Kuppens, T; Cornelissen, T; Carleer, R; Yperman, J; Schreurs, S; Jans, M; Thewys, T
2010-12-01
The disposal problem associated with phytoextraction of farmland polluted with heavy metals by means of willow requires a biomass conversion technique which meets both ecological and economical needs. Combustion and gasification of willow require special and costly flue gas treatment to avoid re-emission of the metals in the atmosphere, whereas flash pyrolysis mainly results in the production of (almost) metal free bio-oil with a relatively high water content. Flash co-pyrolysis of biomass and waste of biopolymers synergistically improves the characteristics of the pyrolysis process: e.g. reduction of the water content of the bio-oil, more bio-oil and less char production and an increase of the HHV of the oil. This research paper investigates the economic consequences of the synergistic effects of flash co-pyrolysis of 1:1 w/w ratio blends of willow and different biopolymer waste streams via cost-benefit analysis and Monte Carlo simulations taking into account uncertainties. In all cases economic opportunities of flash co-pyrolysis of biomass with biopolymer waste are improved compared to flash pyrolysis of pure willow. Of all the biopolymers under investigation, polyhydroxybutyrate (PHB) is the most promising, followed by Eastar, Biopearls, potato starch, polylactic acid (PLA), corn starch and Solanyl in order of decreasing profits. Taking into account uncertainties, flash co-pyrolysis is expected to be cheaper than composting biopolymer waste streams, except for corn starch. If uncertainty increases, composting also becomes more interesting than flash co-pyrolysis for waste of Solanyl. If the investment expenditure is 15% higher in practice than estimated, the preference for flash co-pyrolysis compared to composting biopolymer waste becomes less clear. Only when the system of green current certificates is dismissed, composting clearly is a much cheaper processing technique for disposing of biopolymer waste. Copyright © 2010 Elsevier Ltd. All rights reserved.
Zhang, Jining; Lü, Fan; Zhang, Hua; Shao, Liming; Chen, Dezhen; He, Pinjing
2015-01-01
Sewage sludge biochars were obtained at different pyrolysis temperatures from 300°C to 900°C and their macro- and microscale properties were analyzed. The biochar's plant-available nutrients and humus-like substances in the water-extractable phase and fixed nutrients in the solid fraction were evaluated for their potential agronomic implications. FT-IR, Raman, XRD, XPS, and SEM techniques were used to investigate the chemical structure, functional groups, and microcrystal structure on the surface of the biochar. The results revealed minor chemical changes and dramatic mass loss in the biochar obtained at 300–500°C, whereas significant chemical changes in the biochar were obtained at 600–900°C. The concentrations of plant-available nutrients as well as fulvic- and humic-acid-like materials decreased in the biochar samples obtained at higher temperatures. These results implied that the biochar samples pyrolyzed at 300–500°C could be a direct nutrient source and used to neutralize alkaline soil. The surface area and porosity of the biochar samples increased with temperature, which increased their adsorption capacity. Rearrangement occurred at higher temperature 600–900°C, resulting in the biochar becoming increasingly polyaromatic and its graphite-like carbon becoming organized. PMID:25802185
Carbon Coating Of Copper By Arc-Discharge Pyrolysis
NASA Technical Reports Server (NTRS)
Ebihara, Ben T.; Jopek, Stanley
1988-01-01
Adherent, abrasion-resistant coat deposited with existing equipment. Carbon formed and deposited as coating on copper substrate by pyrolysis of hydrocarbon oil in electrical-arc discharges. Technique for producing carbon deposits on copper accomplished with electrical-discharge-machining equipment used for cutting metals. Applications for new coating technique include the following: solar-energy-collecting devices, coating of metals other than copper with carbon, and carburization of metal surfaces.
Microscale pH Titrations Using an Automatic Pipet.
ERIC Educational Resources Information Center
Flint, Edward B.; Kortz, Carrie L.; Taylor, Max A.
2002-01-01
Presents a microscale pH titration technique that utilizes an automatic pipet. A small aliquot (1-5 mL) of the analyte solution is titrated with repeated additions of titrant, and the pH is determined after each delivery. The equivalence point is determined graphically by either the second derivative method or a Gran plot. The pipet can be…
Microscale architecture in biomaterial scaffolds for spatial control of neural cell behavior
NASA Astrophysics Data System (ADS)
Meco, Edi; Lampe, Kyle J.
2018-02-01
Biomaterial scaffolds mimic aspects of the native central nervous system (CNS) extracellular matrix (ECM) and have been extensively utilized to influence neural cell (NC) behavior in in vitro and in vivo settings. These biomimetic scaffolds support NC cultures, can direct the differentiation of NCs, and have recapitulated some native NC behavior in an in vitro setting. However, NC transplant therapies and treatments used in animal models of CNS disease and injury have not fully restored functionality. The observed lack of functional recovery occurs despite improvements in transplanted NC viability when incorporating biomaterial scaffolds and the potential of NC to replace damaged native cells. The behavior of NCs within biomaterial scaffolds must be directed in order to improve the efficacy of transplant therapies and treatments. Biomaterial scaffold topography and imbedded bioactive cues, designed at the microscale level, can alter NC phenotype, direct migration, and differentiation. Microscale patterning in biomaterial scaffolds for spatial control of NC behavior has enhanced the capabilities of in vitro models to capture properties of the native CNS tissue ECM. Patterning techniques such as lithography, electrospinning and 3D bioprinting can be employed to design the microscale architecture of biomaterial scaffolds. Here, the progress and challenges of the prevalent biomaterial patterning techniques of lithography, electrospinning, and 3D bioprinting are reported. This review analyzes NC behavioral response to specific microscale topographical patterns and spatially organized bioactive cues.
Applications of Microscale Technologies for Regenerative Dentistry
Hacking, S.A.; Khademhosseini, A.
2009-01-01
While widespread advances in tissue engineering have occurred over the past decade, many challenges remain in the context of tissue engineering and regeneration of the tooth. For example, although tooth development is the result of repeated temporal and spatial interactions between cells of ectoderm and mesoderm origin, most current tooth engineering systems cannot recreate such developmental processes. In this regard, microscale approaches that spatially pattern and support the development of different cell types in close proximity can be used to regulate the cellular microenvironment and, as such, are promising approaches for tooth development. Microscale technologies also present alternatives to conventional tissue engineering approaches in terms of scaffolds and the ability to direct stem cells. Furthermore, microscale techniques can be used to miniaturize many in vitro techniques and to facilitate high-throughput experimentation. In this review, we discuss the emerging microscale technologies for the in vitro evaluation of dental cells, dental tissue engineering, and tooth regeneration. Abbreviations: AS, adult stem cell; BMP, bone morphogenic protein; ECM, extracellular matrix; ES, embryonic stem cell; HA, hydroxyapatite; FGF-2, fibroblast growth factor; iPS, inducible pleuripotent stem cell; IGF-1, insulin-like growth factor; PDGF, platelet-derived growth factor; PDMS, poly(dimethylsiloxane); PGA, polyglycolate; PGS, polyglycerol sebacate; PLGA, poly-L-lactate-co-glycolate; PLL, poly-L-lactate; RGD, Arg-Gly-Asp attachment site; TCP, tricalcium phosphate; TGF-β, transforming growth factor beta; and VEGF, vascular endothelial growth factor. PMID:19493883
Microscale bioprocess optimisation.
Micheletti, Martina; Lye, Gary J
2006-12-01
Microscale processing techniques offer the potential to speed up the delivery of new drugs to the market, reducing development costs and increasing patient benefit. These techniques have application across both the chemical and biopharmaceutical sectors. The approach involves the study of individual bioprocess operations at the microlitre scale using either microwell or microfluidic formats. In both cases the aim is to generate quantitative bioprocess information early on, so as to inform bioprocess design and speed translation to the manufacturing scale. Automation can enhance experimental throughput and will facilitate the parallel evaluation of competing biocatalyst and process options.
Pyrolysis Mass Spectrometry of Complex Organic Materials.
ERIC Educational Resources Information Center
Meuzelaar, Henk L. C.; And Others
1984-01-01
Illustrates the state of the art in pyrolysis mass spectrometry techniques through applications in: (1) structural determination and quality control of synthetic polymers; (2) quantitative analysis of polymer mixtures; (3) classification and structural characterization of fossil organic matter; and (4) nonsupervised numerical extraction of…
New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging
Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori; ...
2015-01-30
We report on the first ever use of non-destructive micrometer-scale synchrotron-computed microtomography (CMT) for biochar material characterization as a function of pyrolysis temperature. This innovative approach demonstrated an increase in micron-sized marcropore fraction of the Cotton Hull (CH) sample, resulting in up to 29% sample porosity. We have also found that initial porosity development occurred at low temperatures (below 350°C) of pyrolysis, consistent with chemical composition of CH. This innovative technique can be highly complementary to traditional BET measurements, considering that Barrett–Joyner–Halenda (BJH) analysis of pore size distribution cannot detect these macropores. Such information can be of substantial relevance tomore » environmental applications, given that water retention by biochars added to soils is controlled by macropore characteristic among the other factors. In addition, complementing our data with SEM, EDX, and XRF characterization techniques allowed us to develop a better understanding of evolution of biochar properties during its production, such presence of metals and initial morphological features of biochar before pyrolysis. These results have significant implications for using biochar as a soil additive and for clarifying the mechanisms of biofuel production by pyrolysis.« less
New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori
We report on the first ever use of non-destructive micrometer-scale synchrotron-computed microtomography (CMT) for biochar material characterization as a function of pyrolysis temperature. This innovative approach demonstrated an increase in micron-sized marcropore fraction of the Cotton Hull (CH) sample, resulting in up to 29% sample porosity. We have also found that initial porosity development occurred at low temperatures (below 350°C) of pyrolysis, consistent with chemical composition of CH. This innovative technique can be highly complementary to traditional BET measurements, considering that Barrett–Joyner–Halenda (BJH) analysis of pore size distribution cannot detect these macropores. Such information can be of substantial relevance tomore » environmental applications, given that water retention by biochars added to soils is controlled by macropore characteristic among the other factors. In addition, complementing our data with SEM, EDX, and XRF characterization techniques allowed us to develop a better understanding of evolution of biochar properties during its production, such presence of metals and initial morphological features of biochar before pyrolysis. These results have significant implications for using biochar as a soil additive and for clarifying the mechanisms of biofuel production by pyrolysis.« less
Behavior of chlorine during coal pyrolysis
Shao, D.; Hutchinson, E.J.; Cao, H.; Pan, W.-P.; Chou, C.-L.
1994-01-01
The behavior of chlorine in Illinois coals during pyrolysis was evaluated by combined thermo-gravimetry-Fourier transform infrared spectroscopy-ion chromatography (TG-FTIR-IC) techniques. It was found that more than 90% of chlorine in Illinois coals (IBC-103, 105, 106, and 109) was liberated as HCl gas during pyrolysis from 300 to 600??C, with the rate reaching a maximum at 440 ??C. Similarity of the HCl and NH3 release profiles during pyrolysis of IBC-109 supports the hypothesis that the chlorine in coal may be associated with nitrogen and the chlorine is probably bonded to the basic nitrogen sites on the inner walls of coal micropores. ?? 1994 American Chemical Society.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Huang, Rixiang; Zhang, Bei; Saad, Emily M.
Thermal and hydrothermal treatments are promising techniques for sewage sludge management that can potentially facilitate safe waste disposal, energy recovery, and nutrient recovery/recycling. Content and speciation of heavy metals in the treatment products affect the potential environmental risks upon sludge disposal and/or application of the treatment products. Therefore, it is important to study the speciation transformation of heavy metals and the effects of treatment conditions. By combining synchrotron X-ray spectroscopy/microscopy analysis and sequential chemical extraction, this study systematically characterized the speciation of Zn and Cu in municipal sewage sludges and their chars derived from pyrolysis (a representative thermal treatment technique)more » and hydrothermal carbonization (HTC; a representative hydrothermal treatment technique). Spectroscopy analysis revealed enhanced sulfidation of Zn and Cu by anaerobic digestion and HTC treatments, as compared to desulfidation by pyrolysis. Overall, changes in the chemical speciation and matrix properties led to reduced mobility of Zn and Cu in the treatment products. These results provide insights into the reaction mechanisms during pyrolysis and HTC treatments of sludges and can help evaluate the environmental/health risks associated with the metals in the treatment products.« less
Finding the chemistry in biomass pyrolysis: Millisecond chemical kinetics and visualization
NASA Astrophysics Data System (ADS)
Krumm, Christoph
Biomass pyrolysis is a promising thermochemical method for producing fuels and chemicals from renewable sources. Development of a fundamental understanding of biomass pyrolysis chemistry is difficult due to the multi-scale and multi-phase nature of the process; biomass length scales span 11 orders of magnitude and pyrolysis phenomena include solid, liquid, and gas phase chemistry in addition to heat and mass transfer. These complexities have a significant effect on chemical product distributions and lead to variability between reactor technologies. A major challenge in the study of biomass pyrolysis is the development of kinetic models capable of describing hundreds of millisecond-scale reactions of biomass into lower molecular weight products. In this work, a novel technique for studying biomass pyrolysis provides the first- ever experimental determination of kinetics and rates of formation of the primary products from cellulose pyrolysis, providing insight into the millisecond-scale chemical reaction mechanisms. These findings highlight the importance of heat and mass transport limitations for cellulose pyrolysis chemistry and are used to identify the length scales at which transport limitations become relevant during pyrolysis. Through this technique, a transition is identified, known as the reactive melting point, between low and high temperature depolymerization. The transition between two mechanisms of cellulose decompositions unifies the mechanisms that govern low temperature char formation, intermediate pyrolysis conditions, and high temperature gas formation. The conditions under which biomass undergoes pyrolysis, including modes of heat transfer, have been shown to significantly affect the distribution of biorenewable chemical and fuel products. High-speed photography is used to observe the liftoff of initially crystalline cellulose particles when impinged on a heated surface, known as the Leidenfrost effect for room-temperature liquids. Order-of-magnitude changes in the lifetime of cellulose particles are observed as a result of changing modes in heat transfer as cellulose intermediate liquid droplets wet and de-wet polished ceramic surfaces. Introduction of surface macroporosity is shown to completely inhibit the cellulose Leidenfrost effect, providing avenues for surface modification and reactor design to control particle heat transfer in industrial pyrolysis applications. Cellulosic particles on surfaces consisting of microstructured, asymmetric ratchets were observed to spontaneously move orthogonal to ratchet wells above the cellulose reactive Leidenfrost temperature (>750 °C). Evaluation of the accelerating particles supported the mechanism of propelling viscous forces (50-200 nN) from rectified pyrolysis vapors, thus providing the first example of biomass conveyors with no moving parts driven by high temperature for biofuel reactors. Combined knowledge of pyrolysis chemistry, kinetics, and heat and mass transport effects direct the design of the next generation pyrolysis reactors for tuning bio- oil quality and design of improved catalytic upgrading technology.
Advances in microscale separations towards nanoproteomics applications
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yi, Lian; Piehowski, Paul D.; Shi, Tujin
Microscale separations (e.g., liquid chromatography or capillary electrophoresis) coupled with mass spectrometry (MS) has become the primary tool for advanced proteomics, an indispensable technology for gaining understanding of complex biological processes. While significant advances have been achieved in MS-based proteomics, the current platforms still face a significant challenge in overall sensitivity towards nanoproteomics (i.e., with less than 1 g total amount of proteins available) applications such as cellular heterogeneity in tissue pathologies. Herein, we review recent advances in microscale separation techniques and integrated sample processing systems that improve the overall sensitivity and coverage of the proteomics workflow, and their contributionsmore » towards nanoproteomics applications.« less
Review of NMR characterization of pyrolysis oils
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun
Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterizationmore » and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.« less
Review of NMR characterization of pyrolysis oils
Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; ...
2016-08-24
Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterizationmore » and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.« less
Steam Pyrolysis of Polyimides: Effects of Steam on Raw Material Recovery.
Kumagai, Shogo; Hosaka, Tomoyuki; Kameda, Tomohito; Yoshioka, Toshiaki
2015-11-17
Aromatic polyimides (PIs) have excellent thermal stability, which makes them difficult to recycle, and an effective way to recycle PIs has not yet been established. In this work, steam pyrolysis of the aromatic PI Kapton was performed to investigate the recovery of useful raw materials. Steam pyrolysis significantly enhanced the gasification of Kapton at 900 °C, resulting in 1963.1 mL g(-1) of a H2 and CO rich gas. Simultaneously, highly porous activated carbon with a high BET surface area was recovered. Steam pyrolysis increased the presence of polar functional groups on the carbon surface. Thus, it was concluded that steam pyrolysis shows great promise as a recycling technique for the recovery of useful synthetic gases and activated carbon from PIs without the need for catalysts and organic solvents.
Microwave pyrolysis of oily sludge with activated carbon.
Chen, Yi-Rong
2016-12-01
The aim of this study is to explore catalytic microwave pyrolysis of crude oil storage tank sludge for fuels using granular activated carbon (GAC) as a catalyst. The effect of GAC loading on the yield of pyrolysis products was also investigated. Heating rate of oily sludge and yield of microwave pyrolysis products such as oil and fuel gas was found to depend on the ratio of GAC to oily sludge. The optimal GAC loading was found to be 10%, while much smaller and larger feed sizes adversely influenced production. During oily sludge pyrolysis, a maximum oil yield of 77.5% was achieved. Pyrolytic oils with high concentrations of diesel oil and gasoline (about 70 wt% in the pyrolytic oil) were obtained. The leaching of heavy metals, such as Cr, As and Pb, was also suppressed in the solid residue after pyrolysis. This technique provides advantages such as harmless treatment of oily sludge and substantial reduction in the consumption of energy, time and cost.
Sun, Yu'an; Liu, Baoxia; Wang, Guoqing; Zhang, Rongjie; Xie, Bing
2005-01-01
The thermal behavior of vitamin D3 was studied based on pyrolysis-GC-MS technique. It was pyrolyzed at 600 degrees C, 750 degrees C, 900 degrees C, respectively. The pyrolysis product were separated With an HP-5 column and identified by the NIST mass spectral search program in combination with the correlation of boiling point and retention time (BP-RT). There are totally 50 components, including mono aromatics and polycyclic aromatic hydrocarbons (PAHs), were determined. It is shown that the contents of the PAHs are increasing with the increasing of the pyrolysis temperature. The contents of the determined components vary from 0.04% to 37.08%.
Oxalate Synthesis and Pyrolysis: A Colorful Introduction to Stoichiometry
ERIC Educational Resources Information Center
Vannatta, Michael W.; Richards-Babb, Michelle; Sweeney, Robert J.
2010-01-01
Metal oxalate synthesis and pyrolysis provides an opportunity for students to (i) learn stoichiometry, (ii) experience the consequences of proper stoichiometric calculations and experimental techniques, and (iii) be introduced to the relevance of chemistry by highlighting oxalates in context, for example, usages and health effects. At our…
A review on thermal and catalytic pyrolysis of plastic solid waste (PSW).
Al-Salem, S M; Antelava, A; Constantinou, A; Manos, G; Dutta, A
2017-07-15
Plastic plays an important role in our daily lives due to its versatility, light weight and low production cost. Plastics became essential in many sectors such as construction, medical, engineering applications, automotive, aerospace, etc. In addition, economic growth and development also increased our demand and dependency on plastics which leads to its accumulation in landfills imposing risk on human health, animals and cause environmental pollution problems such as ground water contamination, sanitary related issues, etc. Hence, a sustainable and an efficient plastic waste treatment is essential to avoid such issues. Pyrolysis is a thermo-chemical plastic waste treatment technique which can solve such pollution problems, as well as, recover valuable energy and products such as oil and gas. Pyrolysis of plastic solid waste (PSW) has gained importance due to having better advantages towards environmental pollution and reduction of carbon footprint of plastic products by minimizing the emissions of carbon monoxide and carbon dioxide compared to combustion and gasification. This paper presents the existing techniques of pyrolysis, the parameters which affect the products yield and selectivity and identify major research gaps in this technology. The influence of different catalysts on the process as well as review and comparative assessment of pyrolysis with other thermal and catalytic plastic treatment methods, is also presented. Copyright © 2017 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
David, K.; Ben, H.; Muzzy, J.
2012-03-01
Pyrolysis is a promising approach to utilize biomass for biofuels. One of the key challenges for this conversion is how to analyze complicated components in the pyrolysis oils. Water contents of pyrolysis oils are normally analyzed by Karl Fischer titration. The use of 2-chloro-4,4,5,5,-tetramethyl-1,3,2-dioxaphospholane followed by {sup 31}P NMR analysis has been used to quantitatively analyze the structure of hydroxyl groups in lignin and whole biomass. Results: {sup 31}P NMR analysis of pyrolysis oils is a novel technique to simultaneously characterize components and analyze water contents in pyrolysis oils produced from various biomasses. The water contents of various pyrolysis oilsmore » range from 16 to 40 wt%. The pyrolysis oils obtained from Loblolly pine had higher guaiacyl content, while that from oak had a higher syringyl content. Conclusion: The comparison with Karl Fischer titration shows that {sup 31}P NMR could also reliably be used to measure the water content of pyrolysis oils. Simultaneously with analysis of water content, quantitative characterization of hydroxyl groups, including aliphatic, C-5 substituted/syringyl, guaiacyl, p-hydroxyl phenyl and carboxylic hydroxyl groups, could also be provided by {sup 31}P NMR analysis.« less
NASA Astrophysics Data System (ADS)
Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.
2017-06-01
Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.
Microscale surface modifications for heat transfer enhancement.
Bostanci, Huseyin; Singh, Virendra; Kizito, John P; Rini, Daniel P; Seal, Sudipta; Chow, Louis C
2013-10-09
In this experimental study, two surface modification techniques were investigated for their effect on heat transfer enhancement. One of the methods employed the particle (grit) blasting to create microscale indentations, while the other used plasma spray coating to create microscale protrusions on Al 6061 (aluminum alloy 6061) samples. The test surfaces were characterized using scanning electron microscopy (SEM) and confocal scanning laser microscopy. Because of the surface modifications, the actual surface area was increased up to 2.8× compared to the projected base area, and the arithmetic mean roughness value (Ra) was determined to vary from 0.3 μm for the reference smooth surface to 19.5 μm for the modified surfaces. Selected samples with modified surfaces along with the reference smooth surface were then evaluated for their heat transfer performance in spray cooling tests. The cooling system had vapor-atomizing nozzles and used anhydrous ammonia as the coolant in order to achieve heat fluxes up to 500 W/cm(2) representing a thermal management setting for high power systems. Experimental results showed that the microscale surface modifications enhanced heat transfer coefficients up to 76% at 500 W/cm(2) compared to the smooth surface and demonstrated the benefits of these practical surface modification techniques to enhance two-phase heat transfer process.
Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products.
Couch, David E; Buckingham, Grant T; Baraban, Joshua H; Porterfield, Jessica P; Wooldridge, Laura A; Ellison, G Barney; Kapteyn, Henry C; Murnane, Margaret M; Peters, William K
2017-07-20
We report the combination of tabletop vacuum ultraviolet photoionization with photoion-photoelectron coincidence spectroscopy for sensitive, isomer-specific detection of nascent products from a pyrolysis microreactor. Results on several molecules demonstrate two essential capabilities that are very straightforward to implement: the ability to differentiate isomers and the ability to distinguish thermal products from dissociative ionization. Here, vacuum ultraviolet light is derived from a commercial tabletop femtosecond laser system, allowing data to be collected at 10 kHz; this high repetition rate is critical for coincidence techniques. The photoion-photoelectron coincidence spectrometer uses the momentum of the ion to identify dissociative ionization events and coincidence techniques to provide a photoelectron spectrum specific to each mass, which is used to distinguish different isomers. We have used this spectrometer to detect the pyrolysis products that result from the thermal cracking of acetaldehyde, cyclohexene, and 2-butanol. The photoion-photoelectron spectrometer can detect and identify organic radicals and reactive intermediates that result from pyrolysis. Direct comparison of laboratory and synchrotron data illustrates the advantages and potential of this approach.
Detecting Pyrolysis Products from Bacteria on Mars
NASA Technical Reports Server (NTRS)
Glavin, Daniel; Schubert, Michael; Botta, Oliver; Kminek, Gerhard; Bada, Jeffrey L.
2001-01-01
A pyrolysis/sublimation technique was developed to isolate volatile amine compounds from a Mars soil analogue inoculated with approx. 10 billion Escherichia coli cells. In this technique, the inoculated soil is heated to 500 C for several seconds at Martian ambient pressure and the sublimate, collected by a cold finger, then analyzed using high performance liquid chromatography. Methylamine and ethylamine, produced from glycine and alanine decarboxylation, were the most abundant amine compounds detected after pyrolysis of the cells. A heating cycle similar to that utilized in our experiment was also used to release organic compounds from the Martian soil in the 1976 Viking gas chromatography/mass spectrometry (GC/MS) pyrolysis experiment. The Viking GC/MS did not detect any organic compounds of Martian origin above a level of a few parts per billion in the Martian surface soil. Although the Viking GC/MS instruments were not specifically designed to search for the presence of living cells on Mars, our experimental results indicate that at the part per billion level, the degradation products generated from several million bacterial cells per gram of Martian soil would not have been detected.
Advances in microscale separations towards nanoproteomics applications
Yi, Lian; Piehowski, Paul D.; Shi, Tujin; ...
2017-07-21
Microscale separation (e.g., liquid chromatography or capillary electrophoresis) coupled with mass spectrometry (MS) has become the primary tool for advanced proteomics, an indispensable technology for gaining understanding of complex biological processes. In recent decades significant advances have been achieved in MS-based proteomics. But, the current proteomics platforms still face an analytical challenge in overall sensitivity towards nanoproteomics applications for starting materials of less than 1 μg total proteins (e.g., cellular heterogeneity in tissue pathologies). We review recent advances in microscale separation techniques and integrated sample processing strategies that improve the overall sensitivity and proteome coverage of the proteomics workflow, andmore » their contributions towards nanoproteomics applications.« less
Advances in microscale separations towards nanoproteomics applications
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yi, Lian; Piehowski, Paul D.; Shi, Tujin
Microscale separation (e.g., liquid chromatography or capillary electrophoresis) coupled with mass spectrometry (MS) has become the primary tool for advanced proteomics, an indispensable technology for gaining understanding of complex biological processes. In recent decades significant advances have been achieved in MS-based proteomics. But, the current proteomics platforms still face an analytical challenge in overall sensitivity towards nanoproteomics applications for starting materials of less than 1 μg total proteins (e.g., cellular heterogeneity in tissue pathologies). We review recent advances in microscale separation techniques and integrated sample processing strategies that improve the overall sensitivity and proteome coverage of the proteomics workflow, andmore » their contributions towards nanoproteomics applications.« less
NASA Technical Reports Server (NTRS)
Van De Meent, D.; Brown, S. C.; Philp, R. P.; Simoneit, B. R. T.
1980-01-01
A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.
Goodacre, R; Hiom, S J; Cheeseman, S L; Murdoch, D; Weightman, A J; Wade, W G
1996-02-01
Curie-point pyrolysis mass spectra were obtained from 29 oral asaccharolytic Eubacterium strains and 6 abscess isolates previously identified as Peptostreptococcus heliotrinreducens. Pyrolysis mass spectrometry (PyMS) with cluster analysis was able to clarify the taxonomic position of this group of organisms. Artificial neural networks (ANNS) were then trained by supervised learning (with the back-propagation algorithm) to recognize the strains from their pyrolysis mass spectra; all Eubacterium strains were correctly identified, and the abscess isolates were identified as un-named Eubacterium taxon C2 and were distinct from the type strain of P. heliotrinreducens. These results demonstrate that the combination of PyMS and ANNs provides a rapid and accurate identification technique.
Characterization of Source Signatures of Fine Roadway Particles by Pyrolysis-GC-MS
NASA Astrophysics Data System (ADS)
van Bergen, S. K.; Holmén, B. A.
2001-12-01
Fine particulate matter, defined as particles with an aerodynamic diameter less than 2.5 μ m (PM2.5), is of growing concern due to its detrimental effects on human health and the environment. Roadway traffic generates a significant fraction of PM2.5 in urban areas. Since exposure to fine particles derived from mobile sources commonly occurs, understanding the physicochemical processes that contribute to the generation, transport and atmospheric reactivity of roadway PM is important. Factors that influence the properties of roadway PM include: the mass, number and size distribution of the particles as well as their chemical composition. These factors are partially determined by the sources of the roadway particles. The focus of this effort is to identify unique organic chemical profiles of known roadway sources of PM using a new rapid characterization technique. A pyrolysis GC-MS analytical method is being developed to uniquely characterize the sources of roadway PM2.5 such as brake dust, tire wear, and direct emissions from diesel and gasoline engines. The source profiles will be used in conjunction with measurements of the composition of ambient roadway PM to determine the importance of the various roadway sources. The advantages of this technique over conventional solvent extractions include: smaller (mg) sample mass requirements, short extraction times and minimal sample handing. Preliminary two-step pyrolysis results will be presented for PM samples from individual sources and an ambient roadway. Specific analytical issues that will be discussed include: modifications of commercial pyrolysis hardware to improve reproducibility; desorption versus pyrolysis; developing appropriate pyrolysis programs for heterogenous sample materials; and method detection limits.
Quantitative Insights into the Fast Pyrolysis of Extracted Cellulose, Hemicelluloses, and Lignin
Windt, Michael; Ziegler, Bernhard; Appelt, Jörn; Saake, Bodo; Meier, Dietrich; Bridgwater, Anthony
2017-01-01
Abstract The transformation of lignocellulosic biomass into bio‐based commodity chemicals is technically possible. Among thermochemical processes, fast pyrolysis, a relatively mature technology that has now reached a commercial level, produces a high yield of an organic‐rich liquid stream. Despite recent efforts to elucidate the degradation paths of biomass during pyrolysis, the selectivity and recovery rates of bio‐compounds remain low. In an attempt to clarify the general degradation scheme of biomass fast pyrolysis and provide a quantitative insight, the use of fast pyrolysis microreactors is combined with spectroscopic techniques (i.e., mass spectrometry and NMR spectroscopy) and mixtures of unlabeled and 13C‐enriched materials. The first stage of the work aimed to select the type of reactor to use to ensure control of the pyrolysis regime. A comparison of the chemical fragmentation patterns of “primary” fast pyrolysis volatiles detected by using GC‐MS between two small‐scale microreactors showed the inevitable occurrence of secondary reactions. In the second stage, liquid fractions that are also made of primary fast pyrolysis condensates were analyzed by using quantitative liquid‐state 13C NMR spectroscopy to provide a quantitative distribution of functional groups. The compilation of these results into a map that displays the distribution of functional groups according to the individual and main constituents of biomass (i.e., hemicelluloses, cellulose and lignin) confirmed the origin of individual chemicals within the fast pyrolysis liquids. PMID:28644517
Quantitative Insights into the Fast Pyrolysis of Extracted Cellulose, Hemicelluloses, and Lignin.
Carrier, Marion; Windt, Michael; Ziegler, Bernhard; Appelt, Jörn; Saake, Bodo; Meier, Dietrich; Bridgwater, Anthony
2017-08-24
The transformation of lignocellulosic biomass into bio-based commodity chemicals is technically possible. Among thermochemical processes, fast pyrolysis, a relatively mature technology that has now reached a commercial level, produces a high yield of an organic-rich liquid stream. Despite recent efforts to elucidate the degradation paths of biomass during pyrolysis, the selectivity and recovery rates of bio-compounds remain low. In an attempt to clarify the general degradation scheme of biomass fast pyrolysis and provide a quantitative insight, the use of fast pyrolysis microreactors is combined with spectroscopic techniques (i.e., mass spectrometry and NMR spectroscopy) and mixtures of unlabeled and 13 C-enriched materials. The first stage of the work aimed to select the type of reactor to use to ensure control of the pyrolysis regime. A comparison of the chemical fragmentation patterns of "primary" fast pyrolysis volatiles detected by using GC-MS between two small-scale microreactors showed the inevitable occurrence of secondary reactions. In the second stage, liquid fractions that are also made of primary fast pyrolysis condensates were analyzed by using quantitative liquid-state 13 C NMR spectroscopy to provide a quantitative distribution of functional groups. The compilation of these results into a map that displays the distribution of functional groups according to the individual and main constituents of biomass (i.e., hemicelluloses, cellulose and lignin) confirmed the origin of individual chemicals within the fast pyrolysis liquids. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Llana-Ruíz-Cabello, María; Pichardo, Silvia; Jiménez-Morillo, Nicasio T; Bermúdez, José M; Aucejo, Susana; González-Vila, Francisco J; Cameán, Ana M; González-Pérez, José A
2016-07-01
Environmental, economic and safety challenges motivate shift towards safer materials for food packaging. New bioactive packaging techniques, i.e. addition of essential plant oils (EOs), are gaining attention by creating barriers to protect products from spoilage. Analytical pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) was used to fingerprint a bioactive polylactic acid (PLA) with polybutylene succinate (PBS) (950 g kg(-1) :50 g kg(-1) ) film extruded with variable quantities (0, 20, 50 and 100 g kg(-1) ) of Origanum vulgare EO. Main PLA:PBS pyrolysis products were lactide enantiomers and monomer units from the major PLA fraction and succinic acid anhydride from the PBS fraction. Oregano EO pyrolysis released cymene, terpinene and thymol/carvacrol peaks as diagnostic peaks for EO. In fact, linear correlation coefficients better than 0.950R(2) value (P < 0.001) were found between the chromatographic area of the diagnostic peaks and the amount of oregano EO in the bioplastic. The pyrolytic behaviour of a bio-based active package polymer including EO is studied in detail. Identified diagnostic compounds provide a tool to monitor the quantity of EO incorporated into the PLA:PBS polymeric matrix. Analytical pyrolysis is proposed as a rapid technique for the identification and quantification of additives within bio-based plastic matrices. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.
NASA Astrophysics Data System (ADS)
Xiao, Li
Despite the great passion and endless efforts on development of renewable energy from biomass, the commercialization and scale up of biofuel production is still under pressure and facing challenges. New ideas and facilities are being tested around the world targeting at reducing cost and improving product value. Cutting edge technologies involving analytical chemistry, statistics analysis, industrial engineering, computer simulation, and mathematics modeling, etc. keep integrating modern elements into this classic research. One of those challenges of commercializing biofuel production is the complexity from chemical composition of biomass feedstock and the products. Because of this, feedstock selection and process optimization cannot be conducted efficiently. This dissertation attempts to further evaluate biomass thermal decomposition process using both traditional methods and advanced technique (Pyrolysis Molecular Beam Mass Spectrometry). Focus has been made on data base generation of thermal decomposition products from biomass at different temperatures, finding out the relationship between traditional methods and advanced techniques, evaluating process efficiency and optimizing reaction conditions, comparison of typically utilized biomass feedstock and new search on innovative species for economical viable feedstock preparation concepts, etc. Lab scale quartz tube reactors and 80il stainless steel sample cups coupled with auto-sampling system were utilized to simulate the complicated reactions happened in real fluidized or entrained flow reactors. Two main high throughput analytical techniques used are Near Infrared Spectroscopy (NIR) and Pyrolysis Molecular Beam Mass Spectrometry (Py-MBMS). Mass balance, carbon balance, and product distribution are presented in detail. Variations of thermal decomposition temperature range from 200°C to 950°C. Feedstocks used in the study involve typical hardwood and softwood (red oak, white oak, yellow poplar, loblolly pine), fast growing energy crops (switchgrass), and popular forage crop (alfalfa), as well as biochar derived from those materials and their mixtures. It demonstrated that Py-MBMS coupled with MVA could be used as fast analytical tools for the study of not only biomass composition but also its thermal decomposition behaviors. It found that the impact of biomass composition heavily depends on the thermal decomposition temperature because at different temperature, the composition of biomass decomposed and the impact of minerals on the decomposition reaction varies. At low temperature (200-500°C), organic compounds attribute to the majority of variation in thermal decomposition products. At higher temperature, inorganics dramatically changed the pyrolysis pathway of carbohydrates and possibly lignin. In gasification, gasification tar formation is also observed to be impacted by ash content in vapor and char. In real reactor, biochar structure also has interactions with other fractions to make the final pyrolysis and gasification product. Based on the evaluation of process efficiencies during torrefaction, temperature ranging from 275°C to 300°C with short residence time (<10min) are proposed to be optimal torrefaction conditions. 500°C is preferred to 700°C as primary pyrolysis temperature in two stage gasification because higher primary pyrolysis temperature resulted in more tar and less gasification char. Also, in terms of carbon yield, more carbon is lost in tar while less carbon is retained in gas product using 700°C as primary pyrolysis temperature. In addition, pyrolysis char is found to produce less tar and more gas during steam gasification compared with gasification of pyrolysis vapor. Thus it is suggested that torrefaction might be an efficient pretreatment for biomass gasification because it can largely improve the yield of pyrolysis char during the primary pyrolysis step of gasification thus reduce the total tar of the overall gasification products. Future work is suggested in the end.
Laser pyrolysis fabrication of ferromagnetic gamma'-Fe4N and FeC nanoparticles
NASA Technical Reports Server (NTRS)
Grimes, C. A.; Qian, D.; Dickey, E. C.; Allen, J. L.; Eklund, P. C.
2000-01-01
Using the laser pyrolysis method, single phase gamma'-Fe4N nanoparticles were prepared by a two step method involving preparation of nanoscale iron oxide and a subsequent gas-solid nitridation reaction. Single phase Fe3C and Fe7C3 could be prepared by laser pyrolysis from Fe(CO)5 and 3C2H4 directly. Characterization techniques such as XRD, TEM and vibrating sample magnetometer were used to measure phase structure, particle size and magnetic properties of these nanoscale nitride and carbide particles. c2000 American Journal of Physics.
Antimony-Doped Tin Oxide Thin Films Grown by Home Made Spray Pyrolysis Technique
NASA Astrophysics Data System (ADS)
Yusuf, Gbadebo; Babatola, Babatunde Keji; Ishola, Abdulahi Dimeji; Awodugba, Ayodeji O.; Solar cell Collaboration
2016-03-01
Transparent conducting antimony-doped tin oxide (ATO) films have been deposited on glass substrates by home made spray pyrolysis technique. The structural, electrical and optical properties of the ATO films have been investigated as a function of Sb-doping level and annealing temperature. The optimum target composition for high conductivity and low resistivity was found to be 20 wt. % SnSb2 + 90 wt. ATO. Under optimized deposition conditions of 450oC annealing temperature, electrical resistivity of 5.2×10-4 Ω -cm, sheet resistance of 16.4 Ω/sq, average optical transmittance of 86% in the visible range, and average optical band-gap of 3.34eV were obtained. The film deposited at lower annealing temperature shows a relatively rough, loosely bound slightly porous surface morphology while the film deposited at higher annealing temperature shows uniformly distributed grains of greater size. Keywords: Annealing, Doping, Homemade spray pyrolysis, Tin oxide, Resistivity
Two-scale modeling of joining of the aluminum alloys by a cohesive zone element technique
NASA Astrophysics Data System (ADS)
Zuo, Yinan; Wulfinghoff, Stephan; Reese, Stefanie
2016-10-01
The roll bonding of aluminum sheets is numerically investigated. In the first part of the paper, a cohesive zone element formulation in the framework of zero-thickness interface elements is developed. Based on a traction-separation law, this enables the modeling of bonding and debonding on both macroscale and microscale. Simulations on microscale are done to show the mechanism of bonding and the influence of different factors on the bonding strength.
Pyrolytic sugars from cellulosic biomass
NASA Astrophysics Data System (ADS)
Kuzhiyil, Najeeb
Sugars are the feedstocks for many promising advanced cellulosic biofuels. Traditional sugars derived from starch and sugar crops are limited in their availability. In principle, more plentiful supply of sugars can be obtained from depolymerization of cellulose, the most abundant form of biomass in the world. Breaking the glycosidic bonds between the pyranose rings in the cellulose chain to liberate glucose has usually been pursued by enzymatic hydrolysis although a purely thermal depolymerization route to sugars is also possible. Fast pyrolysis of pure cellulose yields primarily levoglucosan, an anhydrosugar that can be hydrolyzed to glucose. However, naturally occurring alkali and alkaline earth metals (AAEM) in biomass are strongly catalytic toward ring-breaking reactions that favor formation of light oxygenates over anhydrosugars. Removing the AAEM by washing was shown to be effective in increasing the yield of anhydrosugars; but this process involves removal of large amount of water from biomass that renders it energy intensive and thereby impractical. In this work passivation of the AAEM (making them less active or inactive) using mineral acid infusion was explored that will increase the yield of anhydrosugars from fast pyrolysis of biomass. Mineral acid infusion was tried by previous researchers, but the possibility of chemical reactions between infused acid and AAEM in the biomass appears to have been overlooked, possibly because metal cations might be expected to already be substantially complexed to chlorine or other strong anions that are found in biomass. Likewise, it appears that previous researchers assumed that as long as AAEM cations were in the biomass, they would be catalytically active regardless of the nature of their complexion with anions. On the contrary, we hypothesized that AAEM can be converted to inactive or less active salts using mineral acids. Various biomass feedstocks were infused with mineral (hydrochloric, nitric, sulfuric and phosphoric acids) and organic acids (formic and acetic acids) followed by analytical pyrolysis on a micropyrolyzer/GC/MS/FID system. It was found that sulfuric and phosphoric acids are very effective in passivating the AAEM thereby increasing the yield of anhydrosugars. An excellent correlation was discovered between the amount of acid required to obtain the maximum yield of anhydrosugars and the amount of AAEM contained in the biomass feedstock. In the micro-scale studies, up to 56% of the cellulose contained in the biomass was converted into anhydrosugars which is close to the 57% conversion obtained from pure cellulose pyrolysis. It is known that LG polymerization and subsequent charring occur at temperatures above 275°C depending on the vapor pressure of LG in the gas stream. A study of pyrolysis of acid-infused biomass feedstocks at various temperatures revealed that LG recovery is best at lower temperatures than the conventional pyrolysis temperature range of 450-500°C. Pyrolysis of acid-infused biomass failed in a continuous fluidized bed reactor due to clogging of the bed. The feedstock formed vitreous material along with the fluidizing sand that was formed from poor pyrolysis of lignin. However, more investigation of this phenomenon is a subject for future work. Pyrolysis experiments on an auger type reactor were successful in producing bio-oils with unprecedented amounts of sugars. Though there was increase in charring when compared to the control feedstock, pyrolysis of red oak infused with 0.4 wt% of sulfuric acid produced bio-oil with 18wt% of sugars. One of the four fractions of bio-oil collected contained most of the sugars, which shows significant potential for separating the sugars from bio-oil using simple means. This work points towards a new pathway for making advanced biofuels viz. upgrading pyrolytic sugars from biomass that could compete with enzymatic sugars from biomass.
Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.
2017-01-01
Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes. PMID:28660882
Sfetsas, Themistoklis; Michailof, Chrysa; Lappas, Angelos; Li, Qiangyi; Kneale, Brian
2011-05-27
Pyrolysis oils have attracted a lot of interest, as they are liquid energy carriers and general sources of chemicals. In this work, gas chromatography with flame ionization detector (GC-FID) and two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) techniques were used to provide both qualitative and quantitative results of the analysis of three different pyrolysis oils. The chromatographic methods and parameters were optimized and solvent choice and separation restrictions are discussed. Pyrolysis oil samples were diluted in suitable organic solvent and were analyzed by GC×GC-TOFMS. An average of 300 compounds were detected and identified in all three samples using the ChromaToF (Leco) software. The deconvoluted spectra were compared with the NIST software library for correct matching. Group type classification was performed by use of the ChromaToF software. The quantification of 11 selected compounds was performed by means of a multiple-point external calibration curve. Afterwards, the pyrolysis oils were extracted with water, and the aqueous phase was analyzed both by GC-FID and, after proper change of solvent, by GC×GC-TOFMS. As previously, the selected compounds were quantified by both techniques, by means of multiple point external calibration curves. The parameters of the calibration curves were calculated by weighted linear regression analysis. The limit of detection, limit of quantitation and linearity range for each standard compound with each method are presented. The potency of GC×GC-TOFMS for an efficient mapping of the pyrolysis oil is undisputable, and the possibility of using it for quantification as well has been demonstrated. On the other hand, the GC-FID analysis provides reliable results that allow for a rapid screening of the pyrolysis oil. To the best of our knowledge, very few papers have been reported with quantification attempts on pyrolysis oil samples using GC×GC-TOFMS most of which make use of the internal standard method. This work provides the ground for further analysis of pyrolysis oils of diverse sources for a rational design of both their production and utilization process. Copyright © 2010 Elsevier B.V. All rights reserved.
A geochemical study of macerals from a Miocene lignite and an Eocene bituminous coal, Indonesia
Stankiewicz, B.A.; Kruge, M.A.; Mastalerz, Maria
1996-01-01
Optical and chemical studies of maceral concentrates from a Miocene lignite and an Eocene high-volatile bituminous C coal from southeastern Kalimantan, Indonesia were undertaken using pyro-Lysis, optical, electron microprobe and FTIR techniques Pyrolysis products of vitrinite from bituminous coal were dominated by straight-chain aliphatics and phenols. The huminite of the Miocene lignite produced mostly phenolic compounds upon pyrolysis. Differences in the pyrolysis products between the huminite and vitrinite samples reflect both maturation related and paleobotanical differences. An undefined aliphatic source and/or bacterial biomass were the likely contributors of n-alkyl moieties to the vitrinite. The resinite fraction in the lignite yielded dammar-derived pyrolysis products, as well as aliphatics and phenols as the products of admixed huminite and other liptinites. The optically defined resinite-rich fraction of the bituminous coal from Kalimantan produced abundant n-aliphatic moieties upon pyrolysis, but only two major resin markers (cadalene and 1,6-dimethylnaphthalene). This phenomenon is likely due to the fact that Eocene resins were not dammar-related. Data from the electron microprobe and Fourier transform infrared spectrometry strongly support the results obtained by Py GC MS and microscopy.
Processing of uranium oxide and silicon carbide based fuel using polymer infiltration and pyrolysis
NASA Astrophysics Data System (ADS)
Singh, Abhishek K.; Zunjarrao, Suraj C.; Singh, Raman P.
2008-09-01
Ceramic composite pellets consisting of uranium oxide, UO 2, contained within a silicon carbide matrix, were fabricated using a novel processing technique based on polymer infiltration and pyrolysis (PIP). In this process, particles of depleted uranium oxide, in the form of U 3O 8, were dispersed in liquid allylhydridopolycarbosilane (AHPCS), and subjected to pyrolysis up to 900 °C under a continuous flow of ultra high purity argon. The pyrolysis of AHPCS, at these temperatures, produced near-stoichiometric amorphous silicon carbide ( a-SiC). Multiple polymer infiltration and pyrolysis (PIP) cycles were performed to minimize open porosity and densify the silicon carbide matrix. Analytical characterization was conducted to investigate chemical interaction between U 3O 8 and SiC. It was observed that U 3O 8 reacted with AHPCS during the very first pyrolysis cycle, and was converted to UO 2. As a result, final composition of the material consisted of UO 2 particles contained in an a-SiC matrix. The physical and mechanical properties were also quantified. It is shown that this processing scheme promotes uniform distribution of uranium fuel source along with a high ceramic yield of the parent matrix.
Investigation on V2O5 Thin Films Prepared by Spray Pyrolysis Technique
NASA Astrophysics Data System (ADS)
Anasthasiya, A. Nancy Anna; Gowtham, K.; Shruthi, R.; Pandeeswari, R.; Jeyaprakash, B. G.
The spray pyrolysis technique was employed to deposit V2O5 thin films on a glass substrate. By varying the precursor solution volume from 10mL to 50mL in steps of 10mL, films of various thicknesses were prepared. Orthorhombic polycrystalline V2O5 films were inferred from the XRD pattern irrespective of precursor solution volume. The micro-Raman studies suggested that annealed V2O5 thin film has good crystallinity. The effect of precursor solution volume on morphological and optical properties were analysed and reported.
Nonlinear optical characterization of ZnS thin film synthesized by chemical spray pyrolysis method
NASA Astrophysics Data System (ADS)
G, Sreeja V.; V, Sabitha P.; Anila, E. I.; R, Reshmi; John, Manu Punnan; Radhakrishnan, P.
2014-10-01
ZnS thin film was prepared by Chemical Spray Pyrolysis (CSP) method. The sample was characterized by X-ray diffraction method and Z scan technique. XRD pattern showed that ZnS thin film has hexagonal structure with an average size of about 5.6nm. The nonlinear optical properties of ZnS thin film was studied by open aperture Z-Scan technique using Q-switched Nd-Yag Laser at 532nm. The Z-scan plot showed that the investigated ZnS thin film has saturable absorption behavior. The nonlinear absorption coefficient and saturation intensity were also estimated.
NASA Technical Reports Server (NTRS)
Arevalo, Ricardo, Jr.; Coyle, Barry; Paulios, Demetrios; Stysley, Paul; Feng, Steve; Getty, Stephanie; Binkerhoff, William
2015-01-01
Compared to wet chemistry and pyrolysis techniques, in situ laser-based methods of chemical analysis provide an ideal way to characterize precious planetary materials without requiring extensive sample processing. In particular, laser desorption and ablation techniques allow for rapid, reproducible and robust data acquisition over a wide mass range, plus: Quantitative, spatially-resolved measurements of elemental and molecular (organic and inorganic) abundances; Low analytical blanks and limits-of-detection ( ng g-1); and, the destruction of minimal quantities of sample ( g) compared to traditional solution and/or pyrolysis analyses (mg).
Rapid identification of bacteria with miniaturized pyrolysis/GC analysis
NASA Astrophysics Data System (ADS)
Morgan, Catherine H.; Mowry, Curtis; Manginell, Ronald P.; Frye-Mason, Gregory C.; Kottenstette, Richard J.; Lewis, Patrick
2001-02-01
Identification of bacteria and other biological moieties finds a broad range of applications in the environmental, biomedical, agricultural, industrial, and military arenas. Linking these applications are biological markers such as fatty acids, whose mass spectral profiles can be used to characterize biological samples and to distinguish bacteria at the gram-type, genera, and even species level. Common methods of sample analysis require sample preparation that is both lengthy and labor intensive, especially for whole cell bacteria. The background technique relied on here utilizes chemical derivatization of fatty acids to the more volatile fatty acid methyl esters (FAMEs), which can be separated on a gas chromatograph column or input directly into a mass spectrometer. More recent publications demonstrate improved sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis at the inlet; although much faster than traditional techniques, these systems still rely on bench-top analytical equipment and individual sample preparation. Development of a miniaturized pyrolysis/GC instrument by this group is intended to realize the benefits of FAME identification of bacteria and other biological samples while further facilitating sample handling and instrument portability. The technologies being fabricated and tested have the potential of achieving pyrolysis and FAME separation on a very small scale, with rapid detection time (1-10 min from introduction to result), and with a modular sample inlet. Performance results and sensor characterization will be presented for the first phase of instrument development, encompassing the microfabricated pyrolysis and gas chromatograph elements.
Lewis, James M T; Najorka, Jens; Watson, Jonathan S; Sephton, Mark A
2018-04-01
Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as "Hematite Ridge"), which may have formed from goethite precursors. Key Words: Mars-Pyrolysis-Jarosite-Goethite-Hematite-Biosignatures. Astrobiology 18, 454-464.
Specialists' workshop on fast pyrolysis of biomass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1980-01-01
This workshop brought together most of those who are currently working in or have published significant findings in the area of fast pyrolysis of biomass or biomass-derived materials, with the goal of attaining a better understanding of the dominant mechanisms which produce olefins, oxygenated liquids, char, and tars. In addition, background papers were given in hydrocarbon pyrolysis, slow pyrolysis of biomass, and techniques for powdered-feedstock preparation in order that the other papers did not need to introduce in depth these concepts in their presentations for continuity. In general, the authors were requested to present summaries of experimental data with asmore » much interpretation of that data as possible with regard to mechanisms and process variables such as heat flux, temperatures, partial pressure, feedstock, particle size, heating rates, residence time, etc. Separate abstracts have been prepared of each presentation for inclusion in the Energy Data Base. (DMC)« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCown, F.E.
UCC Research Corporation, along with most of the companies involved in coal development, initially was thinking in terms of high pressure systems, flash pyrolysis, and hydrogenation. Most goverment funding has also been provided for projects using these techniques. However, information from several sources, only recently available to UCC Research Corporation, has effected a change in our recommended direction on the subject project. First, information being obtained in-house at UCC Research on another project using low temperature/pressure pyrolysis looked very favorable. Secondly, the initial review of the design, cost and capabilities of the pyrolysis equipment originally proposed indicated that substantial advantagesmore » could be gained at only a modest increase in cost, by changing to a low pressure unit. Finally, it was discovered that a company in England, using almost identical pyrolysis conditions as those being used at UCC Research, was producing coal liquids commercially, and had been in business many years. In consideration of the above information, UCC Research is recommending that the pyrolysis system for the subject project be changed to a low pressure/temperature design, utilizing the information obtained via our in-house research and from the company in England.« less
Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis
NASA Technical Reports Server (NTRS)
Leif, Roald N.; Simoneit, Bernd R. T.
1995-01-01
A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.
Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.
Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin
2016-11-01
The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. Copyright © 2016 Elsevier Ltd. All rights reserved.
Recycling of electronic waste: Printed wiring boards
NASA Astrophysics Data System (ADS)
Luyima, Alex
Pyrolysis and leaching are the dominant techniques applied in the recycling of waste printed wiring boards (PWBs). Waste PWB pyrolysis is a highly polluting technology and produces brominated pyrolysis oils in addition to hydrogen bromide (HBr) gas. Moreover, leaching as a treatment process of waste PWBs is not well investigated. In this work, the pyrolysis of waste PWBs has been studied with the aim of reducing the amount of brominated oils and HBr gas evolved. The effects of powder inorganic chemicals (CaO, CaCO3, Fe 2O3, Al2O3, Y-Zeolite, and ZSM-5) additions on the pyrolysis of waste PWBs has been studied through experiments using a thermogravimetric-differential thermal analyzer connected to a mass spectrometer (TG-DTA-MS) and in a tube furnace at 900 °C. It has been shown that the kinetic models by Friedman, Flynn-Wall-Ozawa, and Kissinger are applicable to waste PWB pyrolysis at temperatures below 400 °C. Moreover, CaO, CaCO3, Fe2O3, Y-Zeolite, and ZSM-5 show a potential to reduce the amount of HBr gas evolved during pyrolysis in TG-DTA-MS. However, in the tube furnace pyrolysis experiments, CaO and CaCO3 were found to be the most effective chemical additions, with more than 90% reduction in total bromine (HBr and other brominated gases) evolved. It has also been demonstrated that the sequential leaching of waste PWBs with hydrochloric acid, nitric acid and aqua regia is capable of selective recovery of base and precious metals contained in waste PWBs.
Microscale patterning of thermoplastic polymer surfaces by selective solvent swelling.
Rahmanian, Omid; Chen, Chien-Fu; DeVoe, Don L
2012-09-04
A new method for the fabrication of microscale features in thermoplastic substrates is presented. Unlike traditional thermoplastic microfabrication techniques, in which bulk polymer is displaced from the substrate by machining or embossing, a unique process termed orogenic microfabrication has been developed in which selected regions of a thermoplastic surface are raised from the substrate by an irreversible solvent swelling mechanism. The orogenic technique allows thermoplastic surfaces to be patterned using a variety of masking methods, resulting in three-dimensional features that would be difficult to achieve through traditional microfabrication methods. Using cyclic olefin copolymer as a model thermoplastic material, several variations of this process are described to realize growth heights ranging from several nanometers to tens of micrometers, with patterning techniques include direct photoresist masking, patterned UV/ozone surface passivation, elastomeric stamping, and noncontact spotting. Orogenic microfabrication is also demonstrated by direct inkjet printing as a facile photolithography-free masking method for rapid desktop thermoplastic microfabrication.
From a meso- to micro-scale connectome: array tomography and mGRASP
Rah, Jong-Cheol; Feng, Linqing; Druckmann, Shaul; Lee, Hojin; Kim, Jinhyun
2015-01-01
Mapping mammalian synaptic connectivity has long been an important goal of neuroscience because knowing how neurons and brain areas are connected underpins an understanding of brain function. Meeting this goal requires advanced techniques with single synapse resolution and large-scale capacity, especially at multiple scales tethering the meso- and micro-scale connectome. Among several advanced LM-based connectome technologies, Array Tomography (AT) and mammalian GFP-Reconstitution Across Synaptic Partners (mGRASP) can provide relatively high-throughput mapping synaptic connectivity at multiple scales. AT- and mGRASP-assisted circuit mapping (ATing and mGRASPing), combined with techniques such as retrograde virus, brain clearing techniques, and activity indicators will help unlock the secrets of complex neural circuits. Here, we discuss these useful new tools to enable mapping of brain circuits at multiple scales, some functional implications of spatial synaptic distribution, and future challenges and directions of these endeavors. PMID:26089781
Graphical Interface for the Study of Gas-Phase Reaction Kinetics: Cyclopentene Vapor Pyrolysis
NASA Astrophysics Data System (ADS)
Marcotte, Ronald E.; Wilson, Lenore D.
2001-06-01
The undergraduate laboratory experiment on the pyrolysis of gaseous cyclopentene has been modernized to improve safety, speed, and precision and to better reflect the current practice of physical chemistry. It now utilizes virtual instrument techniques to create a graphical computer interface for the collection and display of experimental data. An electronic pressure gauge has replaced the mercury manometer formerly needed in proximity to the 500 °C pyrolysis oven. Students have much better real-time information available to them and no longer require multiple lab periods to get rate constants and acceptable Arrhenius parameters. The time saved on manual data collection is used to give the students a tour of the computer interfacing hardware and software and a hands-on introduction to gas-phase reagent preparation using a research-grade high-vacuum system. This includes loading the sample, degassing it by the freeze-pump-thaw technique, handling liquid nitrogen and working through the logic necessary for each reconfiguration of the diffusion pump section and the submanifolds.
Russell, Joanna; Singer, Brian W; Perry, Justin J; Bacon, Anne
2011-05-01
A collection of more than 70 synthetic organic pigments were analysed using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We report on the analysis of diketo-pyrrolo-pyrrole, isoindolinone and perylene pigments which are classes not previously reported as being analysed by this technique. We also report on a number of azo pigments (2-naphthol, naphthol AS, arylide, diarylide, benzimidazolone and disazo condensation pigments) and phthalocyanine pigments, the Py-GC-MS analysis of which has not been previously reported. The members of each class were found to fragment in a consistent way and the pyrolysis products are reported. The technique was successfully applied to the analysis of paints used by the artist Francis Bacon (1909-1992), to simultaneously identify synthetic organic pigments and synthetic binding media in two samples of paint taken from Bacon's studio and micro-samples taken from three of his paintings and one painting attributed to him.
Volatile Analysis by Pyrolysis of Regolith (Vapor) for Planetary Resource Prospecting
NASA Technical Reports Server (NTRS)
Glavin, D. P.; Malespin, C. A.; Ten Kate, I. L.; Mcadam, A.; Getty, S. A.; Mumm, E.; Franz, H. B.; Southard, A. E.; Bleacher, J. E.; Mahaffy, P. R.
2016-01-01
Measuring the chemical composition of planetary bodies and their atmospheres is key to understanding the formation of the Solar System and the evolution of the planets and their moons. In situ volatile measurements enable a ground-truth assessment of the distribution and abundance of resources such as water-ice and oxygen, important for a sustained human presence on the Moon and beyond. The Volatile Analysis by Pyrolysis of Regolith (VAPoR) instrument is a compact pyrolysis mass spectrometer designed to detect volatiles released from solid samples that are heated to elevated temperatures and is one technique that should be considered for resource prospecting on the Moon, Mars, and asteroids.
Understanding the Behavior of the Oligomeric Fractions During Pyrolysis Oils Upgrading
NASA Astrophysics Data System (ADS)
Stankovikj, Filip
Fast pyrolysis oils represent most viable renewable sources for production of fuels and chemicals, and they could supplement significant portion of the depleting fossil fuels in near future. Progress on their utilization is impeded by their thermal and storage instability, lack of understanding of their complex composition and behavior during upgrading, including the poorly described water soluble fraction (WS). This work offers two new methodologies for simplified, and sensible description of the pyrolysis oils in terms of functional groups and chemical macro-families, augments our understanding of the composition of the WS, and the behavior of the heavy non-volatile fraction during pyrolysis oils stabilization. The concept of analyzing the volatile and non-volatile fraction in terms of functional groups has been introduced, and the quantification power of spectroscopic techniques (FTIR, 1H-NMR, UV fluorescence) for phenols, carbonyl and carboxyl groups was shown. The FT-ICR-MS van Krevelen diagram revealed the importance of dehydration reactions in pyrolysis oils and the presence of "pyrolytic humins" was hypothesized. For the first time the WS was analyzed with plethora of analytical techniques. This lead to proposition of a new characterization scheme based on functional groups, describing 90-100 wt.% of the bio-oils. The structure of idealized "pyrolytic humin" was further described as a random combination of 3-8 units of dehydrated sugars, coniferyl-type phenols, furans, and carboxylic acids attached on a 2,5-dioxo-6-hydroxyhexanal (DHH) backbone rich in carbonyl groups. TG-FTIR studies resulted in defining rules for fitting pyrolysis oils' DTG curves and assignment of TG residue. This second method is reliable for estimation of water content, light volatiles, WS and WIS. Finally, stabilization of two oils was analyzed through the prism of functional groups. Carbonyl and hydroxyl groups interconverted. The first attempt to follow silent 31P-NMR oxygen was presented; the O content reduced from 6 to 2%, which correlated well with the additional water formed. The water formation increased with stabilization temperature (3 to 10%), dominated by repolymerization instead deoxygenation. This last study presents a methodological framework for analysis of pyrolysis oils hydrotreatment; it simplifies modeling of these systems, vital for further understanding of bio-oil upgrading.
Effect of torrefaction on biomass structure and hydrocarbon production from fast pyrolysis
Neupane, Sneha; Adhikari, Sushil; Wang, Zhouhong; ...
2015-01-27
Torrefaction has been shown to improve the chemical composition of bio-oils produced from fast pyrolysis by lowering its oxygen content and enhancing the aromatic yield. A Py-GC/MS study was employed to investigate the effect of torrefaction temperatures (225, 250 and 275 °C) and residence times (15, 30 and 45 min) on product distribution from non-catalytic and H +ZSM-5 catalyzed pyrolysis of pinewood. During torrefaction, structural transformations in biomass constitutive polymers: hemicellulose, cellulose and lignin took place, which were evaluated using component analysis, solid state CP/MAS 13C NMR and XRD techniques. Torrefaction caused deacetylation and decomposition of hemicellulose, cleavage of arylmore » ether linkages and demethoxylation of lignin, degradation of cellulose and an overall increase in aromaticity of biomass, all of which affected the product yield from pyrolysis of torrefied biomass. For non-catalytic pyrolysis, selectivity of phenolic compounds increased with an increase in torrefaction severity while that of furan compounds decreased. In the case of catalytic pyrolysis, the sample torrefied at 225 °C-30 min and 250 °C-15 min resulted in a significant increase in aromatic hydrocarbon (HC) and also total carbon yield (approx. 1.6 times higher) as compared to catalytic pyrolysis of non-torrefied pine. Cleavage of aryl ether linkages and demethoxylation in lignin due to torrefaction caused increased yield of phenolic compounds, which in the presence of a catalyst were dehydrated to form aromatic HC.« less
A steady state model of agricultural waste pyrolysis: A mini review.
Trninić, M; Jovović, A; Stojiljković, D
2016-09-01
Agricultural waste is one of the main renewable energy resources available, especially in an agricultural country such as Serbia. Pyrolysis has already been considered as an attractive alternative for disposal of agricultural waste, since the technique can convert this special biomass resource into granular charcoal, non-condensable gases and pyrolysis oils, which could furnish profitable energy and chemical products owing to their high calorific value. In this regard, the development of thermochemical processes requires a good understanding of pyrolysis mechanisms. Experimental and some literature data on the pyrolysis characteristics of corn cob and several other agricultural residues under inert atmosphere were structured and analysed in order to obtain conversion behaviour patterns of agricultural residues during pyrolysis within the temperature range from 300 °C to 1000 °C. Based on experimental and literature data analysis, empirical relationships were derived, including relations between the temperature of the process and yields of charcoal, tar and gas (CO2, CO, H2 and CH4). An analytical semi-empirical model was then used as a tool to analyse the general trends of biomass pyrolysis. Although this semi-empirical model needs further refinement before application to all types of biomass, its prediction capability was in good agreement with results obtained by the literature review. The compact representation could be used in other applications, to conveniently extrapolate and interpolate these results to other temperatures and biomass types. © The Author(s) 2016.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pendse, Hemant P.
Maine and its industries identified more efficient utilization of biomass as a critical economic development issue. In Phase I of this implementation project, a research team was assembled, research equipment was implemented and expertise was demonstrated in pyrolysis, hydrodeoxygenation of pyrolysis oils, catalyst synthesis and characterization, and reaction engineering. Phase II built upon the infrastructure to innovate reaction pathways and process engineering, and integrate new approaches for fuels and chemical production within pulp and paper and other industries within the state. This research cluster brought together chemists, engineers, physicists and students from the University of Maine, Bates College, and Bowdoinmore » College. The project developed collaborations with Oak Ridge National Laboratory and Brookhaven National Laboratory. The specific research projects within this proposal were of critical interest to the DoE - in particular the biomass program within EERE and the catalysis/chemical transformations program within BES. Scientific and Technical Merit highlights of this project included: (1) synthesis and physical characterization of novel size-selective catalyst/supports using engineered mesoporous (1-10 nm diameter pores) materials, (2) advances in fundamental knowledge of novel support/ metal catalyst systems tailored for pyrolysis oil upgrading, (3) a microcalorimetric sensing technique, (4) improved methods for pyrolysis oil characterization, (5) production and characterization of woody biomass-derived pyrolysis oils, (6) development of two new patented bio oil pathways: thermal deoxygenation (TDO) and formate assisted pyrolysis (FASP), and (7) technoeconomics of pyrolysis of Maine forest biomass. This research cluster has provided fundamental knowledge to enable and assess pathways to thermally convert biomass to hydrocarbon fuels and chemicals.« less
Paschke, Meike; Hutzler, Christoph; Henkler, Frank; Luch, Andreas
2016-11-01
According to European legislation, tobacco additives may not increase the toxicity or the addictive potency of the product, but there is an ongoing debate on how to reliably characterize and measure such properties. Further, too little is known on pyrolysis patterns of tobacco additives to assume that no additional toxicological risks need to be suspected. An on-line pyrolysis technique was used and coupled to gas chromatography-mass spectrometry (GC/MS) to identify the pattern of chemical species formed upon thermal decomposition of 19 different tobacco additives like raw cane sugar, licorice or cocoa. To simulate the combustion of a cigarette it was necessary to perform pyrolysis at inert conditions as well as under oxygen supply. All individual additives were pyrolyzed under inert or oxidative conditions at 350, 700 and 1000°C, respectively, and the formation of different toxicants was monitored. We observed the generation of vinyl acrylate, fumaronitrile, methacrylic anhydride, isobutyric anhydride and 3-buten-2-ol exclusively during pyrolysis of tobacco additives. According to the literature, these toxicants so far remained undetectable in tobacco or tobacco smoke. Further, the formation of 20 selected polycyclic aromatic hydrocarbons (PAHs) with molecular weights of up to 278Da was monitored during pyrolysis of cocoa in a semi-quantitative approach. It was shown that the adding of cocoa to tobacco had no influence on the relative amounts of the PAHs formed. Copyright © 2016 Elsevier GmbH. All rights reserved.
NASA Astrophysics Data System (ADS)
Morikawa, Junko; Zamengo, Massimiliano; Kato, Yukitaka
2016-05-01
The global interest in energy applications activates the advanced study about the molten salts in the usage of fluids in the power cycle, such as for transport and heat storage in solar power facilities. However, the basic properties of molten salts show a general scattering in characterization especially in thermal properties. It is suggested that new studies are required on the measurement of thermal properties of solar salts using recent technologies. In this study, micro-scale heat transfer and phase change in molten salts are presented using our originally developed device: the micro-bolometer Infrared focal plane arrays (IR FPA) measuring system is a portable type instrument, which is re-designed to measure the thermal phenomena in high temperature up to 700 °C or higher. The superimpose system is newly setup adjusted to the signal processing in high temperature to realize the quantitative thermal imaging, simultaneously. The portable type apparatus for a quantitative micro-scale thermography using a micro-bolometer has been proposed based on an achromatic lens design to capture a micro-scale image in the long-wave infrared, a video signal superimposing for the real time emissivity correction, and a pseudo acceleration of a timeframe. Combined with the superimpose technique, the micro-scale thermal imaging in high temperature is achieved and the molten flows of the solar salts, sodium nitrate, and potassium nitrate are successfully observed. The solar salt, the mixture of sodium nitrate and potassium nitrate, shows a different shape of exothermic heat front morphology in the lower phase transition (solidification) temperature than the nitrates on cooling. The proposed measuring technique will be utilized to accelerate the screening step to determine the phase diagram and the eutectics of the multiple mixtures of candidate molten salts, which may be used as heat transport medium from the concentrated solar power to a processing plant for thermal energy storage.
NASA Astrophysics Data System (ADS)
Zhang, Guoqiang; Tateno, Kouta; Sogawa, Tetsuomi; Gotoh, Hideki
2018-04-01
We report diameter-tailored luminescence in telecom band of InP/InAs multi-heterostructure nanowires with continuously-modulated diameter from microscale to nanoscale. By using the self-catalyzed vapor-solid-liquid approach, we tune the indium particle size, and consequently the InP/InAs nanowire diameter, during growth by modulating the flow rate of the indium source material. This technique allows a high degree of continuous tuning in a wide scale from microscale to nanoscale. Hence it offers an original way to bridge the gap between microscale-featured photolithographic and nanoscale-featured nanolithographic processes and to incorporate InAs quantum disks with tunable diameters into a single InP/InAs quantum heterostructure nanowire. We realized site-defined nanowires with nanoscale diameters initiated from site-defined microscale-diameter particles made with a conventional photolithographic process. The luminescence wavelength from InAs quantum disks is directly connected to the nanowire diameter, by which the strain in the InAs quantum disks is tailored. This work provides new opportunities in the fabrication and design of nanowire devices that extends beyond what is achievable with the current technologies and enables the nanowire shape to be engineered thus offering the potential to broaden the application range of nanowire devices.
Zhang, Guoqiang; Tateno, Kouta; Sogawa, Tetsuomi; Gotoh, Hideki
2018-04-02
We report diameter-tailored luminescence in telecom band of InP/InAs multi-heterostructure nanowires with continuously-modulated diameter from microscale to nanoscale. By using the self-catalyzed vapor-solid-liquid approach, we tune the indium particle size, and consequently the InP/InAs nanowire diameter, during growth by modulating the flow rate of the indium source material. This technique allows a high degree of continuous tuning in a wide scale from microscale to nanoscale. Hence it offers an original way to bridge the gap between microscale-featured photolithographic and nanoscale-featured nanolithographic processes and to incorporate InAs quantum disks with tunable diameters into a single InP/InAs quantum heterostructure nanowire. We realized site-defined nanowires with nanoscale diameters initiated from site-defined microscale-diameter particles made with a conventional photolithographic process. The luminescence wavelength from InAs quantum disks is directly connected to the nanowire diameter, by which the strain in the InAs quantum disks is tailored. This work provides new opportunities in the fabrication and design of nanowire devices that extends beyond what is achievable with the current technologies and enables the nanowire shape to be engineered thus offering the potential to broaden the application range of nanowire devices.
NASA Astrophysics Data System (ADS)
Cubillos, G. I.; Bethencourt, M.; Olaya, J. J.
2015-02-01
ZrOxNy/ZrO2 thin films were deposited on stainless steel using two different methods: ultrasonic spray pyrolysis-nitriding (SPY-N) and the DC unbalanced magnetron sputtering technique (UBMS). Using the first method, ZrO2 was initially deposited and subsequently nitrided in an anhydrous ammonia atmosphere at 1023 K at atmospheric pressure. For UBMS, the film was deposited in an atmosphere of air/argon with a Φair/ΦAr flow ratio of 3.0. Structural analysis was carried out through X-ray diffraction (XRD), and morphological analysis was done through scanning electron microscopy (SEM) and atomic force microscopy (AFM). Chemical analysis was carried out using X-ray photoelectron spectroscopy (XPS). ZrOxNy rhombohedral polycrystalline film was produced with spray pyrolysis-nitriding, whereas using the UBMS technique, the oxynitride films grew with cubic Zr2ON2 crystalline structures preferentially oriented along the (2 2 2) plane. Upon chemical analysis of the surface, the coatings exhibited spectral lines of Zr3d, O1s, and N1s, characteristic of zirconium oxynitride/zirconia. SEM analysis showed the homogeneity of the films, and AFM showed morphological differences according to the deposition technique of the coatings. Zirconium oxynitride films enhanced the stainless steel's resistance to corrosion using both techniques. The protective efficacy was evaluated using electrochemical techniques based on linear polarization (LP). The results indicated that the layers provide good resistance to corrosion when exposed to chloride-containing media.
Microscale Digital Vacuum Electronic Gates
NASA Technical Reports Server (NTRS)
Manohara, Harish (Inventor); Mojarradi, Mohammed M. (Inventor)
2014-01-01
Systems and methods in accordance with embodiments of the invention implement microscale digital vacuum electronic gates. In one embodiment, a microscale digital vacuum electronic gate includes: a microscale field emitter that can emit electrons and that is a microscale cathode; and a microscale anode; where the microscale field emitter and the microscale anode are disposed within at least a partial vacuum; where the microscale field emitter and the microscale anode are separated by a gap; and where the potential difference between the microscale field emitter and the microscale anode is controllable such that the flow of electrons between the microscale field emitter and the microscale anode is thereby controllable; where when the microscale anode receives a flow of electrons, a first logic state is defined; and where when the microscale anode does not receive a flow of electrons, a second logic state is defined.
Microscale immobilized enzyme reactors in proteomics: latest developments.
Safdar, Muhammad; Spross, Jens; Jänis, Janne
2014-01-10
Enzymatic digestion of proteins is one of the key steps in proteomic analyses. There has been a steady progress in the applied digestion protocols in the past, starting from conventional time-consuming in-solution or in-gel digestion protocols to rapid and efficient methods utilizing different types of microscale enzyme reactors. Application of such microreactors has been proven beneficial due to lower sample consumption, higher sensitivity and straightforward coupling with LC-MS set-ups. Novel stationary phases, immobilization techniques and device formats are being constantly developed and tested to optimize digestion efficiency of proteolytic enzymes. This review focuses on the latest developments associated with the preparation and application of microscale enzyme reactors for proteomics applications since 2008 onwards. A special attention has been paid to the discussion of different stationary phases applied for immobilization purposes. Copyright © 2013 Elsevier B.V. All rights reserved.
A non-contact measurement technique at the micro scale
NASA Astrophysics Data System (ADS)
Ghosh, Santaneel
During their production and normal use, electronic packages experience large temperature excursions, leading to high thermo-mechanical stress gradients that cause fatigue failure of the solder joints. In order to prevent premature failure and prolong the fatigue life of solder joints, there is a pressing need for the characterization of the solder, especially lead-free solder, at the micro-level (joint size). The characterization and modeling of solder behavior at the appropriate scale is a major issue. However, direct measurement techniques are not applicable to characterize the deformation response of solder joints because of their micro scale dimensions. Therefore, a non-contact measurement technique utilizing a Scanning Electron Microscope (SEM) in conjunction with Digital Image Correlation (DIC) has been developed. Validation was achieved by performing a four-point bending test in both an in-house optical system with DIC and inside the SEM. This non-contact measurement technique was then used to extract the stress-strain response of the solder. Mechanical tests were performed on solder joints that were created using the same type of solder balls used in the electronic industry and were representative of normal joint scales. The SEM-DIC technique has been proven to be applicable for the determining the stress-strain response of solder material at the micro-scale. This study resulted in a validated material characterization technique specifically designed for micro-scale material response. One of the main contributions of this study is that the method is a lot simpler and cheaper, yet highly effective, compared to the previous methods. This technique is also readily applicable to the measurement of the stress-strain response of any micro-scale specimen, such as other metals, polymers, etc. Also, the measured displacement field by obtained by DIC can be used as the base for calculating the strain field on the surface of a specimen.
Microscale and nanoscale strain mapping techniques applied to creep of rocks
NASA Astrophysics Data System (ADS)
Quintanilla-Terminel, Alejandra; Zimmerman, Mark E.; Evans, Brian; Kohlstedt, David L.
2017-07-01
Usually several deformation mechanisms interact to accommodate plastic deformation. Quantifying the contribution of each to the total strain is necessary to bridge the gaps from observations of microstructures, to geomechanical descriptions, to extrapolating from laboratory data to field observations. Here, we describe the experimental and computational techniques involved in microscale strain mapping (MSSM), which allows strain produced during high-pressure, high-temperature deformation experiments to be tracked with high resolution. MSSM relies on the analysis of the relative displacement of initially regularly spaced markers after deformation. We present two lithography techniques used to pattern rock substrates at different scales: photolithography and electron-beam lithography. Further, we discuss the challenges of applying the MSSM technique to samples used in high-temperature and high-pressure experiments. We applied the MSSM technique to a study of strain partitioning during creep of Carrara marble and grain boundary sliding in San Carlos olivine, synthetic forsterite, and Solnhofen limestone at a confining pressure, Pc, of 300 MPa and homologous temperatures, T/Tm, of 0.3 to 0.6. The MSSM technique works very well up to temperatures of 700 °C. The experimental developments described here show promising results for higher-temperature applications.
Morphological impact of zinc oxide layers on the device performance in thin-film transistors.
Faber, Hendrik; Klaumünzer, Martin; Voigt, Michael; Galli, Diana; Vieweg, Benito F; Peukert, Wolfgang; Spiecker, Erdmann; Halik, Marcus
2011-03-01
Zinc oxide thin-films are prepared either by spin coating of an ethanolic dispersion of nanoparticles (NP, diameter 5 nm) or by spray pyrolysis of a zinc acetate dihydrate precursor. High-resolution electron microscopy studies reveal a monolayer of particles for the low temperature spin coating approach and larger crystalline domains of more than 30 nm for the spray pyrolysis technique. Thin-film transistor devices (TFTs) based on spray pyrolysis films exhibit higher electron mobilities of up to 24 cm2 V(-1) s(-1) compared to 0.6 cm2 V(-1) s(-1) for NP based TFTs. These observations were dedicated to a reduced number of grain boundaries within the transistor channel.
Najorka, Jens; Watson, Jonathan S.; Sephton, Mark A.
2018-01-01
Abstract Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as “Hematite Ridge”), which may have formed from goethite precursors. Key Words: Mars—Pyrolysis—Jarosite—Goethite—Hematite—Biosignatures. Astrobiology 18, 454–464. PMID:29298093
Auto shredder residue recycling: Mechanical separation and pyrolysis.
Santini, Alessandro; Passarini, Fabrizio; Vassura, Ivano; Serrano, David; Dufour, Javier; Morselli, Luciano
2012-05-01
Directive 2000/53/EC sets a goal of 85% material recycling from end-of-life vehicles (ELVs) by the end of 2015. The current ELV recycling rate is around 80%, while the remaining waste is called automotive shredder residue (ASR), or car fluff. In Europe, this is mainly landfilled because it is extremely heterogeneous and often polluted with car fluids. Despite technical difficulties, in the coming years it will be necessary to recover materials from car fluff in order to meet the ELV Directive requirement. This study deals with ASR pretreatment and pyrolysis, and aims to determine whether the ELV material recycling target may be achieved by car fluff mechanical separation followed by pyrolysis with a bench scale reactor. Results show that flotation followed by pyrolysis of the light, organic fraction may be a suitable ASR recycling technique if the oil can be further refined and used as a chemical. Moreover, metals are liberated during thermal cracking and can be easily separated from the pyrolysis char, amounting to roughly 5% in mass. Lastly, pyrolysis can be a good starting point from a "waste-to-chemicals" perspective, but further research should be done with a focus on oil and gas refining, in order both to make products suitable for the chemical industry and to render the whole recycling process economically feasible. Copyright © 2011 Elsevier Ltd. All rights reserved.
Catalytic pyrolysis of car tire waste using expanded perlite.
Kar, Y
2011-08-01
In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100mL/min and a heating rate of 10°C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02wt.% at 425°C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11wt.% at the ratio of 0.10 with the yield increase of 8.48wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, (1)H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C(5)-C(15) organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties. Copyright © 2011 Elsevier Ltd. All rights reserved.
NASA Technical Reports Server (NTRS)
Pineda, Evan J.; Bednarcyk, Brett A.; Arnold, Steven M.
2014-01-01
It is often advantageous to account for the microstructure of the material directly using multiscale modeling. For computational tractability, an idealized repeating unit cell (RUC) is used to capture all of the pertinent features of the microstructure. Typically, the RUC is dimensionless and depends only on the relative volume fractions of the different phases in the material. This works well for non-linear and inelastic behavior exhibiting a positive-definite constitutive response. Although, once the material exhibits strain softening, or localization, a mesh objective failure theories, such as smeared fracture theories, nodal and element enrichment theories (XFEM), cohesive elements or virtual crack closure technique (VCCT), can be utilized at the microscale, but the dimensions of the RUC must then be defined. One major challenge in multiscale progressive damage modeling is relating the characteristic lengths across the scales in order to preserve the energy that is dissipated via localization at the microscale. If there is no effort to relate the size of the macroscale element to the microscale RUC, then the energy that is dissipated will remain mesh dependent at the macroscale, even if it is regularized at the microscale. Here, a technique for mapping characteristic lengths across the scales is proposed. The RUC will be modeled using the generalized method of cells (GMC) micromechanics theory, and local failure in the matrix constituent subcells will be modeled using the crack band theory. The subcell characteristic lengths used in the crack band calculations will be mapped to the macroscale finite element in order to regularize the local energy in a manner consistent with the global length scale. Examples will be provided with and without the regularization, and they will be compared to a baseline case where the size and shape of the element and RUC are coincident (ensuring energy is preserved across the scales).
Simultaneous biosorption of selenium, arsenic and molybdenum with modified algal-based biochars.
Johansson, Charlotte L; Paul, Nicholas A; de Nys, Rocky; Roberts, David A
2016-01-01
Ash disposal waters from coal-fired power stations present a challenging water treatment scenario as they contain high concentrations of the oxyanions Se, As and Mo which are difficult to remove through conventional techniques. In an innovative process, macroalgae can be treated with Fe and processed through slow pyrolysis into Fe-biochar which has a high affinity for oxyanions. However, the effect of production conditions on the efficacy of Fe-biochar is poorly understood. We produced Fe-biochar from two algal sources; "Gracilaria waste" (organic remnants after agar is extracted from cultivated Gracilaria) and the freshwater macroalgae Oedogonium. Pyrolysis experiments tested the effects of the concentration of Fe(3+) in pre-treatment, and pyrolysis temperatures, on the efficacy of the Fe-biochar. The efficacy of Fe-biochar increased with increasing concentrations of Fe(3+) in the pre-treatment solutions, and decreased with increasing pyrolysis temperatures. The optimized Fe-biochar for each biomass was produced by treatment with a 12.5% w/v Fe(3+) solution, followed by slow pyrolysis at 300 °C. The Fe-biochar produced in this way had higher a biosorption capacity for As and Mo (62.5-80.7 and 67.4-78.5 mg g(-1) respectively) than Se (14.9-38.8 mg g(-1)) in single-element mock effluents, and the Fe-biochar produced from Oedogonium had a higher capacity for all elements than the Fe-biochar produced from Gracilaria waste. Regardless, the optimal Fe-biochars from both biomass sources were able to effectively treat Se, As and Mo simultaneously in an ash disposal effluent from a power station. The production of Fe-biochar from macroalgae is a promising technique for treatment of complex effluents containing oxyanions. Copyright © 2015 Elsevier Ltd. All rights reserved.
Catalytic pyrolysis of waste furniture sawdust for bio-oil production.
Uzun, Başak B; Kanmaz, Gülin
2014-07-01
In this study, the catalytic pyrolysis of waste furniture sawdust in the presence of ZSM-5, H-Y and MCM-41 (10 wt % of the biomass sample) was carried out in order to increase the quality of the liquid product at the various pyrolysis temperatures of 400, 450, 500 and 550(o)C. In the non-catalytic work, the maximum oil yield was obtained as 42% at 500(o)C in a fixed-bed reactor system. In the catalytic work, the maximum oil yield was decreased to 37.48, 30.04 and 29.23% in the presence of ZSM-5, H-Y and MCM-41, respectively. The obtained pyrolysis oils were analyzed by various spectroscopic and chromatographic techniques. It was determined that the use of a catalyst decreased acids and increased valuable organics found in the bio-oil. The removal of oxygen from bio-oil was confirmed with the results of the elemental analysis and gas chromatography-mass spectrometry. © The Author(s) 2014.
Recent Advances in Analytical Pyrolysis to Investigate Organic Materials in Heritage Science.
Degano, Ilaria; Modugno, Francesca; Bonaduce, Ilaria; Ribechini, Erika; Colombini, Maria Perla
2018-06-18
The molecular characterization of organic materials in samples from artworks and historical objects traditionally entailed qualitative and quantitative analyses by HPLC and GC. Today innovative approaches based on analytical pyrolysis enable samples to be analysed without any chemical pre-treatment. Pyrolysis, which is often considered as a screening technique, shows previously unexplored potential thanks to recent instrumental developments. Organic materials that are macromolecular in nature, or undergo polymerization upon curing and ageing can now be better investigated. Most constituents of paint layers and archaeological organic substances contain major insoluble and chemically non-hydrolysable fractions that are inaccessible to GC or HPLC. To date, molecular scientific investigations of the organic constituents of artworks and historical objects have mostly focused on the minor constituents of the sample. This review presents recent advances in the qualitative and semi-quantitative analyses of organic materials in heritage objects based on analytical pyrolysis coupled with mass spectrometry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Mass spectrometric studies of trimethylindium pyrolysis
NASA Technical Reports Server (NTRS)
Buchan, N. I.; Larsen, C. A.; Stringfellow, G. B.
1988-01-01
The kinetics of the pyrolysis of trimethylindium (TMIn) in He, D2, and H2 carriers was investigated using the atmospheric pressure flow-tube apparatus described by Larsen et al. (1987) and a time-of-flight mass spectrometer. The rate constant for the pyrolysis of TMIn in He was found to be comparable to that found by Jacko and Price (1964) for TMIn in toluene carrier (a radical scavenger), indicating that TMIn decomposes in He not by radical attack of methyl groups, but by homolytic fission. The decomposition of TMIn is enhanced in D2 and H2 carriers, where the principal products are CH3D and C2H6, and CH4 and C2H6, respectively, indicating that the reaction pathway in these carriers is different from those in He and toluene. The pyrolysis in H2 and D2 is attributed to a radical attack by H or D on TMIn. A reaction mechanism involving a short-lived hypervalent DTMIn species was proposed and was tested using numerical modeling techniques.
Catalytic Fast Pyrolysis of Cellulose by Integrating Dispersed Nickel Catalyst with HZSM-5 Zeolite
NASA Astrophysics Data System (ADS)
Lei, Xiaojuan; Bi, Yadong; Zhou, Wei; Chen, Hui; Hu, Jianli
2018-01-01
The effect of integrating dispersed nickel catalyst with HZSM-5 zeolite on upgrading of vapors produced from pyrolysis of lignocellulosic biomass was investigated. The active component nickel nitrate was introduced onto the cellulose substrate by impregnation technique. Based on TGA experimental results, we discovered that nickel nitrate first released crystallization water, and then successively decomposed into nickel oxide which was reduced in-situ to metallic nickel through carbothermal reduction reaction. In-situ generated nickel nanoparticles were found highly dispersed over carbon substrate, which were responsible for catalyzing reforming and cracking of tars. In catalytic fast pyrolysis of cellulose, the addition of nickel nitrate caused more char formation at the expense of the yield of the condensable liquid products. In addition, the selectivity of linear oxygenates was increased whereas the yield of laevoglucose was reduced. Oxygen-containing compounds in pyrolysis vapors were deoxygenated into aromatics using HZSM-5. Moreover, the amount of condensable liquid products was decreased with the addition of HZSM-5.
How Does CIGS Performance Depend on Temperature at the Microscale?
DOE Office of Scientific and Technical Information (OSTI.GOV)
Stuckelberger, Michael E.; Nietzold, Tara; West, Bradley M.
Unveiling the correlation among electrical performance, elemental distribution, and defects at the microscale is crucial for the understanding and improvement of the overall solar cell performance. While this is true in general for solar cells with polycrystalline absorber layers, it is particularly critical for defect engineering of the complex quaternary CuIn xGa 1-xSe 2 (CIGS) material system. Studying these relationships under standard ambient conditions can provide important insights but does not provide input on the behavior of the cell under real operating conditions. In this contribution, we take a close look at the complex temperature dependence of defects and voltagemore » in CIGS at the microscale. We have developed correlative X-raymicroscopymethods and adapted them for temperature-dependent measurements of the locally generated voltage and elemental compositions at the microscale. We have applied these techniques to industrial CIGS solar cells covering temperatures from room temperature up to 100 degrees C. Finally, we find underperforming areas spanning multiple grains that do not correlate with the elemental distribution of major absorber constituents. However, we demonstrate that low-performing areas perform better at higher temperatures relative to the high-performing areas.« less
How Does CIGS Performance Depend on Temperature at the Microscale?
Stuckelberger, Michael E.; Nietzold, Tara; West, Bradley M.; ...
2017-11-03
Unveiling the correlation among electrical performance, elemental distribution, and defects at the microscale is crucial for the understanding and improvement of the overall solar cell performance. While this is true in general for solar cells with polycrystalline absorber layers, it is particularly critical for defect engineering of the complex quaternary CuIn xGa 1-xSe 2 (CIGS) material system. Studying these relationships under standard ambient conditions can provide important insights but does not provide input on the behavior of the cell under real operating conditions. In this contribution, we take a close look at the complex temperature dependence of defects and voltagemore » in CIGS at the microscale. We have developed correlative X-raymicroscopymethods and adapted them for temperature-dependent measurements of the locally generated voltage and elemental compositions at the microscale. We have applied these techniques to industrial CIGS solar cells covering temperatures from room temperature up to 100 degrees C. Finally, we find underperforming areas spanning multiple grains that do not correlate with the elemental distribution of major absorber constituents. However, we demonstrate that low-performing areas perform better at higher temperatures relative to the high-performing areas.« less
MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Beyenal, Haluk; McLEan, Jeff; Majors, Paul
2013-11-14
The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in themore » subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.« less
García-Negrón, Valerie; Phillip, Nathan D.; Li, Jianlin; ...
2016-11-18
Lignin, an abundant organic polymer and a byproduct of pulp and biofuel production, has potential applications owing to its high carbon content and aromatic structure. Processing structure relationships are difficult to predict because of the heterogeneity of lignin. Here, this work discusses the roles of unit operations in the carbonization process of softwood lignin, and their resulting impacts on the material structure and electrochemical properties in application as the anode in lithium-ion cells. The processing variables include the lignin source, temperature, and duration of thermal stabilization, pyrolysis, and reduction. Materials are characterized at the atomic and microscales. High-temperature carbonization, atmore » 2000 °C, produces larger graphitic domains than at 1050 °C, but results in a reduced capacity. Coulombic efficiencies over 98 % are achieved for extended galvanostatic cycling. Consequently, a properly designed carbonization process for lignin is well suited for the generation of low-cost, high-efficiency electrodes.« less
Breast Cancer Nodes Detection Using Ultrasonic Microscale Subarrayed MIMO RADAR
Siwamogsatham, Siwaruk; Pomalaza-Ráez, Carlos
2014-01-01
This paper proposes the use of ultrasonic microscale subarrayed MIMO RADARs to estimate the position of breast cancer nodes. The transmit and receive antenna arrays are divided into subarrays. In order to increase the signal diversity each subarray is assigned a different waveform from an orthogonal set. High-frequency ultrasonic transducers are used since a breast is considered to be a superficial structure. Closed form expressions for the optimal Neyman-Pearson detector are derived. The combination of the waveform diversity present in the subarrayed deployment and traditional phased-array RADAR techniques provides promising results. PMID:25309591
Microscale Patterning of Thermoplastic Polymer Surfaces by Selective Solvent Swelling
Rahmanian, Omid; Chen, Chien-Fu; DeVoe, Don L.
2012-01-01
A new method for the fabrication of microscale features in thermoplastic substrates is presented. Unlike traditional thermoplastic microfabrication techniques, in which bulk polymer is displaced from the substrate by machining or embossing, a unique process termed orogenic microfabrication has been developed in which selected regions of a thermoplastic surface are raised from the substrate by an irreversible solvent swelling mechanism. The orogenic technique allows thermoplastic surfaces to be patterned using a variety of masking methods, resulting in three-dimensional features that would be difficult to achieve through traditional microfabrication methods. Using cyclic olefin copolymer as a model thermoplastic material, several variations of this process are described to realize growth heights ranging from several nanometers to tens of microns, with patterning techniques include direct photoresist masking, patterned UV/ozone surface passivation, elastomeric stamping, and noncontact spotting. Orogenic microfabrication is also demonstrated by direct inkjet printing as a facile photolithography-free masking method for rapid desktop thermoplastic microfabrication. PMID:22900539
2016-06-24
wall Radar technique has been built and preliminary results of pyrolysis of iso-butane have been obtained. Qualitative measurements of ethylene in...The (2+1) REMPI ionizations of ethylene (C2H4, 11B3u(π,3p) Rydberg manifold) was selectively induced at 310─325nm. The ethylene was detectable at...quantitative measurements of ethylene as one of the pyrolysis products by using coherent microwave Rayleigh scattering (Radar) from Resonant Enhanced Multi
NASA Astrophysics Data System (ADS)
Langowski, Bryan Alfred
A micropatterning process creates distinct microscale domains on substrate surfaces that differ from the surfaces' original chemical/physical properties. Numerous micropatterning methods exist, each having relative advantages and disadvantages in terms of cost, ease, reproducibility, and versatility. Polymeric surfaces micropatterned with biomolecules have many applications, but are specifically utilized in tissue engineering as cell scaffolds that attempt to controlled tissue generation in vivo and ex vivo. As the physical and chemical cues presented by micropatterned substrates control resulting cellular behavior, characterization of these cues via surface-sensitive analytical techniques is essential in developing cell scaffolds that mimic complex in vivo physicochemical environments. The initial focus of this thesis is the chemical and physical characterization of plasma-treated, microcontact-printed (muCP) polymeric substrates used to direct nerve cell behavior. Unmodified and oxygen plasma-treated poly(methyl methacrylate) (PMMA) substrates were analyzed by surface sensitive techniques to monitor plasma-induced chemical and physical modifications. Additionally, protein-micropattern homogeneity and size were microscopically evaluated. Lastly, poly(dimethylsiloxane) (PDMS) stamps and contaminated PMMA substrates were characterized by spectroscopic and microscopic methods to identify a contamination source during microcontact printing. The final focus of this thesis is the development of microscale plasma-initiated patterning (muPIP) as a versatile, reproducible micropatterning method. Using muPIP, polymeric substrates were micropatterned with several biologically relevant inks. Polymeric substrates were characterized following muPIP by surface-sensitive techniques to identify the technique's underlying physical and chemical bases. In addition, neural stem cell response to muPIP-generated laminin micropatterns was microscopically and biologically evaluated. Finally, enhanced versatility of muPIP in generating microscale poly-L-lysine gradients was demonstrated.
Vacuum Pyrolysis and Related ISRU Techniques
NASA Technical Reports Server (NTRS)
Cardiff, Eric H.; Pomeroy, Brian R.; Banks, Ian S.; Benz, Alexis
2007-01-01
A number of ISRU-related techniques have been developed at NASA Goddard Space Flight Center. The focus of the team has been on development of the vacuum pyrolysis technique for the production of oxygen from the lunar regolith. However, a number of related techniques have also been developed, including solar concentration, solar heating of regolith, resistive heating of regolith, sintering, regolith boiling, process modeling, parts manufacturing, and instrumentation development. An initial prototype system was developed to vaporize regolith simulants using a approx. l square meter Fresnel lens. This system was successfully used to vaporize quantities of approx. lg, and both mass spectroscopy of the gasses produced and Scanning Electron Microscopy (SEM) of the slag were done to show that oxygen was produced. Subsequent tests have demonstrated the use of a larger system With a 3.8m diameter reflective mirror to vaporize the regolith. These results and modeling of the vacuum pyrolysis reaction have indicated that the vaporization of the oxides in the regolith will occur at lower temperature for stronger vacuums. The chemical modeling was validated by testing of a resistive heating system that vaporized quantities of approx. 10g of MLS-1A. This system was also used to demonstrate the sintering of regolith simulants at reduced temperatures in high vacuum. This reduction in the required temperature prompted the development of a small-scale resistive heating system for application as a scientific instrument as well as a proof-of principle experiment for oxygen production.
Pyrolysis Model Development for a Multilayer Floor Covering
McKinnon, Mark B.; Stoliarov, Stanislav I.
2015-01-01
Comprehensive pyrolysis models that are integral to computational fire codes have improved significantly over the past decade as the demand for improved predictive capabilities has increased. High fidelity pyrolysis models may improve the design of engineered materials for better fire response, the design of the built environment, and may be used in forensic investigations of fire events. A major limitation to widespread use of comprehensive pyrolysis models is the large number of parameters required to fully define a material and the lack of effective methodologies for measurement of these parameters, especially for complex materials. The work presented here details a methodology used to characterize the pyrolysis of a low-pile carpet tile, an engineered composite material that is common in commercial and institutional occupancies. The studied material includes three distinct layers of varying composition and physical structure. The methodology utilized a comprehensive pyrolysis model (ThermaKin) to conduct inverse analyses on data collected through several experimental techniques. Each layer of the composite was individually parameterized to identify its contribution to the overall response of the composite. The set of properties measured to define the carpet composite were validated against mass loss rate curves collected at conditions outside the range of calibration conditions to demonstrate the predictive capabilities of the model. The mean error between the predicted curve and the mean experimental mass loss rate curve was calculated as approximately 20% on average for heat fluxes ranging from 30 to 70 kW·m−2, which is within the mean experimental uncertainty. PMID:28793556
Method for Hot Real-Time Sampling of Pyrolysis Vapors
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pomeroy, Marc D
Biomass Pyrolysis has been an increasing topic of research, in particular as a replacement for crude oil. This process utilizes moderate temperatures to thermally deconstruct the biomass which is then condensed into a mixture of liquid oxygenates to be used as fuel precursors. Pyrolysis oils contain more than 400 compounds, up to 60 percent of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during the condensation and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition beforemore » condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors, many challenges must be overcome. Sampling must occur within a narrow range of temperatures to reduce product composition changes from overheating or partial condensation or plugging of lines from condensed products. Residence times must be kept at a minimum to reduce further reaction chemistries. Pyrolysis vapors also form aerosols that are carried far downstream and can pass through filters resulting in build-up in downstream locations. The co-produced bio-char and ash from the pyrolysis process can lead to plugging of the sample lines, and must be filtered out at temperature, even with the use of cyclonic separators. A practical approach for considerations and sampling system design, as well as lessons learned are integrated into the hot analytical sampling system of the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU) to provide industrially relevant demonstrations of thermochemical transformations of biomass feedstocks at the pilot scale.« less
Organic geochemical analysis of sedimentary organic matter associated with uranium
Leventhal, J.S.; Daws, T.A.; Frye, J.S.
1986-01-01
Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples. ?? 1986.
Pyrolysis-combustion 14C dating of soil organic matter
Wang, Hongfang; Hackley, Keith C.; Panno, S.V.; Coleman, D.D.; Liu, J.C.-L.; Brown, J.
2003-01-01
Radiocarbon (14C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory 14C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded 14C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (??13C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and ??13C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of 14C dates and ??13C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for 14C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent. ?? 2003 University of Washington. Published by Elsevier Inc. All rights reserved.
Erping, Li; Haoyun, Chen; Yanyang, Shang; Jun, Pan; Qing, Hu
2017-11-01
In this paper, the pyrolysis characteristics of six typical components in municipal solid waste (MSW) were investigated through a TG-FTIR combined technique and it was concluded that the main pyrolysis process of the biomass components (including food residues, sawdust and paper) occurred at 150-600°C. The main volatiles were multi-component gas including H 2 O, CO 2 , and CO. The main pyrolysis temperatures of three artificial products (PP, PVC and leather) was ranged from 200to 500°C. The wavelength of small molecule gases (CH 4 , CO 2 and CO) and the the chemical bonds (CO and CC) were observed in the infrared spectrum Based on the pyrolysis temperature interval and volatile constituent, a new "double-solution" process of pyrolysis and oxygen-enrichment decomposition MSW was designed. To achieve this process, a double-solution project was built for the direct treatment of MSW (10t/d). The complete setup of equipment and analysis of the byproducts has been reported in this paper to indicate the performance of this process. Energy balance and economic benefits were analysed for the process supporting. It was successfully demonstrated that the double-solution process was the environmentally friendly alternative method for MSW treatment in Chinese rural areas. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Chavan, Apparao R.; Chilwar, R. R.; Shisode, M. V.; Hivrekar, Mahesh M.; Mande, V. K.; Jadhav, K. M.
2018-05-01
The nanocrystalline NiFe2O4 thin film has been prepared using a spray pyrolysis technique on glass substrate. The prepared thin film was characterized by using X-ray diffraction (XRD), Fourier transform Infrared spectroscopy (FTIR), and Field Emission-Scanning Electron Microscopy (FE-SEM) characterization techniques for the structural and microstructural analysis. The magnetic property was measured using vibrating sample magnetometer (VSM) at room temperature. X-ray diffraction studies show the formation of single phase spinel structure of the thin film. The octahedral and tetrahedral vibration in the sample was studied by Fourier transform infrared (FT-IR) spectra. Magnetic hysteresis loop was recorded for thin film at room temperature. At 15 kOe, saturation magnetization (Ms) was found to increase while coercivity (Hc) decreases with thickness of the NiFe2O4 thin film.
Pyrolysis of hornbeam (Carpinus betulus L.) sawdust: Characterization of bio-oil and bio-char.
Moralı, Uğur; Yavuzel, Nazan; Şensöz, Sevgi
2016-12-01
Slow pyrolysis of hornbeam (Carpinus betulus L.) sawdust was performed to produce bio-oil and bio-char. The operational variables were as follows: pyrolysis temperature (400-600°C), heating rate (10-50°Cmin -1 ) and nitrogen flow rate (50-150cm 3 min -1 ). Physicochemical and thermogravimetric characterizations of hornbeam sawdust were performed. The characteristics of bio-oil and bio-char were analyzed on the basis of various spectroscopic and chromatographic techniques such as FTIR, GC-MS, 1H NMR, SEM, BET. Higher heating value, density and kinematic viscosity of the bio-oil with maximum yield of 35.28% were 23.22MJkg -1 , 1289kgm -3 and 0.6mm 2 s -1 , respectively. The bio-oil with relatively high fuel potential can be obtained from the pyrolysis of the hornbeam sawdust and the bio-char with a calorific value of 32.88MJkg -1 is a promising candidate for solid fuel applications that also contributes to the preservation of the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.
Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products
DOE Office of Scientific and Technical Information (OSTI.GOV)
Couch, David E.; Buckingham, Grant T.; Baraban, Joshua H.
Here, we report the combination of tabletop vacuum ultraviolet photoionization with photoion--photoelectron coincidence spectroscopy for sensitive, isomer-specific detection of nascent products from a pyrolysis microreactor. Results on several molecules demonstrate two essential capabilities that are very straightforward to implement: the ability to differentiate isomers, and to distinguish thermal products from dissociative ionization. We derive vacuum ultraviolet light is from a commercial tabletop femtosecond laser system, allowing data to be collected at 10 kHz; this high repetition rate is critical for coincidence techniques. The photoion—photoelectron coincidence spectrometer uses the momentum of the ion to identify dissociative ionization events, and coincidence techniquesmore » to provide a photoelectron spectrum specific to each mass, which is used to distinguish different isomers. We also have used this spectrometer to detect the pyrolysis products that result from the thermal cracking of acetaldehyde, cyclohexene, and 2-butanol. The photoion—photoelectron spectrometer can detect and identify organic radicals and reactive intermediates that result from pyrolysis. Direct comparison of laboratory and synchrotron data illustrate the advantages and potential of this approach.« less
Bruno, Thomas J; Nichols, Jessica E
2013-04-19
In previous work, dynamic headspace vapor collection on short, porous layer open tubular (PLOT) capillary columns maintained at low temperature was introduced. In this paper, that metrology is extended with the introduction of a small in situ pyrolysis platform that provides for rapid heating and rapid vapor capture for a wide variety of samples. The new approach is referred to as pyro-PLOT-cryo. The pyrolysis platform is made from two small copper lead wires that hold a basket formed from small diameter, high resistance stainless steel or NiCr wire. The basket is formed to accept a small sample, the mass of which can typically range from 0.2 to 0.05 mg. The pyrolysis is performed by use of a resistor capacitor circuit of the type used in spot welders. We have provided examples of the application of this technique with the analysis of facial cosmetics, plastic explosives, organometallic gasoline additives, polymers, and in micro scale chemical reactions. Additional modifications and future work are also discussed. Published by Elsevier B.V.
Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products
Couch, David E.; Buckingham, Grant T.; Baraban, Joshua H.; ...
2017-06-29
Here, we report the combination of tabletop vacuum ultraviolet photoionization with photoion--photoelectron coincidence spectroscopy for sensitive, isomer-specific detection of nascent products from a pyrolysis microreactor. Results on several molecules demonstrate two essential capabilities that are very straightforward to implement: the ability to differentiate isomers, and to distinguish thermal products from dissociative ionization. We derive vacuum ultraviolet light is from a commercial tabletop femtosecond laser system, allowing data to be collected at 10 kHz; this high repetition rate is critical for coincidence techniques. The photoion—photoelectron coincidence spectrometer uses the momentum of the ion to identify dissociative ionization events, and coincidence techniquesmore » to provide a photoelectron spectrum specific to each mass, which is used to distinguish different isomers. We also have used this spectrometer to detect the pyrolysis products that result from the thermal cracking of acetaldehyde, cyclohexene, and 2-butanol. The photoion—photoelectron spectrometer can detect and identify organic radicals and reactive intermediates that result from pyrolysis. Direct comparison of laboratory and synchrotron data illustrate the advantages and potential of this approach.« less
Comparison of results of an obstacle resolving microscale model with wind tunnel data
NASA Astrophysics Data System (ADS)
Grawe, David; Schlünzen, K. Heinke; Pascheke, Frauke
2013-11-01
The microscale transport and stream model MITRAS has been improved and a new technique has been implemented to improve numerical stability for complex obstacle configurations. Results of the updated version have been compared with wind tunnel data using an evaluation method that has been established for simple obstacle configurations. MITRAS is a part of the M-SYS model system for the assessment of ambient air quality. A comparison of model results for the flow field against quality ensured wind tunnel data has been carried out for both idealised and realistic test cases. Results of the comparison show a very good agreement of the wind field for most test cases and identify areas of possible improvement of the model. The evaluated MITRAS results can be used as input data for the M-SYS microscale chemistry model MICTM. This paper describes how such a comparison can be carried out for simple as well as realistic obstacle configurations and what difficulties arise.
NASA Astrophysics Data System (ADS)
Gockeln, Michael; Pokhrel, Suman; Meierhofer, Florian; Glenneberg, Jens; Schowalter, Marco; Rosenauer, Andreas; Fritsching, Udo; Busse, Matthias; Mädler, Lutz; Kun, Robert
2018-01-01
Reduction of lithium-ion battery (LIB) production costs is inevitable to make the use of LIB technology more viable for applications such as electric vehicles or stationary storage. To meet the requirements in today's LIB cost efficiency, our current research focuses on an alternative electrode fabrication method, characterized by a combination of double flame spray pyrolysis and lamination technique (DFSP/lamination). In-situ carbon coated nano-Li4Ti5O12 (LTO/C) was synthesized using versatile DFSP. The as-prepared composite powder was then directly laminated onto a conductive substrate avoiding the use of any solvent or binder for electrode preparation. The influence of lamination pressures on the microstructure and electrochemical performance of the electrodes was also investigated. Enhancements in intrinsic electrical conductivity were found for higher lamination pressures. Capacity retention of highest pressurized DFSP/lamination-prepared electrode was 87.4% after 200 dis-/charge cycles at 1C (vs. Li). In addition, LTO/C material prepared from the double flame spray pyrolysis was also used for fabricating electrodes via doctor blading technique. Laminated electrodes obtained higher specific discharge capacities compared to calendered and non-calendered blade-casted electrodes due to superior microstructural properties. Such a fast and industrially compelling integrative DFSP/lamination tool could be a prosperous, next generation technology for low-cost LIB electrode fabrication.
NASA Astrophysics Data System (ADS)
Zięba-Palus, Janina; Nowińska, Sabina; Kowalski, Rafał
2016-12-01
Infrared spectroscopy and pyrolysis GC/MS were applied in the comparative analysis of adhesive tapes. By providing information about the polymer composition, it was possible to classify both backings and adhesives of tapes into defined chemical classes. It was found that samples of the same type (of backings and adhesives) and similar infrared spectra can in most cases be effectively differentiated using Py-GC/MS, sometimes based only on the presence of peaks of very low intensity originating from minor components. The results obtained enabled us to draw the conclusion that Py-GC/MS appears to be a valuable analytical technique for examining tapes, which is complementary to infrared spectroscopy. Identification of pyrolysis products enables discrimination of samples. Both methods also provide crucial information that is useful for identification of adhesive tapes found at the crime scene.
NASA Technical Reports Server (NTRS)
Holzer, G.; Oro, J.
1977-01-01
The influence of ammonia on the pyrolysis pattern of selected organic substances sorbed on an inorganic phase was investigated. The thermal degradation products were identified by gas chromatography-mass spectrometry. The feasibility of this technique was tested on a meteoritic sample. All substances examined react with ammonia at the pyrolysis temperature of 500 C, the major products being nitriles and heterocyclic compounds in which nitrogen was incorporated. Based on these results, a model for the non-equilibrium production of organic compounds on Jupiter is discussed. The investigation was performed in connection with the Viking lander molecular analysis. The results obtained indicate that the concentrations of ammonia in the retrorocket fuel exhaust would have been probably too small to produce significant changes in the Martian soil organic compounds if any were found.
Photoactive lead oxide thin films by spray pyrolysis
NASA Astrophysics Data System (ADS)
Bhagat, Dharini; Waldiya, Manmohansingh; Mukhopadhyay, Indrajit
2018-05-01
We report the synthesis of photoactive lead monoxide thin films on fluorine doped tin oxide substrate by cost effective spray pyrolysis technique using aqueous solution of lead acetate trihydrate. Influence of substrate temperature on the structural and optical properties of thin films was studied. Polymorph of lead monoxide, litharge (α-PbO), was obtained when the substrate temperature was kept constant at 360 °C. XRD analysis revealed that the deposits were tetragonal structured with preferred orientation along 002 plane. Band gap value was found to be 1.93ev from diffuse reflectance spectra.
Thermal History Of PMRs Via Pyrolysis-Gas Chromatography
NASA Technical Reports Server (NTRS)
Gluyas, Richard E.; Alston, William B.; Snyder, William J.
1994-01-01
Pyrolysis-gas chromatography (PY-GC) useful as analytical technique to determine extents of cure or postcure of PMR-15 polyimides and to lesser extent, cumulative thermal histories of PMR-15 polyimides exposed to high temperatures. Also applicable for same purposes to other PMR polyimides and to composite materials containing PMR polyimides. Valuable in reducing costs and promoting safety in aircraft industry by helping to identify improperly cured or postcured PMR-15 composite engine and airframe components and helping to identify composite parts nearing ends of their useful lives.
Crepier, Julien; Le Masle, Agnès; Charon, Nadège; Albrieux, Florian; Heinisch, Sabine
2017-08-11
The characterization of complex mixtures is a challenging issue for the development of innovative processes dedicated to biofuels and bio-products production. The huge number of compounds present in biomass fast pyrolysis oils combined with the large diversity of chemical functions represent a bottleneck as regards analytical technique development. For the extensive characterization of complex samples, supercritical fluid chromatography (SFC) can be alternative to usual separation techniques such as gas (GC) or liquid chromatography (LC). In this study, an approach is proposed to define the best conditions for the SFC separation of a fast pyrolysis bio-oil. This approach was based on SFC data obtained directly from the bio-oil itself instead of selecting model compounds as usually done. SFC conditions were optimized by using three specific, easy-to-use and quantitative criteria aiming at maximizing the separation power. Polar stationary phases (ethylpyridine bonded silica) associated to a mix of acetonitrile and water as polarity modifier provided the best results, with more than 120 peaks detected in SFC-UV. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Lee, Ching-Sung; Hsu, Wei-Chou; Huang, Yi-Ping; Liu, Han-Yin; Yang, Wen-Luh; Yang, Shen-Tin
2018-06-01
Comparative study on a novel Al2O3-dielectric graded-barrier (GB) AlxGa1‑xN/AlN/GaN/Si (x = 0.22 ∼ 0.3) metal-oxide-semiconductor heterostructure field-effect transistor (MOS-HFET) formed by using the ultrasonic spray pyrolysis deposition (USPD) technique has been made with respect to a conventional-barrier (CB) Al0.26Ga0.74N/AlN/GaN/Si MOS-HFET and the reference Schottky-gate HFET devices. The GB AlxGa1‑xN was devised to improve the interfacial quality and enhance the Schottky barrier height at the same time. A cost-effective ultrasonic spray pyrolysis deposition (USPD) method was used to form the high-k Al2O3 gate dielectric and surface passivation on the AlGaN barrier of the present MOS-HFETs. Comprehensive device performances, including maximum extrinsic transconductance (g m,max), maximum drain-source current density (I DS,max), gate-voltage swing (GVS) linearity, breakdown voltages, subthreshold swing (SS), on/off current ratio (I on /I off ), high frequencies, and power performance are investigated.
Pyrolysis of plastic waste for liquid fuel production as prospective energy resource
NASA Astrophysics Data System (ADS)
Sharuddin, S. D. A.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.
2018-03-01
The worldwide plastic generation expanded over years because of the variety applications of plastics in numerous sectors that caused the accumulation of plastic waste in the landfill. The growing of plastics demand definitely affected the petroleum resources availability as non-renewable fossil fuel since plastics were the petroleum-based material. A few options that have been considered for plastic waste management were recycling and energy recovery technique. Nevertheless, several obstacles of recycling technique such as the needs of sorting process that was labour intensive and water pollution that lessened the process sustainability. As a result, the plastic waste conversion into energy was developed through innovation advancement and extensive research. Since plastics were part of petroleum, the oil produced through the pyrolysis process was said to have high calorific value that could be used as an alternative fuel. This paper reviewed the thermal and catalytic degradation of plastics through pyrolysis process and the key factors that affected the final end product, for instance, oil, gaseous and char. Additionally, the liquid fuel properties and a discussion on several perspectives regarding the optimization of the liquid oil yield for every plastic were also included in this paper.
Overhead Projector Demonstrations.
ERIC Educational Resources Information Center
Kolb, Doris, Ed.
1989-01-01
Described are three chemistry demonstrations: (1) a simple qualitative technique for taste pattern recognition in structure-activity relationships; (2) a microscale study of gaseous diffusion using bleach, HCl, ammonia, and phenolphthalein; and (3) the rotation of polarized light by stereoisomers of limonene. (MVL)
NASA Astrophysics Data System (ADS)
Reddemann, Manuel A.; Mathieu, Florian; Kneer, Reinhold
2013-11-01
Aiming at a maximum spatial resolution and a minimum motion blur, a new simple double-imaging transmitted light microscopy technique is developed in this work enabling a fundamental investigation of primary breakup of a microscale liquid jet. Contrary to conventional far-field visualization techniques, the working distance is minimized to increase the numerical aperture. The resulting images provide information about shapes, length scales and velocities of primary liquid structures. The method is applied to an optically dense spray leaving a 109-μm diesel nozzle at various injection pressures under atmospheric conditions. A phenomenological study on the temporal spray evolution is done with focus on droplet and ligament formation. Different breakup processes are identified and described. It is found that the jet is characterized by long ligaments parallel or angular to the inner jet region. These ligaments result from collapsing films developing at the spray edge. A significant influence of outlet velocity variation on shape and velocity of these ligaments is observed. The experimental results prove that a transmitted light microscopy technique with reduced working distance is an appropriate tool for a better understanding of primary breakup for small-scaled diesel nozzles and a valuable complement to highly complex measurement techniques.
Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis
NASA Technical Reports Server (NTRS)
Francois, P.; Szopa, C.; Buch, A.; Coll, P.; McAdam, A. C.; Mahaffy, P. R.; Freissinet, C.; Glavin, D. P.; Navarro-Gonzalez, R.; Cabane, M.
2016-01-01
Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.
NASA Astrophysics Data System (ADS)
Wilkinson, Taylor Marie
Oil shales are naturally occurring heterogeneous composites with micro-scale, micro-structural variations. They may be found throughout the world, with large deposits located in the United States; shales are composed of organic matter known as kerogen, clays, calcite, quartz, and other minerals. Typically their microstructure consists of a composite network where the organic matter is housed in open and closed pores between different mineral phases that range in size from sub-micron to several microns. Currently, it is unknown how the micro-scale heterogeneity of the shale will impact hydraulic fracture, which is the key extraction technique used for these materials. In this thesis, high-resolution topographic and modulus maps were collected from oil shales with the use of new nanoindentation techniques in order to characterize the micro-scale, micro-structural variations that are typical for these materials. Dynamic modulus mapping allows for substantially higher spatial resolution of properties across grains and intragranular regions of kerogen than has previously been produced with standard quasistatic indentation methods. For accurate scanning, surface variations were minimized to maintain uniform contact of the tip and appropriate quasi-static and dynamic forces were used to maintain displacement amplitudes that avoid plastic deformation of the sample. Sample preparation to minimize surface roughness was completed with the use of focused ion beam milling, however, some variation was still noted. Due to the large changes in modulus values between the constituents of the shale, there were variations in the recorded displacement amplitude values as well. In order to distinguish biased data due to surface topography or a lack of displacement amplitude, filtering techniques were developed, optimization and implemented. Variations in surface topography, which resulted in the indenter tip not being able to accurately resolve surface features, and inadequate displacement amplitude values that prohibit differentiation between material changes and the noise floor of the machine, were removed. These filters resulted in a more valid interpretation of the micro-scale, micro-structural features and arrangement, as well as the mechanical properties, that are common to oil shales.
Middendorf, Jill M; Shortkroff, Sonya; Dugopolski, Caroline; Kennedy, Stephen; Siemiatkoski, Joseph; Bartell, Lena R; Cohen, Itai; Bonassar, Lawrence J
2017-11-07
Many studies have measured the global compressive properties of tissue engineered (TE) cartilage grown on porous scaffolds. Such scaffolds are known to exhibit strain softening due to local buckling under loading. As matrix is deposited onto these scaffolds, the global compressive properties increase. However the relationship between the amount and distribution of matrix in the scaffold and local buckling is unknown. To address this knowledge gap, we studied how local strain and construct buckling in human TE constructs changes over culture times and GAG content. Confocal elastography techniques and digital image correlation (DIC) were used to measure and record buckling modes and local strains. Receiver operating characteristic (ROC) curves were used to quantify construct buckling. The results from the ROC analysis were placed into Kaplan-Meier survival function curves to establish the probability that any point in a construct buckled. These analysis techniques revealed the presence of buckling at early time points, but bending at later time points. An inverse correlation was observed between the probability of buckling and the total GAG content of each construct. This data suggests that increased GAG content prevents the onset of construct buckling and improves the microscale compressive tissue properties. This increase in GAG deposition leads to enhanced global compressive properties by prevention of microscale buckling. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Morikawa, Junko
2015-05-01
The mobile type apparatus for a quantitative micro-scale thermography using a micro-bolometer was developed based on our original techniques such as an achromatic lens design to capture a micro-scale image in long-wave infrared, a video signal superimposing for the real time emissivity correction, and a pseudo acceleration of a timeframe. The total size of the instrument was designed as it was put in the 17 cm x 28 cm x 26 cm size carrying box. The video signal synthesizer enabled to record a direct digital signal of monitoring temperature or positioning data. The encoded digital signal data embedded in each image was decoded to read out. The protocol to encode/decode the measured data was originally defined. The mixed signals of IR camera and the imposed data were applied to the pixel by pixel emissivity corrections and the pseudo-acceleration of the periodical thermal phenomena. Because the emissivity of industrial materials and biological tissues were usually inhomogeneous, it has the different temperature dependence on each pixel. The time-scale resolution for the periodic thermal event was improved with the algorithm for "pseudoacceleration". It contributes to reduce the noise by integrating the multiple image data, keeping a time resolution. The anisotropic thermal properties of some composite materials such as thermal insulating materials of cellular plastics and the biometric composite materials were analyzed using these techniques.
Farahani, Rouhollah D; Dubé, Martine; Therriault, Daniel
2016-07-01
The integration of nanotechnology into three-dimensional printing (3DP) offers huge potential and opportunities for the manufacturing of 3D engineered materials exhibiting optimized properties and multifunctionality. The literature relating to different 3DP techniques used to fabricate 3D structures at the macro- and microscale made of nanocomposite materials is reviewed here. The current state-of-the-art fabrication methods, their main characteristics (e.g., resolutions, advantages, limitations), the process parameters, and materials requirements are discussed. A comprehensive review is carried out on the use of metal- and carbon-based nanomaterials incorporated into polymers or hydrogels for the manufacturing of 3D structures, mostly at the microscale, using different 3D-printing techniques. Several methods, including but not limited to micro-stereolithography, extrusion-based direct-write technologies, inkjet-printing techniques, and popular powder-bed technology, are discussed. Various examples of 3D nanocomposite macro- and microstructures manufactured using different 3D-printing technologies for a wide range of domains such as microelectromechanical systems (MEMS), lab-on-a-chip, microfluidics, engineered materials and composites, microelectronics, tissue engineering, and biosystems are reviewed. Parallel advances on materials and techniques are still required in order to employ the full potential of 3D printing of multifunctional nanocomposites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Weiss, J.M.; Mckay, A.J.; Derito, C.; Watanabe, C.; Thorn, K.A.; Madsen, E.L.
2004-01-01
TNT (trinitrotoluene) is a contaminant of global environmental significance, yet determining its environmental fate has posed longstanding challenges. To date, only differential extraction-based approaches have been able to determine the presence of covalently bound, reduced forms of TNT in field soils. Here, we employed thermal elution, pyrolysis, and gas chromatography/mass spectrometry (GC/MS) to distinguish between covalently bound and noncovalently bound reduced forms of TNT in soil. Model soil organic matter-based matrixes were used to develop an assay in which noncovalently bound (monomeric) aminodinitrotoluene (ADNT) and diaminonitrotoluene (DANT) were desorbed from the matrix and analyzed at a lower temperature than covalently bound forms of these same compounds. A thermal desorption technique, evolved gas analysis, was initially employed to differentiate between covalently bound and added 15N-labeled monomeric compounds. A refined thermal elution procedure, termed "double-shot analysis" (DSA), allowed a sample to be sequentially analyzed in two phases. In phase 1, all of an added 15N-labeled monomeric contaminant was eluted from the sample at relatively low temperature. In phase 2 during high-temperature pyrolysis, the remaining covalently bound contaminants were detected. DSA analysis of soil from the Louisiana Army Ammunition Plant (LAAP; ???5000 ppm TNT) revealed the presence of DANT, ADNT, and TNT. After scrutinizing the DSA data and comparing them to results from solvent-extracted and base/acid-hydrolyzed LAAP soil, we concluded that the TNT was a noncovalently bound "carryover" from phase 1. Thus, the pyrolysis-GC/MS technique successfully defined covalently bound pools of ADNT and DANT in the field soil sample.
Coal Producer's Rubber Waste Processing Development
NASA Astrophysics Data System (ADS)
Makarevich, Evgeniya; Papin, Andrey; Nevedrov, Alexander; Cherkasova, Tatyana; Ignatova, Alla
2017-11-01
A large amount of rubber-containing waste, the bulk of which are worn automobile tires and conveyor belts, is produced at coal mining and coal processing enterprises using automobile tires, conveyor belts, etc. The volume of waste generated increases every year and reaches enormous proportions. The methods for processing rubber waste can be divided into three categories: grinding, pyrolysis (high and low temperature), and decomposition by means of chemical solvents. One of the known techniques of processing the worn-out tires is their regeneration, aimed at producing the new rubber substitute used in the production of rubber goods. However, the number of worn tires used for the production of regenerate does not exceed 20% of their total quantity. The new method for processing rubber waste through the pyrolysis process is considered in this article. Experimental data on the upgrading of the carbon residue of pyrolysis by the methods of heavy media separation, magnetic and vibroseparation, and thermal processing are presented.
NASA Technical Reports Server (NTRS)
Matney, M. L.; Limero, T. F.; James, J. T.
1994-01-01
Biological particulates collected on air filters during shuttle missions (STS-40 and STS-42) were identified using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). A method was developed for identifying the atmospheric particles and their sources through the analysis of standard materials and the selection of "marker" compounds specific to the particle type. Pyrolysis spectra of biological standards were compared with those of airborne particles collected during two space shuttle missions; marker compounds present in the shuttle particle spectra were matched with those of the standards to identify the source of particles. Particles of 0,5--1-mm diameter and weighing as little as 40 micrograms could be identified using this technique. The Py-GC/MS method identified rat food and soilless plant-growth media as two sources of particles collected from the shuttle atmosphere during flight.
Micro-Scale Regenerative Heat Exchanger
NASA Technical Reports Server (NTRS)
Moran, Matthew E.; Stelter, Stephan; Stelter, Manfred
2004-01-01
A micro-scale regenerative heat exchanger has been designed, optimized and fabricated for use in a micro-Stirling device. Novel design and fabrication techniques enabled the minimization of axial heat conduction losses and pressure drop, while maximizing thermal regenerative performance. The fabricated prototype is comprised of ten separate assembled layers of alternating metal-dielectric composite. Each layer is offset to minimize conduction losses and maximize heat transfer by boundary layer disruption. A grating pattern of 100 micron square non-contiguous flow passages were formed with a nominal 20 micron wall thickness, and an overall assembled ten-layer thickness of 900 microns. Application of the micro heat exchanger is envisioned in the areas of micro-refrigerators/coolers, micropower devices, and micro-fluidic devices.
NASA Astrophysics Data System (ADS)
Pagni, Richard M.
2003-04-01
I am uncertain exactly how this experiment-free book is supposed to be used. I can suggest a few possibilities, however. It could be used as a primary text if the experiments are presented separately, perhaps to an honors class. It could supplement the authors’ more traditional lab manual or any other lab manual. It could also serve as an instructional manual for inexperienced, and often insecure, students, helping them get confidence and skill in carrying out the myriad activities in the organic laboratory. I will use this very nice book as a reference the next time I teach the laboratory course.
Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth
Werner, Florian; Mueller, Carsten W.; Thieme, Jurgen; ...
2017-06-09
Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soilmore » depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Lastly, our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.« less
Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth
DOE Office of Scientific and Technical Information (OSTI.GOV)
Werner, Florian; Mueller, Carsten W.; Thieme, Jurgen
Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soilmore » depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Lastly, our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.« less
Hu, Jinyong; Wang, Hong
2014-01-01
Three-dimensional (3D) backside reflector, compared with flat reflectors, can improve the probability of finding the escape cone for reflecting lights and thus enhance the light-extraction efficiency (LEE) for GaN-based light-emitting diode (LED) chips. A triangle-lattice of microscale SiO2 cone array followed by a 16-pair Ti3O5/SiO2 distributed Bragg reflector (16-DBR) was proposed to be attached on the backside of sapphire substrate, and the light-output enhancement was demonstrated by numerical simulation and experiments. The LED chips with flat reflectors or 3D reflectors were simulated using Monte Carlo ray tracing method. It is shown that the LEE increases as the reflectivity of backside reflector increases, and the light-output can be significantly improved by 3D reflectors compared to flat counterparts. It can also be observed that the LEE decreases as the refractive index of the cone material increases. The 3D 16-DBR patterned by microscale SiO2 cone array benefits large enhancement of LEE. This microscale pattern was prepared by standard photolithography and wet-etching technique. Measurement results show that the 3D 16-DBR can provide 12.1% enhancement of wall-plug efficiency, which is consistent with the simulated value of 11.73% for the enhancement of LEE. PMID:25133262
Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fletcher, Thomas; Pugmire, Ronald
2015-01-01
Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogensmore » were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.« less
Fabrication of spherical biochar by a two-step thermal process from waste potato peel.
Yang, Xiao; Kwon, Eilhann E; Dou, Xiaomin; Zhang, Ming; Kim, Ki-Hyun; Tsang, Daniel C W; Ok, Yong Sik
2018-06-01
The aim of this study was to develop a new approach for the preparation of spherical biochar (SBC) by employing a two-step thermal technology to potato peel waste (PPW). Potato starch (PS), as a carbon-rich material with microscale spherical shape, was separated from PPW as a precursor to synthesizing SBC. The synthesis process comprised (1) pre-oxidization (preheating under air) of PS at 220 °C and (2) subsequent pyrolysis of the pretreated sample at 700 °C. Results showed that the produced SBC successfully retained the original PS morphology and that pre-oxidization was the key for its shape maintenance, as it reduced surface tension and enhanced structural stability. The SBC possessed excellent chemical inertness (high aromaticity) and uniform particle size (10-30 μm). Zero-cost waste material with a facile and easy-to-control process allows the method to be readily scalable for industrialization, while offering a new perspective on the full use of PPW. Copyright © 2018 Elsevier B.V. All rights reserved.
JPL in-house fluidized-bed reactor research
NASA Technical Reports Server (NTRS)
Rohatgi, N. K.
1984-01-01
Fluidized bed reactor research techniques for fabrication of quartz linears was reviewed. Silane pyrolysis was employed in this fabrication study. Metallic contaminant levels in the silicon particles were below levels detectable by emission spectroscopy.
Aysu, Tevfik
2016-11-01
The catalytic pyrolysis of Cirsium arvense was performed with titania supported catalysts under the operating conditions of 500°C, 40°C/min heating rate, 100mL/min N2 flow rate in a fixed bed reactor for biofuel production. The effect of catalysts on product yields was investigated. The amount of pyrolysis products (bio-char, bio-oil, gas) and the composition of the produced bio-oils were determined by proton nuclear magnetic resonance ((1)H NMR), Fourier transform infrared spectroscopy (FT-IR), gas chromatography/mass spectrometry (GC-MS) and elemental analysis (EA) techniques. Thistle bio-oils had lower O/C and H/C molar ratios compared to feedstock. The highest bio-char and bio-oil yields of 29.32wt% and 36.71wt% were obtained in the presence of Ce/TiO2 and Ni/TiO2 catalysts respectively. GC-MS identified 97 different compounds in the bio-oils obtained from thistle pyrolysis. (1)H NMR analysis showed that the bio-oils contained ∼55-77% aliphatic and ∼6-19% aromatic structural units. Copyright © 2016 Elsevier Ltd. All rights reserved.
Development of SiC/SiC composites by PIP in combination with RS
NASA Astrophysics Data System (ADS)
Kotani, Masaki; Kohyama, Akira; Katoh, Yutai
2001-02-01
In order to improve the mechanical performances of SiC/SiC composite, process improvement and modification of polymer impregnation and pyrolysis (PIP) and reaction sintering (RS) process were investigated. The fibrous prepregs were prepared by a polymeric intra-bundle densification technique using Tyranno-SA™ fiber. For inter-bundle matrix, four kinds of process options utilizing polymer pyrolysis and reaction sintering were studied. The process conditions were systematically optimized through fabricating monoliths. Then, SiC/SiC composites were fabricated using optimized inter-bundle matrix slurries in each process for the first inspection of process requirements.
Oyster Shell Recycling and Bone Waste Treatment Using Plasma Pyrolysis
NASA Astrophysics Data System (ADS)
Jae, Ou Chae; Knak, S. P.; Knak, A. N.; Koo, H. J.; Ravi, V.
2006-11-01
Investigations on the recycling of oyster shells and bone waste treatment using the plasma pyrolysis technique are presented in this paper. A arc based plasma torch operated at 25 kW was employed for the experiments. Fresh oyster shells were recycled using the plasma torch to convert them to a useful product such as CaO. Bone waste was treated to remove the infectious organic part and to vitrify the inorganic part. The time required for treatment in both cases was significantly short. Significant reduction in the weight of the samples was observed in both cases.
NASA Astrophysics Data System (ADS)
Panetta, R. J.; Hsiao, G.
2011-12-01
Trace levels of organic contaminants such as short alcohols and terpenoids have been shown to cause spectral interference in water isotope analysis by spectroscopic techniques. The result is degraded precision and accuracy in both δD and δ18O for samples such as beverages, plant extracts or slightly contaminated waters. An initial approach offered by manufacturers is post-processing software that analyzes spectral features to identify and flag contaminated samples. However, it is impossible for this software to accurately reconstruct the water isotope signature, thus it is primarily a metric for data quality. Here, we describe a novel in-line pyrolysis system (Micro-Pyrolysis Technology, MPT) placed just prior to the inlet of a cavity ring-down spectroscopy (CRDS) analyzer that effectively removes interfering organic molecules without altering the isotope values of the water. Following injection of the water sample, N2 carrier gas passes the sample through a micro-pyrolysis tube heated with multiple high temperature elements in an oxygen-free environment. The temperature is maintained above the thermal decomposition threshold of most organic compounds (≤ 900 oC), but well below that of water (~2000 oC). The main products of the pyrolysis reaction are non-interfering species such as elemental carbon and H2 gas. To test the efficacy and applicability of the system, waters of known isotopic composition were spiked with varying amounts of common interfering alcohols (methanol, ethanol, propanol, hexanol, trans-2-hexenol, cis-3-hexanol up to 5 % v/v) and common soluble plant terpenoids (carveol, linalool, geraniol, prenol). Spiked samples with no treatment to remove the organics show strong interfering absorption peaks that adversely affect the δD and δ18O values. However, with the MPT in place, all interfering absorption peaks are removed and the water absorption spectrum is fully restored. As a consequence, the δD and δ18O values also return to their original values, demonstrating effective removal of interfering species with no isotopic fractionation during the pyrolysis. Tests of water spiked quantitatively show the MPT is most effective at removing interferences up to 1 % v/v. This level is typical for plant extracts and interstitial waters, i.e. the majority of natural samples that suffer from spectral interference.
Feng, Huan; Tappero, Ryan; Zhang, Weiguo; ...
2015-07-26
This study is focused on micro-scale measurement of metal (Ca, Cl, Fe, K, Mn, Cu, Pb, and Zn) distributions in Spartina alterniflora root system. The root samples were collected in the Yangtze River intertidal zone in July 2013. Synchrotron X-ray fluorescence (XRF), computed microtomography (CMT), and X-ray absorption near-edge structure (XANES) techniques, which provide micro-meter scale analytical resolution, were applied to this study. Although it was found that the metals of interest were distributed in both epidermis and vascular tissue with the varying concentrations, the results showed that Fe plaque was mainly distributed in the root epidermis. Other metals (e.g.,more » Cu, Mn, Pb, and Zn) were correlated with Fe in the epidermis possibly due to scavenge by Fe plaque. Relatively high metal concentrations were observed in the root hair tip. As a result, this micro-scale investigation provides insights of understanding the metal uptake and spatial distribution as well as the function of Fe plaque governing metal transport in the root system.« less
NASA Astrophysics Data System (ADS)
Ismail, Raid A.; Khashan, Khawla S.; Jawad, Muslim F.; Mousa, Ali M.; Mahdi, Farah
2018-05-01
In this study, low cost ZnO/Si and ZnO/MgO/Si heterojunction (HJ) photodetectors were fabricated using laser ablation and spray Pyrolysis techniques. MgO nanofibers were synthesized by laser ablation of Mg target in distilled water. Also; the ZnO films were prepared by spray pyrolysis technique. The optical and structural properties of nanostructured MgO were investigated using XRD, SEM and FT-IR. The XRD results showed that the MgO was polycrystalline with cubic structure. SEM investigation confirmed the formation of MgO nanofibers and sub-microparticles. The optical energy gaps of MgO and ZnO were calculated and found to be 5.7 eV and 3.3 eV, respectively. For the electrical properties; responsivity, quantum efficiency, specific detectivity, and speed of response of the photodetector were measured and found to enhance after the insertion of nanostructured MgO film. The Photoresponse results at 3 V reverse bias showed that the maximum responsivity of ZnO/Si and ZnO/MgO/Si photodetectors were 185 and 331 mAW‑1 at 500 nm, respectively. The specific detectivity of ZnO/MgO/Si Photodetector was higher than that of ZnO/Si.
Jung, Youngho; Shim, Jaeho; Kwon, Kyungmook; You, Jong-Bum; Choi, Kyunghan; Yu, Kyoungsik
2016-01-01
Optofluidic manipulation mechanisms have been successfully applied to micro/nano-scale assembly and handling applications in biophysics, electronics, and photonics. Here, we extend the laser-based optofluidic microbubble manipulation technique to achieve hybrid integration of compound semiconductor microdisk lasers on the silicon photonic circuit platform. The microscale compound semiconductor block trapped on the microbubble surface can be precisely assembled on a desired position using photothermocapillary convective flows induced by focused laser beam illumination. Strong light absorption within the micro-scale compound semiconductor object allows real-time and on-demand microbubble generation. After the assembly process, we verify that electromagnetic radiation from the optically-pumped InGaAsP microdisk laser can be efficiently coupled to the single-mode silicon waveguide through vertical evanescent coupling. Our simple and accurate microbubble-based manipulation technique may provide a new pathway for realizing high precision fluidic assembly schemes for heterogeneously integrated photonic/electronic platforms as well as microelectromechanical systems. PMID:27431769
NASA Technical Reports Server (NTRS)
Stroud, C. W.
1994-01-01
The transient response of a thermal protection material to heat applied to the surface can be calculated using the CHAP III computer program. CHAP III can be used to analyze pyrolysis gas chemical kinetics in detail and examine pyrolysis reactions-indepth. The analysis includes the deposition of solid products produced by chemical reactions in the gas phase. CHAP III uses a modelling technique which can approximate a wide range of ablation problems. The energy equation used in CHAP III incorporates pyrolysis (both solid and gas reactions), convection, conduction, storage, work, kinetic energy, and viscous dissipation. The chemically reacting components of the solid are allowed to vary as a function of position and time. CHAP III employs a finite difference method to approximate the energy equations. Input values include specific heat, thermal conductivity, thermocouple locations, enthalpy, heating rates, and a description of the chemical reactions expected. The output tabulates the temperature at locations throughout the ablator, gas flow within the solid, density of the solid, weight of pyrolysis gases, and rate of carbon deposition. A sample case is included, which analyzes an ablator material containing several pyrolysis reactions subjected to an environment typical of entry at lunar return velocity. CHAP III is written in FORTRAN IV for batch execution and has been implemented on a CDC CYBER 170 series computer operating under NOS with a central memory requirement of approximately 102K (octal) of 60 bit words. This program was developed in 1985.
Kalinke, Cristiane; Mangrich, Antonio Sálvio; Marcolino-Junior, Luiz H; Bergamini, Márcio F
2016-11-15
Biochar is a carbonaceous material similar produced by pyrolysis of biomass under oxygen-limited conditions. Pyrolysis temperature is an important parameter that can alters biochar characteristics (e.g. surface area, pore size distribution and surface functional groups) and affects it efficacy for adsorption of several probes. In this work, biochar samples have been prepared from castor oil cake using different temperatures of pyrolysis (200-600°C). For the first time, a voltammetric procedure based on carbon paste modified electrode (CPME) was used to investigate the effect of temperature of pyrolysis on the adsorptive characteristics of biochar for Pb(II), Cd(II) and Cu(II) ions. Besides the electrochemical techniques, several characterizations have been performed to evaluate the physicochemical properties of biochar in function of the increase of the pyrolysis temperature. Results suggest that biochar pyrolized at 400°C (BC400) showed a better potential for ions adsorption. The CPME modified with BC400 showed better relative current signal with adsorption affinity: Pb(II)>Cd(II)>Cu(II). Kinetic studies revealed that the pseudo-second order model describes more accurately the adsorption process suggesting that the surface reactions control the adsorption rate. Values found for amount adsorbed were 15.94±0.09; 4.29±0.13 and 2.38±0.39μgg(-1) for Pb(II), Cd(II) and Cu(II) ions, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.
The transport phase of pyrolytic oil exiting a fast fluidized bed reactor
NASA Astrophysics Data System (ADS)
Daugaard, Daren Einar
An unresolved and debated aspect in the fast pyrolysis of biomass is whether the bio-oil exits as a vapor or as an aerosol from the pyrolytic reactor. The determination of the bio-oil transport phase will have direct and significant impact on the design of fast pyrolysis systems. Optimization of both the removal of particulate matter and collection of bio-oil will require this information. In addition, the success of catalytic reforming of bio-oil to high-value chemicals will depend upon this transport phase. A variety of experimental techniques were used to identify the transport phase. Some tests were as simple as examining the catch of an inline filter while others attempted to deduce whether vapor or aerosol predominated by examining the pressure drop across a flow restriction. In supplementary testing, the effect of char on aerosol formation and the potential impact of cracking during direct contact filtering are evaluated. The study indicates that for pyrolysis of red oak approximately 90 wt-% of the collected bio-oil existed as a liquid aerosol. Conversely, the pyrolysis of corn starch produced bio-oil predominately in the vapor phase at the exit of the reactor. Furthermore, it was determined that the addition of char promotes the production of aerosols during pyrolysis of corn starch. Direct contact filtering of the product stream did not collect any liquids and the bio-oil yield was not significantly reduced indicating measurable cracking or coking did not occur.
Zhang, Hedong; Gao, Zuopeng; Liu, Yang; Ran, Chunmei; Mao, Xiao; Kang, Qinhao; Ao, Wenya; Fu, Jie; Li, Jing; Liu, Guangqing; Dai, Jianjun
2018-05-01
This study investigated the pyrolysis characteristic of textile dyeing sludge (DS) using an auger pyrolyser under microwave irradiation at different pyrolysis temperature. The migration and distribution characteristic of heavy metals and their potential ecological risks were investigated using inductively coupled plasma mass spectrometry (ICP-MS) techniques. Temperature and additives (e.g. Ca-bentonite, kaolin and CaO) significantly affected product distribution and yields. Heavy metals showed different enrichment characteristics during pyrolysis and a great percentage of the heavy metals was retained in the sludge char (SC), depending on different temperatures and additives. CaO had a strong ability for retention of S, Pb and Ni. Ca-bentonite, kaolin and CaO had considerable ability to retain Cr at 650 ℃. Ca-bentonite and CaO had positive effects on Ni retention at 450 °C and 650 °C. As was enriched at 450 °C with addition of Ca-bentonite. Cu and Zn were enriched at 450 °C and 850 °C without additives and the corresponding residue ratios (RRs) were 88.68-100%, which indicated good stability of these heavy metals during microwave pyrolysis of DS. The heavy metal contents in SC were lower than those in the national standards (CJ/T 362-2011, China) and these heavy metals showed slight potential ecological risk to the environment. Copyright © 2018 Elsevier B.V. All rights reserved.
Narin, B; Ozyörük, Y; Ulas, A
2014-05-30
This paper describes a two-dimensional code developed for analyzing two-phase deflagration-to-detonation transition (DDT) phenomenon in granular, energetic, solid, explosive ingredients. The two-dimensional model is constructed in full two-phase, and based on a highly coupled system of partial differential equations involving basic flow conservation equations and some constitutive relations borrowed from some one-dimensional studies that appeared in open literature. The whole system is solved using an optimized high-order accurate, explicit, central-difference scheme with selective-filtering/shock capturing (SF-SC) technique, to augment central-diffencing and prevent excessive dispersion. The sources of the equations describing particle-gas interactions in terms of momentum and energy transfers make the equation system quite stiff, and hence its explicit integration difficult. To ease the difficulties, a time-split approach is used allowing higher time steps. In the paper, the physical model for the sources of the equation system is given for a typical explosive, and several numerical calculations are carried out to assess the developed code. Microscale intergranular and/or intragranular effects including pore collapse, sublimation, pyrolysis, etc. are not taken into account for ignition and growth, and a basic temperature switch is applied in calculations to control ignition in the explosive domain. Results for one-dimensional DDT phenomenon are in good agreement with experimental and computational results available in literature. A typical shaped-charge wave-shaper case study is also performed to test the two-dimensional features of the code and it is observed that results are in good agreement with those of commercial software. Copyright © 2014 Elsevier B.V. All rights reserved.
Hong, Xiaowei; Stegemann, Jan P.; Deng, Cheri X.
2016-01-01
Characterization of the microscale mechanical properties of biomaterials is a key challenge in the field of mechanobiology. Dual-mode ultrasound elastography (DUE) uses high frequency focused ultrasound to induce compression in a sample, combined with interleaved ultrasound imaging to measure the resulting deformation. This technique can be used to non-invasively perform creep testing on hydrogel biomaterials to characterize their viscoelastic properties. DUE was applied to a range of hydrogel constructs consisting of either hydroxyapatite (HA)-doped agarose, HA-collagen, HA-fibrin, or preosteoblast-seeded collagen constructs. DUE provided spatial and temporal mapping of local and bulk displacements and strains at high resolution. Hydrogel materials exhibited characteristic creep behavior, and the maximum strain and residual strain were both material- and concentration-dependent. Burger’s viscoelastic model was used to extract characteristic parameters describing material behavior. Increased protein concentration resulted in greater stiffness and viscosity, but did not affect the viscoelastic time constant of acellular constructs. Collagen constructs exhibited significantly higher modulus and viscosity than fibrin constructs. Cell-seeded collagen constructs became stiffer with altered mechanical behavior as they developed over time. Importantly, DUE also provides insight into the spatial variation of viscoelastic properties at sub-millimeter resolution, allowing interrogation of the interior of constructs. DUE presents a novel technique for non-invasively characterizing hydrogel materials at the microscale, and therefore may have unique utility in the study of mechanobiology and the characterization of hydrogel biomaterials. PMID:26928595
Hong, Xiaowei; Stegemann, Jan P; Deng, Cheri X
2016-05-01
Characterization of the microscale mechanical properties of biomaterials is a key challenge in the field of mechanobiology. Dual-mode ultrasound elastography (DUE) uses high frequency focused ultrasound to induce compression in a sample, combined with interleaved ultrasound imaging to measure the resulting deformation. This technique can be used to non-invasively perform creep testing on hydrogel biomaterials to characterize their viscoelastic properties. DUE was applied to a range of hydrogel constructs consisting of either hydroxyapatite (HA)-doped agarose, HA-collagen, HA-fibrin, or preosteoblast-seeded collagen constructs. DUE provided spatial and temporal mapping of local and bulk displacements and strains at high resolution. Hydrogel materials exhibited characteristic creep behavior, and the maximum strain and residual strain were both material- and concentration-dependent. Burger's viscoelastic model was used to extract characteristic parameters describing material behavior. Increased protein concentration resulted in greater stiffness and viscosity, but did not affect the viscoelastic time constant of acellular constructs. Collagen constructs exhibited significantly higher modulus and viscosity than fibrin constructs. Cell-seeded collagen constructs became stiffer with altered mechanical behavior as they developed over time. Importantly, DUE also provides insight into the spatial variation of viscoelastic properties at sub-millimeter resolution, allowing interrogation of the interior of constructs. DUE presents a novel technique for non-invasively characterizing hydrogel materials at the microscale, and therefore may have unique utility in the study of mechanobiology and the characterization of hydrogel biomaterials. Copyright © 2016 Elsevier Ltd. All rights reserved.
Pyrolysis Strategies for Effective Utilization of Lignocellulosic and Algal Biomass
NASA Astrophysics Data System (ADS)
Maddi, Balakrishna
Pyrolysis is a processing technique involving thermal degradation of biomass in the absence of oxygen. The bio-oils obtained following the condensation of the pyrolysis vapors form a convenient starting point for valorizing the major components of lignocellulosic as well as algal biomass feed stocks for the production of fuels and value-added chemicals. Pyrolysis can be implemented on whole biomass or on residues left behind following standard fractionation methods. Microalgae and oil seeds predominantly consist of protein, carbohydrate and triglycerides, whereas lignocellulose is composed of carbohydrates (cellulose and hemicellulose) and lignin. The differences in the major components of these two types of biomass will necessitate different pyrolysis strategies to derive the optimal benefits from the resulting bio-oils. In this thesis, novel pyrolysis strategies were developed that enable efficient utilization of the bio-oils (and/or their vapors) from lignocellulose, algae, as well as oil seed feed stocks. With lignocellulosic feed stocks, pyrolysis of whole biomass as well as the lignin residue left behind following well-established pretreatment and saccharification (i.e., depolymerization of cellulose and hemicellulose to their monomeric-sugars) of the biomass was studied with and without catalysts. Following this, pyrolysis of (lipid-deficient) algae and lignocellulosic feed stocks, under similar reactor conditions, was performed for comparison of product (bio-oil, gas and bio-char) yields and composition. In spite of major differences in component bio-polymers, feedstock properties relevant to thermo-chemical conversions, such as overall C, H and O-content, C/O and H/C molar ratio as well as calorific values, were found to be similar for algae and lignocellulosic material. Bio-oil yields from algae and some lignocellulosic materials were similar; however, algal bio-oils were compositionally different and contained several N-compounds (most likely from protein degradation). Algal bio-char also had a significantly higher N-content. Overall, our results suggest that it is feasible to convert algal cultures deficient in lipids, such as nuisance algae obtained from natural blooms, into liquid fuels by thermochemical methods. Next, pyrolysis characteristics of each of the major components present in lignocellulosic as well as algal biomass were studied independently in a thermo-gravimetric analyzer, using model compounds. From those studies, we have established that, with algae and oil seed feed stocks, triglycerides degrade at distinctly higher temperatures (T>350 C) compared to both protein and carbohydrate fractions (T ~ 250-350 C). Similar trend was not seen for lignocellulosic biomass, where degradation temperature interval of lignin overlapped with that of carbohydrates. This unique trend observed for algal biomass (and oil seeds) can be exploited in multiple ways. First, it permits to separately collect high value triglyceride degradation products not contaminated with N-compounds from protein and oxygenates from carbohydrates; this observation formed the basis of a novel "pyrolytic fractionation technique" developed in this thesis. Second, it led to the development of a new and simple analytical method for rapid estimation of the triglyceride content of oleaginous feed stocks. Pyrolytic fractionation is a two-step pyrolysis approach that can be implemented for oleaginous feed stocks (algae and oil-seeds) to separately recover triglyceride degradation products as a "high-quality" bio-oil fraction. The first step is a low-temperature pyrolysis (T ~ 300-320 C) to produce bio-oils from degradation of protein and carbohydrate fractions. Solid residues left behind can subsequently be subjected to a second higher temperature pyrolysis (T ~ 420-430 C) to volatilize and/or degrade triglycerides to produce fatty acids and their derivatives (such as mono-, di- and tri-glycerides) and long chain hydrocarbons. Proof-of-concept micro-pyrolyser (Pyroprobe) and lab-scale fixed-bed experiments were performed using oleaginous algae (Chlorella Sp.) to establish pyrolytic fractionation technique and also to determine the yields of triglyceride-specific bio-oils. As expected, triglyceride-specific bio-oils have hydrocarbons and free fatty acids that were nearly free of water, organic acids and carbohydrate degradation products. Another unique feature of the fractional pyrolysis method is that it allows upgrading of the triglyceride-specific bio-oil vapors via in situ gas-phase hydro-deoxygenation to drop-in fuels (hydrocarbons), without the need to condense the vapors. Similarly, these vapors can also be converted to other value-added products such as fatty acid methyl esters and amides though efficient catalytic and non-catalytic in situ gas-phase conversion methods. Energy requirements for this new pyrolytic fractionation method were also assessed, using energy estimates for the individual steps obtained via differential scanning calorimetry experiments. A comparison of these energy needs against those of alternative thermal processing methods of algae (hydro-thermal processing) proposed in the literature established the viability of this new method. Finally, a new TGA-based analytical method was developed in this thesis for rapid quantification of the triglyceride content of oleaginous feed stocks, by exploiting the non-overlapping thermal degradation range of triglycerides and the other major components.
2010-05-11
convective heat transfer , researchers have been drawn to the high heat flux potentials of microfluidic devices. Microchannel flows, with hydraulic...novel heat transfer enhancement technique proven on the conventional scale to the mini and microchannel scales. 1.3 Background: Conventional...S.G., 2004, “Single-Phase Heat Transfer Enhancement Techniques in Microchannel and Minichannel Flows,” International Conference on Microchannels
Microscale Determination of Vitamin C by Weight Titrimetry
NASA Astrophysics Data System (ADS)
East, Gaston A.; Nascimento, Erica C.
2002-01-01
A laboratory experiment involving the quantitative microscale determination of ascorbic acid in pharmaceutical tablets of vitamin C by weight-titrimetry using (diacetoxyiodo)benzene as titrant and differential electrolytic potentiometry to locate the end-point is presented. The experiment affords an opportunity for students to explore nonconventional techniques such as the use of a novel organic oxidimetric titrant, titration in a semiaqueous medium, gravimetric titration, and an electrometric method of end-point detection using polarized electrodes. Synthesis, purification, and purity checking of the titrant may also be included in the project. Some advantages of the method are very low reagent consumption, low-cost equipment, improved sensitivity, and high precision and accuracy. Furthermore, the experiment will help the student to relate chemical analysis to everyday life.
Synthesis micro-scale boron nitride nanotubes at low substrate temperature
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sajjad, Muhammad, E-mail: msajjadd@gmail.com; Makarov, Vladimir; Morell, Gerardo
2016-07-15
High temperature synthesis methods produce defects in 1D nanomaterials, which ultimately limit their applications. We report here the synthesis of micro-scale boron nitride nanotubes (BNNT) at low substrate temperature (300 {sup o}C) using a pulsed CO{sub 2} laser deposition technique in the presence of catalyst. The electron microscopic analyses have shown the nanotubes distributed randomly on the surface of the substrate. The average diameter (∼0.25 μm) of a nanotube, which is the highest reported value to date, is estimated by SEM data and confirmed by TEM measurements. These nanotubes are promising for high response deep-UV photo-luminescent devices. A detailed synthesismore » mechanism is presented and correlated with the experimental results.« less
Wang, Zhuochen; Zhe, Jiang
2011-04-07
Manipulation of microscale particles and fluid liquid droplets is an important task for lab-on-a-chip devices for numerous biological researches and applications, such as cell detection and tissue engineering. Particle manipulation techniques based on surface acoustic waves (SAWs) appear effective for lab-on-a-chip devices because they are non-invasive, compatible with soft lithography micromachining, have high energy density, and work for nearly any type of microscale particles. Here we review the most recent research and development of the past two years in SAW based particle and liquid droplet manipulation for lab-on-a-chip devices including particle focusing and separation, particle alignment and patterning, particle directing, and liquid droplet delivery.
Optical Scattering Characterization for the Glennan Microsystems Microscale Particulate Classifier
NASA Technical Reports Server (NTRS)
Lock, James A.
2002-01-01
Small sensors that are tolerant to mechanically and thermally harsh environments present the possibility for in-situ particle characterization in propulsion, industrial, and planetary science applications. Under a continuing grant from the Glennan Microsystems Initiative to the Microgravity Fluids Physics Branch of the NASA-Glenn Research Center, a Microscale Particle Classifier (MiPAC) instrument is being developed. The MiPAC instrument will be capable of determining the size distribution of airborne particles from about 1 nm to 30 micrometers, and will provide partial information as to the concentration, charge state, shape, and structure of the particles, while being an order of magnitude smaller in size and lighter in weight than presently commercially available instruments. The portion of the instrument that will characterize the nm-range particles will employ electrical mobility techniques and is being developed under a separate grant to Prof. David Pui of the University of Minnesota. The portion of the instrument that will characterize the micrometer-size particles such as dirt, pollens, spores, molds, soot, and combustion aerosols will use light scattering techniques. The development of data analysis techniques to be employed in the light scattering portion of the instrument is covered by this grant.
Sugumaran, Vatsala; Prakash, Shanti; Ramu, Emmandi; Arora, Ajay Kumar; Bansal, Veena; Kagdiyal, Vivekanand; Saxena, Deepak
2017-07-15
Bio-oil obtained from pyrolysis is highly complicated mixture with valued chemicals. In order to reduce the complexity for unambiguous characterization of components present in bio-oil, solvent extractions using different solvents with increasing polarity have been adopted. The fractions have been analyzed by Fourier transform infrared (FTIR) spectroscopy for identifying the functional groups and Gas chromatography-mass spectrometry (GC-MS), for detailed characterization of components present in various fractions, thereby providing in-depth information at molecular level of various components in bio-oil. This paper reveals the potential of the analytical techniques in identification and brings out the similarities as well as differences in the components present in the bio-oil obtained from two non-edible oil seed-cakes, viz., Jatropha and Karanjia. Copyright © 2017 Elsevier B.V. All rights reserved.
Analyses of moisture in polymers and composites
NASA Technical Reports Server (NTRS)
Ryan, L. E.; Vaughan, R. W.
1980-01-01
A suitable method for the direct measurement of moisture concentrations after humidity/thermal exposure on state of the art epoxy and polyimide resins and their graphite and glass fiber reinforcements was investigated. Methods for the determination of moisture concentration profiles, moisture diffusion modeling and moisture induced chemical changes were examined. Carefully fabricated, precharacterized epoxy and polyimide neat resins and their AS graphite and S glass reinforced composites were exposed to humid conditions using heavy water (D20), at ambient and elevated temperatures. These specimens were fixtured to theoretically limit the D20 permeation to a unidirectional penetration axis. The analytical techniques evaluated were: (1) laser pyrolysis gas chromatography mass spectrometry; (2) solids probe mass spectrometry; (3) laser pyrolysis conventional infrared spectroscopy; and (4) infrared imaging thermovision. The most reproducible and sensitive technique was solids probe mass spectrometry. The fabricated exposed specimens were analyzed for D20 profiling after humidity/thermal conditioning at three exposure time durations.
Zhao, Bingwei; Wang, Xin; Yang, Xiaoyi
2015-12-01
Co-pyrolysis characteristics of Isochrysis (high lipid) and Chlorella (high protein) were investigated qualitatively and quantitatively based on DTG curves, biocrude yield and composition by individual pyrolysis and co-pyrolysis. DTG curves in co-pyrolysis have been compared accurately with those in individual pyrolysis. An interaction has been detected at 475-500°C in co-pyrolysis based on biocrude yields, and co-pyrolysis reaction mechanism appear three-dimensional diffusion in comparison with random nucleation followed by growth in individual pyrolysis based on kinetic analysis. There is no obvious difference in the maximum biocrude yields for individual pyrolysis and co-pyrolysis, but carboxylic acids (IC21) decreased and N-heterocyclic compounds (IC12) increased in co-pyrolysis. Simulation results of biocrude yield by Components Biofuel Model and Kinetics Biofuel Model indicate that the processes of co-pyrolysis comply with those of individual pyrolysis in solid phase by and large. Variation of percentage content in co-pyrolysis and individual pyrolysis biocrude indicated interaction in gas phase. Copyright © 2015. Published by Elsevier Ltd.
Vertically Aligned Carbon Nanotubes at Different Temperatures by Spray Pyrolysis Techniques
NASA Astrophysics Data System (ADS)
Afre, Rakesh A.; Soga, T.; Jimbo, T.; Kumar, Mukul; Ando, Y.; Sharon, M.
Vertically aligned arrays of multi-walled carbon nanotubes (VACNTs) were grown by spray pyrolysis of turpentine oil and ferrocene mixture at temperatures higher than 700°C. Using this simple method, we report the successful growth of vertically aligned nanotubes of ~300μm length and diameter in the range of ?20-80nm on Si(100) substrate. The ferrocene acts as an in situ Fe catalyst precursor, forming the nano-sized metallic iron particles for formation of VACNTs on the Si substrate. The morphological characteristics of VACNTs are confirmed by SEM, TEM and Raman spectroscopy and growth mechanism is discussed in short.
Recent developments in microscale sensors allows the non-destructive and in–situ measurement of both the absolute and changes in chemical concentrations in engineered and natural aquatic systems. Microelectrodes represent a unique tool for studying in–situ chemical reactions in b...
Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance
NASA Astrophysics Data System (ADS)
Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen
2018-01-01
Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.
Brooijmans, T; Okhuijsen, R; Oerlemans, I; Schoenmakers, P J; Peters, R
2018-05-14
Pyrolysis - gas chromatography - (PyGC) is a common method to analyse the composition of natural and synthetic resins. The analysis of acid functionality in, for example, waterborne polyacrylates and polyurethanes polymers has proven to be difficult due to solubility issues, inter- and intramolecular interaction effects, lack of detectability in chromatographic analysis, and lack of thermal stability. Conventional analytical techniques, such as PyGC, cannot be used for the direct detection and identification of acidic monomers, due to thermal rearrangements that take place during pyrolysis. To circumvent this, the carboxylic acid groups are protected prior to thermal treatment by reaction with 2-bromoacetophenone. Reaction conditions are investigated and optimised wrt. conversion measurements. The aproach is applied to waterborne polyacryalates and the results are discussed. This approach enables identification and (semi)quantitative analysis of different acid functionalities in waterborne polymers by PyGC. Copyright © 2018 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Kumar, A. Madhan; Babu, R. Suresh; Obot, I. B.; Adesina, Akeem Yusuf; Ibrahim, Ahmed; de Barros, A. L. F.
2018-05-01
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.
NASA Astrophysics Data System (ADS)
Kumar, A. Madhan; Babu, R. Suresh; Obot, I. B.; Adesina, Akeem Yusuf; Ibrahim, Ahmed; de Barros, A. L. F.
2018-01-01
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.
Chemical recycling of plastic wastes made from polyethylene (LDPE and HDPE) and polypropylene (PP).
Achilias, D S; Roupakias, C; Megalokonomos, P; Lappas, A A; Antonakou, Epsilon V
2007-11-19
The recycling of either model polymers or waste products based on low-density polyethylene (LDPE), high-density polyethylene (HDPE) or polypropylene (PP) is examined using the dissolution/reprecipitation method, as well as pyrolysis. In the first technique, different solvents/non-solvents were examined at different weight percent amounts and temperatures using as raw material both model polymers and commercial products (packaging film, bags, pipes, food-retail outlets). The recovery of polymer in every case was greater than 90%. FT-IR spectra and tensile mechanical properties of the samples before and after recycling were measured. Furthermore, catalytic pyrolysis was carried out in a laboratory fixed bed reactor with an FCC catalyst using again model polymers and waste products as raw materials. Analysis of the derived gases and oils showed that pyrolysis gave a mainly aliphatic composition consisting of a series of hydrocarbons (alkanes and alkenes), with a great potential to be recycled back into the petrochemical industry as a feedstock for the production of new plastics or refined fuels.
Properties of oil and char derived from slow pyrolysis of Tetraselmis chui.
Grierson, Scott; Strezov, Vladimir; Shah, Pushan
2011-09-01
Pyrolysis of biomass is a means to industrially manufacture renewable oil and gas, in addition to biochar for soil amendment and long-term carbon fixation. In this work, oil and char derived from the slow pyrolysis of the unicellular marine diatom Tetraselmis chui are analysed using a variety of techniques. The pyrolytic oil fraction exhibits a wide variety of fatty acids, alkanes, alkenes, amides, aldehydes, terpenes, pyrrolidinines, phytol and phenols, with a high heating value (HHV) of 28 MJ/kg. The biochar produced has a HHV of 14.5 MJ/kg and reveals a number of properties that are potentially valuable from an agronomic point of view, including high cation exchange capacity (CEC), large concentration of N, and a low C:N ratio. The quantity of C in T. chui biochar that can be expected to stabilise in soil amounts to approximately 9%/wt of the original feedstock, leading to a potential net reduction in atmospheric CO(2). Copyright © 2011 Elsevier Ltd. All rights reserved.
Low temperature pyrolysis of coal or oil shale in the presence of calcium compounds
Khan, M. Rashid
1988-01-01
A coal pyrolysis technique or process is described in which particulate coal is pyrolyzed in the presence of about 5 to 21 wt. % of a calcium compound selected from calcium oxide, calcined (hydrate) dolomite, or calcined calcium hydrate to produce a high quality hydrocarbon liquid and a combustible product gas which are characterized by low sulfur content. The pyrolysis is achieved by heating the coal-calcium compound mixture at a relatively slow rate at a temperature of about 450.degree. to 700.degree. C. over a duration of about 10 to 60 minutes in a fixed or moving bed reactor. The gas exhibits an increased yield in hydrogen and C.sub.1 -C.sub.8 hydrocarbons and a reduction in H.sub.2 S over gas obtainable by pyrolyzing cola without the calcium compound. The liquid product obtained is of a sufficient quality to permit its use directly as a fuel and has a reduced sulfur and oxygen content which inhibits polymerization during storage.
Thermal Analysis of the Fastrac Chamber/Nozzle
NASA Technical Reports Server (NTRS)
Davis, Darrell
2001-01-01
This paper will describe the thermal analysis techniques used to predict temperatures in the film-cooled ablative rocket nozzle used on the Fastrac 60K rocket engine. A model was developed that predicts char and pyrolysis depths, liner thermal gradients, and temperatures of the bondline between the overwrap and liner. Correlation of the model was accomplished by thermal analog tests performed at Southern Research, and specially instrumented hot fire tests at the Marshall Space Flight Center. Infrared thermography was instrumental in defining nozzle hot wall surface temperatures. In-depth and outboard thermocouple data was used to correlate the kinetic decomposition routine used to predict char and pyrolysis depths. These depths were anchored with measured char and pyrolysis depths from cross-sectioned hot-fire nozzles. For the X-34 flight analysis, the model includes the ablative Thermal Protection System (TPS) material that protects the overwrap from the recirculating plume. Results from model correlation, hot-fire testing, and flight predictions will be discussed.
Thermal Analysis of the MC-1 Chamber/Nozzle
NASA Technical Reports Server (NTRS)
Davis, Darrell W.; Phelps, Lisa H. (Technical Monitor)
2001-01-01
This paper will describe the thermal analysis techniques used to predict temperatures in the film-cooled ablative rocket nozzle used on the MC-1 60K rocket engine. A model was developed that predicts char and pyrolysis depths, liner thermal gradients, and temperatures of the bondline between the overwrap and liner. Correlation of the model was accomplished by thermal analog tests performed at Southern Research, and specially instrumented hot fire tests at the Marshall Space Flight Center. Infrared thermography was instrumental in defining nozzle hot wall surface temperatures. In-depth and outboard thermocouple data was used to correlate the kinetic decomposition routine used to predict char and pyrolysis depths. These depths were anchored with measured char and pyrolysis depths from cross-sectioned hot-fire nozzles. For the X-34 flight analysis, the model includes the ablative Thermal Protection System (TPS) material that protects the overwrap from the recirculating plume. Results from model correlation, hot-fire testing, and flight predictions will be discussed.
NASA Astrophysics Data System (ADS)
Rasoulnezhad, Hossein; Hosseinzadeh, Ghader; Ghasemian, Naser; Hosseinzadeh, Reza; Homayoun Keihan, Amir
2018-05-01
Nanostructured TiO2 and Fe-doped TiO2 thin films with high transparency were deposited on glass substrate through ultrasonic-assisted spray pyrolysis technique and were used in the visible light photocatalytic degradation of MB dye. The resulting thin films were characterized by scanning electron microscopy (SEM), Raman spectroscopy, photoluminescence spectroscopy, x-ray diffraction (XRD), and UV-visible absorption spectroscopy techniques. Based on Raman spectroscopy results, both of the TiO2 and Fe-doped TiO2 films have anatase crystal structure, however, because of the insertion of Fe in the structure of TiO2 some point defects and oxygen vacancies are formed in the Fe-doped TiO2 thin film. Presence of Fe in the structure of TiO2 decreases the band gap energy of TiO2 and also reduces the electron–hole recombination rate. Decreasing of the electron–hole recombination rate and band gap energy result in the enhancement of the visible light photocatalytic activity of the Fe-doped TiO2 thin film.
Lécuyer, Christophe; Fourel, François; Martineau, François; Amiot, Romain; Bernard, Aurélien; Daux, Valérie; Escarguel, Gilles; Morrison, John
2007-01-01
A high-precision, and rapid on-line method for oxygen isotope analysis of silver phosphate is presented. The technique uses high-temperature elemental analyzer (EA)-pyrolysis interfaced in continuous flow (CF) mode to an isotopic ratio mass spectrometer (IRMS). Calibration curves were generated by synthesizing silver phosphate with a 13 per thousand spread in delta(18)O values. Calibration materials were obtained by reacting dissolved potassium dihydrogen phosphate (KH(2)PO(4)) with water samples of various oxygen isotope compositions at 373 K. Validity of the method was tested by comparing the on-line results with those obtained by classical off-line sample preparation and dual inlet isotope measurement. In addition, silver phosphate precipitates were prepared from a collection of biogenic apatites with known delta(18)O values ranging from 12.8 to 29.9 per thousand (V-SMOW). Reproducibility of +/- 0.2 per thousand was obtained by the EA-Py-CF-IRMS method for sample sizes in the range 400-500 microg. Both natural and synthetic samples are remarkably well correlated with conventional (18)O/(16)O determinations. Silver phosphate is a very stable material and easy to degas and, thus, could be considered as a good candidate to become a reference material for the determination of (18)O/(16)O ratios of phosphate by high-temperature pyrolysis. Copyright 2006 John Wiley & Sons, Ltd.
NASA Technical Reports Server (NTRS)
Crawford, D. A.; Barnouin-Jha, O. S.; Cintala, M. J.
2003-01-01
The propagation of shock waves through target materials is strongly influenced by the presence of small-scale structure, fractures, physical and chemical heterogeneities. Pre-existing fractures often create craters that appear square in outline (e.g. Meteor Crater). Reverberations behind the shock from the presence of physical heterogeneity have been proposed as a mechanism for transient weakening of target materials. Pre-existing fractures can also affect melt generation. In this study, we are attempting to bridge the gap in numerical modeling between the micro-scale and the continuum, the so-called meso-scale. To accomplish this, we are developing a methodology to be used in the shock physics hydrocode (CTH) using Monte-Carlo-type methods to investigate the shock properties of heterogeneous materials. By comparing the results of numerical experiments at the micro-scale with experimental results and by using statistical techniques to evaluate the performance of simple constitutive models, we hope to embed the effect of physical heterogeneity into the field variables (pressure, stress, density, velocity) allowing us to directly imprint the effects of micro-scale heterogeneity at the continuum level without incurring high computational cost.
Microfabricated ion trap array
Blain, Matthew G [Albuquerque, NM; Fleming, James G [Albuquerque, NM
2006-12-26
A microfabricated ion trap array, comprising a plurality of ion traps having an inner radius of order one micron, can be fabricated using surface micromachining techniques and materials known to the integrated circuits manufacturing and microelectromechanical systems industries. Micromachining methods enable batch fabrication, reduced manufacturing costs, dimensional and positional precision, and monolithic integration of massive arrays of ion traps with microscale ion generation and detection devices. Massive arraying enables the microscale ion traps to retain the resolution, sensitivity, and mass range advantages necessary for high chemical selectivity. The reduced electrode voltage enables integration of the microfabricated ion trap array with on-chip circuit-based rf operation and detection electronics (i.e., cell phone electronics). Therefore, the full performance advantages of the microfabricated ion trap array can be realized in truly field portable, handheld microanalysis systems.
NASA Astrophysics Data System (ADS)
Larsen, J. D.; Schaap, M. G.
2013-12-01
Recent advances in computing technology and experimental techniques have made it possible to observe and characterize fluid dynamics at the micro-scale. Many computational methods exist that can adequately simulate fluid flow in porous media. Lattice Boltzmann methods provide the distinct advantage of tracking particles at the microscopic level and returning macroscopic observations. While experimental methods can accurately measure macroscopic fluid dynamics, computational efforts can be used to predict and gain insight into fluid dynamics by utilizing thin sections or computed micro-tomography (CMT) images of core sections. Although substantial effort have been made to advance non-invasive imaging methods such as CMT, fluid dynamics simulations, and microscale analysis, a true three dimensional image segmentation technique has not been developed until recently. Many competing segmentation techniques are utilized in industry and research settings with varying results. In this study lattice Boltzmann method is used to simulate stokes flow in a macroporous soil column. Two dimensional CMT images were used to reconstruct a three dimensional representation of the original sample. Six competing segmentation standards were used to binarize the CMT volumes which provide distinction between solid phase and pore space. The permeability of the reconstructed samples was calculated, with Darcy's Law, from lattice Boltzmann simulations of fluid flow in the samples. We compare simulated permeability from differing segmentation algorithms to experimental findings.
Resin infiltration transfer technique
Miller, David V [Pittsburgh, PA; Baranwal, Rita [Glenshaw, PA
2009-12-08
A process has been developed for fabricating composite structures using either reaction forming or polymer infiltration and pyrolysis techniques to densify the composite matrix. The matrix and reinforcement materials of choice can include, but are not limited to, silicon carbide (SiC) and zirconium carbide (ZrC). The novel process can be used to fabricate complex, net-shape or near-net shape, high-quality ceramic composites with a crack-free matrix.
Pyrolysis characteristics of typical biomass thermoplastic composites
NASA Astrophysics Data System (ADS)
Cai, Hongzhen; Ba, Ziyu; Yang, Keyan; Zhang, Qingfa; Zhao, Kunpeng; Gu, Shiyan
The biomass thermoplastic composites were prepared by extrusion molding method with poplar flour, rice husk, cotton stalk and corn stalk. The thermo gravimetric analyzer (TGA) has also been used for evaluating the pyrolysis process of the composites. The results showed that the pyrolysis process mainly consists of two stages: biomass pyrolysis and the plastic pyrolysis. The increase of biomass content in the composite raised the first stage pyrolysis peak temperature. However, the carbon residue was reduced and the pyrolysis efficiency was better because of synergistic effect of biomass and plastic. The composite with different kinds of biomass have similar pyrolysis process, and the pyrolysis efficiency of the composite with corn stalk was best. The calcium carbonate could inhibit pyrolysis process and increase the first stage pyrolysis peak temperature and carbon residue as a filling material of the composite.
The use of microtomography in structural geology: A new methodology to analyse fault faces
NASA Astrophysics Data System (ADS)
Jacques, Patricia D.; Nummer, Alexis Rosa; Heck, Richard J.; Machado, Rômulo
2014-09-01
This paper describes a new methodology to kinematically analyze faults in microscale dimensions (voxel size = 40 μm), using images obtained by X-ray computed microtomography (μCT). The equipment used is a GE MS8x-130 scanner. It was developed using rocks samples from Santa Catarina State, Brazil, and constructing micro Digital Elevation Models (μDEMs) for the fault surface, for analysing microscale brittle structures including striations, roughness and steps. Shaded relief images were created for the μDEMs, which enabled the generation of profiles to classify the secondary structures associated with the main fault surface. In the case of a sample with mineral growth that covers the fault surface, it is possible to detect the kinematic geometry even with the mineral cover. This technique proved to be useful for determining the sense of movement of faults, especially when it is not possible to determine striations in macro or microscopic analysis. When the sample has mineral deposit on the surface (mineral cover) this technique allows a relative chronology and geometric characterization between the faults with and without covering.
Methods and apparatuses for preparing upgraded pyrolysis oil
Brandvold, Timothy A; Baird, Lance Awender; Frey, Stanley Joseph
2013-10-01
Methods and apparatuses for preparing upgraded pyrolysis oil are provided herein. In an embodiment, a method of preparing upgraded pyrolysis oil includes providing a biomass-derived pyrolysis oil stream having an original oxygen content. The biomass-derived pyrolysis oil stream is hydrodeoxygenated under catalysis in the presence of hydrogen to form a hydrodeoxygenated pyrolysis oil stream comprising a cyclic paraffin component. At least a portion of the hydrodeoxygenated pyrolysis oil stream is dehydrogenated under catalysis to form the upgraded pyrolysis oil.
NASA Astrophysics Data System (ADS)
Pathan, Idris G.; Suryawanshi, Dinesh N.; Bari, Anil R.; Patil, Lalchand A.
2018-05-01
This work presents the effect of iron doping having different volume ratios (1 ml, 2.5 ml and 5 ml) on the structural, microstructural and electrical properties of zinc stannate thin films, prepared by spray pyrolysis method. These properties were characterized with X-ray diffraction (XRD) and Transmission Electron Microscope (TEM). In our study, XRD pattern indicates that ZnSnO3 has a perovskite phase with face exposed hexahedron structure. The electron diffraction fringes observed are in consistent with the peak observed in XRD patterns. Moreover the sensor reported in our study is cost-effective, user friendly and easy to fabricate.
Tan, Joo Shun; Abbasiliasi, Sahar; Kadkhodaei, Saeid; Tam, Yew Joon; Tang, Teck-Kim; Lee, Yee-Ying; Ariff, Arbakariya B
2018-01-04
Demand for high-throughput bioprocessing has dramatically increased especially in the biopharmaceutical industry because the technologies are of vital importance to process optimization and media development. This can be efficiently boosted by using microtiter plate (MTP) cultivation setup embedded into an automated liquid-handling system. The objective of this study was to establish an automated microscale method for upstream and downstream bioprocessing of α-IFN2b production by recombinant Escherichia coli. The extraction performance of α-IFN2b by osmotic shock using two different systems, automated microscale platform and manual extraction in MTP was compared. The amount of α-IFN2b extracted using automated microscale platform (49.2 μg/L) was comparable to manual osmotic shock method (48.8 μg/L), but the standard deviation was 2 times lower as compared to manual osmotic shock method. Fermentation parameters in MTP involving inoculum size, agitation speed, working volume and induction profiling revealed that the fermentation conditions for the highest production of α-IFN2b (85.5 μg/L) was attained at inoculum size of 8%, working volume of 40% and agitation speed of 1000 rpm with induction at 4 h after the inoculation. Although the findings at MTP scale did not show perfect scalable results as compared to shake flask culture, but microscale technique development would serve as a convenient and low-cost solution in process optimization for recombinant protein.
NASA Technical Reports Server (NTRS)
Kihm, K. D.; Allen, J. S.; Hallinan, K. P.; Pratt, D. M.
2004-01-01
In order to enhance the fundamental understanding of thin film evaporation and thereby improve the critical design concept for two-phase heat transfer devices, microscale heat and mass transport is to be investigated for the transition film region using state-of-the-art optical diagnostic techniques. By utilizing a microgravity environment, the length scales of the transition film region can be extended sufficiently, from submicron to micron, to probe and measure the microscale transport fields which are affected by intermolecular forces. Extension of the thin film dimensions under microgravity will be achieved by using a conical evaporator made of a thin silicon substrate under which concentric and individually controlled micro-heaters are vapor-deposited to maintain either a constant surface temperature or a controlled temperature variation. Local heat transfer rates, required to maintain the desired wall temperature boundary condition, will be measured and recorded by the concentric thermoresistance heaters controlled by a Wheatstone bridge circuit, The proposed experiment employs a novel technique to maintain a constant liquid volume and liquid pressure in the capillary region of the evaporating meniscus so as to maintain quasi-stationary conditions during measurements on the transition film region. Alternating use of Fizeau interferometry via white and monochromatic light sources will measure the thin film slope and thickness variation, respectively. Molecular Fluorescence Tracking Velocimetry (MFTV), utilizing caged fluorophores of approximately 10-nm in size as seeding particles, will be used to measure the velocity profiles in the thin film region. An optical sectioning technique using confocal microscopy will allow submicron depthwise resolution for the velocity measurements within the film for thicknesses on the order of a few microns. Digital analysis of the fluorescence image-displacement PDFs, as described in the main proposal, can further enhance the depthwise resolution.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Martinez, H.M.; Torres, J., E-mail: njtorress@unal.edu.co; Lopez Carreno, L.D.
2013-01-15
Polycrystalline molybdenum tri-oxide thin films were prepared using the spray pyrolysis technique; a 0.1 M solution of ammonium molybdate tetra-hydrated was used as a precursor. The samples were prepared on Corning glass substrates maintained at temperatures ranging between 423 and 673 K. The samples were characterized through micro Raman, X-ray diffraction, optical transmittance and DC electrical conductivity. The species MoO{sub 3} (H{sub 2}O){sub 2} was found in the sample prepared at a substrate temperature of 423 K. As the substrate temperature rises, the water disappears and the samples crystallize into {alpha}-MoO{sub 3}. The optical gap diminishes as the substrate temperaturemore » rises. Two electrical transport mechanisms were found: hopping under 200 K and intrinsic conduction over 200 K. The MoO{sub 3} films' sensitivity was analyzed for CO and H{sub 2}O in the temperature range 160 to 360 K; the results indicate that CO and H{sub 2}O have a reduction character. In all cases, it was found that the sensitivity to CO is lower than that to H{sub 2}O. - Highlights: Black-Right-Pointing-Pointer A low cost technique is used which produces good material. Black-Right-Pointing-Pointer Thin films are prepared using ammonium molybdate tetra hydrated. Black-Right-Pointing-Pointer The control of the physical properties of the samples could be done. Black-Right-Pointing-Pointer A calculation method is proposed to determine the material optical properties. Black-Right-Pointing-Pointer The MoO{sub 3} thin films prepared by spray pyrolysis could be used as gas sensor.« less
Chou, I.-Ming; Lake, M.A.; Griffin, R.A.
1988-01-01
A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.
Fabrication of 3D Carbon Microelectromechanical Systems (C-MEMS).
Pramanick, Bidhan; Martinez-Chapa, Sergio O; Madou, Marc; Hwang, Hyundoo
2017-06-17
A wide range of carbon sources are available in nature, with a variety of micro-/nanostructure configurations. Here, a novel technique to fabricate long and hollow glassy carbon microfibers derived from human hairs is introduced. The long and hollow carbon structures were made by the pyrolysis of human hair at 900 °C in a N2 atmosphere. The morphology and chemical composition of natural and pyrolyzed human hairs were investigated using scanning electron microscopy (SEM) and electron-dispersive X-ray spectroscopy (EDX), respectively, to estimate the physical and chemical changes due to pyrolysis. Raman spectroscopy was used to confirm the glassy nature of the carbon microstructures. Pyrolyzed hair carbon was introduced to modify screen-printed carbon electrodes ; the modified electrodes were then applied to the electrochemical sensing of dopamine and ascorbic acid. Sensing performance of the modified sensors was improved as compared to the unmodified sensors. To obtain the desired carbon structure design, carbon micro-/nanoelectromechanical system (C-MEMS/C-NEMS) technology was developed. The most common C-MEMS/C-NEMS fabrication process consists of two steps: (i) the patterning of a carbon-rich base material, such as a photosensitive polymer, using photolithography; and (ii) carbonization through the pyrolysis of the patterned polymer in an oxygen-free environment. The C-MEMS/NEMS process has been widely used to develop microelectronic devices for various applications, including in micro-batteries, supercapacitors, glucose sensors, gas sensors, fuel cells, and triboelectric nanogenerators. Here, recent developments of a high-aspect ratio solid and hollow carbon microstructures with SU8 photoresists are discussed. The structural shrinkage during pyrolysis was investigated using confocal microscopy and SEM. Raman spectroscopy was used to confirm the crystallinity of the structure, and the atomic percentage of the elements present in the material before and after pyrolysis was measured using EDX.
Cleavage and crosslinking of polymeric coal structures during pyrolysis. Final report
DOE Office of Scientific and Technical Information (OSTI.GOV)
McMillen, D.F.; Malhotra, R.
1992-02-01
The ultimate objective of this project was to develop a better understanding of volatiles production to help optimize the yield and character of condensable coproducts during coal pyrolysis or mild gasification. The specific objectives were to (1) Develop pyrolysis procedures that minimize secondary reactions; and (2) Develop coal pretreatments that current knowledge suggests will prorate bond scission or prevent retrograde reactions. Our approach was to study the pyrolysis of coals and tar-loaded coals by using several techniques that span a range of heating rates and pressures. Slow-heating pyrolyses were performed at low pressures in the inlet of a field ionizationmore » mass spectrometer and at atmospheric pressures in a thermogravimetric analyzer. Moderately rapid-heating pyrolyses were performed in a vacuum TGA apparatus and in sealed silica ampules heated in a molten-salt bath. The fastest heating rates were achieved with laser pyrolysis at about 30,000 X/s. The high tar yield seen in this work where the entire volume of the coal particle becomes hot and fluid at very nearly the same time, taken together with the evident non-vapor transport of the tar under these conditions, emphasizes the importance of better understanding the development of fluidity during coal heating. This specifically includes the profound effects--long-recognized but poorly understood that mild oxidation has in suppressing coal fluidity. It also includes the more recently recognized fact that heating in the presence of an inert gas produced substantially greater fluidity than does heating in the presence of combustion gases, even if the conditions are very fuel rich and all the oxygen itself has already been consumed when the coal particles are encountered.« less
Cleavage and crosslinking of polymeric coal structures during pyrolysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
McMillen, D.F.; Malhotra, R.
1992-02-01
The ultimate objective of this project was to develop a better understanding of volatiles production to help optimize the yield and character of condensable coproducts during coal pyrolysis or mild gasification. The specific objectives were to (1) Develop pyrolysis procedures that minimize secondary reactions; and (2) Develop coal pretreatments that current knowledge suggests will prorate bond scission or prevent retrograde reactions. Our approach was to study the pyrolysis of coals and tar-loaded coals by using several techniques that span a range of heating rates and pressures. Slow-heating pyrolyses were performed at low pressures in the inlet of a field ionizationmore » mass spectrometer and at atmospheric pressures in a thermogravimetric analyzer. Moderately rapid-heating pyrolyses were performed in a vacuum TGA apparatus and in sealed silica ampules heated in a molten-salt bath. The fastest heating rates were achieved with laser pyrolysis at about 30,000 X/s. The high tar yield seen in this work where the entire volume of the coal particle becomes hot and fluid at very nearly the same time, taken together with the evident non-vapor transport of the tar under these conditions, emphasizes the importance of better understanding the development of fluidity during coal heating. This specifically includes the profound effects--long-recognized but poorly understood that mild oxidation has in suppressing coal fluidity. It also includes the more recently recognized fact that heating in the presence of an inert gas produced substantially greater fluidity than does heating in the presence of combustion gases, even if the conditions are very fuel rich and all the oxygen itself has already been consumed when the coal particles are encountered.« less
A simple and rapid procedure for measuring total mercury in fish tissues is evaluated and
compared with conventional techniques. Using an automated instrument incorporating combustion, preconcentration by amalgamation with gold, and atomic absorption spectrometry (AAS), mill...
Custom-designed nanomaterial libraries for testing metal oxide toxicity
Pokhrel, Suman; Nel, André E.; Mädler, Lutz
2014-01-01
Conspectus Advances in aerosol technology over the past 10 years have provided methods that enable the generation and design of ultrafine nanoscale materials for different applications. The particles are produced combusting a precursor solution and its chemical reaction in the in the gas phase. Flame spray pyrolysis (FSP) is a highly versatile technique for single step and scalable synthesis of nanoscale materials. New innovations in particle synthesis using FSP technology and its precursor chemistry have enabled flexible dry synthesis of loosely-agglomerated highly crystalline ultrafine powders (porosity ≥ 90%) of binary, ternary and mixed binary or ternary oxides. The flame spray pyrolysis lies at the intersection of combustion science, aerosols technology and materials chemistry. The interdisciplinary research is not only inevitable but is becoming increasingly crucial in the design of nanoparticles (NPs) made in the gas phase. The increasing demand especially in the bio-applications for particles with specific material composition, high purity and crystallinity can be often fulfilled with the fast, single step FSP technique. PMID:23194152
Torabifard, Mina; Arjmandi, Reza; Rashidi, Alimorad; Nouri, Jafar; Mohammadfam, Iraj
2018-01-10
The health and environmental effects of chemical processes can be assessed during the initial stage of their production. In this paper, the Chemical Screening Tool for Exposure and Environmental Release (ChemSTEER) software was used to compare the health and environmental risks of spray pyrolysis and wet chemical techniques for the fabrication of nanostructured metal oxide on a semi-industrial scale with a capacity of 300 kg/day in Iran. The pollution sources identified in each production process were pairwise compared in Expert Choice software using indicators including respiratory damage, skin damage, and environmental damages including air, water, and soil pollution. The synthesis of nanostructured zinc oxide using the wet chemical technique (with 0.523 wt%) leads to lower health and environmental risks compared to when spray pyrolysis is used (with 0.477 wt%). The health and environmental risk assessment of nanomaterial production processes can help select safer processes, modify the operation conditions, and select or modify raw materials that can help eliminate the risks.
Conventional and fast pyrolysis of automobile shredder residues (ASR).
Zolezzi, Marcello; Nicolella, Cristiano; Ferrara, Sebastiano; Iacobucci, Cesare; Rovatti, Mauro
2004-01-01
This work aims at comparing performance and product yields in conventional pyrolysis and fast pyrolysis of automotive shredded residues. In both processes, carbon conversion to gaseous and liquid products was more than 80%. Gas production was maximised in conventional pyrolysis (about 35% by weight of the initial ASR weight), while fast pyrolysis led to an oil yield higher than 55%. Higher heating values (HHV) of both conventional pyrolysis gas and fast pyrolysis oil increased from 8.8 to 25.07 MJ/Nm3 and from 28.8 and 36.27 MJ/kg with increasing pyrolysis temperature. Copyright 2004 Elsevier Ltd.
Collection, Measurement and Treatment of Microorganism Using Dielectrophoretic Micro Devices
NASA Astrophysics Data System (ADS)
Uchida, Satoshi
Constant monitoring of manufacturing processes has been essential in food industry because of global expansion of microbial infection. Micro-scale dielectrophoretic method is an attractive technique for direct operation and quantitative detection of bioparticles. The electrical system is capable of rapid and simple treatments corresponding to severe legal control for food safety. In this paper, newly developed techniques are reviewed for bacterial concentration, detection and sterilization using dielectrophoresis in a micro reactor. The perspective to an integrated micro device of those components is also discussed.
Wang, Huihui; Wang, Xin; Cui, Yanshan; Xue, Zhongcai; Ba, Yuxin
2018-05-11
Slow pyrolysis of bamboo was conducted at 400-600 °C and pyrolysis products were characterized with FTIR, BET, XRD, SEM, EDS and GC to establish a pyrolysis product yield prediction model and biochar formation mechanism. Pyrolysis biochar yield was predicted based on content of cellulose, hemicellulose and lignin in biomass with their carbonization index of 0.20, 0.35 and 0.45. The formation mechanism of porous structure in pyrolysis biochar was established based on its physicochemical property evolution and emission characteristics of pyrolysis gas. The main components (cellulose, hemicellulose and lignin) had different pyrolysis or chemical reaction pathways to biochar. Lignin had higher aromatic structure, which resulted higher biochar yield. It was the main biochar precursor during biomass pyrolysis. Cellulose was likely to improve porous structure of pyrolysis biochar due to its high mass loss percentage. Higher pyrolysis temperatures (600 °C) promoted inter- and intra-molecular condensation reactions and aromaticity in biochar. Copyright © 2018 Elsevier Ltd. All rights reserved.
Novel fabrication of silicon carbide based ceramics for nuclear applications
NASA Astrophysics Data System (ADS)
Singh, Abhishek Kumar
Advances in nuclear reactor technology and the use of gas-cooled fast reactors require the development of new materials that can operate at the higher temperatures expected in these systems. These materials include refractory alloys based on Nb, Zr, Ta, Mo, W, and Re; ceramics and composites such as SiC--SiCf; carbon--carbon composites; and advanced coatings. Besides the ability to handle higher expected temperatures, effective heat transfer between reactor components is necessary for improved efficiency. Improving thermal conductivity of the fuel can lower the center-line temperature and, thereby, enhance power production capabilities and reduce the risk of premature fuel pellet failure. Crystalline silicon carbide has superior characteristics as a structural material from the viewpoint of its thermal and mechanical properties, thermal shock resistance, chemical stability, and low radioactivation. Therefore, there have been many efforts to develop SiC based composites in various forms for use in advanced energy systems. In recent years, with the development of high yield preceramic precursors, the polymer infiltration and pyrolysis (PIP) method has aroused interest for the fabrication of ceramic based materials, for various applications ranging from disc brakes to nuclear reactor fuels. The pyrolysis of preceramic polymers allow new types of ceramic materials to be processed at relatively low temperatures. The raw materials are element-organic polymers whose composition and architecture can be tailored and varied. The primary focus of this study is to use a pyrolysis based process to fabricate a host of novel silicon carbide-metal carbide or oxide composites, and to synthesize new materials based on mixed-metal silicocarbides that cannot be processed using conventional techniques. Allylhydridopolycarbosilane (AHPCS), which is an organometal polymer, was used as the precursor for silicon carbide. Inert gas pyrolysis of AHPCS produces near-stoichiometric amorphous silicon carbide (a-SiC) at 900--1150 °C. Results indicated that this processing technique can be effectively used to fabricate various silicon carbide composites with UC or UO2 as the nuclear component.
Reaction Scale and Green Chemistry: Microscale or Macroscale, Which is Greener?
ERIC Educational Resources Information Center
Duarte, Rita C. C.; Ribeiro, M. Gabriela T. C.; Machado, Adelio A. S. C.
2017-01-01
The different ways microscale and green chemistry allow reducing the deleterious impacts of chemistry on human health and the environment are discussed in terms of their different basic paradigms: green chemistry follows the ecologic paradigm and microscale the risk paradigm. A study of the synthesis of 1-bromobutane at macro- ? microscale (109.3…
Method and apparatus for actively controlling a micro-scale flexural plate wave device
Dohner, Jeffrey L.
2001-01-01
An actively controlled flexural plate wave device provides a micro-scale pump. A method of actively controlling a flexural plate wave device produces traveling waves in the device by coordinating the interaction of a magnetic field with actively controlled currents. An actively-controlled flexural plate wave device can be placed in a fluid channel and adapted for use as a micro-scale fluid pump to cool or drive micro-scale systems, for example, micro-chips, micro-electrical-mechanical devices, micro-fluid circuits, or micro-scale chemical analysis devices.
The High-Resolution Wave-Propagation Method Applied to Meso- and Micro-Scale Flows
NASA Technical Reports Server (NTRS)
Ahmad, Nashat N.; Proctor, Fred H.
2012-01-01
The high-resolution wave-propagation method for computing the nonhydrostatic atmospheric flows on meso- and micro-scales is described. The design and implementation of the Riemann solver used for computing the Godunov fluxes is discussed in detail. The method uses a flux-based wave decomposition in which the flux differences are written directly as the linear combination of the right eigenvectors of the hyperbolic system. The two advantages of the technique are: 1) the need for an explicit definition of the Roe matrix is eliminated and, 2) the inclusion of source term due to gravity does not result in discretization errors. The resulting flow solver is conservative and able to resolve regions of large gradients without introducing dispersion errors. The methodology is validated against exact analytical solutions and benchmark cases for non-hydrostatic atmospheric flows.
Innovative Tools and Technology for Analysis of Single Cells and Cell-Cell Interaction.
Konry, Tania; Sarkar, Saheli; Sabhachandani, Pooja; Cohen, Noa
2016-07-11
Heterogeneity in single-cell responses and intercellular interactions results from complex regulation of cell-intrinsic and environmental factors. Single-cell analysis allows not only detection of individual cellular characteristics but also correlation of genetic content with phenotypic traits in the same cell. Technological advances in micro- and nanofabrication have benefited single-cell analysis by allowing precise control of the localized microenvironment, cell manipulation, and sensitive detection capabilities. Additionally, microscale techniques permit rapid, high-throughput, multiparametric screening that has become essential for -omics research. This review highlights innovative applications of microscale platforms in genetic, proteomic, and metabolic detection in single cells; cell sorting strategies; and heterotypic cell-cell interaction. We discuss key design aspects of single-cell localization and isolation in microfluidic systems, dynamic and endpoint analyses, and approaches that integrate highly multiplexed detection of various intracellular species.
Predicting the structure of screw dislocations in nanoporous materials
NASA Astrophysics Data System (ADS)
Walker, Andrew M.; Slater, Ben; Gale, Julian D.; Wright, Kate
2004-10-01
Extended microscale crystal defects, including dislocations and stacking faults, can radically alter the properties of technologically important materials. Determining the atomic structure and the influence of defects on properties remains a major experimental and computational challenge. Using a newly developed simulation technique, the structure of the 1/2a <100> screw dislocation in nanoporous zeolite A has been modelled. The predicted channel structure has a spiral form that resembles a nanoscale corkscrew. Our findings suggest that the dislocation will enhance the transport of molecules from the surface to the interior of the crystal while retarding transport parallel to the surface. Crucially, the dislocation creates an activated, locally chiral environment that may have enantioselective applications. These predictions highlight the influence that microscale defects have on the properties of structurally complex materials, in addition to their pivotal role in crystal growth.
Torri, Cristian; Samorì, Chiara; Adamiano, Alessio; Fabbri, Daniele; Faraloni, Cecilia; Torzillo, Giuseppe
2011-09-01
The aim of this work was to investigate the potential conversion of Chlamydomonas reinhardtii biomass harvested after hydrogen production. The spent algal biomass was converted into nitrogen-rich bio-char, biodiesel and pyrolysis oil (bio-oil). The yield of lipids (algal oil), obtained by solvent extraction, was 15 ± 2% w/w(dry-biomass). This oil was converted into biodiesel with a 8.7 ± 1% w/w(dry-biomass) yield. The extraction residue was pyrolysed in a fixed bed reactor at 350 °C obtaining bio-char as the principal fraction (44 ± 1% w/w(dry-biomass)) and 28 ± 2% w/w(dry-biomass) of bio-oil. Pyrolysis fractions were characterized by elemental analysis, while the chemical composition of bio-oil was fully characterized by GC-MS, using various derivatization techniques. Energy outputs resulting from this approach were distributed in hydrogen (40%), biodiesel (12%) and pyrolysis fractions (48%), whereas bio-char was the largest fraction in terms of mass. Copyright © 2011 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
DuMont, Jaime Willadean
In this thesis, in situ Fourier transform infrared (FTIR) spectroscopy was used to study: i) the growth and pyrolysis of molecular layer deposition (MLD) films. ii) the surface chemistry of atomic layer etching (ALE) processes. Atomic layer processes such as molecular layer deposition (MLD) and atomic layer etching (ALE) are techniques that can add or remove material with atomic level precision using sequential, self-limiting surface reactions. Deposition and removal processes at the atomic scale are powerful tools for many industrial and research applications such as energy storage and semiconductor nanofabrication. The first section of this thesis describes the chemistry of reactions leading to the MLD of aluminum and tin alkoxide polymer films known as "alucone" and "tincone", respectively. The subsequent pyrolysis of these films to produce metal oxide/carbon composites was also investigated. In situ FTIR spectroscopy was conducted to monitor surface species during MLD film growth and to monitor the films background infrared absorbance versus pyrolysis temperature. Ex situ techniques such as transmission electron microscopy (TEM), four-point probe and X-ray diffraction (XRD) were utilized to study the properties of the films post-pyrolysis. TEM confirmed that the pyrolyzed films maintained conformality during post-processing. Four-point probe monitored film resistivity versus pyrolysis temperature and XRD determined the film crystallinity. The second section of this thesis focuses on the surface chemistry of Al2O3 and SiO2 ALE processes, respectively. Thermal ALE processes have been recently developed which utilize sequential fluorination and ligand exchange reactions. An intimate knowledge of the surface chemistry is important in understanding the ALE process. In this section, the competition between the Al2O3 etching and AlF 3 growth that occur during sequential HF (fluorinating agent) and TMA (ligand exchange) exposures is investigated using in situ FTIR spectroscopy. Also included in this section is the first demonstration of thermal ALE for SiO2. In situ FTIR spectroscopy was conducted to monitor the loss of bulk Si-O vibrational modes corresponding to the removal of SiO2. FTIR was also used to monitor surface species during each ALE half cycle and to verify self-limiting behavior. X-ray reflectivity experiments were conducted to establish etch rates on thermal oxide silicon wafers.
NASA Technical Reports Server (NTRS)
Socki, Richard A.; Fu, Qi; Niles, Paul B.
2011-01-01
We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).
A Comprehensive Study on Pyrolysis Mechanism of Substituted β-O-4 Type Lignin Dimers.
Jiang, Xiaoyan; Lu, Qiang; Hu, Bin; Liu, Ji; Dong, Changqing; Yang, Yongping
2017-11-09
In order to understand the pyrolysis mechanism of β- O -4 type lignin dimers, a pyrolysis model is proposed which considers the effects of functional groups (hydroxyl, hydroxymethyl and methoxyl) on the alkyl side chain and aromatic ring. Furthermore, five specific β- O -4 type lignin dimer model compounds are selected to investigate their integrated pyrolysis mechanism by density functional theory (DFT) methods, to further understand and verify the proposed pyrolysis model. The results indicate that a total of 11 pyrolysis mechanisms, including both concerted mechanisms and homolytic mechanisms, might occur for the initial pyrolysis of the β- O -4 type lignin dimers. Concerted mechanisms are predominant as compared with homolytic mechanisms throughout unimolecular decomposition pathways. The competitiveness of the eleven pyrolysis mechanisms are revealed via different model compounds, and the proposed pyrolysis model is ranked in full consideration of functional groups effects. The proposed pyrolysis model can provide a theoretical basis to predict the reaction pathways and products during the pyrolysis process of β- O -4 type lignin dimers.
A Comprehensive Study on Pyrolysis Mechanism of Substituted β-O-4 Type Lignin Dimers
Jiang, Xiaoyan; Lu, Qiang; Hu, Bin; Liu, Ji; Dong, Changqing; Yang, Yongping
2017-01-01
In order to understand the pyrolysis mechanism of β-O-4 type lignin dimers, a pyrolysis model is proposed which considers the effects of functional groups (hydroxyl, hydroxymethyl and methoxyl) on the alkyl side chain and aromatic ring. Furthermore, five specific β-O-4 type lignin dimer model compounds are selected to investigate their integrated pyrolysis mechanism by density functional theory (DFT) methods, to further understand and verify the proposed pyrolysis model. The results indicate that a total of 11 pyrolysis mechanisms, including both concerted mechanisms and homolytic mechanisms, might occur for the initial pyrolysis of the β-O-4 type lignin dimers. Concerted mechanisms are predominant as compared with homolytic mechanisms throughout unimolecular decomposition pathways. The competitiveness of the eleven pyrolysis mechanisms are revealed via different model compounds, and the proposed pyrolysis model is ranked in full consideration of functional groups effects. The proposed pyrolysis model can provide a theoretical basis to predict the reaction pathways and products during the pyrolysis process of β-O-4 type lignin dimers. PMID:29120350
NASA Astrophysics Data System (ADS)
Hameed, M. Shahul; Princice, J. Joseph; Babu, N. Ramesh; Zahirullah, S. Syed; Deshmukh, Sampat G.; Arunachalam, A.
2018-05-01
Transparent conductive Sn doped ZnO nanorods have been deposited at various doping level by spray pyrolysis technique on glass substrate. The structural, surface morphological and optical properties of these films have been investigated with the help of X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM) and UV-Vis spectrophotometer respectively. XRD patterns revealed a successful high quality growth of single crystal ZnO nanorods with hexagonal wurtzite structure having (002) preferred orientation. The scanning electron microscope (SEM) image of the prepared films exposed the uniform distribution of Sn doped ZnO nanorod shaped grains. All these films were highly transparent in the visible region with average transmittance of 90%.
Studies on annealed ZnO:V thin films deposited by nebulised spray pyrolysis method
NASA Astrophysics Data System (ADS)
Malini, D. Rachel
2018-04-01
Structural, optical and photoluminescence properties of annealed ZnO:V thin films deposited by nebulized spray pyrolysis technique by varying vanadium concentration are studied. Thickness of thin films varies from 1.52µm to 7.78µm. V2O5, VO2 and ZnO peaks are observed in XRD patterns deposited with high vanadium concentration and the intensity of peaks corresponding to ZnO decreases in those samples. Morphological properties were studied by analysing SEM images and annealed thin films deposited at ZnO:V = 50:50 possess dumb bell shape grains. Emission peaks corresponding to both Augur transition and deep level transition are observed in the PL spectra of the samples.
NASA Astrophysics Data System (ADS)
El Radaf, I. M.; Nasr, Mahmoud; Mansour, A. M.
2018-01-01
Au/p-CoS/n-Si/Al heterojunction device was fabricated by spray pyrolysis technique. The structural and morphological features were examined by x-ray diffraction, scanning electron microscope and energy dispersive x-ray analysis. The capacitance-voltage characteristics of the prepared heterojunction were analyzed at room temperature in the dark. The current-voltage characteristics were examined under dark and different incident light intensities 20-100 mW cm-2. The rectification ratio, series resistance, shunt resistance, diode ideality factor and the effective barrier height were determined at dark and illumination conditions. The photovoltaic parameters such as short circuit current density, open circuit voltage, fill factor and power conversion efficiency were calculated at different incident light intensities.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kumar, Vipin, E-mail: vipinkumar28@yahoo.co.in; Sharma, D. K.; Agrawal, Sonalika
Cd{sub 1-X}Zn{sub X}S thin films (X = 0.2, 0.4, 0.6, 0.8) have been grown on glass substrate by spray pyrolysis technique using equimolar concentration aqueous solution of cadmium chloride, zinc acetate and thiourea. Prepared thin films have been characterized by UV-VIS spectrophotometer. The optical band gap of the films has been studied by transmission spectra in wavelength range 325-600nm. It has been observed that optical band gap increases with increasing zinc concentration. The optical band gap of these thin films varies from 2.59 to 3.20eV with increasing Zn content.
Cyclopentadiene evolution during pyrolysis-gas chromatography of PMR polyimides
NASA Technical Reports Server (NTRS)
Alston, William B.; Gluyas, Richard E.; Snyder, William J.
1992-01-01
The effect of formulated molecular weight (FMW), extent of cure, and cumulative aging on the amount of cyclopentadiene (CPD) evolved from Polymerization of Monomeric Reactants (PMR) polyimides were investigated by pyrolysis-gas chromotography (PY-GC). The PMR polyimides are additional crosslinked resins formed from an aromatic diamine, a diester of an aromatic tetracarboxylic acid and a monoester of 5-norbornene-2, 3-dicarboxylic acid. The PY-GC results were related to the degree of crosslinking and to the thermo-oxidative stability (weight loss) of PMR polyimides. Thus, PY-GC has shown to be a valid technique for the characterization of PMR polyimide resins and composites via correlation of the CPD evolved versus the thermal history of the PMR sample.
NASA Astrophysics Data System (ADS)
Rahaman, Sabina; Sunil, M. Anantha; Shaik, Habibuddin; Ghosh, Kaustab
2018-05-01
Deposition of Cu2SnS3 (CTS) thin films is successfully carried out on soda lime glass substrate using low cost ultrasonic spray pyrolysis technique. Vacuum annealing of CTS films is carried out at different temperatures 350°C, 400°C and 450°C. The present work is to study the effect of annealing temperature on the crystal structure, surface morphology and optical properties of CTS thin films. Structural studies confirm the formation of CTS phase. Raman analysis is carried out to study presence of defects with annealing temperature. Optical studies confirm that film prepared at 450°C temperature is suitable as absorber material for photovoltaic applications.
Sample extraction and injection with a microscale preconcentrator.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Robinson, Alex Lockwood; Chan, Helena Kai Lun
2007-09-01
This report details the development of a microfabricated preconcentrator that functions as a fully integrated chemical extractor-injector for a microscale gas chromatograph (GC). The device enables parts-per-billion detection and quantitative analysis of volatile organic compounds (VOCs) in indoor air with size and power advantages over macro-scale systems. The 44 mm{sup 3} preconcentrator extracts VOCs using highly adsorptive, granular forms of graphitized carbon black and carbon molecular sieves. The micron-sized silicon cavities have integrated heating and temperature sensing allowing low power, yet rapid heating to thermally desorb the collected VOCs (GC injection). The keys to device construction are a new adsorbent-solventmore » filling technique and solvent-tolerant wafer-level silicon-gold eutectic bonding technology. The product is the first granular adsorbent preconcentrator integrated at the wafer level. Other advantages include exhaustive VOC extraction and injection peak widths an order of magnitude narrower than predecessor prototypes. A mass transfer model, the first for any microscale preconcentrator, is developed to describe both adsorption and desorption behaviors. The physically intuitive model uses implicit and explicit finite differences to numerically solve the required partial differential equations. The model is applied to the adsorption and desorption of decane at various concentrations to extract Langmuir adsorption isotherm parameters from effluent curve measurements where properties are unknown a priori.« less
Ghanbari, J; Naghdabadi, R
2009-07-22
We have used a hierarchical multiscale modeling scheme for the analysis of cortical bone considering it as a nanocomposite. This scheme consists of definition of two boundary value problems, one for macroscale, and another for microscale. The coupling between these scales is done by using the homogenization technique. At every material point in which the constitutive model is needed, a microscale boundary value problem is defined using a macroscopic kinematical quantity and solved. Using the described scheme, we have studied elastic properties of cortical bone considering its nanoscale microstructural constituents with various mineral volume fractions. Since the microstructure of bone consists of mineral platelet with nanometer size embedded in a protein matrix, it is similar to the microstructure of soft matrix nanocomposites reinforced with hard nanostructures. Considering a representative volume element (RVE) of the microstructure of bone as the microscale problem in our hierarchical multiscale modeling scheme, the global behavior of bone is obtained under various macroscopic loading conditions. This scheme may be suitable for modeling arbitrary bone geometries subjected to a variety of loading conditions. Using the presented method, mechanical properties of cortical bone including elastic moduli and Poisson's ratios in two major directions and shear modulus is obtained for different mineral volume fractions.
Nanoscale and Microscale Iron Emulsions for Treating DNAPL
NASA Technical Reports Server (NTRS)
Geiger, Cherie L.
2002-01-01
This study demonstrated the feasibility of using emulsified nanoscale and microscale iron particles to enhance dehalogenation of (Dense Non-Aqueous Phase Liquid) DNAPL free-phase. The emulsified system consisted of a surfactant-stabilized, biodegradable oil-in-water emulsion with nanoscale or microscale iron particles contained within the emulsion droplets. It was demonstrated that DNAPLs, such as trichloroethene (TCE), diffuse through the oil membrane of the emulsion particle whereupon they reach an aqueous interior and the surface of an iron particle where dehalogenation takes place. The hydrocarbon reaction by-products of the dehalogenation reaction, primarily ethene (no chlorinated products detected), diffuse out of the emulsion droplet. This study also demonstrated that an iron-emulsion system could be delivered in-situ to the DNAPL pool in a soil matrix by using a simulated push well technique. Iron emulsions degraded pure TCE at a rate comparable to the degradation of dissolved phase TCE by iron particles, while pure iron had a very low degradation rate for free-phase TCE. The iron-emulsion systems can be injected into a sand matrix where they become immobilized and are not moved by flowing water. It has been documented that surfactant micelles possess the ability to pull pooled TCE into emulsion droplets where degradation of TCE takes place.
Cavitation in flow through a micro-orifice inside a silicon microchannel
NASA Astrophysics Data System (ADS)
Mishra, Chandan; Peles, Yoav
2005-01-01
Hydrodynamic cavitation in flows through a micro-orifice entrenched in a microchannel has been detected and experimentally investigated. Microfabrication techniques have been employed to design and develop a microfluidic device containing an 11.5μm wide micro-orifice inside a 100.2μm wide and 101.3μm deep microchannel. The flow of de-ionized water through the micro-orifice reveals the presence of multifarious cavitating flow regimes. This investigation divulges both similarities and differences between cavitation in micro-orifices and cavitation in their macroscale counterparts. The low incipient cavitation number obtained from the current experiments suggests a dominant size scale effect. Choking cavitation is observed to be independent of any pressure or velocity scale effects. However, choking is significantly influenced by the small stream nuclei residence time at such scales. Flow rate choking leads to the establishment of a stationary cavity. Large flow and cavitation hysteresis have been detected at the microscale leading to very high desinent cavitation numbers. The rapid transition from incipient bubbles to choking cavitation and subsequent supercavitation suggests the presence of radically different flow patterns at the microscale. Supercavitation results in a thick cavity, which extends throughout the microchannel, and is encompassed by the liquid. Cavitation at the microscale is expected to considerably influence the design of innovative high-speed microfluidic systems.
Fundamentals of microfluidic cell culture in controlled microenvironments†
Young, Edmond W. K.; Beebe, David J.
2010-01-01
Microfluidics has the potential to revolutionize the way we approach cell biology research. The dimensions of microfluidic channels are well suited to the physical scale of biological cells, and the many advantages of microfluidics make it an attractive platform for new techniques in biology. One of the key benefits of microfluidics for basic biology is the ability to control parameters of the cell microenvironment at relevant length and time scales. Considerable progress has been made in the design and use of novel microfluidic devices for culturing cells and for subsequent treatment and analysis. With the recent pace of scientific discovery, it is becoming increasingly important to evaluate existing tools and techniques, and to synthesize fundamental concepts that would further improve the efficiency of biological research at the microscale. This tutorial review integrates fundamental principles from cell biology and local microenvironments with cell culture techniques and concepts in microfluidics. Culturing cells in microscale environments requires knowledge of multiple disciplines including physics, biochemistry, and engineering. We discuss basic concepts related to the physical and biochemical microenvironments of the cell, physicochemical properties of that microenvironment, cell culture techniques, and practical knowledge of microfluidic device design and operation. We also discuss the most recent advances in microfluidic cell culture and their implications on the future of the field. The goal is to guide new and interested researchers to the important areas and challenges facing the scientific community as we strive toward full integration of microfluidics with biology. PMID:20179823
Low-temperature co-pyrolysis behaviours and kinetics of oily sludge: effect of agricultural biomass.
Zhou, Xiehong; Jia, Hanzhong; Qu, Chengtun; Fan, Daidi; Wang, Chuanyi
2017-02-01
Pyrolysis is potentially an effective treatment of oily sludge for oil recovery, and its kinetics and efficiency are expected to be affected by additives. In the present study, the pyrolysis parameters, including heating rate, final pyrolysis temperature, and pyrolysis time of oily sludge in the presence of agricultural biomass, apricot shell, were systematically explored. As a result, maximum oil recovery is achieved when optimizing the pyrolysis conditionas15 K/min, 723 K, and 3 h for heating rate, final pyrolysis temperature, and pyrolysis time, respectively. Thermogravimetric experiments of oily sludge samples in the presence of various biomasses conducted with non-isothermal temperature programmes suggest that the pyrolysis process contains three stages, and the main decomposition reaction occurs in the range of 400-740 K. Taking Flynn-Wall-Ozawa analysis of the derivative thermogravimetry and thermogravimetry results, the activation energy (E a ) values for the pyrolysis of oily sludge in the presence and absence of apricot shell were derived to be 35.21 and 39.40 kJ mol -1 , respectively. The present work supports that the presence of biomass promotes the pyrolysis of oily sludge, implying its great potential as addictive in the industrial pyrolysis of oily sludge.
Derivation of hydrous pyrolysis kinetic parameters from open-system pyrolysis
NASA Astrophysics Data System (ADS)
Tseng, Yu-Hsin; Huang, Wuu-Liang
2010-05-01
Kinetic information is essential to predict the temperature, timing or depth of hydrocarbon generation within a hydrocarbon system. The most common experiments for deriving kinetic parameters are mainly by open-system pyrolysis. However, it has been shown that the conditions of open-system pyrolysis are deviant from nature by its low near-ambient pressure and high temperatures. Also, the extrapolation of heating rates in open-system pyrolysis to geological conditions may be questionable. Recent study of Lewan and Ruble shows hydrous-pyrolysis conditions can simulate the natural conditions better and its applications are supported by two case studies with natural thermal-burial histories. Nevertheless, performing hydrous pyrolysis experiment is really tedious and requires large amount of sample, while open-system pyrolysis is rather convenient and efficient. Therefore, the present study aims at the derivation of convincing distributed hydrous pyrolysis Ea with only routine open-system Rock-Eval data. Our results unveil that there is a good correlation between open-system Rock-Eval parameter Tmax and the activation energy (Ea) derived from hydrous pyrolysis. The hydrous pyrolysis single Ea can be predicted from Tmax based on the correlation, while the frequency factor (A0) is estimated based on the linear relationship between single Ea and log A0. Because the Ea distribution is more rational than single Ea, we modify the predicted single hydrous pyrolysis Ea into distributed Ea by shifting the pattern of Ea distribution from open-system pyrolysis until the weight mean Ea distribution equals to the single hydrous pyrolysis Ea. Moreover, it has been shown that the shape of the Ea distribution is very much alike the shape of Tmax curve. Thus, in case of the absence of open-system Ea distribution, we may use the shape of Tmax curve to get the distributed hydrous pyrolysis Ea. The study offers a new approach as a simple method for obtaining distributed hydrous pyrolysis Ea with only routine open-system Rock-Eval data, which will allow for better estimating hydrocarbon generation.
129Xe NMR studies of biochar made from biobased materials
USDA-ARS?s Scientific Manuscript database
Biochar is created by pyrolysis of biobased materials under controlled oxidative environments. The product is charcoal-like and can be used as filtration medium, sequestrant for metallic ions, soil conditioner, and other applications. In our work we have found 129Xe NMR to be an excellent technique...
Comparison of biochar formation from various agricultural by-products using FTIR spectroscopy
USDA-ARS?s Scientific Manuscript database
Biochar is charred material produced by the pyrolysis of organic biomass. In this work, Fourier transform infrared (FTIR) spectra of different agricultural by-products feedstock and their derived biochars were collected to explore the potential of FTIR technique as a simple and rapid method for char...
Additive Manufacturing of Metal Structures at the Micrometer Scale.
Hirt, Luca; Reiser, Alain; Spolenak, Ralph; Zambelli, Tomaso
2017-05-01
Currently, the focus of additive manufacturing (AM) is shifting from simple prototyping to actual production. One driving factor of this process is the ability of AM to build geometries that are not accessible by subtractive fabrication techniques. While these techniques often call for a geometry that is easiest to manufacture, AM enables the geometry required for best performance to be built by freeing the design process from restrictions imposed by traditional machining. At the micrometer scale, the design limitations of standard fabrication techniques are even more severe. Microscale AM thus holds great potential, as confirmed by the rapid success of commercial micro-stereolithography tools as an enabling technology for a broad range of scientific applications. For metals, however, there is still no established AM solution at small scales. To tackle the limited resolution of standard metal AM methods (a few tens of micrometers at best), various new techniques aimed at the micrometer scale and below are presently under development. Here, we review these recent efforts. Specifically, we feature the techniques of direct ink writing, electrohydrodynamic printing, laser-assisted electrophoretic deposition, laser-induced forward transfer, local electroplating methods, laser-induced photoreduction and focused electron or ion beam induced deposition. Although these methods have proven to facilitate the AM of metals with feature sizes in the range of 0.1-10 µm, they are still in a prototype stage and their potential is not fully explored yet. For instance, comprehensive studies of material availability and material properties are often lacking, yet compulsory for actual applications. We address these items while critically discussing and comparing the potential of current microscale metal AM techniques. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Baird, Lance Awender; Brandvold, Timothy A.
Processes and apparatuses for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil are provided herein. An exemplary process for washing a spent ion exchange bed employed in purification of biomass-derived pyrolysis oil includes the step of providing a ion-depleted pyrolysis oil stream having an original oxygen content. The ion-depleted pyrolysis oil stream is partially hydrotreated to reduce the oxygen content thereof, thereby producing a partially hydrotreated pyrolysis oil stream having a residual oxygen content that is less than the original oxygen content. At least a portion of the partially hydrotreated pyrolysis oil stream is passed throughmore » the spent ion exchange bed. Water is passed through the spent ion exchange bed after passing at least the portion of the partially hydrotreated pyrolysis oil stream therethrough.« less
Quality improvement of pyrolysis oil from waste rubber by adding sawdust.
Wang, Wen-liang; Chang, Jian-min; Cai, Li-ping; Shi, Sheldon Q
2014-12-01
This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG-FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis-gas chromatography (GC)-mass spectrometry (Py-GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil. Copyright © 2014 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.; Jordán, Antonio; Zavala, Lorena M.; de la Rosa, José M.; González-Pérez, José A.
2015-04-01
This research deals with the assessment of organic matter structural differences in soil physical fractions before and after lipid extractions. Soil samples were collected in sandy soils, Arenosols (WRB 2006) from the Doñana National Park (SW Spain) under different vegetation cover: cork oak (Quercus suber, QS), eagle fern (Pteridium aquilinum, PA), pine (Pinus pinea, PP) and rockrose (Halimium halimifolium, HH). Two size fractions; coarse (C: 1-2 mm) and fine (F: 0.05-0.25 mm) were studied from each soil. . In addition, the two fractions from each soil were exhaustively Soxhlet extracted with a Dichlorometane-Methanol (3:1) mixture to obtain the lipid-free fractions (LF) from each size fraction (LFC and LFF). The composition of the organic matter at a molecular level in the different soil fractions was approached by analytical pyrolysis (Py-GC/MS) and FT-IR spectroscopy. These techniques are complementary and have been found suitable for the structural characterization of complex organic matrices (Moldoveanu, 1998; Piccolo and Stevenson, 1982); whereas Py-GC/MS provides detailed structural information of individual compounds present and a finger-printing of soil organic matter, FT-IR is informative about major functional groups present. The advantages of these techniques are well known: no need for pretreatment are fast to perform, highly reproducible and only small amount of samples are needed. Soil size fractions show contrasting differences in organic matter content (C 4-7 % and F > 40 %) and conspicuous differences were found in the pyrolysis products released by the fractions studied. The main families of pyrolysis compounds have well defined macromolecular precursors, such as lignin, polypeptides, polysaccharides and lipids (González-Vila et al., 2001). The C fractions yield higher relative abundance of lignin and polysaccharide derived pyrolysis compounds. Regarding the differences in the soil organic matter as affected by the different vegetation covers, the C fraction from the PA soil presented a higher abundance of lignin derived pyrolysis products than the soils under the other vegetation. This is somehow unexpected since PA is a pteridophyte, not arboreal vegetation, i.e. low lignin content and, these lignin moieties probably remain in the soil from past vegetation or originate from surrounding woody arboreal vegetation. In contrast the F fractions released mainly lipids and aromatic compound of unspecific origin. Series of alkane/alkene pairs were present in all the pyrograms with varying abundance and composition. Lignin and polysaccharide derived pyrolysis compounds were scarce in the F fractions in all the cases, in fact, no sugar derived compounds were found in the HH sample. Regarding the composition of the LF soil fractions, the pyrolytic behavior of the LFC fractions was quite similar to the not extracted corresponding C soil fraction, showing a high proportion of lignin and sugar derived pyrolysis compounds. The LFF fractions also showed the same behavior as the C fraction, but with no lipid derived compounds which effectively indicates the occurrence of a selective and efficient removal of soil free lipids. Agreement was found between analytical pyrolysis results and FT-IR spectral features highlighting functional differences between fractions i.e. a decrease of OH- groups and an increase in aliphatics in the F fraction. With respect to the LF fractions, FT-IR spectra analysis was also consistent with the pyrolysis results with a slight increase in the lignin signals for LFF soil fractions under PA, PP and HH. For the soil under QS no differences were found between the LFF fractions and the whole organic matter in the F fraction, probably due to the high amount of organic matter in this fraction. In conclusion, despite the "a priori" low organic complexity of the collection of soils studied here, ostensible differences were found in the organic matter present in C and F soil size fractions under different vegetation covers, and not only in its intimate chemical composition, but also in its functionality. Whereas the C soil size fractions are composed mainly by relatively well recognized lignocellulosic plant residues, the F soil size fractions have a clearly distinct type of organic matter, more mature/evolved that clearly resembles the characteristics of customary wet extracted humic materials as characterized elsewhere (Stevenson, 1994; González-Pérez et al., 2013). REFERENCES: González-Pérez JA, González-Vila FJ, Almendros G, Knicker H, De la Rosa JM, Hernández Z. 2013. Revisiting Structural insights provided by analytical pyrolysis about humic substances and related bio- and geopolymers. Functions of Natural Organic Matter in Changing Environment, 3-6. DOI: 10.1007/978-94-007-5634-21 González-Vila FJ, Tinoco P, Almendros G, Martin F. 2001. Pyrolysis-GCMS analysis of the formation and degradation stages of charred residues from lignocellulosic biomass. Journal of Agricultural and Food Chemistry 49: 1128-1131. DOI: 10.1021/jf0006325. Moldoveanu SC. 1998. Analytical pyrolysis of natural organic polymers. Techniques and Instrumentation in Analytical Chemistry 20: 3-496. ISBN: 978-0-444-82203-1 Piccolo A, Stevenson FJ. 1982. Infrared-spectra of Cu2+, Pb2+, and Ca2+ complexes of soil humic substances. Geoderma 27: 195-208. DOI: 10.1016/0016-7061(82)90030-1 Stevenson, FJ. 1994. Humus chemistry. Genesis, composition, reactions (2nd edn.), John Wiley & Sons, Inc.: New York, NY, 166-187. DOI: 10.1021/ed072pA93.6. WRB 2006. World Reference Base for Soil Resources. Rome 2006 ACKNOWLEDGMENTS: This study is part of the results of the GEOFIRE Project (CGL2012-38655-C04-01) (BES-2013-062573), funded by the Spanish Ministry for Economy and Competitiveness. Dr. J.M. de la Rosa is the recipient of a fellowship from the JAE-Doc subprogram financed by the CSIC and the European Social Fund.
Methane Pyrolysis and Disposing Off Resulting Carbon
NASA Technical Reports Server (NTRS)
Sharma, P. K.; Rapp, D.; Rahotgi, N. K.
1999-01-01
Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is a waste of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduce the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (i) recover hydrogen from the excess methane produced by the S/E process, (ii) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (iii) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. The goals of a research program on recovery of hydrogen from methane are (in descending priority order): 1) Study the kinetics of pyrolysis to arrive at a pyrolysis reactor design that produces high yields in a confined volume at the lowest possible operating temperature; 2) Study the kinetics of carbon burnoff to determine whether high yields can be obtained in a confined volume at acceptable operating temperatures; and 3) Investigate catalytic techniques for depositing carbon as a fine soot which can be physically separated from the reactor. In the JPL program, we have made significant measurements in regard to goal 1, cursory measurements in regard to goal 2, and would plan to pursue goal 3 if additional resources are secured.
DIRECT LIQUEFACTION PROOF OF CONCEPT
DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
The eighth bench scale test of POC program, Run PB-08, was successfully completed from August 8 to August 26, 1997. A total of five operating conditions were tested aiming at evaluating the reactivity of different pyrolysis oils in liquefaction of a Wyoming sub-bituminous coal (Black Thunder coal). For the first time, water soluble promoters were incorporated into the iron-based GelCat to improve the dispersion of the promoter metals in the feed blend. The concentration of the active metals, Mo and Fe, was 100 and 1000 ppm of moisture-free coal, respectively. Black Thunder coal used in this run was the samemore » batch as tested in HTI�s Run POC-02. Similar to Runs PB-01 through 7, this run employed two back mixed slurry reactors, an interstage gas/slurry separator and a direct-coupled hydrotreater. In addition to the hot vapor from the second stage separator, the first stage separator overhead liquid was also fed to the hydrotreater, which was packed with Criterion C-411 hydrotreating catalyst. Pyrolysis oil was produced off-line from a pyrolysis unit acquired from University of Wyoming. Solids rejection was achieved by purging out pressure filter solid. The recycle solvents consisted of O-6 separator bottoms and pressure filter liquid (PFL). The Run PB-08 proceeded very smoothly without any interruptions. Coal conversion consistently above 90W% was achieved. High resid conversion and distillate yield have been obtained from co-processing of coal and 343°C+ (650°F+) pyrolysis oil. Light gas (C 1-C 3 ) yield was minimized and hydrogen consumption was reduced due to the introduction of pyrolysis oil, compared with conventional coal-derived solvent. Catalytic activity was improved by incorporating a promoter metal into the iron-based GelCat. It seemed that lowering the first stage temperature to 435°C might increase the hydrogenation function of the promoter metal. In comparison with previous coal-waste coprocessing run (PB-06), significant improvements in the process performance were achieved due to catalyst modification and integration of pyrolysis technique into liquefaction.« less
Comparison of artificial maturation of lignite in hydrous and nonhydrous conditions
Behar, F.; Lewan, M.D.; Lorant, F.; Vandenbroucke, M.
2003-01-01
The objectives of the study are to compare product compositions and yields generated from lignite artificially matured by open nonhydrous pyrolysis, closed nonhydrous pyrolysis, and hydrous pyrolysis. The pyrolysis products were fractionated into CO2, H2O, CH4, C2-C5, C8-C14, C14+ saturates, C14+ aromatics and NSOs (resins+asphaltenes). All three methods generated high and similar quantities of water during pyrolysis that ranged between 14.6 and 15.2 wt.% of the original lignite. As a result of this high water content generated by the lignite, the experiments with no added water are referred to as nonhydrous rather than anhydrous. Rock-Eval pyrolysis and elemental analyses were conducted on the recovered lignite after solvent extraction to determine their residual hydrocarbon generation potential and to plot their position in a van Krevelen diagram, respectively. Residual lignite from the closed nonhydrous and hydrous experiments showed relationships between vitrinite reflectance (%Ro) values and atomic H/C ratios that occurred within the fields observed for natural maturation of coal. Although no significant differences in the atomic H/C ratios were observed between closed nonhydrous and hydrous pyrolysis, the vitrinite reflectance values were on the average 0.2% Ro lower in the residual lignite from the nonhydrous experiments. The remaining hydrocarbon generation potential as determined by Rock-Eval pyrolysis of the residual lignite showed that the nonhydrous residuals had on the average 16 mg more hydrocarbon potential per gram of original lignite than the hydrous residuals. This suggests there is a better release of the pyrolysis products from the lignite network in the hydrous experiments once generation occurs. For gas generation, at maximum yields, open nonhydrous pyrolysis generates the most hydrocarbon gas (21.0 mg/g original lignite), which is 20% more than closed nonhydrous pyrolysis and 29% more than hydrous pyrolysis. Closed nonhydrous pyrolysis generates on the average 14% more gas than hydrous pyrolysis, but the proportionality of the generated hydrocarbon gases is essentially the same for both pyrolysis methods. At maximum yields, CO2 generation is greatest in hydrous pyrolysis (99.5 mg/g original lignite), with yields being 37 percent higher than closed nonhydrous pyrolysis and 26% higher than open nonhydrous pyrolysis. The maximum yields of C14+ products are highest and similar for open nonhydrous pyrolysis and hydrous pyrolysis (125.6 and 125.9 mg/g lignite, respectively), and are more than 70% higher than closed nonhydrous pyrolysis. This difference in the maximum yields of C14+ products can be explained by differences in the proportionality between either cracking reactions that result in liquid product and char formation or trapping of generated products within the coal network (cross-linking reactions). Maximum yields of C14+ aliphatics from hydrous experiments may not have been attained, but the maximums that were observed and their GC traces are similar for the three pyrolysis systems.
Gauvin, Robert; Khademhosseini, Ali
2011-01-01
Micro- and nanoscale technologies have emerged as powerful tools in the fabrication of engineered tissues and organs. Here we focus on the application of these techniques to improve engineered tissue architecture and function using modular and directed self-assembly and highlight the emergence of this new class of materials for biomedical applications. PMID:21627163
Build your own soil: exploring microfluidics to create microbial habitat structures
Aleklett, Kristin; Kiers, E Toby; Ohlsson, Pelle; Shimizu, Thomas S; Caldas, Victor EA; Hammer, Edith C
2018-01-01
Soil is likely the most complex ecosystem on earth. Despite the global importance and extraordinary diversity of soils, they have been notoriously challenging to study. We show how pioneering microfluidic techniques provide new ways of studying soil microbial ecology by allowing simulation and manipulation of chemical conditions and physical structures at the microscale in soil model habitats. PMID:29135971
Kim, Gun; Loreto, Giovanni; Kim, Jin-Yeon; Kurtis, Kimberly E; Wall, James J; Jacobs, Laurence J
2018-08-01
This research conducts in situ nonlinear ultrasonic (NLU) measurements for real time monitoring of load-induced damage in concrete. For the in situ measurements on a cylindrical specimen under sustained load, a previously developed second harmonic generation (SHG) technique with non-contact detection is adapted to a cylindrical specimen geometry. This new setup is validated by demonstrating that the measured nonlinear Rayleigh wave signals are equivalent to those in a flat half space, and thus the acoustic nonlinearity parameter, β can be defined and interpreted in the same way. Both the acoustic nonlinearity parameter and strain are measured to quantitatively assess the early-age damage in a set of concrete specimens subjected to either 25 days of creep, or 11 cycles of cyclic loading at room temperature. The experimental results show that the acoustic nonlinearity parameter is sensitive to early-stage microcrack formation under both loading conditions - the measured β can be directly linked to the accumulated microscale damage. This paper demonstrates the potential of NLU for the in situ monitoring of mechanical load-induced microscale damage in concrete components. Copyright © 2018 Elsevier B.V. All rights reserved.
Art on the Nanoscale and Beyond.
Yetisen, Ali K; Coskun, Ahmet F; England, Grant; Cho, Sangyeon; Butt, Haider; Hurwitz, Jonty; Kolle, Mathias; Khademhosseini, Ali; Hart, A John; Folch, Albert; Yun, Seok Hyun
2016-03-02
Methods of forming and patterning materials at the nano- and microscales are finding increased use as a medium of artistic expression, and as a vehicle for communicating scientific advances to a broader audience. While sharing many attributes of other art forms, miniaturized art enables the direct engagement of sensory aspects such as sight and touch for materials and structures that are otherwise invisible to the eye. The historical uses of nano-/microscale materials and imaging techniques in arts and sciences are presented. The motivations to create artwork at small scales are discussed, and representations in scientific literature and exhibitions are explored. Examples are presented using semiconductors, microfluidics, and nanomaterials as the artistic media; these utilized techniques including micromachining, focused ion beam milling, two-photon polymerization, and bottom-up nanostructure growth. Finally, the technological factors that limit the implementation of artwork at miniature scales are identified, and potential future directions are discussed. As research marches toward even smaller length scales, innovative and engaging visualizations and artistic endeavors will have growing implications on education, communication, policy making, media activism, and public perception of science and technology. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Gleason, Frank H.; Crawford, John W.; Neuhauser, Sigrid; Henderson, Linda E.; Lilje, Osu
2012-01-01
Zoosporic true fungi have frequently been identified in samples from soil and freshwater ecosystems using baiting and molecular techniques. In fact some species can be components of the dominant groups of microorganisms in particular soil habitats. Yet these microorganisms have not yet been directly observed growing in soil ecosystems. Significant physical characteristics and features of the three-dimensional structures of soils which impact microorganisms at the microscale level are discussed. A thorough knowledge of soil structures is important for studying the distribution of assemblages of these fungi and understanding their ecological roles along spatial and temporal gradients. A number of specific adaptations and resource seeking strategies possibly give these fungi advantages over other groups of microorganisms in soil ecosystems. These include chemotactic zoospores, mechanisms for adhesion to substrates, rhizoids which can penetrate substrates in small spaces, structures which are resistant to environmental extremes, rapid growth rates and simple nutritional requirements. These adaptations are discussed in the context of the characteristics of soils ecosystems. Recent advances in instrumentation have led to the development of new and more precise methods for studying microorganisms in three-dimensional space. New molecular techniques have made identification of microbes possible in environmental samples. PMID:22308003
Reprint of: Pyrolysis technologies for municipal solid waste: A review
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Dezhen, E-mail: chendezhen@tongji.edu.cn; Yin, Lijie; Wang, Huan
2015-03-15
Highlights: • MSW pyrolysis reactors, products and environmental impacts are reviewed. • MSW pyrolysis still has to deal with flue gas emissions and products’ contamination. • Definition of standardized products is suggested to formalize MSW pyrolysis technology. • Syngas is recommended to be the target product for single MSW pyrolysis technology. - Abstract: Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis inmore » regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO{sub 2} and NH{sub 3}, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested.« less
Pyrolysis technologies for municipal solid waste: A review
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Dezhen, E-mail: chendezhen@tongji.edu.cn; Yin, Lijie; Wang, Huan
2014-12-15
Highlights: • MSW pyrolysis reactors, products and environmental impacts are reviewed. • MSW pyrolysis still has to deal with flue gas emissions and products’ contamination. • Definition of standardized products is suggested to formalize MSW pyrolysis technology. • Syngas is recommended to be the target product for single MSW pyrolysis technology. - Abstract: Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis inmore » regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO{sub 2} and NH{sub 3}, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested.« less
From micro-scale 3D simulations to macro-scale model of periodic porous media
NASA Astrophysics Data System (ADS)
Crevacore, Eleonora; Tosco, Tiziana; Marchisio, Daniele; Sethi, Rajandrea; Messina, Francesca
2015-04-01
In environmental engineering, the transport of colloidal suspensions in porous media is studied to understand the fate of potentially harmful nano-particles and to design new remediation technologies. In this perspective, averaging techniques applied to micro-scale numerical simulations are a powerful tool to extrapolate accurate macro-scale models. Choosing two simplified packing configurations of soil grains and starting from a single elementary cell (module), it is possible to take advantage of the periodicity of the structures to reduce the computation costs of full 3D simulations. Steady-state flow simulations for incompressible fluid in laminar regime are implemented. Transport simulations are based on the pore-scale advection-diffusion equation, that can be enriched introducing also the Stokes velocity (to consider the gravity effect) and the interception mechanism. Simulations are carried on a domain composed of several elementary modules, that serve as control volumes in a finite volume method for the macro-scale method. The periodicity of the medium involves the periodicity of the flow field and this will be of great importance during the up-scaling procedure, allowing relevant simplifications. Micro-scale numerical data are treated in order to compute the mean concentration (volume and area averages) and fluxes on each module. The simulation results are used to compare the micro-scale averaged equation to the integral form of the macroscopic one, making a distinction between those terms that could be computed exactly and those for which a closure in needed. Of particular interest it is the investigation of the origin of macro-scale terms such as the dispersion and tortuosity, trying to describe them with micro-scale known quantities. Traditionally, to study the colloidal transport many simplifications are introduced, such those concerning ultra-simplified geometry that usually account for a single collector. Gradual removal of such hypothesis leads to a detailed description of colloidal transport mechanisms. Starting from nearly realistic 3D geometries, the ultimate purpose of this work is that of develop an improved understanding of the fate of colloidal particles through, for example, an accurate description of the deposition efficiency, in order design efficient remediation techniques. G. Boccardo, D.L. Marchisio, R.Sethi, Journal of colloid and interface science, Vol 417C, pp 227-237, 2014 M. Icardi, G. Boccardo, D.L. Marchisio, T. Tosco, R.Sethi, Physical Review E - Statistical, Nonlinear, and Soft Matter Physics, 2014 S. Torkzaban, S.S. Tazehkand, S.L. Walker, S.A. Bradford, Water resources research, Vol 44, 2008 S.M. Hassanizadeh, Adv in Water Resources, Vol. 2, pp 131-144, 1979 S. Whitaker, AIChE Journal, Vol. 13 No. 3, pp 420-428, May 1967
Analytical Protocols for Analysis of Organic Molecules in Mars Analog Materials
NASA Technical Reports Server (NTRS)
Mahaffy, Paul R.; Brinkerhoff, W.; Buch, A.; Demick, J.; Glavin, D. P.
2004-01-01
A range of analytical techniques and protocols that might be applied b in situ investigations of martian fines, ices, and rock samples are evaluated by analysis of organic molecules m Mars analogues. These simulants 6om terrestrial (i.e. tephra from Hawaii) or extraterrestrial (meteoritic) samples are examined by pyrolysis gas chromatograph mass spectrometry (GCMS), organic extraction followed by chemical derivatization GCMS, and laser desorption mass spectrometry (LDMS). The combination of techniques imparts analysis breadth since each technique provides a unique analysis capability for Certain classes of organic molecules.
Modeling of Density-Dependent Flow based on the Thermodynamically Constrained Averaging Theory
NASA Astrophysics Data System (ADS)
Weigand, T. M.; Schultz, P. B.; Kelley, C. T.; Miller, C. T.; Gray, W. G.
2016-12-01
The thermodynamically constrained averaging theory (TCAT) has been used to formulate general classes of porous medium models, including new models for density-dependent flow. The TCAT approach provides advantages that include a firm connection between the microscale, or pore scale, and the macroscale; a thermodynamically consistent basis; explicit inclusion of factors such as a diffusion that arises from gradients associated with pressure and activity and the ability to describe both high and low concentration displacement. The TCAT model is presented and closure relations for the TCAT model are postulated based on microscale averages and a parameter estimation is performed on a subset of the experimental data. Due to the sharpness of the fronts, an adaptive moving mesh technique was used to ensure grid independent solutions within the run time constraints. The optimized parameters are then used for forward simulations and compared to the set of experimental data not used for the parameter estimation.
NASA Astrophysics Data System (ADS)
Hawkins, Cameron; Tschuaner, Oliver; Fussell, Zachary; Smith, Jesse
2017-06-01
A novel approach that spatially identifies inhomogeneities from microscale (defects, con-formational disorder) to mesoscale (voids, inclusions) is developed using synchrotron x-ray methods: tomography, Lang topography, and micro-diffraction mapping. These techniques pro-vide a non-destructive method for characterization of mm-sized samples prior to shock experiments. These characterization maps can be used to correlate continuum level measurements in shock compression experiments to the mesoscale and microscale structure. Specifically examined is a sample of C4. We show extensive conformational disorder in gamma-RDX, which is the main component. Further, we observe that the minor HMX-component in C4 contains at least two different phases: alpha- and beta-HMX. This work supported by National Security Technologies, LLC, under Contract No. DE-AC52-06NA25946 with the U.S. Department of Energy and by the Site-Directed Research and Development Program. DOE/NV/25946-3071.
NASA Technical Reports Server (NTRS)
Li, C.-J.; Sun, Q.; Lagowski, J.; Gatos, H. C.
1985-01-01
The microscale characterization of electronic defects in (SI) GaAs has been a challenging issue in connection with materials problems encountered in GaAs IC technology. The main obstacle which limits the applicability of high resolution electron beam methods such as Electron Beam-Induced Current (EBIC) and cathodoluminescence (CL) is the low concentration of free carriers in semiinsulating (SI) GaAs. The present paper provides a new photo-EBIC characterization approach which combines the spectroscopic advantages of optical methods with the high spatial resolution and scanning capability of EBIC. A scanning electron microscope modified for electronic characterization studies is shown schematically. The instrument can operate in the standard SEM mode, in the EBIC modes (including photo-EBIC and thermally stimulated EBIC /TS-EBIC/), and in the cathodo-luminescence (CL) and scanning modes. Attention is given to the use of CL, Photo-EBIC, and TS-EBIC techniques.
Zhang, Yanhong; Huang, Hong; Xia, Zhengbin; Chen, Huanqin
2008-07-01
Thermal degradation of pyrolysis of waste circuit boards was investigated by high-resolution pyrolysis gas chromatography-mass spectrometry (PyGC-MS) and thermogravimetry (TG). In helium atmosphere, the products of FR-4 waste printed circuit board were pyrolyzed at 350, 450, 550, 650, and 750 degrees degrees C, separately, and the pyrolysis products were identified by online MS. The results indicated that the pyrolysis products of the FR-4 waste circuit board were three kinds of substances, such as the low boiling point products, phenol, bisphenol and their related products. Moreover, under 300 degrees degrees C, only observed less pyrolysis products. As the increase of pyrolysis temperature, the relative content of the low boiling point products increased. In the range of 450-650 degrees degrees C, the qualitative analysis and character were similar, and the relative contents of phenol and bisphenol were higher. The influence of pyrolysis temperature on pyrolyzate yields was studied. On the basis of the pyrolyzate profile and the dependence of pyrolyzate yields on pyrolysis temperature, the thermal degradation mechanism of brominated epoxy resin was proposed.
NASA Astrophysics Data System (ADS)
Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.
2017-10-01
In this work, co-pyrolysis of rice straw and polyethylene terephthalate (PET) was carried out at different temperatures (450,500,550, and 600°C) at ratio 1:1 by using fixed bed drop-type pyrolyzer. The purpose of this work is to determine the effect of pyrolysis temperature on the product yield. As the temperature increased, the pyrolysis oil increased until it reaches certain high temperature (600°C), the pyrolysis oil decreased as of more NCG were produced. The temperature 550°C is considered as the optimum pyrolysis temperature since it produced the highest amount of pyrolysis oil with 36 wt.%. In pyrolysis oil, the calorific value (13.98kJ/g) was low because of the presence of high water content (52.46 wt.%). Main chemicals group from pyrolysis oil were an aldehyde, ketones, acids, aromatics, and phenol and all compound have abundant of hydrogen and carbon were identified. Co-pyrolysis of rice straw and PET produced a higher amount of carbon oxides and recycling back the NCG could increase liquid and char yields.
Meso- to micro-scale coupled simulations of flow over complex terrain at the Perdigao site
NASA Astrophysics Data System (ADS)
Neher, J.; van Veen, L.; Chow, F. K.; Mirocha, J. D.; Lundquist, J. K.
2017-12-01
In this work, the site of the 2017 Perdigao field campaign is analyzed with high resolution large-eddy simulations generated using the Weather Research and Forecasting (WRF) model as a coupled mesoscale to microscale model. The fine topographic features of the site, with its ridgelines a mere 1.2 km apart, the occurrence of intermittent turbulence at night, and the presence of a wind turbine on one of the ridgelines pose a challenge for many current numerical models. Key test cases in the observational data that demonstrate these modelling difficulties are identified, and advanced modeling techniques for overcoming these issues in the WRF model are presented. These techniques include vertical grid nesting for control of the grid aspect ratio, the cell perturbation method for accelerating the generation of turbulence at the boundary, the dynamic reconstruction model as a closure model that allows for backscatter of turbulence, and the actuator disk model for representing the turbine wake. Multiple nesting configurations are considered, with special consideration given to spanning the `grey zone' where neither PBL nor LES closures are effective. Comparisons between model results and measured sounding, meteorological tower, and Lidar data are used to evaluate the effectiveness of these techniques, and the model results are evaluated to provide a broader view of the flow field and the turbine wake interactions at the site.
Low oxygen biomass-derived pyrolysis oils and methods for producing the same
Marinangeli, Richard; Brandvold, Timothy A; Kocal, Joseph A
2013-08-27
Low oxygen biomass-derived pyrolysis oils and methods for producing them from carbonaceous biomass feedstock are provided. The carbonaceous biomass feedstock is pyrolyzed in the presence of a catalyst comprising base metal-based catalysts, noble metal-based catalysts, treated zeolitic catalysts, or combinations thereof to produce pyrolysis gases. During pyrolysis, the catalyst catalyzes a deoxygenation reaction whereby at least a portion of the oxygenated hydrocarbons in the pyrolysis gases are converted into hydrocarbons. The oxygen is removed as carbon oxides and water. A condensable portion (the vapors) of the pyrolysis gases is condensed to low oxygen biomass-derived pyrolysis oil.
Quality improvement of pyrolysis oil from waste rubber by adding sawdust
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Wen-liang; Chang, Jian-min, E-mail: cjianmin@bjfu.edu.cn; Cai, Li-ping
Highlights: • Rubber-pyrolysis oil is difficult to be fuel due to high proportion of PAHs. • The efficiency of pyrolysis was increased as the percentage of sawdust increased. • The adding of sawdust improved pyrolysis oil quality by reducing the PAHs content. • Adding sawdust reduced nitrogen/sulfur in oil and was easier to convert to diesel. - Abstract: This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during themore » pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.« less
Experimental study on the heat transfer characteristics of waste printed circuit boards pyrolysis.
Ma, Hongting; Du, Na; Lin, Xueyin; Li, Chen; Lai, Junwen; Li, Zihao
2018-08-15
In order to study the appropriate and advanced technology for recycling waste printed circuit boards (PCBs), a fixed bed pyrolysis device with stirring function has been designed and developed. The effect of rotating speed on the temperature distribution and mass change in the pyrolysis process of FR-4 PCB has been analyzed. The heat transfer and pyrolysis characteristics of different granular layers with and without stirring have been investigated. The results indicate that the stirring can change the main way of heat transfer from conduction to convection in the PCB layers. As the increase of rotating speed, the temperature rising rate of material at the bottom of the pyrolysis furnace gradually decreases, while the heating rate is increasing at the upper layer, and the temperature difference between the upper and bottom layers is gradually reduced. When the rotating speed varies from 0r/min to 18r/min, the weight loss of the material increases from 3.97% to 6.76%, and the overall pyrolysis degree is improved. During the pyrolysis process, the material layer can be divided into three zones along the vertical direction, namely complete pyrolysis zone, partial pyrolysis zone and non-pyrolysis zone. As the rotating speed is 0r/min, the thickness of each zones is 6cm, 6cm and 3cm, respectively. However, when the rotating speed is increased to 18r/min, the non-pyrolysis zone disappears, and the thickness of complete pyrolysis zone and partial pyrolysis zone increase to 9cm and 6cm, respectively. Copyright © 2018 Elsevier B.V. All rights reserved.
Co-pyrolysis of rice straw and polypropylene using fixed-bed pyrolyzer
NASA Astrophysics Data System (ADS)
Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Mazlan, M. A.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.
2016-11-01
The present work encompasses the impact of temperature (450, 500, 550, 600 °C) on the properties of pyrolysis oil and on other product yield for the co-pyrolysis of Polypropylene (PP) plastics and rice straw. Co-pyrolysis of PP plastic and rice straw were conducted in a fixed-bed drop type pyrolyzer under an inert condition to attain maximum oil yield. Physically, the pyrolysis oil is dark-brown in colour with free flowing and has a strong acrid smell. Copyrolysis between these typically obtained in maximum pyrolysis oil yields up to 69% by ratio 1:1 at a maximum temperature of 550 °C. From the maximum yield of pyrolysis oil, characterization of pyrolysis product and effect of biomass type of the composition were evaluated. Pyrolysis oil contains a high water content of 66.137 wt.%. Furfural, 2- methylnaphthalene, tetrahydrofuran (THF), toluene and acetaldehyde were the major organic compounds found in pyrolysis oil of rice straw mixed with PP. Bio-char collected from co-pyrolysis of rice straw mixed with PP plastic has high calorific value of 21.190 kJ/g and also carbon content with 59.02 wt.% and could contribute to high heating value. The non-condensable gases consist of hydrogen, carbon monoxide, and methane as the major gas components.
Immobilized enzyme studies in a microscale bioreactor.
Jones, Francis; Forrest, Scott; Palmer, Jim; Lu, Zonghuan; Elmore, John; Elmore, Bill B
2004-01-01
Novel microreactors with immobilized enzymes were fabricated using both silicon and polymer-based microfabrication techniques. The effectiveness of these reactors was examined along with their behavior over time. Urease enzyme was successfully incorporated into microchannels of a polymeric matrix of polydimethylsiloxane and through layer-bylayer self-assembly techniques onto silicon. The fabricated microchannels had cross-sectional dimensions ranging from tens to hundreds of micrometers in width and height. The experimental results for continuous-flow microreactors are reported for the conversion of urea to ammonia by urease enzyme. Urea conversions of >90% were observed.
Char yield on pyrolysis of cellulose
A. Broido; Maxine A. Nelson
1975-01-01
Whether the pyrolysis of cellulose is conducted in an inert medium or in air, partial pyrolysis at a lower temperature increases the char yield subsequently obtained after 1 hour at 370°C. The results are consistent with a pyrolysis scheme in which two competing sequences of cellulose pyrolysis reactions are initiated by (1) an intermolecular dehydration leading to...
Honma, Sensho; Hata, Toshimitsu; Watanabe, Takashi
2014-01-01
The influence of catalysts on the compositions of char and pyrolysis oil obtained by pyrolysis of wood biomass with pulse current heating was studied. The effects of catalysts on product compositions were analyzed using GC-MS and TEM. The compositions of some aromatic compounds changed noticeably when using a metal oxide species as the catalyst. The coexistence or dissolution of amorphous carbon and iron oxide was observed in char pyrolyzed at 800°C with Fe3O4. Pyrolysis oil compositions changed remarkably when formed in the presence of a catalyst compared to that obtained from the uncatalyzed pyrolysis of wood meal. We observed a tendency toward an increase in the ratio of polyaromatic hydrocarbons in the pyrolysis oil composition after catalytic pyrolysis at 800°C. Pyrolysis of biomass using pulse current heating and an adequate amount of catalyst is expected to yield a higher content of specific polyaromatic compounds. PMID:25614894
A Comparative study of microwave-induced pyrolysis of lignocellulosic and algal biomass.
Wang, Nan; Tahmasebi, Arash; Yu, Jianglong; Xu, Jing; Huang, Feng; Mamaeva, Alisa
2015-08-01
Microwave (MW) pyrolysis of algal and lignocellulosic biomass samples were studied using a modified domestic oven. The pyrolysis temperature was recorded continuously by inserting a thermocouple into the samples. Temperatures as high as 1170 and 1015°C were achieved for peanut shell and Chlorella vulgaris. The activation energy for MW pyrolysis was calculated by Coats-Redfern method and the values were 221.96 and 214.27kJ/mol for peanut shell and C. vulgaris, respectively. Bio-oil yields reached to 27.7wt.% and 11.0wt.% during pyrolysis of C. vulgaris and peanut shell, respectively. The bio-oil samples from pyrolysis were analyzed by a gas chromatography-mass spectrometry (GC-MS). Bio-oil from lignocellulosic biomass pyrolysis contained more phenolic compounds while that from microalgae pyrolysis contained more nitrogen-containing species. Fourier transform infrared spectroscopy (FTIR) analysis results showed that concentration of OH, CH, CO, OCH3, and CO functional groups in char samples decreased significantly after pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.
Wang, Shuang; Xia, Zhen; Hu, Yamin; He, Zhixia; Uzoejinwa, Benjamin Bernard; Wang, Qian; Cao, Bin; Xu, Shanna
2017-03-01
Co-pyrolysis conversion of seaweed (Enteromorpha clathrat and Sargassum fusiforme) polysaccharides and cellulose has been investigated. From the Py-GC/MS results, Enteromorpha clathrata (EN) polysaccharides pyrolysis mainly forms furans; while the products of Sargassum fusiforme (SA) polysaccharides pyrolysis are mainly acid esters. The formation mechanisms of H 2 O, CO 2 , and SO 2 during the pyrolysis of seaweed polysaccharides were analyzed using the thermogravimetric-mass spectrometry. Meanwhile the pyrolysis of seaweed polysaccharide based on the Amber and the ReaxFF force fields, has also been proposed and simulated respectively. The simulation results coincided with the experimental results. During the fast pyrolysis, strong synergistic effects among cellulose and seaweed polysaccharide molecules have been simulated. By comparing the experimental and simulation value, it has been found that co-pyrolysis could increase the number of molecular fragments, increase the pyrolysis conversion rate, and increase gas production rate at the middle temperature range. Copyright © 2016 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hong, Yongchun; Hensley, Alyssa; McEwen, Jean-Sabin
Catalytic fast pyrolysis is the most promising approach for biofuel production, due to its simple process and versatility to handle lignocellulosic biomass feedstocks with varying and complex compositions. Compared with in situ catalytic fast pyrolysis, ex situ catalytic pyrolysis has the flexibility of optimizing the pyrolysis step and catalytic process individually to improve the quality of pyrolysis oil (stability, oxygen content, acid number, etc.) and to maximize the carbon efficiency in the conversion of biomass to pyrolysis oil. Hydrodeoxygenation is one of the key catalytic functions in ex situ catalytic fast pyrolysis. Recently, Fe-based catalysts have been reported to exhibitmore » superior catalytic properties in hydrodeoxygenation of model compounds in pyrolysis oil, which potentially makes the ex situ pyrolysis of biomass commercially viable due to the abundance and low cost of Fe. Here, we briefly summarize the recent progress on Fe-based catalysts for hydrodeoxygenation of biomass, and provide perspectives on how to further improve Fe-based catalysts (activity and stability) for their potential applications in the emerging area of biomass conversion.« less
Laser-assisted solar cell metallization processing
NASA Technical Reports Server (NTRS)
Dutta, S.
1984-01-01
Laser assisted processing techniques utilized to produce the fine line, thin metal grid structures that are required to fabricate high efficiency solar cells are investigated. The tasks comprising these investigations are summarized. Metal deposition experiments are carried out utilizing laser assisted pyrolysis of a variety of metal bearing polymer films and metalloorganic inks spun onto silicon substrates. Laser decomposition of spun on silver neodecanoate ink yields very promising results. Solar cell comb metallization patterns are written using this technique.
Properties of mixed molybdenum oxide iridium oxide thin films synthesized by spray pyrolysis
NASA Astrophysics Data System (ADS)
Patil, P. S.; Kawar, R. K.; Sadale, S. B.; Inamdar, A. I.; Deshmukh, H. P.
2006-09-01
Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.
NASA Astrophysics Data System (ADS)
Fleury, Jules; Brunier, Guillaume; Michaud, Emma; Anthony, Edward; Dussouillez, Philippe; Morvan, Sylvain
2016-04-01
Mud banks are the loci of rich bio-geo-chemical processes occuring rapidly at infra-tide frequency. Their surface topography is commonly affected by many of these processes, including bioturbation, water drainage or dessication. Quantifying surface morphology and changes on a mud bank at the micro-scale is a challenging task due to a number of issues. First, the water-saturated nature of the soil makes it difficult to measure High Resolution Topography (HRT) with classical methods. Second, setting up an instrumented experiment without disrupting the signal being studied is hardly achieved at micro-scale. Finally, the highly mobile nature of this environment enhancing strong spatio-temporal heterogeneity is hard to capture. Terrestrial Laser Scanning (TLS) and SfM (Surface from Motion)-Photogrammetry are two techniques that enable mapping of micro-scale features, but the first technique is not suitable because of the poor quality of the backscattered laser signal on wet surfaces and the need to set up several measuring stations on a complex, unstable substrate. Thus, we set up an experiment to assess the feasibility and the accuracy of SfM in such a context. We took the opportunity of the installation of a pontoon dedicated to the study of bio-geochemical processes within benthic mesocosms installed on a mud bank inhabited by pioneer mangroves trees to develop an adapted photogrammetry protocol based on a full-frame remotely triggered camera sensor mounted on a pole. The incident light on the surface was also controlled with a light-diffusing device. We obtained sub-millimetric resolution 3D-topography and visible imagery. Surveys were carried out every 2 hours at low tide to detect surface changes due to water content variation as well as bioturbation mainly caused by crabs digging galleries and feeding on sediment surface. Both the qualitative and quantitative results seem very promising and lead us to expect new insights into heterogeneous surface processes on a highly dynamic mud bank. Remaining issues are finding appropriate validation data at such a high level of resolution in order to assess accuracy, and developing an acquisition method at a frequency high enough to enable us to decipher bulk soil movement from local changing features.
Yang, Xiaoning; Sun, Lushi; Xiang, Jun; Hu, Song; Su, Sheng
2013-02-01
Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of whole recycling process. Copyright © 2012 Elsevier Ltd. All rights reserved.
Chi, Yongchao; Xue, Junjie; Zhuo, Jiankun; Zhang, Dahu; Liu, Mi; Yao, Qiang
2018-08-15
Fast pyrolysis is one of the most economical and efficient technologies to convert biomass to bio-oil and valuable chemical products. Co-pyrolysis with hydrogen rich materials such as plastics over zeolite catalysts is one of the significant solutions to various problems of bio-oil such as high oxygen content, low heat value and high acid content. This paper studied pyrolysis of cellulose and polypropylene (PP) separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41. The pyrolysis over different heating rates (10K/min, 20K/min, 30K/min) was studied by Thermogravimetry Analysis (TGA) and kinetic parameters were obtained by Coats-Redfern method and isoconversion method. TG and DTG data shows that the two catalysts advance the pyrolysis reaction of PP significantly and reduce its peak temperature of DTG curve from 458°C to 341°C. The activation energy of pyrolysis of PP also has a remarkable reduction over the two catalysts. Py-GC/MS method was used to obtain the product distribution of pyrolysis of cellulose and PP separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41 at constant temperature of 650°C. Experiment results proved that co-pyrolysis with PP bring significant changes to the product distribution of cellulose. Oxygenated compounds such as furans are decreased, while yields of olefins and aromatics increase greatly. The yield of furans increases with the catalysis of MCM-41 as for the pyrolysis of cellulose and co-pyrolysis, while the yield of olefins and aromatics both experience significant growth over Al-MCM-41, which can be explained by the abundant acid centers in Al-MCM-41. Copyright © 2018 Elsevier B.V. All rights reserved.
Artificial maturation of oil shale: The Irati Formation from the Parana Basin, Brazil
NASA Astrophysics Data System (ADS)
Gayer, James L.
Oil shale samples from the Irati Formation in Brazil were evaluated from an outcrop block, denoted Block 003. The goals of this thesis include: 1) Characterizing the Irati Formation, 2) Comparing the effects of two different types of pyrolysis, anhydrous and hydrous, and 3) Utilizing a variety of geophysical experiments to determine the changes associated with each type of pyrolysis. Primary work included determining total organic carbon, source rock analysis, mineralogy, computer tomography x-ray scans, and scanning electron microscope images before and after pyrolysis, as well as acoustic properties of the samples during pyrolysis. Two types of pyrolysis (hydrous and anhydrous) were performed on samples cored at three different orientations (0°, 45°, and 90°) with respect to the axis of symmetry, requiring six total experiments. During pyrolysis, the overall effective pressure was maintained at 800 psi, and the holding temperature was 365°C. The changes and deformation in the hydrous pyrolysis samples were greater compared to the anhydrous pyrolysis. The velocities gave the best indication of changes occurring during pyrolysis, but it was difficult to maintain the same amplitude and quality of waveforms at higher temperatures. The velocity changes were due to a combination of factors, including thermal deformation of the samples, fracture porosity development, and the release of adsorbed water and bitumen from the sample. Anhydrous pyrolysis in this study did not reduce TOC, while TOC was reduced due to hydrous pyrolysis by 5%, and velocities in the hydrous pyrolysis decreased by up to 30% at 365°C compared to room temperature. Data from this study and future data that can be acquired with the improved high-temperature, high-pressure experiment will assist in future economic production from oil shale at lower temperatures under hydrous pyrolysis conditions.
Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.
1987-01-01
A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 ??C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 ??C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur. ?? 1987.
NASA Astrophysics Data System (ADS)
Li, Gang; Bai, Weiyang
2018-04-01
Hierarchical flower-like cobalt tetroxide (Co3O4) was successfully synthesized via a facile precipitation method in combination with heat treatment of the cobalt oxalate precursor. The samples were systematically characterized by thermo gravimetric analysis and derivative thermo gravimetric analysis (TGA-DTG), X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and N2 adsorption-desorption measurements. The results indicate that the as-fabricated Co3O4 exhibits uniform flower-like morphologies with diameters of 8-12 μm, which are constructed by one-dimensional nanowires. Furthermore, catalytic effect of this hierarchical porous Co3O4 on ammonium perchlorate (AP) pyrolysis was investigated using differential scanning calorimetry (DSC) techniques. It is found that the pyrolysis temperature of AP shifts 142 °C downward with a 2 wt% addition content of Co3O4. Meanwhile, the addition of Co3O4 results in a dramatic reduction of the apparent activation energy of AP pyrolysis from 216 kJ mol-1 to 152 kJ mol-1, determined by the Kissinger correlation. The results endorse this material as a potential catalyst in AP decomposition.
Thermal/Pyrolysis Gas Flow Analysis of Carbon Phenolic Material
NASA Technical Reports Server (NTRS)
Clayton, J. Louie
2001-01-01
Provided in this study are predicted in-depth temperature and pyrolysis gas pressure distributions for carbon phenolic materials that are externally heated with a laser source. Governing equations, numerical techniques and comparisons to measured temperature data are also presented. Surface thermochemical conditions were determined using the Aerotherm Chemical Equilibrium (ACE) program. Surface heating simulation used facility calibrated radiative and convective flux levels. Temperatures and pyrolysis gas pressures are predicted using an upgraded form of the SINDA/CMA program that was developed by NASA during the Solid Propulsion Integrity Program (SPIP). Multispecie mass balance, tracking of condensable vapors, high heat rate kinetics, real gas compressibility and reduced mixture viscosity's have been added to the algorithm. In general, surface and in-depth temperature comparisons are very good. Specie partial pressures calculations show that a saturated water-vapor mixture is the main contributor to peak in-depth total pressure. Further, for most of the cases studied, the water-vapor mixture is driven near the critical point and is believed to significantly increase the local heat capacity of the composite material. This phenomenon if not accounted for in analysis models may lead to an over prediction in temperature response in charring regions of the material.
Conversion and Extraction of Insoluble Organic Materials in Meteorites
NASA Technical Reports Server (NTRS)
Locke, Darren R.; Burton, Aaron S.; Niles, Paul B.
2016-01-01
We endeavor to develop and implement methods in our laboratory to convert and extract insoluble organic materials (IOM) from low car-bon bearing meteorites (such as ordinary chondrites) and Precambrian terrestrial rocks for the purpose of determining IOM structure and prebiotic chemistries preserved in these types of samples. The general scheme of converting and extracting IOM in samples is summarized in Figure 1. First, powdered samples are solvent extracted in a micro-Soxhlet apparatus multiple times using solvents ranging from non-polar to polar (hexane - non-polar, dichloromethane - non-polar to polar, methanol - polar protic, and acetonitrile - polar aprotic). Second, solid residue from solvent extractions is processed using strong acids, hydrochloric and hydrofluoric, to dissolve minerals and isolate IOM. Third, the isolated IOM is subjected to both thermal (pyrolysis) and chemical (oxidation) degradation to release compounds from the macromolecular material. Finally, products from oxidation and pyrolysis are analyzed by gas chromatography - mass spectrometry (GCMS). We are working toward an integrated method and analysis scheme that will allow us to determine prebiotic chemistries in ordinary chondrites and Precambrian terrestrial rocks. Powerful techniques that we are including are stepwise, flash, and gradual pyrolysis and ruthenium tetroxide oxidation. More details of the integrated scheme will be presented.
Tsai, Wen-Tien; Lee, Mei-Kuei; Chang, Jeng-Hung; Su, Ting-Yi; Chang, Yuan-Ming
2009-05-01
In this study, gas chromatography-mass spectrometry (GC-MS) was used to analyze the pyrolytic bio-oils and gas fractions derived from the pyrolysis of industrial sewage sludges using induction-heating technique. The liquid products were obtained from the cryogenic condensation of the devolatilization fraction in a nitrogen atmosphere using a heating rate of 300 degrees C/min ranging from 25 to 500 degrees C. The analytical results showed that the pyrolysis bio-oils were very complex mixtures of organic compounds and contained a lot of nitrogenated and/or oxygenated compounds such as aliphatic hydrocarbons, phenols, pyridines, pyrroles, amines, ketones, and so on. These organic hydrocarbons containing nitrogen and/or oxygen should originate from the protein and nucleic acid textures of the microbial organisms present in the sewage sludge. The non-condensable devolatilization fractions were also composed of nitrogenated and oxygenated compounds, but contained small fractions of phenols, 1H-indoles, and fatty carboxylic acids. On the other hand, the compositions in the non-condensable gas products were principally carbon dioxide, carbon monoxide and methane analyzed by gas chromatography-thermal conductivity detector (GC-TCD).
Biofuel from jute stick by pyrolysis technology
NASA Astrophysics Data System (ADS)
Ferdous, J.; Parveen, M.; Islam, M. R.; Haniu, H.; Takai, K.
2017-06-01
In this study the conversion of jute stick into biofuels and chemicals by externally heated fixed-bed pyrolysis reactor have been taken into consideration. The solid jute stick was characterized through proximate and ultimate analysis, gross calorific values and thermo-gravimetric analysis to investigate their suitability as feedstock for this consideration. The solid biomass particles were fed into the reactor by gravity feed type reactor feeder. The products were oil, char and gases. The liquid and char products were collected separately while the gas was flared into the atmosphere. The process conditions were varied by fixed-bed temperature; feed stock particle size, N2 gas flow rate and running time. All parameters were found to influence the product yields significantly. The maximum liquid yields were 50 wt% of solid jute stick at reactor temperature 425°C for N2 gas flow rate 6 l/min, feed particle size 1180-1700 µm and running time 30 min. Liquid products obtained at these conditions were characterized by physical properties, chemical analysis and GC-MS techniques. The results show that it is possible to obtained liquid products that are comparable to petroleum fuels and valuable chemical feedstock from the selected biomass if the pyrolysis conditions are chosen accordingly.
Fabrication and characterization of three-dimensional carbon electrodes for lithium-ion batteries
NASA Astrophysics Data System (ADS)
Teixidor, Genis Turon; Zaouk, Rabih B.; Park, Benjamin Y.; Madou, Marc J.
This paper presents fabrication and testing results of three-dimensional carbon anodes for lithium-ion batteries, which are fabricated through the pyrolysis of lithographically patterned epoxy resins. This technique, known as Carbon-MEMS, provides great flexibility and an unprecedented dimensional control in shaping carbon microstructures. Variations in the pattern density and in the pyrolysis conditions result in anodes with different specific and gravimetric capacities, with a three to six times increase in specific capacity with respect to the current thin-film battery technology. Newly designed cross-shaped Carbon-MEMS arrays have a much higher mechanical robustness (as given by their moment of inertia) than the traditionally used cylindrical posts, but the gravimetric analysis suggests that new designs with thinner features are required for better carbon utilization. Pyrolysis at higher temperatures and slower ramping up schedules reduces the irreversible capacity of the carbon electrodes. We also analyze the addition of Meso-Carbon Micro-Beads (MCMB) particles on the reversible and irreversible capacities of new three-dimensional, hybrid electrodes. This combination results in a slight increase in reversible capacity and a big increase in the irreversible capacity of the carbon electrodes, mostly due to the non-complete attachment of the MCMB particles.
NASA Astrophysics Data System (ADS)
Irani, Rowshanak; Rozati, Seyed Mohammad; Beke, Szabolcs
2018-04-01
V2O5 thin films were deposited with different precursor concentrations of 0.01, 0.05, and 0.1 M on glass substrates by spray pyrolysis technique, then the optimized films were annealed in different ambients (air, oxygen, and vacuum). The results showed that by increasing the concentration, the films grew along the (001) direction with an orthorhombic structure. Field emission scanning electron microscopy showed that nanorods were formed when depositing 0.05 molar of VCl3. We conclude that with the precursor concentration, the surface nanostructure can be well-controlled. Annealing improved the crystallinity under all ambients, but the best crystallinity was achieved in vacuum. It was revealed that the as-deposited films had the highest transmission, whereas the films annealed in air had the lowest. When annealed in air, the optical band gap decreased from 2.45 to 2.32 eV. The sheet resistance, resistivity, mobility, conductivity, and carrier concentration were measured for all the prepared V2O5 films.
NASA Astrophysics Data System (ADS)
Abd-Alghafour, N. M.; Ahmed, Naser M.; Hassan, Zai; Mohammad, Sabah M.
2016-07-01
Vanadium oxide (V2O5) thin films were deposited on glass substrates by using a cost-efficient spray pyrolysis technique. The films were grown at 350° through thermal decomposition of VCl3 in deionized water with different solution spray rates. The high resolution X-ray diffraction results revealed the formation of nanocrystalline films having orthorhombic structures with preferential orientation along (101) direction. The spray rate influenced the surface morphology and crystallite size of the films. The crystallite size was found to increase whereas the micro-strain was decreased by increasing the spray deposition rates. The increase in crystallite size and decrease in the macrostrain resulted in an improvement in the films' crystallinity. The UV-Visible spectroscopy analysis indicated that the average transmittance of all films lies in the range 75-80 %. The band gap of V2O5 film was decreased from 2.65 to 2.46 eV with increase of the spray deposition rate from 5 ml/min to 10 ml/min. first, second, and third level headings (first level heading).
Scalable synthesis of aligned carbon nanotubes bundles using green natural precursor: neem oil
NASA Astrophysics Data System (ADS)
Kumar, Rajesh; Tiwari, Radhey Shyam; Srivastava, Onkar Nath
2011-12-01
Practical application of aligned carbon nanotubes (ACNTs) would have to be determined by a matter of its economical and large-scale preparation. In this study, neem oil (also named Margoaa oil, extracted from the seeds of the neem-- Azadirachta indica) was used as carbon source to fabricate the bundles of ACNTs. ACNTs have been synthesized by spray pyrolysis of neem oil and ferrocene mixture at 825°C. The major components of neem oil are hydrocarbon with less amount of oxygen, which provided the precursor species in spray pyrolysis growth of CNTs. The bundles of ACNTs have been grown directly inside the quartz tube. The as-grown ACNTs have been characterized through Raman spectroscopy, scanning and transmission electron microscopic (SEM/TEM) techniques. SEM images reveal that the bundles of ACNTs are densely packed and are of several microns in length. High-resolution TEM analysis reveals these nanotubes to be multi-walled CNTs. These multi-walled CNTs were found to have inner diameter between 15 and 30 nm. It was found that present technique gives high yield with high density of bundles of ACNTs.
Scalable synthesis of aligned carbon nanotubes bundles using green natural precursor: neem oil.
Kumar, Rajesh; Tiwari, Radhey Shyam; Srivastava, Onkar Nath
2011-01-18
Practical application of aligned carbon nanotubes (ACNTs) would have to be determined by a matter of its economical and large-scale preparation. In this study, neem oil (also named Margoaa oil, extracted from the seeds of the neem--Azadirachta indica) was used as carbon source to fabricate the bundles of ACNTs. ACNTs have been synthesized by spray pyrolysis of neem oil and ferrocene mixture at 825°C. The major components of neem oil are hydrocarbon with less amount of oxygen, which provided the precursor species in spray pyrolysis growth of CNTs. The bundles of ACNTs have been grown directly inside the quartz tube. The as-grown ACNTs have been characterized through Raman spectroscopy, scanning and transmission electron microscopic (SEM/TEM) techniques. SEM images reveal that the bundles of ACNTs are densely packed and are of several microns in length. High-resolution TEM analysis reveals these nanotubes to be multi-walled CNTs. These multi-walled CNTs were found to have inner diameter between 15 and 30 nm. It was found that present technique gives high yield with high density of bundles of ACNTs.
NASA Astrophysics Data System (ADS)
Chandel, Tarun; Halaszova, Sona; Prochazka, Michal; Hasko, Daniel; Velic, Dusan; Thakur, Vikas; Dwivedi, Shailendra Kumar; Zaman, M. Buhanuz; Rajaram, Poolla
2018-05-01
Nanocrystalline thin films of Cu2ZnSnS4 (CZTS) were grown on the glass substrates using the spray pyrolysis technique. The films were grown at a substrate temperature of 300 °C after which they were annealed at 350 °C in vacuum. X-ray diffraction (XRD) studies showed that the films crystallized in the kesterite structure. Energy dispersive analysis of X-rays (EDAX) studies showed that the films possess the desired stoichiometry i.e. the proportion of Cu:Zn:Sn:S in the CZTS solid solution is close to 2:1:1:4. Secondary Ions Mass Spectroscopy (SIMS) depth profiling confirmed the uniformity in elemental composition along the depth of the films. SEM studies showed that the films are covered with CZTS particles forming sheet like structures. AFM studies show that the size of the particles on the surface of the films is around 10-15 nm. UV-VIS-NIR transmission spectra were used to determine the optical band gap of the CZTS films which was found to be around 1.55eV.
Properties of NiO thin films deposited by intermittent spray pyrolysis process
NASA Astrophysics Data System (ADS)
Reguig, B. A.; Khelil, A.; Cattin, L.; Morsli, M.; Bernède, J. C.
2007-02-01
NiO thin films have been grown on glass substrates by intermittent spray pyrolysis deposition of NiCl 2·6H 2O diluted in distilled water, using a simple "perfume atomizer". The effect of the solution molarity on their properties was studied and compared to those of NiO thin films deposited with a classical spray system. It is shown that NiO thin films crystallized in the NiO structure are achieved after deposition. Whatever the precursor molarity, the grain size is around 25-30 nm. The crystallites are preferentially oriented along the (1 1 1) direction. All the films are p-type. However, the thickness and the conductivity of the NiO films depend on the precursor contraction. By comparison with the properties of films deposited by classical spray technique, it is shown that the critical precursor concentration, which induces strong thin films properties perturbations, is higher when a perfume atomizer is used. This broader stability domain can be attributed to better chlorides decomposition during the rest time used in the perfume atomizer technique.
Processes for converting lignocellulosics to reduced acid pyrolysis oil
Kocal, Joseph Anthony; Brandvold, Timothy A
2015-01-06
Processes for producing reduced acid lignocellulosic-derived pyrolysis oil are provided. In a process, lignocellulosic material is fed to a heating zone. A basic solid catalyst is delivered to the heating zone. The lignocellulosic material is pyrolyzed in the presence of the basic solid catalyst in the heating zone to create pyrolysis gases. The oxygen in the pyrolysis gases is catalytically converted to separable species in the heating zone. The pyrolysis gases are removed from the heating zone and are liquefied to form the reduced acid lignocellulosic-derived pyrolysis oil.
Ferrell, Jack R.; Olarte, Mariefel V.; Christensen, Earl D.; ...
2016-07-05
Here, we discuss the standardization of analytical techniques for pyrolysis bio-oils, including the current status of methods, and our opinions on future directions. First, the history of past standardization efforts is summarized, and both successful and unsuccessful validation of analytical techniques highlighted. The majority of analytical standardization studies to-date has tested only physical characterization techniques. In this paper, we present results from an international round robin on the validation of chemical characterization techniques for bio-oils. Techniques tested included acid number, carbonyl titrations using two different methods (one at room temperature and one at 80 °C), 31P NMR for determination ofmore » hydroxyl groups, and a quantitative gas chromatography–mass spectrometry (GC-MS) method. Both carbonyl titration and acid number methods have yielded acceptable inter-laboratory variabilities. 31P NMR produced acceptable results for aliphatic and phenolic hydroxyl groups, but not for carboxylic hydroxyl groups. As shown in previous round robins, GC-MS results were more variable. Reliable chemical characterization of bio-oils will enable upgrading research and allow for detailed comparisons of bio-oils produced at different facilities. Reliable analytics are also needed to enable an emerging bioenergy industry, as processing facilities often have different analytical needs and capabilities than research facilities. We feel that correlations in reliable characterizations of bio-oils will help strike a balance between research and industry, and will ultimately help to -determine metrics for bio-oil quality. Lastly, the standardization of additional analytical methods is needed, particularly for upgraded bio-oils.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ferrell, Jack R.; Olarte, Mariefel V.; Christensen, Earl D.
Here, we discuss the standardization of analytical techniques for pyrolysis bio-oils, including the current status of methods, and our opinions on future directions. First, the history of past standardization efforts is summarized, and both successful and unsuccessful validation of analytical techniques highlighted. The majority of analytical standardization studies to-date has tested only physical characterization techniques. In this paper, we present results from an international round robin on the validation of chemical characterization techniques for bio-oils. Techniques tested included acid number, carbonyl titrations using two different methods (one at room temperature and one at 80 °C), 31P NMR for determination ofmore » hydroxyl groups, and a quantitative gas chromatography–mass spectrometry (GC-MS) method. Both carbonyl titration and acid number methods have yielded acceptable inter-laboratory variabilities. 31P NMR produced acceptable results for aliphatic and phenolic hydroxyl groups, but not for carboxylic hydroxyl groups. As shown in previous round robins, GC-MS results were more variable. Reliable chemical characterization of bio-oils will enable upgrading research and allow for detailed comparisons of bio-oils produced at different facilities. Reliable analytics are also needed to enable an emerging bioenergy industry, as processing facilities often have different analytical needs and capabilities than research facilities. We feel that correlations in reliable characterizations of bio-oils will help strike a balance between research and industry, and will ultimately help to -determine metrics for bio-oil quality. Lastly, the standardization of additional analytical methods is needed, particularly for upgraded bio-oils.« less
DART-MS: A New Analytical Technique for Forensic Paint Analysis.
Marić, Mark; Marano, James; Cody, Robert B; Bridge, Candice
2018-06-05
Automotive paint evidence is one of the most significant forms of evidence obtained in automotive-related incidents. Therefore, the analysis of automotive paint evidence is imperative in forensic casework. Most analytical schemes for automotive paint characterization involve optical microscopy, followed by infrared spectroscopy and pyrolysis-gas chromatography mass spectrometry ( py-GCMS) if required. The main drawback with py-GCMS, aside from its destructive nature, is that this technique is relatively time intensive in comparison to other techniques. Direct analysis in real-time-time-of-flight mass spectrometry (DART-TOFMS) may provide an alternative to py-GCMS, as the rapidity of analysis and minimal sample preparation affords a significant advantage. In this study, automotive clear coats from four vehicles were characterized by DART-TOFMS and a standard py-GCMS protocol. Principal component analysis was utilized to interpret the resultant data and suggested the two techniques provided analogous sample discrimination. Moreover, in some instances DART-TOFMS was able to identify components not observed by py-GCMS and vice versa, which indicates that the two techniques may provide complementary information. Additionally, a thermal desorption/pyrolysis DART-TOFMS methodology was also evaluated to characterize the intact paint chips from the vehicles to ascertain if the linear temperature gradient provided additional discriminatory information. All the paint samples were able to be discriminated based on the distinctive thermal desorption plots afforded from this technique, which may also be utilized for sample discrimination. On the basis of the results, DART-TOFMS may provide an additional tool to the forensic paint examiner.
Microscale photo interpretation of forest and nonforest land classes
NASA Technical Reports Server (NTRS)
Aldrich, R. C.; Greentree, W. J.
1972-01-01
Remote sensing of forest and nonforest land classes are discussed, using microscale photointerpretation. Results include: (1.) Microscale IR color photography can be interpreted within reasonable limits of error to estimate forest area. (2.) Forest interpretation is best on winter photography with 97 percent or better accuracy. (3.) Broad forest types can be classified on microscale photography. (4.) Active agricultural land is classified most accurately on early summer photography. (5.) Six percent of all nonforest observations were misclassified as forest.
Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q
2017-03-01
The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin. Copyright © 2016. Published by Elsevier Ltd.
The slow and fast pyrolysis of cherry seed.
Duman, Gozde; Okutucu, Cagdas; Ucar, Suat; Stahl, Ralph; Yanik, Jale
2011-01-01
The slow and fast pyrolysis of cherry seeds (CWS) and cherry seeds shells (CSS) was studied in fixed-bed and fluidized bed reactors at different pyrolysis temperatures. The effects of reactor type and temperature on the yields and composition of products were investigated. In the case of fast pyrolysis, the maximum bio-oil yield was found to be about 44 wt% at pyrolysis temperature of 500 °C for both CWS and CSS, whereas the bio yields were of 21 and 15 wt% obtained at 500 °C from slow pyrolysis of CWS and CSS, respectively. Both temperature and reactor type affected the composition of bio-oils. The results showed that bio-oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel for combustion systems in industry and the bio-oil produced from fast pyrolysis can be evaluated as a chemical feedstock. Copyright © 2010 Elsevier Ltd. All rights reserved.
Effects of feedstock characteristics on microwave-assisted pyrolysis - A review.
Zhang, Yaning; Chen, Paul; Liu, Shiyu; Peng, Peng; Min, Min; Cheng, Yanling; Anderson, Erik; Zhou, Nan; Fan, Liangliang; Liu, Chenghui; Chen, Guo; Liu, Yuhuan; Lei, Hanwu; Li, Bingxi; Ruan, Roger
2017-04-01
Microwave-assisted pyrolysis is an important approach to obtain bio-oil from biomass. Similar to conventional electrical heating pyrolysis, microwave-assisted pyrolysis is significantly affected by feedstock characteristics. However, microwave heating has its unique features which strongly depend on the physical and chemical properties of biomass feedstock. In this review, the relationships among heating, bio-oil yield, and feedstock particle size, moisture content, inorganics, and organics in microwave-assisted pyrolysis are discussed and compared with those in conventional electrical heating pyrolysis. The quantitative analysis of data reported in the literature showed a strong contrast between the conventional processes and microwave based processes. Microwave-assisted pyrolysis is a relatively new process with limited research compared with conventional electrical heating pyrolysis. The lack of understanding of some observed results warrant more and in-depth fundamental research. Copyright © 2017 Elsevier Ltd. All rights reserved.
Fractional condensation of pyrolysis vapors produced from Nordic feedstocks in cyclone pyrolysis
Johansson, Ann-Christine; Lisa, Kristiina; Sandström, Linda; ...
2016-12-06
Pyrolysis oil is a complex mixture of different chemical compounds with a wide range of molecular weights and boiling points. Due to its complexity, an efficient fractionation of the oil may be a more promising approach of producing liquid fuels and chemicals than treating the whole oil. In this work a sampling system based on fractional condensation was attached to a cyclone pyrolysis pilot plant to enable separation of the produced pyrolysis vapors into five oil fractions. The sampling system was composed of cyclonic condensers and coalescing filters arranged in series. Our objective was to characterize the oil fractions producedmore » from three different Nordic feedstocks and suggest possible applications. The oil fractions were thoroughly characterized using several analytical techniques including water content; elemental composition; heating value, and chemical compound group analysis using solvent fractionation, quantitative 13C NMR and 1H NMR and GC x GC - TOFMS. The results show that the oil fractions significantly differ from each other both in chemical and physical properties. The first fractions and the fraction composed of aerosols were highly viscous and contained larger energy-rich compounds of mainly lignin-derived material. The middle fraction contained medium-size compounds with relatively high concentration of water, sugars, alcohols, hydrocarbonyls and acids and finally the last fraction contained smaller molecules such as water, aldehydes, ketones and acids. But, the properties of the respective fractions seem independent on the studied feedstock types, i.e. the respective fractions produced from different feedstock are rather similar. Furthermore, this promotes the possibility to vary the feedstock depending on availability while retaining the oil properties. Possible applications of the five fractions vary from oil for combustion and extraction of the pyrolytic lignin in the early fractions to extraction of sugars from the early and middle fractions, and extraction of acids and aldehydes in the later fractions.« less
Fractional condensation of pyrolysis vapors produced from Nordic feedstocks in cyclone pyrolysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Johansson, Ann-Christine; Lisa, Kristiina; Sandström, Linda
Pyrolysis oil is a complex mixture of different chemical compounds with a wide range of molecular weights and boiling points. Due to its complexity, an efficient fractionation of the oil may be a more promising approach of producing liquid fuels and chemicals than treating the whole oil. In this work a sampling system based on fractional condensation was attached to a cyclone pyrolysis pilot plant to enable separation of the produced pyrolysis vapors into five oil fractions. The sampling system was composed of cyclonic condensers and coalescing filters arranged in series. Our objective was to characterize the oil fractions producedmore » from three different Nordic feedstocks and suggest possible applications. The oil fractions were thoroughly characterized using several analytical techniques including water content; elemental composition; heating value, and chemical compound group analysis using solvent fractionation, quantitative 13C NMR and 1H NMR and GC x GC - TOFMS. The results show that the oil fractions significantly differ from each other both in chemical and physical properties. The first fractions and the fraction composed of aerosols were highly viscous and contained larger energy-rich compounds of mainly lignin-derived material. The middle fraction contained medium-size compounds with relatively high concentration of water, sugars, alcohols, hydrocarbonyls and acids and finally the last fraction contained smaller molecules such as water, aldehydes, ketones and acids. But, the properties of the respective fractions seem independent on the studied feedstock types, i.e. the respective fractions produced from different feedstock are rather similar. Furthermore, this promotes the possibility to vary the feedstock depending on availability while retaining the oil properties. Possible applications of the five fractions vary from oil for combustion and extraction of the pyrolytic lignin in the early fractions to extraction of sugars from the early and middle fractions, and extraction of acids and aldehydes in the later fractions.« less
NASA Astrophysics Data System (ADS)
Wang, Y.; Soga, K.; DeJong, J. T.; Kabla, A.
2017-12-01
Microbial-induced carbonate precipitation (MICP), one of the bio-mineralization processes, is an innovative subsurface improvement technique for enhancing the strength and stiffness of soils, and controlling their hydraulic conductivity. These macro-scale engineering properties of MICP treated soils controlled by micro-scale factors of the precipitated carbonate, such as its content, amount and distribution in the soil matrix. The precipitation process itself is affected by bacteria amount, reaction kinetics, porous medium geometry and flow distribution in the soils. Accordingly, to better understand the MICP process at the pore scale a new experimental technique that can observe the entire process of MICP at the pore-scale was developed. In this study, a 2-D transparent microfluidic chip made of Polydimethylsiloxane (PDMS) representing the soil matrix was designed and fabricated. A staged-injection MICP treatment procedure was simulated inside the microfluidic chip while continuously monitored using microscopic techniques. The staged-injection MICP treatment procedure started with the injection of bacteria suspension, followed with the bacteria setting for attachment, and then ended with the multiple injections of cementation liquid. The main MICP processes visualized during this procedure included the bacteria transport and attachment during the bacteria injection, the bacteria attachment and growth during the bacteria settling, the bacteria detachment during the cementation liquid injection, the cementation development during the cementation liquid injection, and the cementation development after the completion of cementation liquid injection. It is suggested that the visualization of the main MICP processes using the microfluidic technique can improve understating of the fundamental mechanisms of MICP and consequently help improve the treatment technique for in situ implementation of MICP.
Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu
2016-12-01
This study was carried out to investigate the kinetics of coffee industrial residue (CIR) pyrolysis, the effect of pyrolysis factors on yield of bio-oil component and components separation of bio-oil. The kinetics of CIR pyrolysis was analyzed using distributed activation energy model (DAEM), based on the experiments in thermogravimetric analyzer (TGA), and it indicated that the average of activation energy (E) is 187.86kJ·mol -1 . The bio-oils were prepared from CIR pyrolysis in vacuum tube furnace, and its components were determined by gas chromatography/mass spectrometry (GC-MS). Among pyrolysis factors, pyrolysis temperature is the most influential factor on components yield of bio-oil, directly concerned with the volatilization and yield of components (palmitic acid, linoleic acid, oleic acid, octadecanoic acid and caffeine). Furthermore, a new method (sequencing temperature-raising pyrolysis) was put forward and applied to the components separation of bio-oil. Based on experiments, a solution of components separation of bio-oil was come out. Copyright © 2016 Elsevier Ltd. All rights reserved.
Yuan, Shuai; Dai, Zheng-hua; Zhou, Zhi-jie; Chen, Xue-li; Yu, Guang-suo; Wang, Fu-chen
2012-04-01
Rapid pyrolysis of rice straw (RS) and Shenfu bituminous coal (SB) separately, and rapid co-pyrolysis of RS/SB blends (mass ratio 1:4, 1:4, and 4:1), were carried out in a high-frequency furnace which can ensure both high heating rate and satisfying contact of fuel particles. Synergies between RS and SB during rapid co-pyrolysis were investigated. Intrinsic and morphological structures of residual char from co-pyrolysis, and their effects on gasification characteristics were also studied. Synergies occurred during rapid co-pyrolysis of RS and SB (RS/SB=1:4) resulting in decreasing char yields and increasing volatile yields. Synergies also happened during gasification of the char derived from co-pyrolysis of RS and SB with mass ratio of 1:4. The increased mass ratio of RS to SB did not only weaken synergies during co-pyrolysis, but significantly reduced the gasification rates of the co-pyrolysis char compared to the calculated values. Results can help to optimize co-conversion process of biomass/coal. Copyright © 2012 Elsevier Ltd. All rights reserved.
In situ SEM observation of microscale strain fields around a crack tip in polycrystalline molybdenum
NASA Astrophysics Data System (ADS)
Li, J. J.; Li, W. C.; Jin, Y. J.; Wang, L. F.; Zhao, C. W.; Xing, Y. M.; Lang, F. C.; Yan, L.; Yang, S. T.
2016-06-01
In situ scanning electron microscopy was employed to investigate the crack initiation and propagation in polycrystalline molybdenum under uniaxial tensile load at room temperature. The microscale grid pattern was fabricated using the sputtering deposition technology on the specimen surface covered with a fine square mesh copper grid. The microscale strain fields around the crack tip were measured by geometric phase analysis technique and compared with the theoretical solutions based on the linear elastic fracture mechanics theory. The results showed that as the displacement increases, the crack propagated mainly perpendicular to the tensile direction during the fracture process of molybdenum. The normal strain ɛ xx and shear strain ɛ xy are relatively small, and the normal strain ɛ yy holds a dominant position in the deformation fields and plays a key role in the whole fracture process of molybdenum. With the increase in displacement, the ɛ yy increases rapidly and the two lobes grow significantly but maintain the same shape and orientation. The experimental ɛ yy is in agreement with the theoretical solution. Along the x-axis in front of the crack tip, there is minor discrepancy between the experimental ɛ yy and theoretical ɛ yy within 25 μm from the crack tip, but the agreement between them is very good far from the crack tip (>25 μm).
NASA Technical Reports Server (NTRS)
2006-01-01
Topics covered include: Measurement and Controls Data Acquisition System IMU/GPS System Provides Position and Attitude Data Using Artificial Intelligence to Inform Pilots of Weather Fast Lossless Compression of Multispectral-Image Data Developing Signal-Pattern-Recognition Programs Implementing Access to Data Distributed on Many Processors Compact, Efficient Drive Circuit for a Piezoelectric Pump; Dual Common Planes for Time Multiplexing of Dual-Color QWIPs; MMIC Power Amplifier Puts Out 40 mW From 75 to 110 GHz; 2D/3D Visual Tracker for Rover Mast; Adding Hierarchical Objects to Relational Database General-Purpose XML-Based Information Managements; Vaporizable Scaffolds for Fabricating Thermoelectric Modules; Producing Quantum Dots by Spray Pyrolysis; Mobile Robot for Exploring Cold Liquid/Solid Environments; System Would Acquire Core and Powder Samples of Rocks; Improved Fabrication of Lithium Films Having Micron Features; Manufacture of Regularly Shaped Sol-Gel Pellets; Regulating Glucose and pH, and Monitoring Oxygen in a Bioreactor; Satellite Multiangle Spectropolarimetric Imaging of Aerosols; Interferometric System for Measuring Thickness of Sea Ice; Microscale Regenerative Heat Exchanger Protocols for Handling Messages Between Simulation Computers Statistical Detection of Atypical Aircraft Flights NASA's Aviation Safety and Modeling Project Multimode-Guided-Wave Ultrasonic Scanning of Materials Algorithms for Maneuvering Spacecraft Around Small Bodies Improved Solar-Radiation-Pressure Models for GPS Satellites Measuring Attitude of a Large, Flexible, Orbiting Structure
Preparation of durable flame retardant PAN fabrics based on amidoximation and phosphorylation
NASA Astrophysics Data System (ADS)
Zhang, Yue; Ren, Yuanlin; Liu, Xiaohui; Huo, Tongguo; Qin, Yiwen
2018-01-01
This paper aims to develop a method to impart polyacrylonitrile (PAN) fabric durable flame retadancy. PAN fabric was modified with hydroxylamine hydrochloride (HA) to prepare amidoxime PAN fabric (A-PAN) followed by phosphorylation with phosphoric acid (PA) to obtain flame retardant PAN fabric (P-A-PAN). Thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), microscale combustion calorimetry (MCC) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to analyze the thermal degradation process and flame retardant mechanisms. The structure of the fabrics was characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). The surface morphology of fabrics was observed by scanning electron microscope (SEM). Moreover, the flame retardancy of fabrics before and after washing was evaluated by Limiting oxygen index (LOI) and horizontal burning test. The results showed that the P-A-PAN possessed an excellent thermal stability with the highest LOI value of 34.1% and the highest char residue of 55.67% at 800 °C. Most importantly, the P-A-PAN possessed a wonderful flame retardant durability with a little decrease of LOI after 20 washing cycles. When they were ignited, the P-A-PAN fabrics before and after washing were both nonflammable due to the char residue formation of modified fabric.
Studies on thermal decomposition behaviors of polypropylene using molecular dynamics simulation
NASA Astrophysics Data System (ADS)
Huang, Jinbao; He, Chao; Tong, Hong; Pan, Guiying
2017-11-01
Polypropylene (PP) is one of the main components of waste plastics. In order to understand the mechanism of PP thermal decomposition, the pyrolysis behaviour of PP has been simulated from 300 to 1000 K in periodic boundary conditions by molecular dynamic method, based on AMBER force field. The simulation results show that the pyrolysis process of PP can mostly be divided into three stages: low temperature pyrolysis stage, intermediate temperature stage and high temperature pyrolysis stage. PP pyrolysis is typical of random main-chain scission, and the possible formation mechanism of major pyrolysis products was analyzed.
Evans, R.J.; Chum, H.L.
1998-10-13
A process is described for using fast pyrolysis in a carrier gas to convert a plastic waste feed stream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feed stream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.
Evans, Robert J.; Chum, Helena L.
1994-01-01
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents, selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.
Evans, Robert J.; Chum, Helena L.
1994-01-01
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.
Evans, Robert J.; Chum, Helena L.
1993-01-01
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.
Evans, Robert J.; Chum, Helena L.
1998-01-01
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.
A microscale emission factor model (MicroFacPM) for predicting real-time site-specific motor vehicle particulate matter emissions was presented in the companion paper entitled "Development of a Microscale Emission Factor Model for Particulate Matter (MicroFacPM) for Predicting Re...
A Novel W-Tube for Microscale Experiments in Chemistry
ERIC Educational Resources Information Center
Gupta, H. O.
2007-01-01
A simple W-shaped apparatus was developed by bending glass tubing to contain all of the chemicals involved and to limit the quantities to microscale. The W-tubes were tested by the teachers and students from a few schools to demonstrate its great utility and convenience in microscale chemistry laboratory.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Draxl, C.; Churchfield, M.; Mirocha, J.
Wind plant aerodynamics are influenced by a combination of microscale and mesoscale phenomena. Incorporating mesoscale atmospheric forcing (e.g., diurnal cycles and frontal passages) into wind plant simulations can lead to a more accurate representation of microscale flows, aerodynamics, and wind turbine/plant performance. Our goal is to couple a numerical weather prediction model that can represent mesoscale flow [specifically the Weather Research and Forecasting model] with a microscale LES model (OpenFOAM) that can predict microscale turbulence and wake losses.
Micro- and macroscale coefficients of friction of cementitious materials
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lomboy, Gilson; Sundararajan, Sriram, E-mail: srirams@iastate.edu; Wang, Kejin
2013-12-15
Millions of metric tons of cementitious materials are produced, transported and used in construction each year. The ease or difficulty of handling cementitious materials is greatly influenced by the material friction properties. In the present study, the coefficients of friction of cementitious materials were measured at the microscale and macroscale. The materials tested were commercially-available Portland cement, Class C fly ash, and ground granulated blast furnace slag. At the microscale, the coefficient of friction was determined from the interaction forces between cementitious particles using an Atomic Force Microscope. At the macroscale, the coefficient of friction was determined from stresses onmore » bulk cementitious materials under direct shear. The study indicated that the microscale coefficient of friction ranged from 0.020 to 0.059, and the macroscale coefficient of friction ranged from 0.56 to 0.75. The fly ash studied had the highest microscale coefficient of friction and the lowest macroscale coefficient of friction. -- Highlights: •Microscale (interparticle) coefficient of friction (COF) was determined with AFM. •Macroscale (bulk) COF was measured under direct shear. •Fly ash had the highest microscale COF and the lowest macroscale COF. •Portland cement against GGBFS had the lowest microscale COF. •Portland cement against Portland cement had the highest macroscale COF.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Churchfield, M. J.; Michalakes, J.; Vanderwende, B.
Wind plant aerodynamics are directly affected by the microscale weather, which is directly influenced by the mesoscale weather. Microscale weather refers to processes that occur within the atmospheric boundary layer with the largest scales being a few hundred meters to a few kilometers depending on the atmospheric stability of the boundary layer. Mesoscale weather refers to large weather patterns, such as weather fronts, with the largest scales being hundreds of kilometers wide. Sometimes microscale simulations that capture mesoscale-driven variations (changes in wind speed and direction over time or across the spatial extent of a wind plant) are important in windmore » plant analysis. In this paper, we present our preliminary work in coupling a mesoscale weather model with a microscale atmospheric large-eddy simulation model. The coupling is one-way beginning with the weather model and ending with a computational fluid dynamics solver using the weather model in coarse large-eddy simulation mode as an intermediary. We simulate one hour of daytime moderately convective microscale development driven by the mesoscale data, which are applied as initial and boundary conditions to the microscale domain, at a site in Iowa. We analyze the time and distance necessary for the smallest resolvable microscales to develop.« less
Shi, Lingna; Wang, Lijun; Zhang, Tao; Li, Jianfa; Huang, Xiaoyi; Cai, Jing; Lü, Jinhong; Wang, Yue
2017-10-01
For the purpose of safe disposal of biomass contaminated by biosorption of heavy metals, phosphate-assisted pyrolysis of water hyacinth biomass contaminated by lead (Pb) was tried to reduce the bioavailability and leaching potential of Pb, using direct pyrolysis without additive as a control method. Direct pyrolysis of the contaminated biomass at low temperatures (300 and 400°C) could reduce the bioavailability of Pb, but the leaching potential of Pb was increased with the rising pyrolysis temperature. While phosphate-assisted pyrolysis significantly enhanced the recovery and stability of Pb in the char. Specifically, the percentages of bioavailable Pb and leachable Pb in the chars obtained by phosphate-assisted pyrolysis at low temperatures were reduced to less than 5% and 7%, respectively. The sequential extraction test indicated the transformation of Pb into more stable fractions after phosphate-assisted pyrolysis, which was related to the formation of Pb phosphate minerals including pyromorphite and lead-substituted hydroxyapatite. Copyright © 2017 Elsevier Ltd. All rights reserved.
Mass spectrometric studies of fast pyrolysis of cellulose
DOE Office of Scientific and Technical Information (OSTI.GOV)
Degenstein, John; Hurt, Matt; Murria, Priya
2015-01-01
A fast pyrolysis probe/linear quadrupole ion trap mass spectrometer combination was used to study the primary fast pyrolysis products (those that first leave the hot pyrolysis surface) of cellulose, cellobiose, cellotriose, cellotetraose, cellopentaose, and cellohexaose, as well as of cellobiosan, cellotriosan, and cellopentosan, at 600°C. Similar products with different branching ratios were found for the oligosaccharides and cellulose, as reported previously. However, identical products (with the exception of two) with similar branching ratios were measured for cellotriosan (and cellopentosan) and cellulose. This result demonstrates that cellotriosan is an excellent small-molecule surrogate for studies of the fast pyrolysis of cellulose andmore » also that most fast pyrolysis products of cellulose do not originate from the reducing end. Based on several observations, the fast pyrolysis of cellulose is suggested to initiate predominantly via two competing processes: the formation of anhydro-oligosaccharides, such as cellobiosan, cellotriosan, and cellopentosan (major route), and the elimination of glycolaldehyde (or isomeric) units from the reducing end of oligosaccharides formed from cellulose during fast pyrolysis.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mukarakate, C.; Robichaud, D.; Donohoe, B.
2012-01-01
We have constructed a captive sample reactor (CSR) to study fast pyrolysis of biomass. The reactor uses a stainless steel wire mesh to surround biomass materials with an isothermal environment by independent controlling of heating rates and pyrolysis temperatures. The vapors produced during pyrolysis are immediately entrained and transported in He carrier gas to a molecular beam mass spectrometer (MBMS). Formation of secondary products is minimized by rapidly quenching the sample support with liquid nitrogen. A range of alkali and alkaline earth metal (AAEM) and transition metal salts were tested to study their effect on composition of primary pyrolysis products.more » Multivariate curve resolution (MCR) analysis of the MBMS data shows that transition metal salts enhance pyrolysis of carbohydrates and AAEM salts enhances pyrolysis of lignin. This was supported by performing similar separate studies on cellulose, hemicellulose and extracted lignin. The effect of salts on char formation is also discussed.« less
Liu, Tingting; Liu, Zhengang; Zheng, Qingfu; Lang, Qianqian; Xia, Yu; Peng, Nana; Gai, Chao
2018-01-01
The heavy metals distribution during hydrothermal carbonization (HTC) of sewage sludge, and pyrolysis of the resultant hydrochar was investigated and compared with raw sludge pyrolysis. The results showed that HTC reduced exchangeable/acid-soluble and reducible fraction of heavy metals and lowered the potential risk of heavy metals in sewage sludge. The pyrolysis favored the transformation of extracted/mobile fraction of heavy metals to residual form especially at high temperature, immobilizing heavy metals in the chars. Compared to the chars from raw sludge pyrolysis, the chars derived from hydrochar pyrolysis was more alkaline and had lower risk and less leachable heavy metals, indicating that pyrolysis imposed more positive effect on immobilization of heavy metals for the hydrochar than for sewage sludge. The present study demonstrated that HTC is a promising pretreatment prior to pyrolysis from the perspective of immobilization of heavy metals in sewage sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.
Chen, Handing; Chen, Xueli; Qin, Yueqiang; Wei, Juntao; Liu, Haifeng
2017-03-01
The influence of torrefaction on the physicochemical characteristics of char during raw and water washed rice straw pyrolysis at 800-1200°C is investigated. Pore structure, aromaticity and gasification activity of pyrolysis chars are compared between raw and torrefied samples. For raw straw, BET specific surface area decreases with the increased torrefaction temperature at the same pyrolysis temperature and it approximately increases linearly with weight loss during pyrolysis. The different pore structure evolutions relate to the different volatile matters and pore structures between raw and torrefied straw. Torrefaction at higher temperature would bring about a lower graphitization degree of char during pyrolysis of raw straw. Pore structure and carbon crystalline structure evolutions of raw and torrefied water washed straw are different from these of raw straw during pyrolysis. For both raw and water washed straw, CO 2 gasification activities of pyrolysis chars are different between raw and torrefied samples. Copyright © 2016 Elsevier Ltd. All rights reserved.
Pyrolysis of tyre powder using microwave thermogravimetric analysis: Effect of microwave power.
Song, Zhanlong; Yang, Yaqing; Zhou, Long; Zhao, Xiqiang; Wang, Wenlong; Mao, Yanpeng; Ma, Chunyuan
2017-02-01
The pyrolytic characteristics of tyre powder treated under different microwave powers (300, 500, and 700 W) were studied via microwave thermogravimetric analysis. The product yields at different power levels were studied, along with comparative analysis of microwave pyrolysis and conventional pyrolysis. The feedstock underwent preheating, intense pyrolysis, and final pyrolysis in sequence. The main and secondary weight loss peaks observed during the intense pyrolysis stage were attributed to the decomposition of natural rubbers and synthetic rubbers, respectively. The total mass loss rates, bulk temperatures, and maximum temperatures were distinctively higher at higher powers. However, the maximum mass loss rate (0.005 s -1 ), the highest yields of liquid product (53%), and the minimum yields of residual solid samples (43.83%) were obtained at 500 W. Compared with conventional pyrolysis, microwave pyrolysis exhibited significantly different behaviour with faster reaction rates, which can decrease the decomposition temperatures of both natural and synthetic rubber by approximately 110 °C-140 °C.
Hu, Guangji; Li, Jianbing; Zhang, Xinying; Li, Yubao
2017-05-01
The treatment of waste biomass (sawdust) through co-pyrolysis with refinery oily sludge was carried out in a fixed-bed reactor. Response surface method was applied to evaluate the main and interaction effects of three experimental factors (sawdust percentage in feedstock, temperature, and heating rate) on pyrolysis oil and char yields. It was found that the oil and char yields increased with sawdust percentage in feedstock. The interaction between heating rate and sawdust percentage as well as between heating rate and temperature was significant on the pyrolysis oil yield. The higher heating value of oil originated from sawdust during co-pyrolysis at a sawdust/oily sludge ratio of 3:1 increased by 5 MJ/kg as compared to that during sawdust pyrolysis alone, indicating a synergistic effect of co-pyrolysis. As a result, petroleum sludge can be used as an effective additive in the pyrolysis of waste biomass for improving its energy recovery. Copyright © 2017 Elsevier Ltd. All rights reserved.
Hübner, Tobias; Mumme, Jan
2015-05-01
Anaerobic digestion of aqueous pyrolysis liquor derived from pyrolysis of solid digestate was tested in batch mode using an un-adapted inoculum. Three pyrolysis liquors produced at 330°C, 430°C and 530°C in four COD-based concentrations of 3, 6, 12 and 30 g L(-1) were investigated. The three lower concentrations showed considerable biogas production, whereas the 30 g L(-1) dosage caused process inhibition. The highest methane yield of 199.1±18.5 mL g(COD)(-1) (COD removal: 56.9±5.3%) was observed for the 330°C pyrolysis liquor, followed by the 430°C sample with only slightly lower values. The 530°C sample dropped to a yield of 129.3±19.7 mL g(COD)(-1) (COD removal: 36.9±5.6%). Most VOCs contained in the pyrolysis liquor (i.e. furfural, phenol, catechol, guaiacol, and levoglucosan) were reduced below detection limit (cresol by 10-60%). Consequently, integrated pyrolysis and anaerobic digestion in addition to thermochemical conversion of digestate also promises bioconversion of pyrolysis liquors. Copyright © 2015 Elsevier Ltd. All rights reserved.
Publications - GMC 127 | Alaska Division of Geological & Geophysical
DGGS GMC 127 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite information. Bibliographic Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite ) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department
Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components
USDA-ARS?s Scientific Manuscript database
Zeolites have been shown to effectively promote cracking reactions during pyrolysis resulting in highly deoxygenated and hydrocarbon-rich compounds and stable pyrolysis oil product. Py/GC-MS was employed to study the catalytic fast pyrolysis of lignocellulosic biomass samples comprising oak, corn...
Structural analysis of pyrolytic lignins isolated from switchgrass fast pyrolysis oil
USDA-ARS?s Scientific Manuscript database
Structural characterization of lignin extracted from the bio-oil produced by fast pyrolysis of switchgrass (Panicum virgatum) is reported. This new information is important to understanding the utility of lignin as a chemical feedstock in a pyrolysis based biorefinery. Pyrolysis induces a variety of...
Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abdelsayed, Victor; Shekhawat, Dushyant; Smith, Mark W.
Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwavemore » pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.« less
Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis
Abdelsayed, Victor; Shekhawat, Dushyant; Smith, Mark W.; ...
2018-01-13
Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwavemore » pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.« less
Reprint of: Pyrolysis technologies for municipal solid waste: a review.
Chen, Dezhen; Yin, Lijie; Wang, Huan; He, Pinjing
2015-03-01
Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO2 and NH3, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested. Copyright © 2015 Elsevier Ltd. All rights reserved.
Evans, R.J.; Chum, H.L.
1994-10-25
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.
Evans, Robert J.; Chum, Helena L.
1994-01-01
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.
Evans, R.J.; Chum, H.L.
1994-04-05
A process is described for using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents, selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 87 figures.
Evans, R.J.; Chum, H.L.
1994-10-25
A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Haddix, Michelle L.; Magrini-Bair, Kim; Evans, Robert J.
Soil organic matter (SOM) is extremely complex. It is composed of hundreds of different organic substances and it has been difficult to quantify these diverse substances in a dynamic-ecosystem functioning standpoint. Analytical pyrolysis has been used to compare chemical differences between soils, but its ability to measure the absolute amount of a specific compound in the soil is still in question. Our objective was to assess whether utilizing pyrolysis-molecular beam mass spectroscopy (py-MBMS) to define the signature of known reference compounds (adenine, indole, palmitic acid, etc.) and biological samples (chitin, fungi, cellulose, etc.) separately and when added to whole soilsmore » it was possible to make py-MBMS more quantitative. Reference compounds, spanning a wide variety of compound categories, and biological samples, expected to be present in SOM, were added to three soils from Colorado, Ohio, and Massachusetts that have varying total C, % clay, and clay type. Py-MBMS, a rapid analysis technique originally developed to analyze complex biomolecules, flash pyrolyzes soil organic matter to form products that are often considered characteristic of the original molecular structure. Samples were pyrolyzed at 550 degrees C by py-MBMS. All samples were weighed and %C and %N determined both before and after pyrolysis to evaluate mass loss, C loss, and N loss for the samples.An average relationship of r2 = 0.76 (P = 0.005) was found for the amount of cellulose added to soil at 25, 50, and 100% of soil C relative to the ion intensity of select mass/charge of the compound.There was a relationship of r2 = 0.93 (P < 0.001) for the amount of indole added to soil at 25, 50, and 100% of soil C and the ion intensity of the associated mass variables (mass/charge). Comparing spectra of pure compounds with the spectra of the compounds added to soil and isolated clay showed that interference could occur based on soil type and compound with the Massachusetts soil with high C (55.8 g C kg-1) and low % clay (5.4%) having the least interference and the Colorado soil with low C (14.6 g C kg-1) and a moderate smectite clay content of 14% having the greatest soil interference. Due to soil interference from clay type and content and varying optimum temperatures of pyrolysis for different compounds it is unlikely that analytical pyrolysis can be quantitative for all types of compounds. Select compound categories such as carbohydrates have the potential to be quantified in soil with analytical pyrolysis due to the fact that they: 1) almost fully pyrolyzed, 2) were represented by a limited number of m/z, and 3) had a strong relationship with the amount added and the total ion intensity produced. The three different soils utilized in this study had similar proportions of C pyrolyzed in the whole soil (54-57%) despite differences in %C and %clay between the soils. Mid-infrared spectroscopic analyses of the soil before and after pyrolysis showed that pyrolysis resulted in reductions in the 3400, 2930-2870, 1660 and 1430 cm-1 bands. These bands are primarily representative of O-H and N-H bonds, C-H stretch, and ..delta.. (CH2) in polysaccharides/lipid and are associated with mineralizable SOM. The incorporation of standards into routine analytical pyrolysis allowed us to assess the quantitative potential of py-MBMS along with the effect of the mineral matrix, which we believe is applicable to all forms of analytical pyrolysis.« less
Takeno, Shinya; Bamba, Takeshi; Nakazawa, Yoshihisa; Fukusaki, Eiichiro; Okazawa, Atsushi; Kobayashi, Akio
2008-04-01
Commercial development of trans-1,4-polyisoprene from Eucommia ulmoides Oliver (EU-rubber) requires specific knowledge on selection of high-rubber-content lines and establishment of agronomic cultivation methods for achieving maximum EU-rubber yield. The development can be facilitated by high-throughput and highly sensitive analytical techniques for EU-rubber extraction and quantification. In this paper, we described an efficient EU-rubber extraction method, and validated that the accuracy was equivalent to that of the conventional Soxhlet extraction method. We also described a highly sensitive quantification method for EU-rubber by Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-gas chromatography/mass spectrometry (PyGC/MS). We successfully applied the extraction/quantification method for study of seasonal changes in EU-rubber content and molecular weight distribution.
Tailoring ZSM-5 Zeolites for the Fast Pyrolysis of Biomass to Aromatic Hydrocarbons.
Hoff, Thomas C; Gardner, David W; Thilakaratne, Rajeeva; Wang, Kaige; Hansen, Thomas W; Brown, Robert C; Tessonnier, Jean-Philippe
2016-06-22
The production of aromatic hydrocarbons from cellulose by zeolite-catalyzed fast pyrolysis involves a complex reaction network sensitive to the zeolite structure, crystallinity, elemental composition, porosity, and acidity. The interplay of these parameters under the reaction conditions represents a major roadblock that has hampered significant improvement in catalyst design for over a decade. Here, we studied commercial and laboratory-synthesized ZSM-5 zeolites and combined data from 10 complementary characterization techniques in an attempt to identify parameters common to high-performance catalysts. Crystallinity and framework aluminum site accessibility were found to be critical to achieve high aromatic yields. These findings enabled us to synthesize a ZSM-5 catalyst with enhanced activity, which offers the highest aromatic hydrocarbon yield reported to date. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
SnS2 Thin Film Deposition by Spray Pyrolysis
NASA Astrophysics Data System (ADS)
Jaber, Abdallah Yahia; Alamri, Saleh Noaiman; Aida, Mohammed Salah
2012-06-01
Tin disulfide (SnS2) thin films have been synthesized using a simplified spray pyrolysis technique using a perfume atomizer. The films were deposited using two different solutions prepared by the dilution of SnCl2 and thiourea in distilled water and in methanol. The obtained films have a microcrystalline structure. The film deposited using methanol as the solvent is nearly stochiometric SnS2 with a spinel phase having a (001) preferential orientation. The film prepared with an aqueous solution is Sn-rich. Scanning electronic microscopy (SEM) images reveal that the film deposited with the aqueous solution is rough and is formed with large wires. However, the film deposited with methanol is dense and smooth. Conductivity measurements indicate that the aqueous solution leads to an n-type semiconductor, while methanol leads to a p-type semiconductor.
Microwave assisted pyrolysis of halogenated plastics recovered from waste computers.
Rosi, Luca; Bartoli, Mattia; Frediani, Marco
2018-03-01
Microwave Assisted Pyrolysis (MAP) of the plastic fraction of Waste from Electric and Electronic Equipment (WEEE) from end-life computers was run with different absorbers and set-ups in a multimode batch reactor. A large amount of various different liquid fractions (up to 76.6wt%) were formed together with a remarkable reduction of the solid residue (up to 14.2wt%). The liquid fractions were characterized using the following different techniques: FT-IR ATR, 1 H NMR and a quantitative GC-MS analysis. The liquid fractions showed low density and viscosity, together with a high concentration of useful chemicals such as styrene (up to 117.7mg/mL), xylenes (up to 25.6mg/mL for p-xylene) whereas halogenated compounds were absent or present in a very low amounts. Copyright © 2017 Elsevier Ltd. All rights reserved.
Rapid habitability assessment of Mars samples by pyrolysis-FTIR
NASA Astrophysics Data System (ADS)
Gordon, Peter R.; Sephton, Mark A.
2016-02-01
Pyrolysis Fourier transform infrared spectroscopy (pyrolysis FTIR) is a potential sample selection method for Mars Sample Return missions. FTIR spectroscopy can be performed on solid and liquid samples but also on gases following preliminary thermal extraction, pyrolysis or gasification steps. The detection of hydrocarbon and non-hydrocarbon gases can reveal information on sample mineralogy and past habitability of the environment in which the sample was created. The absorption of IR radiation at specific wavenumbers by organic functional groups can indicate the presence and type of any organic matter present. Here we assess the utility of pyrolysis-FTIR to release water, carbon dioxide, sulfur dioxide and organic matter from Mars relevant materials to enable a rapid habitability assessment of target rocks for sample return. For our assessment a range of minerals were analyzed by attenuated total reflectance FTIR. Subsequently, the mineral samples were subjected to single step pyrolysis and multi step pyrolysis and the products characterised by gas phase FTIR. Data from both single step and multi step pyrolysis-FTIR provide the ability to identify minerals that reflect habitable environments through their water and carbon dioxide responses. Multi step pyrolysis-FTIR can be used to gain more detailed information on the sources of the liberated water and carbon dioxide owing to the characteristic decomposition temperatures of different mineral phases. Habitation can be suggested when pyrolysis-FTIR indicates the presence of organic matter within the sample. Pyrolysis-FTIR, therefore, represents an effective method to assess whether Mars Sample Return target rocks represent habitable conditions and potential records of habitation and can play an important role in sample triage operations.
Controlling Mass Transport in Microfluidic Devices
Kuo, Jason S.; Chiu, Daniel T.
2017-01-01
Microfluidic platforms offer exquisite capabilities in controlling mass transport for biological studies. In this review, we focus on recent developments in manipulating chemical concentrations at the microscale. Some techniques prevent or accelerate mixing, whereas others shape the concentration gradients of chemical and biological molecules. We also highlight several in vitro biological studies in the areas of organ engineering, cancer, and blood coagulation that have benefited from accurate control of mass transfer. PMID:21456968
Adaption of an In-Situ Microscale Tension Technique to Enable Fatigue Testing (PREPRINT)
2012-08-01
mechanical properties , including fatigue performance, are strongly related to the crystallographic texture of these alloys.[5-7] With the combined use...effects, exploration of deformation micromechanisms, and measurement of the local properties in a bulk material (e.g., variations in the local...Approved for public release; distribution unlimited 9 microstructure of this material , would be expected to exhibit a reduction in mechanical properties
Low loss fusion splicing of micron scale silica fibers.
Pal, Parama; Knox, Wayne H
2008-07-21
Tapered micron-sized optical fibers may be important in the future for development of microscale integrated photonic devices. Complex photonic circuits require many devices and a robust technique for interconnection. We demonstrate splicing of four micron diameter step-index air-clad silica microfibers using a CO2 laser. We obtain splice losses lower than 0.3%. Compared with evanescent coupling of microfibers, our splices are more mechanically stable and efficient.
NASA Technical Reports Server (NTRS)
Popp, B. N.; Hayes, J. M.; Boreham, C. J.
1993-01-01
Molar extinction coefficients for band III of Ni porphyrins are calculated from results of spectrophotometric and manometric analyses of individual etioporphyrins, DPEP, cyclic, and diDPEP porphyrins known to initially be pure from mass spectrometry, 1H NMR, and analytical HPLC studies. A method for determining carbon-isotopic compositions and purity of micromolar quantities of individual porphyrins using combined spectrophotometric and manometric techniques is presented.
Publications - GMC 137 | Alaska Division of Geological & Geophysical
DGGS GMC 137 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of Report Report Information gmc137.pdf (47.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic
Publications - GMC 100 | Alaska Division of Geological & Geophysical
DGGS GMC 100 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc100.pdf (317.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 144 | Alaska Division of Geological & Geophysical
DGGS GMC 144 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite for more information. Bibliographic Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis gmc144.pdf (104.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance
Publications - GMC 30 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 30 Publication Details Title: Geochemical analysis (total organic carbon, rock-eval pyrolysis , Geochemical analysis (total organic carbon, rock-eval pyrolysis, vitrinite reflectance and gc/ms chromato (1.3 M) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of
Publications - GMC 141 | Alaska Division of Geological & Geophysical
DGGS GMC 141 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of Report Report Information gmc141.pdf (70.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic
Publications - GMC 101 | Alaska Division of Geological & Geophysical
DGGS GMC 101 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc101.pdf (201.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 60 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 60 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite , Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance geochemical data for the Nechelik (125.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of
Publications - GMC 27 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 27 Publication Details Title: Geochemical analysis (total organic carbon, rock-eval pyrolysis . Bibliographic Reference Unknown, 1995, Geochemical analysis (total organic carbon, rock-eval pyrolysis, and ; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of
Publications - GMC 103 | Alaska Division of Geological & Geophysical
DGGS GMC 103 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc103.pdf (57.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 23 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 23 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, [n.d.], Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance for Information gmc023.pdf (199.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon
Publications - GMC 22 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 22 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, 1984, Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance for the gmc022.pdf (247.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 102 | Alaska Division of Geological & Geophysical
DGGS GMC 102 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc102.pdf (81.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 124 | Alaska Division of Geological & Geophysical
DGGS GMC 124 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data from the Report Information gmc124.pdf (278.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon
Publications - GMC 68 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 68 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1987, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance geochemical Report Report Information gmc068.pdf (48.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic
40 CFR 721.10579 - Carbon black derived from the pyrolysis of rubber tire shreds (generic).
Code of Federal Regulations, 2013 CFR
2013-07-01
... pyrolysis of rubber tire shreds (generic). 721.10579 Section 721.10579 Protection of Environment... pyrolysis of rubber tire shreds (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as carbon black derived from the pyrolysis of...
Kim, Jeong In; Kim, Cheol Sang
2018-04-18
Cells respond to their microenvironment, which is of a size comparable to that of the cells. The macroscale features of three-dimensional (3D) printing struts typically result in whole cell contact guidance (CCG). In contrast, at the nanoscale, where features are of a size similar to that of receptors of cells, the response of cells is more complex. The cell-nanotopography interaction involves nanoscale adhesion localized structures, which include cell adhesion-related particles that change in response to the clustering of integrin. For this reason, it is necessary to develop a technique for manufacturing tailorable nano/macrohybrid constructs capable of freely controlling the cellular activity. In this study, a hierarchical 3D nano- to microscale hybrid structure was fabricated by combinational processing of 3D printing and electrified inkjet spinning via pin motions. This method overcomes the disadvantages of conventional 3D printing, providing a novel combinatory technique for the fabrication of 3D hybrid constructs with excellent cell proliferation. Through a pin-modified electrified inkjet spinning, we have successfully fabricated customizable nano-/microscale hybrid constructs in a fibrous or mesh form, which can control the cell fate. We have conducted this study of cell-topography interactions from the fabrication approach to accelerate the development of next-generation 3D scaffolds.
Yang, Yue; Cheow, Wean Sin; Hadinoto, Kunn
2012-09-15
Lipid-polymer hybrid nanoparticles have emerged as promising nanoscale carriers of therapeutics as they combine the attractive characteristics of liposomes and polymers. Herein we develop dry powder inhaler (DPI) formulation of hybrid nanoparticles composed of poly(lactic-co-glycolic acid) and soybean lecithin as the polymer and lipid constituents, respectively. The hybrid nanoparticles are transformed into inhalable microscale nanocomposite structures by a novel technique based on electrostatically-driven adsorption of nanoparticles onto polysaccharide carrier particles, which eliminates the drawbacks of conventional techniques based on controlled drying (e.g. nanoparticle-specific formulation, low yield). First, we engineer polysaccharide carrier particles made up of chitosan cross-linked with tripolyphosphate and dextran sulphate to exhibit the desired aerosolization characteristics and physical robustness. Second, we investigate the effects of nanoparticle to carrier mass ratio and salt inclusion on the adsorption efficiency, in terms of the nanoparticle loading and yield, from which the optimal formulation is determined. Desorption of the nanoparticles from the carrier particles in phosphate buffer saline is also examined. Lastly, we characterize aerosolization efficiency of the nanocomposite product in vitro, where the emitted dose and respirable fraction are found to be comparable to the values of conventional DPI formulations. Copyright © 2012 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kazmerski, Lawrence L.; Diniz, Antonia Sonia A. C.; Maia, Cristiana Brasil
Photovoltaic (PV) module soiling is a growing area of concern for performance and reliability. This paper provides evaluations of the fundamental interactions of dust/soiling particles with several PV module surfaces. The purpose is to investigate the basic mechanisms involving the chemistry, morphology, and resulting particle adhesion to the first photon-incident surface. The evaluation and mapping of the chemistry and composition of single dust particles collected from operating PV module surfaces are presented. The first correlated direct measurements of the adhesive force of individual grains from field-operating collectors on identical PV module glass are reported, including correlations with specific compositions. Specialmore » microscale atomic force microscopy techniques are adapted to determine the force between the particle and the module glass surface. Results are presented for samples under dry and moisture-exposed conditions, confirming the effects of cementation for surfaces having soluble mineral and/or organic concentrations. Additionally, the effects of hydrocarbon fuels on the enhanced bonding of soiling particles to surfaces are determined for samples from urban and highly trafficked regions. Comparisons between glass and dust-mitigating superhydrophobic and superhydrophilic coatings are presented. Potential limitations of this proximal probe technique are discussed in terms of results and initial proof-of-concept experiments.« less
Effects of torrefaction and densification on switchgrass pyrolysis products
Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; ...
2014-12-01
Abstract The pyrolysis behaviors of four types of pretreated switchgrass (torrefied at 230 and 270 °C, densification, and torrefaction at 270 ºC followed by densification) were studied at three temperatures (500, 600, 700 ºC) using a pyroprobe attached to a gas chromatogram mass spectroscopy (Py-GC/MS). The torrefaction of switchgrass improved its oxygen to carbon ratio and energy content. Contents of anhydrous sugars and phenols in pyrolysis products of torrefied switchgrass were higher than those in pyrolysis products of raw switchgrass. As the torrefaction temperature increased from 230 to 270 °C, the contents of anhydrous sugars and phenols in pyrolysis productsmore » increased whereas content of guaiacols decreased. High pyrolysis temperature (600 and 700 °C as compared to 500 °C) enhanced decomposition of lignin and anhydrous sugars, leading to increase in phenols, aromatics and furans. Densification enhanced depolymerization of cellulose and hemicellulose during pyrolysis.« less
Publications - GMC 242 | Alaska Division of Geological & Geophysical
DGGS GMC 242 Publication Details Title: Total organic carbon and rock-eval pyrolysis evaluation of 21 Core Laboratories, 1995, Total organic carbon and rock-eval pyrolysis evaluation of 21 hand-picked coal Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon Top of Page Department of Natural Resources, Division
Publications - GMC 136 | Alaska Division of Geological & Geophysical
DGGS GMC 136 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and some vitrinite Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and some vitrinite reflectance data of cuttings Report Information gmc136.pdf (39.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon
Publications - GMC 99 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 99 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch Report Report Information gmc099.pdf (383.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic
Publications - GMC 12 | Alaska Division of Geological & Geophysical Surveys
- 11,850 feet; total organic carbon, rock-eval pyrolysis and visual kerogen/vitrinite reflectance Authors River #1 well 10,255 - 11,850 feet; total organic carbon, rock-eval pyrolysis and visual kerogen gmc012.pdf (384.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 20 | Alaska Division of Geological & Geophysical Surveys
, rock-eval/pyrolysis, total organic carbon) and core logs for the David River USA #1-A, Hoodoo Lake Unit , 1969, Geochemical analysis (vitrinite reflectance, visual kerogen, rock-eval/pyrolysis, total organic gmc020.pdf (3.2 M) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite
Publications - GMC 24 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 24 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, [n.d.], Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance of the Information gmc024.pdf (79.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon
Publications - GMC 123 | Alaska Division of Geological & Geophysical
DGGS GMC 123 Publication Details Title: Total organic carbon and rock-eval pyrolysis data of select organic carbon and rock-eval pyrolysis data of select cuttings from the Chevron USA Akulik #1 well: Alaska Pyrolysis; Rock-Eval Pyrolysis Top of Page Department of Natural Resources, Division of Geological &
Publications - GMC 83 | Alaska Division of Geological & Geophysical Surveys
DGGS GMC 83 Publication Details Title: Rock-eval pyrolysis data and interpretation for the Alaska and Ruth Laboratories, Inc., 1988, Rock-eval pyrolysis data and interpretation for the Alaska Information gmc083.pdf (274.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page Department of Natural
Publications - GMC 284 | Alaska Division of Geological & Geophysical
DGGS GMC 284 Publication Details Title: TOC/rock-eval pyrolysis geochemical data for 26 Alaska North for more information. Bibliographic Reference Unknown, 1999, TOC/rock-eval pyrolysis geochemical data Information gmc284.pdf (1.8 M) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon Top of Page
Li, Hao; Mahyoub, Samah Awadh Ali; Liao, Wenjie; Xia, Shuqian; Zhao, Hechuan; Guo, Mengya; Ma, Peisheng
2017-01-01
The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO 3 ) 3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe 2 O 3 ) particles, showed pronounced effects on the adsorption performance of aromatic contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.
High-resolution mass spectrometric analysis of biomass pyrolysis vapors
Christensen, Earl; Evans, Robert J.; Carpenter, Daniel
2017-01-19
Vapors generated from the pyrolysis of lignocellulosic biomass are made up of a complex mixture of oxygenated compounds. Direct analysis of these vapors provides insight into the mechanisms of depolymerization of cellulose, hemicellulose, and lignin as well as insight into reactions that may occur during condensation of pyrolysis vapors into bio-oil. Studies utilizing pyrolysis molecular beam mass spectrometry have provided valuable information regarding the chemical composition of pyrolysis vapors. Mass spectrometers generally employed with these instruments have low mass resolution of approximately a mass unit. The presence of chemical species with identical unit mass but differing elemental formulas cannot bemore » resolved with these instruments and are therefore detected as a single ion. In this study we analyzed the pyrolysis vapors of several biomass sources using a high-resolution double focusing mass spectrometer. High-resolution analysis of pyrolysis vapors allowed for speciation of several compounds that would be detected as a single ion with unit mass resolution. Lastly, these data not only provide greater detail into the composition of pyrolysis vapors but also highlight differences between vapors generated from multiple biomass feedstocks.« less
Çepelioğullar, Özge; Pütün, Ayşe E
2014-10-01
In this study, thermochemical conversion of plastic wastes (PET and PVC) together with an agricultural waste (hazelnut shell) was investigated. In order to determine the thermal and kinetic behaviours, pyrolysis experiments were carried out from room temperature to 800 °C, with a heating rate of 10 °C min(-1) in the presence of a N2 atmosphere in a thermogravimetric analyzer. With the obtained thermogravimetric data, an appropriate temperature was specified for the pyrolysis of biomass-plastic wastes in a fixed-bed reactor. At the second step, pyrolysis experiments were carried out at the same conditions with the thermogravimetric analyzer, except the final temperature which was up to 500 °C in this case. After pyrolysis experiments, pyrolysis yields were calculated and characterization studies for bio-oil were investigated. Experimental results showed that co-pyrolysis has an important role in the determination of the pyrolysis mechanism and the process conditions while designing/implementing a thermochemical conversion method where biomass-plastic materials were preferred as raw materials. © The Author(s) 2014.
Tracking and visualization of space-time activities for a micro-scale flu transmission study.
Qi, Feng; Du, Fei
2013-02-07
Infectious diseases pose increasing threats to public health with increasing population density and more and more sophisticated social networks. While efforts continue in studying the large scale dissemination of contagious diseases, individual-based activity and behaviour study benefits not only disease transmission modelling but also the control, containment, and prevention decision making at the local scale. The potential for using tracking technologies to capture detailed space-time trajectories and model individual behaviour is increasing rapidly, as technological advances enable the manufacture of small, lightweight, highly sensitive, and affordable receivers and the routine use of location-aware devices has become widespread (e.g., smart cellular phones). The use of low-cost tracking devices in medical research has also been proved effective by more and more studies. This study describes the use of tracking devices to collect data of space-time trajectories and the spatiotemporal processing of such data to facilitate micro-scale flu transmission study. We also reports preliminary findings on activity patterns related to chances of influenza infection in a pilot study. Specifically, this study employed A-GPS tracking devices to collect data on a university campus. Spatiotemporal processing was conducted for data cleaning and segmentation. Processed data was validated with traditional activity diaries. The A-GPS data set was then used for visual explorations including density surface visualization and connection analysis to examine space-time activity patterns in relation to chances of influenza infection. When compared to diary data, the segmented tracking data demonstrated to be an effective alternative and showed greater accuracies in time as well as the details of routes taken by participants. A comparison of space-time activity patterns between participants who caught seasonal influenza and those who did not revealed interesting patterns. This study proved that tracking technology an effective technique for obtaining data for micro-scale influenza transmission research. The findings revealed micro-scale transmission hotspots on a university campus and provided insights for local control and prevention strategies.
Comparison of the pyrolysis behavior of lignins from different tree species.
Wang, Shurong; Wang, Kaige; Liu, Qian; Gu, Yueling; Luo, Zhongyang; Cen, Kefa; Fransson, Torsten
2009-01-01
Despite the increasing importance of biomass pyrolysis, little is known about the pyrolysis behavior of lignin--one of the main components of biomass--due to its structural complexity and the difficulty in its isolation. In the present study, we extracted lignins from Manchurian ash (Fraxinus mandschurica) and Mongolian Scots pine (Pinus sylvestris var. mongolica) using the Bjorkman procedure, which has little effect on the structure of lignin. Fourier transform infrared (FTIR) spectrometry was used to characterize the microstructure of the Bjorkman lignins, i.e., milled wood lignins (MWLs), from the different tree species. The pyrolysis characteristics of MWLs were investigated using a thermogravimetric analyzer, and the release of the main volatile and gaseous products of pyrolysis were detected by FTIR spectroscopy. During the pyrolysis process, MWLs underwent thermo-degradation over a wide temperature range. Manchurian ash MWL showed a much higher thermal degradation rate than Mongolian Scots pine MWL in the temperature range from 290-430 degrees C. High residue yields were achieved at 37 wt.% for Mongolian Scots pine MWL and 26 wt.% for Manchurian ash MWL. In order to further investigate the mechanisms of lignin pyrolysis, we also analyzed the FTIR profiles for the main pyrolysis products (CO(2), CO, methane, methanol, phenols and formaldehyde) and investigated the variation in pyrolysis products between the different MWLs.
Evans, R.J.; Chum, H.L.
1994-06-14
A process is described using fast pyrolysis to convert a plastic waste feed stream containing polycarbonate and ABS to high value monomeric constituents prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of a given polymer to its high value monomeric constituents prior to a temperature range that causes pyrolysis of other plastic components; selecting an acid or base catalysts and an oxide or carbonate support for treating the feed stream to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of the high value monomeric constituents of polycarbonate and ABS in the first temperature program range; differentially heating the feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituents prior to pyrolysis or other plastic components; separating the high value monomeric constituents from the polycarbonate to cause pyrolysis to a different high value monomeric constituent of the plastic waste and differentially heating the feed stream at the second higher temperature program range to cause pyrolysis of different high value monomeric constituents; and separating the different high value monomeric constituents. 68 figs.
Pyrolysis of polystyrene - polyphenylene oxide to recover styrene and useful products
Evans, Robert J.; Chum, Helena L.
1995-01-01
A process of using fast pyrolysis in a carrier gas to convert a polystyrene and polyphenylene oxide plastic waste to a given polystyrene and polyphenylene oxide prior to pyrolysis of other plastic components therein comprising: selecting a first temperature range to cause pyrolysis of given polystyrene and polyphenylene oxide and its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and a support and treating the feed stream with the catalyst to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of high value monomeric constituent of styrene from polystyrene and polyphenylene oxide in the first temperature range; differentially heating the feed stream at a heat rate within the first temperature range to provide differential pyrolysis for selective recovery of the high value monomeric constituent of styrene from polystyrene and polyphenylene oxide prior to pyrolysis of other plastic components; separating the high value monomer constituent of styrene; selecting a second higher temperature range to cause pyrolysis to a different derived high value product of polyphenylene oxide from the plastic waste and differentially heating the feed stream at the higher temperature range to cause pyrolysis of the plastic into a polyphenylene oxide derived product; and separating the different derived high value polyphenylene oxide product.
Evans, Robert J.; Chum, Helena L.
1994-01-01
A process of using fast pyrolysis to convert a plastic waste feed stream containing polycarbonate and ABS to high value monomeric constituents prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of a given polymer to its high value monomeric constituents prior to a temperature range that causes pyrolysis of other plastic components; selecting an acid or base catalysts and an oxide or carbonate support for treating the feed stream to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of the high value monomeric constituents of polycarbonate and ABS in the first temperature program range; differentially heating the feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituents prior to pyrolysis or other plastic components; separating the high value monomeric constituents from the polycarbonate to cause pyrolysis to a different high value monomeric constituent of the plastic waste and differentially heating the feed stream at the second higher temperature program range to cause pyrolysis of different high value monomeric constituents; and separating the different high value monomeric constituents.
Vacuum pyrolysis of waste tires with basic additives.
Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Chang, Jie
2008-11-01
Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na2CO3, NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48 wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 degrees C by adding 3 wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39 wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na2CO3 addition. Pyrolysis gas was mainly composed of H2, CO, CH4, CO2, C2H4 and C2H6. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.
Chum, H.L.; Evans, R.J.
1992-08-04
A process is described for using fast pyrolysis in a carrier gas to convert a waste phenolic resin containing feedstreams in a manner such that pyrolysis of said resins and a given high value monomeric constituent occurs prior to pyrolyses of the resins in other monomeric components therein comprising: selecting a first temperature program range to cause pyrolysis of said resin and a given high value monomeric constituent prior to a temperature range that causes pyrolysis of other monomeric components; selecting, if desired, a catalyst and a support and treating said feedstreams with said catalyst to effect acid or basic catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said first temperature program range to utilize reactive gases such as oxygen and steam in the pyrolysis process to drive the production of specific products; differentially heating said feedstreams at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantity of said high value monomeric constituent prior to pyrolysis of other monomeric components therein; separating said high value monomeric constituent; selecting a second higher temperature program range to cause pyrolysis of a different high value monomeric constituent of said phenolic resins waste and differentially heating said feedstreams at said higher temperature program range to cause pyrolysis of said different high value monomeric constituent; and separating said different high value monomeric constituent. 11 figs.
Chum, Helena L.; Evans, Robert J.
1992-01-01
A process of using fast pyrolysis in a carrier gas to convert a waste phenolic resin containing feedstreams in a manner such that pyrolysis of said resins and a given high value monomeric constituent occurs prior to pyrolyses of the resins in other monomeric components therein comprising: selecting a first temperature program range to cause pyrolysis of said resin and a given high value monomeric constituent prior to a temperature range that causes pyrolysis of other monomeric components; selecting, if desired, a catalyst and a support and treating said feedstreams with said catalyst to effect acid or basic catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said first temperature program range to utilize reactive gases such as oxygen and steam in the pyrolysis process to drive the production of specific products; differentially heating said feedstreams at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantity of said high value monomeric constituent prior to pyrolysis of other monomeric components therein; separating said high value monomeric constituent; selecting a second higher temperature program range to cause pyrolysis of a different high value monomeric constituent of said phenolic resins waste and differentially heating said feedstreams at said higher temperature program range to cause pyrolysis of said different high value monomeric constituent; and separating said different high value monomeric constituent.
NASA Technical Reports Server (NTRS)
Goldstein, Melvyn L.; Parks, George; Gurgiolo, C.; Fazakerley, Andrew N.
2008-01-01
We present determinations of compressibility and vorticity in the magnetosheath and plasma sheet using moments from the four PEACE thermal electron instruments on CLUSTER. The methodology used assumes a linear variation of the moments throughout the volume defined by the four satellites, which allows spatially independent estimates of the divergence, curl, and gradient. Once the vorticity has been computed, it is possible to estimate directly the Taylor microscale. We have shown previously that the technique works well in the solar wind. Because the background flow speed in the magnetosheath and plasma sheet is usually less than the Alfven speed, the Taylor frozen-in-flow approximation cannot be used. Consequently, this four spacecraft approach is the only viable method for obtaining the wave number properties of the ambient fluctuations. Our results using electron velocity moments will be compared with previous work using magnetometer data from the FGM experiment on Cluster.
Practical, microfabrication-free device for single-cell isolation.
Lin, Liang-I; Chao, Shih-Hui; Meldrum, Deirdre R
2009-08-21
Microfabricated devices have great potential in cell-level studies, but are not easily accessible for the broad biology community. This paper introduces the Microscale Oil-Covered Cell Array (MOCCA) as a low-cost device for high throughput single-cell analysis that can be easily produced by researchers without microengineering knowledge. Instead of using microfabricated structures to capture cells, MOCCA isolates cells in discrete aqueous droplets that are separated by oil on patterned hydrophilic areas across a relatively more hydrophobic substrate. The number of randomly seeded Escherichia coli bacteria in each discrete droplet approaches single-cell levels. The cell distribution on MOCCA is well-fit with Poisson distribution. In this pioneer study, we created an array of 900-picoliter droplets. The total time needed to seed cells in approximately 3000 droplets was less than 10 minutes. Compared to traditional microfabrication techniques, MOCCA dramatically lowers the cost of microscale cell arrays, yet enhances the fabrication and operational efficiency for single-cell analysis.
NASA Astrophysics Data System (ADS)
El-Kady, Maher F.; Kaner, Richard B.
2013-02-01
The rapid development of miniaturized electronic devices has increased the demand for compact on-chip energy storage. Microscale supercapacitors have great potential to complement or replace batteries and electrolytic capacitors in a variety of applications. However, conventional micro-fabrication techniques have proven to be cumbersome in building cost-effective micro-devices, thus limiting their widespread application. Here we demonstrate a scalable fabrication of graphene micro-supercapacitors over large areas by direct laser writing on graphite oxide films using a standard LightScribe DVD burner. More than 100 micro-supercapacitors can be produced on a single disc in 30 min or less. The devices are built on flexible substrates for flexible electronics and on-chip uses that can be integrated with MEMS or CMOS in a single chip. Remarkably, miniaturizing the devices to the microscale results in enhanced charge-storage capacity and rate capability. These micro-supercapacitors demonstrate a power density of ~200 W cm-3, which is among the highest values achieved for any supercapacitor.
Controlled microfluidic interfaces for microsensors
NASA Astrophysics Data System (ADS)
Jiang, H.
2009-02-01
Lab on a chip has found many applications in biological and chemical analysis, including pathogen detections. Because these labs on chips involve handling of fluids at the microscale, surface tension profoundly affects the behavior and performance of these systems. Through careful engineering, controlled liquid-liquid or liquid-gas interfaces at the microscale can be formed and used in many interesting applications. In this talk, I will present our work on applying such interfaces to microsensing. These interfaces are created at hydrophobic-hydrophilic boundaries formed within microfluidic channels and pinned by surface tension. We have designed and fabricated a few microsensing techniques including chemical and biological sensing using dissolvable micromembranes in microchannels, chemical and biological sensing at liquid crystals interfacing either air or aqueous solutions, and collection of gaseous samples and aerosols through air-liquid microfludic interfaces. I will next introduce on-chip microlenses and microlens arrays for optical detection, including smart and adaptive liquid microlenses actuated by stimuli-responsive hydrogels, and liquid microlenses in situ formed within microfluidic channels via pneumatic control of droplets.
Continuous separation of colloidal particles using dielectrophoresis.
Yunus, Nurul Amziah Md; Nili, Hossein; Green, Nicolas G
2013-04-01
Dielectrophoresis is the movement of particles in nonuniform electric fields and has been of interest for application to manipulation and separation at and below the microscale. This technique has the advantages of being noninvasive, nondestructive, and noncontact, with the movement of particle achieved by means of electric fields generated by miniaturized electrodes and microfluidic systems. Although the majority of applications have been above the microscale, there is increasing interest in application to colloidal particles around a micron and smaller. This paper begins with a review of colloidal and nanoscale dielectrophoresis with specific attention paid to separation applications. An innovative design of integrated microelectrode array and its application to flow-through, continuous separation of colloidal particles is then presented. The details of the angled chevron microelectrode array and the test microfluidic system are then discussed. The variation in device operation with applied signal voltage is presented and discussed in terms of separation efficiency, demonstrating 99.9% separation of a mixture of colloidal latex spheres. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Modeling Microscale Electro-thermally Induced Vortex Flows
NASA Astrophysics Data System (ADS)
Paul, Rajorshi; Tang, Tian; Kumar, Aloke
2017-11-01
In presence of a high frequency alternating electric field and a laser induced heat source, vortex flows are generated inside micro-channels. Such electro-thermally influenced micro-vortices can be used for manipulating nano-particles, programming colloidal assemblies, trapping biological cells as well as for fabricating designed bacterial biofilms. In this study, a theoretical model is developed for microscale electro-thermally induced vortex flows with multiple heat sources. Semi-analytical solutions are obtained, using Hankel transformation and linear superposition, for the temperature, pressure and velocity fields. The effect of material properties such as electrical and thermal conductivities, as well as experimental parameters such as the frequency and strength of the alternating electric field, and the intensity and heating profile of the laser source, are systematically investigated. Resolution for a pair of laser sources is determined by analyzing the strength of the micro-vortices under the influence of two heating sources. Results from this work will provide useful insights into the design of efficient optical tweezers and Rapid Electrokinetic Patterning techniques.
Rarefaction effects in microchannel gas flow driven by rhythmic wall contractions
NASA Astrophysics Data System (ADS)
Chatterjee, Krishnashis; Staples, Anne; Department of Biomedical Engineering; Mechanics, Virginia Tech Collaboration
2015-11-01
Current state of the art microfluidic devices employ precise and timely operation of a complex arrangement of micropumps and valves for fluid transport. A much more novel flow transport mechanism is found in entomological respiratory systems, which involve rhythmic wall contractions for driving the fluid flow. The practical viability of using this technique in future microfluidic devices has been studied earlier. The present study investigates the incorporation of rarefaction effects in the above model of microscale gas flow by including slip boundary conditions. The Navier Stokes equations for gas flow in rectangular microchannel are solved analytically with microscale and lubrication theory assumptions. First order slip boundary conditions are incorporated to account for the rarefaction effects. The dependence of fluid velocities and pressure gradient on the slip boundary conditions is studied. Time averaged unidirectional fluid flow rates are plotted for different phase lags between the contractions, with and without slip in order to obtain an optimum range under different conditions.
Pawlikowski, Marek; Jankowski, Krzysztof; Skalski, Konstanty
2018-05-30
A new constitutive model for human trabecular bone is presented in the present study. As the model is based on indentation tests performed on single trabeculae it is formulated in a microscale. The constitutive law takes into account non-linear viscoelasticity of the tissue. The elastic response is described by the hyperelastic Mooney-Rivlin model while the viscoelastic effects are considered by means of the hereditary integral in which stress depends on both time and strain. The material constants in the constitutive equation are identified on the basis of the stress relaxation tests and the indentation tests using curve-fitting procedure. The constitutive model is implemented into finite element package Abaqus ® by means of UMAT subroutine. The curve-fitting error is low and the viscoelastic behaviour of the tissue predicted by the proposed constitutive model corresponds well to the realistic response of the trabecular bone. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.
Lin, Jie; Guo, Jianlai; Liu, Chang; Guo, Hang
2016-12-21
To develop a high-performance anode for thin-film lithium-ion batteries (TFBs, with a total thickness on the scale of micrometers), a Cu 2 ZnSnS 4 (CZTS) thin film is fabricated by magnetron sputtering and exhibits an ultrahigh performance of 950 mAh g -1 even after 500 cycles, which is the highest among the reported CZTS for lithium storage so far. The characterization and electrochemical tests reveal that the thin-film structure and additional reactions both contribute to the excellent properties. Furthermore, the microscale TFBs with effective footprints of 0.52 mm 2 utilizing the CZTS thin film as anode are manufactured by microfabrication techniques, showing superior capability than the analogous TFBs with the SnO 2 thin film as anode. This work demonstrates the advantages of exploiting thin-film electrodes and novel materials into micropower sources by electronic manufacture methods.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wickey, K. J.; Chilcote, M.; Johnston-Halperin, E.
2015-01-15
Comprehensive characterization of thermal properties in nanoscale heterostructures requires microscale thermally isolated platforms combined with sensitive thermometry in order to measure small heat accumulations. Amorphous SiN{sub x} membranes are often used for these measurements due to their low thermal conductivity and compatibility with standard fabrication techniques. The total thermal conductance of such SiN{sub x} membranes is typically microwatts per kelvin or higher. Here, we further reduce this thermal coupling to 120 nW/K by using a focused ion beam (FIB) to remove large portions of commercially available amorphous SiN{sub x} membranes, leaving a 100 μm × 100 μm square platform suspendedmore » by 10 μm wide by 325 μm long support legs. We demonstrate the capability of these platforms by measuring the heat capacity of a 6.2 ng Au sample and show that it matches well with established specific heat of bulk Au.« less
Self-activation of biochar from furfural residues by recycled pyrolysis gas.
Yin, Yulei; Gao, Yuan; Li, Aimin
2018-04-17
Biochar samples with controllable specific surface area and mesopore ratio were self-activated from furfural residues by recycled pyrolysis gas. The objective of this study was to develop a new cyclic utilization method for the gas produced by pyrolysis. The influences of preparation parameters on the resulting biochar were studied by varying the pyrolysis-gas flow rate, activation time and temperature. Structural characterization of the produced biochar was performed by analysis of nitrogen adsorption isotherms at 77 K and scanning electron microscope (SEM). The pyrolysis gas compositions before and after activation were determined by a gas chromatograph. The results indicated that the surface area of the biochar was increased from 167 m 2 /g to 567 m 2 /g, the total pore volume increased from 0.121 cm 3 /g to 0.380 cm 3 /g, and the ratio of the mesopore pore volume to the total pore volume increased 17-39.7%. The CO volume fraction of the pyrolysis gas changed from 34.66 to 62.29% and the CO 2 volume fraction decreased from 48.26% to 12.17% under different conditions of pyrolysis-gas flow rate, activation time and temperature. The calorific values of pyrolysis gas changed from 8.82 J/cm 3 to 14.00 J/cm 3 , which were higher than those of conventional pyrolysis gases. The slower pyrolysis-gas flow rate and higher activation time increased the efficiency of the reaction between carbon and pyrolysis gas. These results demonstrated the feasibility of treatment of the furfural residues to produce microporous and mesoporous biochar. The pyrolysis gas that results from the activation process could be used as fuel. Overall, this new self-activation method meets the development requirements of cyclic economy and cleaner production. Copyright © 2018. Published by Elsevier Ltd.
Microbiorobots for Manipulation and Sensing
2016-04-19
integrated into microscale robotics and biosensor systems. The objective of the proposed program is to develop a platform that integrates bacteria with...information represent enormous potential that can be harnessed and integrated into microscale robotics and biosensor systems. The objective of the...applicable in microscale assembly systems and biosensors that require autonomous coordination of bacteria. (a) Papers published in peer-reviewed
Effective, Safe, and Inexpensive Microscale Ultrasonic Setup for Teaching and Research Laboratories.
ERIC Educational Resources Information Center
Montana, Angel M.; Grima, Pedro M.
2000-01-01
Presents a homemade, safe, effective, and inexpensive reactor vessel for ultrasonic horns with applications in microscale experiments in teaching and research laboratories. The reactor vessel is designed for an ultrasonic probe that allows reactions to be run at the microscale level at a wide range of temperatures and under inert atmosphere.…
Busch, Christian; Streibel, Thorsten; Liu, Chuan; McAdam, Kevin G; Zimmermann, Ralf
2012-04-01
A coupling between a cigarette smoking simulator and a time-of-flight mass spectrometer was constructed to allow investigation of tobacco smoke formation under simulated burning conditions. The cigarette smoking simulator is designed to burn a sample in close approximation to the conditions experienced by a lit cigarette. The apparatus also permits conditions outside those of normal cigarette burning to be investigated for mechanistic understanding purposes. It allows control of parameters such as smouldering and puff temperatures, as well as combustion rate and puffing volume. In this study, the system enabled examination of the effects of "smoking" a cigarette under a nitrogen atmosphere. Time-of-flight mass spectrometry combined with a soft ionisation technique is expedient to analyse complex mixtures such as tobacco smoke with a high time resolution. The objective of the study was to separate pyrolysis from combustion processes to reveal the formation mechanism of several selected toxicants. A purposely designed adapter, with no measurable dead volume or memory effects, enables the analysis of pyrolysis and combustion gases from tobacco and tobacco products (e.g. 3R4F reference cigarette) with minimum aging. The combined system demonstrates clear distinctions between smoke composition found under air and nitrogen smoking atmospheres based on the corresponding mass spectra and visualisations using principal component analysis.
NASA Astrophysics Data System (ADS)
Wang, Tehua; Chong, Siying; Wang, Tongtong; Lu, Huiyi; Ji, Min
2018-01-01
In order to correlate the physicochemical properties of carbon-covered alumina (CCA) materials with their catalytic performance for oxidative dehydrogenation of ethylbenzene with CO2 (CO2-ODEB), a series of CCA materials with diverse carbon contents (8.7-31.3 wt%) and pyrolysis temperatures (600-800 °C), which were synthesized via an impregnation method followed by pyrolysis, were applied. These catalytic materials were characterized by TGA, N2 physisorption, XRD, Raman spectroscopy and XPS techniques. It was found that the catalytic performance of these CCA materials highly depended on their physicochemical properties, and the optimum CCA catalyst exhibited much better catalytic stability than conventional hydroxyl carbon nanotubes. Below an optimum value of carbon content, the CCA catalyst preserved the main pore characteristics of the Al2O3 support and its catalytic activity increased with the carbon content. Excessive carbon loading resulted in significant textural alterations and thereby decreased both the ethylbenzene conversion and styrene selectivity. On the other hand, high pyrolysis temperature was detrimental to the ordered graphitic structure of the carbon species within the Al2O3 pore. The decreased ordered graphitic degree was found to be associated with the loss of the surface active carbonyl groups, consequently hampering the catalytic efficiency of the CCA catalyst.
A novel 3D deformation measurement method under optical microscope for micro-scale bulge-test
NASA Astrophysics Data System (ADS)
Wu, Dan; Xie, Huimin
2017-11-01
A micro-scale 3D deformation measurement method combined with optical microscope is proposed in this paper. The method is based on gratings and phase shifting algorithm. By recording the grating images before and after deformation from two symmetrical angles and calculating the phases of the grating patterns, the 3D deformation field of the specimen can be extracted from the phases of the grating patterns. The proposed method was applied to the micro-scale bulge test. A micro-scale thermal/mechanical coupling bulge-test apparatus matched with the super-depth microscope was exploited. With the gratings fabricated onto the film, the deformed morphology of the bulged film was measured reliably. The experimental results show that the proposed method and the exploited bulge-test apparatus can be used to characterize the thermal/mechanical properties of the films at micro-scale successfully.
USDA-ARS?s Scientific Manuscript database
Fast pyrolysis processes are among the most effective methods for liquefaction of lignocellulosic biomass. Catalytic fast pyrolysis (CFP) over HZSM-5 or other zeolites and/or utilization of reactive atmospheres such as in the non-catalytic Tail Gas Reactive Pyrolysis (TRGP) process, a recent patent...
Publications - GMC 114 | Alaska Division of Geological & Geophysical
DGGS GMC 114 Publication Details Title: Total organic carbon and rock eval pyrolysis data and analysis and Ruth Laboratories, Inc., 1989, Total organic carbon and rock eval pyrolysis data and analysis for gmc114.pdf (171.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page Department of Natural Resources
Publications - GMC 290 | Alaska Division of Geological & Geophysical
DGGS GMC 290 Publication Details Title: Organic carbon and rock-eval pyrolysis data of cuttings from Reference Unknown, 1999, Organic carbon and rock-eval pyrolysis data of cuttings from the Husky Oil NPR Products Report Report Information gmc290.pdf (177.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page
Publications - GMC 130 | Alaska Division of Geological & Geophysical
DGGS GMC 130 Publication Details Title: Total organic carbon and rock-eval pyrolysis data of cuttings Reference Unknown, 1989, Total organic carbon and rock-eval pyrolysis data of cuttings and core from the Report Report Information gmc130.pdf (208.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page
Chapter 8: Pyrolysis of Biomass for Aviation Fuel
DOE Office of Scientific and Technical Information (OSTI.GOV)
Robichaud, David J; Jenkins, Rhodri W.; Sutton, Andrew D.
2016-07-15
Pyrolysis, the breaking down of organic material using heat and the absence of oxygen, is a method that has been widely researched for the production of liquid fuels. In this chapter, we review the feedstocks typically used for pyrolysis, the properties and the composition of the liquid fraction (termed 'bio-oil') obtained, the studies in which pyrolysis has been used in an attempt to increase the bio-oil yield, and how the bio-oil has been upgraded to fuel-like molecules. We also discuss the viability of pyrolysis to produce jet fuel hydrocarbons.
Pyrolysis system evaluation study
NASA Technical Reports Server (NTRS)
1974-01-01
An evaluation of two different pyrolysis concepts which recover energy from solid waste was conducted in order to determine the merits of each concept for integration into a Integrated Utility System (IUS). The two concepts evaluated were a Lead Bath Furnace Pyrolysis System and a Slagging Vertical Shaft, Partial Air Oxidation Pyrolysis System. Both concepts will produce a fuel gas from the IUS waste and sewage sludge which can be used to offset primary fuel consumption in addition to the sanitary disposal of the waste. The study evaluated the thermal integration of each concept as well as the economic impact on the IUS resulting from integrating each pyrolysis concepts. For reference, the pyrolysis concepts were also compared to incineration which was considered the baseline IUS solid waste disposal system.
NASA Astrophysics Data System (ADS)
Abd-Alghafour, N. M.; Ahmed, Naser M.; Hassan, Z.; Abubakar, D.; Bououdina, M.
2016-06-01
This paper deals with the investigation of annealing effects on the structural, morphological and optical properties of V2O5 nanorods (NRs) grown on the glass substrates by using chemical spray pyrolysis technique. The as-prepared samples were annealed at 500∘ for 40, 60 and 120 min in a quartz tube furnace. The high resolution X-ray diffraction (XRD) analysis revealed V2O5 NRs with preferred orientation along (001) plane. The crystallite size of the V2O5 NRs was increased by increasing the annealing duration. The morphological observations using field emission scanning electron microscope (FESEM) displayed NRs structures whose diameter and length were found to increase with increase of the annealing duration. The transmission electron microscopy (TEM) analysis confirmed the orthorhombic structures of the NRs. The AFM measurements indicated an increase of the average surface roughness by increasing the annealing time. The Raman spectroscopy revealed V-O-V phonon mode in the NRs annealed for 120 min. The optical bandgap was found in the range 2.6-2.58eV and observed to decrease with various duration annealed.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abd–Alghafour, N. M., E-mail: na2013bil@gmail.com; Ahmed, Naser M.; Hassan, Zai
Vanadium oxide (V{sub 2}O{sub 5}) thin films were deposited on glass substrates by using a cost-efficient spray pyrolysis technique. The films were grown at 350° through thermal decomposition of VCl{sub 3} in deionized water with different solution spray rates. The high resolution X-ray diffraction results revealed the formation of nanocrystalline films having orthorhombic structures with preferential orientation along (101) direction. The spray rate influenced the surface morphology and crystallite size of the films. The crystallite size was found to increase whereas the micro-strain was decreased by increasing the spray deposition rates. The increase in crystallite size and decrease in themore » macrostrain resulted in an improvement in the films’ crystallinity. The UV-Visible spectroscopy analysis indicated that the average transmittance of all films lies in the range 75-80 %. The band gap of V{sub 2}O{sub 5} film was decreased from 2.65 to 2.46 eV with increase of the spray deposition rate from 5 ml/min to 10 ml/min. first, second, and third level headings (first level heading).« less
Synthesis of Al2O3 thin films using laser assisted spray pyrolysis (LASP)
NASA Astrophysics Data System (ADS)
Dhonge, Baban P.; Mathews, Tom; Tripura Sundari, S.; Krishnan, R.; Balamurugan, A. K.; Kamruddin, M.; Subbarao, R. V.; Dash, S.; Tyagi, A. K.
2013-01-01
The present study reports the development of a laser assisted ultrasonic spray pyrolysis technique and synthesis of dense optical alumina films using the same. In this technique ultrasonically generated aerosols of aluminum acetylacetonate dissolved in ethanol and a laser beam (Nd:YAG, CW, 1064 nm) were fed coaxially and concurrently through a quartz tube on to a hot substrate mounted on an X-Y raster stage. At the laser focused spot the precursor underwent solvent evaporation and solute sublimation followed by precursor vapor decomposition giving rise to oxide coating, the substrate is rastered to get large surface area coating. The surface morphology revealed coalescence of particles with increase in laser power. The observed particle sizes were 17 nm for films synthesized without laser and 18, 21 and 25 nm for films made with laser at 25, 38 and 50 W, respectively. Refractive index of the films synthesized increased from 1.56 to 1.62 as the laser power increased from 0 to 50 W. The stoichiometry of films was studied using XPS and the increase in interfacial layer thickness with laser power was observed from dynamic SIMS depth profiling and ellipsometry.
Wan, Yuqing; Wang, Yong; Liu, Zhimin; Qu, Xue; Han, Buxing; Bei, Jianzhong; Wang, Shenguo
2005-07-01
The impact of the surface topography of polylactone-type polymer on cell adhesion was to be concerned because the micro-scale texture of a surface can provide a significant effect on the adhesion behavior of cells on the surface. Especially for the application of tissue engineering scaffold, the pore size could have an influence on cell in-growth and subsequent proliferation. Micro-fabrication technology was used to generate specific topography to investigate the relationship between the cells and surface. In this study the pits-patterned surfaces of polystyrene (PS) film with diameters 2.2 and 0.45 microm were prepared by phase-separation, and the corresponding scale islands-patterned PLLA surface was prepared by a molding technique using the pits-patterned PS as a template. The adhesion and proliferation behavior of OCT-1 osteoblast-like cells morphology on the pits- and islands-patterned surface were characterized by SEM observation, cell attachment efficiency measurement and MTT assay. The results showed that the cell adhesion could be enhanced on PLLA and PS surface with nano-scale and micro-scale roughness compared to the smooth surfaces of the PLLA and PS. The OCT-1 osteoblast-like cells could grow along the surface with two different size islands of PLLA and grow inside the micro-scale pits of the PS. However, the proliferation of cells on the micro- and nano-scale patterned surface has not been enhanced compared with the controlled smooth surface.
Tao, Dingyin; Sun, Liangliang; Zhu, Guijie; Liang, Yu; Liang, Zhen; Zhang, Lihua; Zhang, Yukui
2011-01-01
To improve the efficiency of proteome analysis, a strategy with the combination of protein pre-fractionation by preparative microscale solution isoelectric focusing, peptide separation by μRPLC with serially coupled long microcolumn and protein identification by ESI-MS/MS was proposed. By preparative microscale solution isoelectric focusing technique, proteins extracted from whole cell lysates of Escherichia coli were fractionated into five chambers divided by isoelectric membranes, respectively with pH range from 3.0 to 4.6, 4.6 to 5.4, 5.4 to 6.2, 6.2 to 7.0 and 7.0 to 10.0. Compared to the traditional on-gel IFF, the protein recovery could be obviously improved to over 95%. Subsequently, the enriched and fractionated proteins in each chamber were digested, and further separated by a 30-cm long serially coupled RP microcolumn. Through the detection by ESI-MS/MS, about 200 proteins were identified in each fraction, and in total 835 proteins were identified even with one-dimensional μRPLC-MS/MS system. All these results demonstrate that by such a combination strategy, highly efficient proteome analysis could be achieved, not only due to the in-solution protein enrichment and pre-fractionation with improved protein recovery but also owing to the increased separation capacity of serially coupled long μRPLC columns. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Pyrolysis production of fruit peel biochar for potential use in treatment of palm oil mill effluent.
Lam, Su Shiung; Liew, Rock Keey; Cheng, Chin Kui; Rasit, Nazaitulshila; Ooi, Chee Kuan; Ma, Nyuk Ling; Ng, Jo-Han; Lam, Wei Haur; Chong, Cheng Tung; Chase, Howard A
2018-05-01
Fruit peel, an abundant waste, represents a potential bio-resource to be converted into useful materials instead of being dumped in landfill sites. Palm oil mill effluent (POME) is a harmful waste that should also be treated before it can safely be released to the environment. In this study, pyrolysis of banana and orange peels was performed under different temperatures to produce biochar that was then examined as adsorbent in POME treatment. The pyrolysis generated 30.7-47.7 wt% yield of a dark biochar over a temperature ranging between 400 and 500 °C. The biochar contained no sulphur and possessed a hard texture, low volatile content (≤34 wt%), and high amounts of fixed carbon (≥72 wt%), showing durability in terms of high resistance to chemical reactions such as oxidation. The biochar showed a surface area of 105 m 2 /g and a porous structure containing mesopores, indicating its potential to provide many adsorption sites for use as an adsorbent. The use of the biochar as adsorbent to treat the POME showed a removal efficiency of up to 57% in reducing the concentration of biochemical oxygen demand (BOD), chemical oxygen demand COD, total suspended solid (TSS) and oil and grease (O&G) of POME to an acceptable level below the discharge standard. Our results indicate that pyrolysis shows promise as a technique to transform banana and orange peel into value-added biochar for use as adsorbent to treat POME. The recovery of biochar from fruit waste also shows advantage over traditional landfill approaches in disposing this waste. Copyright © 2018 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Vetter, L.; Schreiner, K. M.; Fernandez, A.; Rosenheim, B. E.; Tornqvist, T. E.
2014-12-01
Radiocarbon analyses are a key tool for quantifying the dynamics of carbon cycling and storage in both modern soils and Quaternary paleosols. Frequently, bulk 14C dates of paleosol organic carbon provide ages older than the time of soil burial, and 14C dates of geochemical fractions such as alkali and acid extracts (operationally defined as humic acids) can provide anomalously old ages when compared to coeval plant macrofossil dates. Ramped pyrolysis radiocarbon analysis of sedimentary organic material has been employed as a tool for investigating 14C age spectra in sediments with multiple organic carbon sources. Here we combine ramped pyrolysis 14C analysis and biomarker analysis (lignin-phenols and other cupric oxide products) to provide information on the source and diagenetic state of the paleosol organic carbon. We apply these techniques to immature early Holocene brackish wetland entisols from three sediment cores in southeastern Louisiana, along with overlying basal peats. Surprisingly, we find narrow 14C age spectra across all thermal aliquots from both paleosols and peats. The weighted bulk 14C ages from paleosols and overlying peats are within analytical error, and are comparable to independently analyzed 14C AMS dates from charcoal fragments and other plant macrofossils from each peat bed. Our results suggest high turnover rates of carbon in soils relative to input of exogenous carbon sources. These data raise broader questions about processes within the active soil and during pedogenesis and burial of paleosols that can effectively homogenize radiocarbon content in soils across the thermochemical spectrum. The concurrence of paleosol and peat 14C ages also suggests that, in the absence of peats with identifiable plant macrofossils, ramped pyrolysis 14C analyses of paleosols may be used to provide ages for sea-level indicators.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schiefelbein, C.; Ho, T.
Changes in the physical properties (measured in terms of vitrinite reflectance, elemental analysis, and C-13 nuclear magnetic resonance) of an immature coal (0.46% R{sub o}) from Craig County, Colorado, that was thermally altered using hydrous pyrolysis were used to establish a correspondence between hydrous pyrolysis time/temperature reaction conditions and relative maturity (expressed in terms of vitrinite reflectance). This correspondence was used to determine the oil generation maturity limits for an immature hydrogen-rich (Type I fluorescing amorphous oil-prone kerogen) source rock from an offshore Congo well that was thermally altered using the same reaction conditions as applied to the immature coal.more » The resulting changes in the physical properties of the altered source rock, measured in terms of decreasing reactive carbon content (from Rock-Eval pyrolysis), were used to construct a hydrocarbon yield curve from which the relative maturity associated with the onset, main phase, and peak of oil generation was determined. Results, substantiated by anhydrous pyrolysis techniques, indicate that the source rock from Congo has a late onset of appreciable ({gt}10% transformation) oil generation (0.9% R{sub o} {plus minus} 0.1%), generates maximum quantities of oil from about 1.1 to 1.3% R{sub o}, and reaches the end (or peak) of the primary oil generating window at approximately 1.4% R{sub o} ({plus minus}0.1%) when secondary cracking reactions become important. However, the bottom of the oil window can be extended to about 1.6% R{sub o} because the heavy molecular weight degradation by-products (asphaltenes) that are not efficiently expelled from source rocks continue to degrade into progressively lower molecular weight hydrocarbons.« less
Microscale Concentration Measurements Using Laser Light Scattering Methods
NASA Technical Reports Server (NTRS)
Niederhaus, Charles; Miller, Fletcher
2004-01-01
The development of lab-on-a-chip devices for microscale biochemical assays has led to the need for microscale concentration measurements of specific analyses. While fluorescence methods are the current choice, this method requires developing fluorophore-tagged conjugates for each analyte of interest. In addition, fluorescent imaging is also a volume-based method, and can be limiting as smaller detection regions are required.
Multi-scale heat and mass transfer modelling of cell and tissue cryopreservation
Xu, Feng; Moon, Sangjun; Zhang, Xiaohui; Shao, Lei; Song, Young Seok; Demirci, Utkan
2010-01-01
Cells and tissues undergo complex physical processes during cryopreservation. Understanding the underlying physical phenomena is critical to improve current cryopreservation methods and to develop new techniques. Here, we describe multi-scale approaches for modelling cell and tissue cryopreservation including heat transfer at macroscale level, crystallization, cell volume change and mass transport across cell membranes at microscale level. These multi-scale approaches allow us to study cell and tissue cryopreservation. PMID:20047939
Catalytic hydroprocessing of fast pyrolysis oils: Impact of biomass feedstock on process efficiency
Carpenter, Daniel; Westover, Tyler; Howe, Daniel; ...
2016-12-01
Here, we report here on an experimental study to produce refinery-ready fuel blendstocks via catalytic hydrodeoxygenation (upgrading) of pyrolysis oil using several biomass feedstocks and various blends. Blends were tested along with the pure materials to determine the effect of blending on product yields and qualities. Within experimental error, oil yields from fast pyrolysis and upgrading are shown to be linear functions of the blend components. Switchgrass exhibited lower fast pyrolysis and upgrading yields than the woody samples, which included clean pine, oriented strand board (OSB), and a mix of pinon and juniper (PJ). The notable exception was PJ, formore » which the poor upgrading yield of 18% was likely associated with the very high viscosity of the PJ fast pyrolysis oil (947 cp). The highest fast pyrolysis yield (54% dry basis) was obtained from clean pine, while the highest upgrading yield (50%) was obtained from a blend of 80% clean pine and 20% OSB (CP 8OSB 2). For switchgrass, reducing the fast pyrolysis temperature to 450 degrees C resulted in a significant increase to the pyrolysis oil yield and reduced hydrogen consumption during hydrotreating, but did not directly affect the hydrotreating oil yield. The water content of fast pyrolysis oils was also observed to increase linearly with the summed content of potassium and sodium, ranging from 21% for clean pine to 37% for switchgrass. Multiple linear regression models demonstrate that fast pyrolysis is strongly dependent upon the contents lignin and volatile matter as well as the sum of potassium and sodium.« less
Co-pyrolysis of sewage sludge and manure.
Ruiz-Gómez, Nadia; Quispe, Violeta; Ábrego, Javier; Atienza-Martínez, María; Murillo, María Benita; Gea, Gloria
2017-01-01
The management and valorization of residual organic matter, such as sewage sludge and manure, is gaining interest because of the increasing volume of these residues, their localized generation and the related problems. The anaerobic digestion of mixtures of sewage sludge and manure could be performed due to the similarities between both residues. The purpose of this study is to evaluate the feasibility of the co-pyrolysis of sewage sludge (SS) and digested manure (DM) as a potential management technology for these residues. Pyrolysis of a sewage sludge/manure blend (50:50%) was performed at 525°C in a stirred batch reactor under N 2 atmosphere. The product yields and some characteristics of the product were analyzed and compared to the results obtained in the pyrolysis of pure residues. Potential synergetic and antagonist effects during the co-pyrolysis process were evaluated. Although sewage sludge and manure seem similar in nature, there are differences in their pyrolysis product properties and distribution due to their distinct ash and organic matter composition. For the co-pyrolysis of SS and DM, the product yields did not show noticeable synergistic effects with the exception of the yields of organic compounds, being slightly higher than the predicted average, and the H 2 yield, being lower than expected. Co-pyrolysis of SS and DM could be a feasible management alternative for these residues in locations where both residues are generated, since the benefits and the drawbacks of the co-pyrolysis are similar to those of the pyrolysis of each residue. Copyright © 2016 Elsevier Ltd. All rights reserved.
Fates of Chemical Elements in Biomass during Its Pyrolysis.
Liu, Wu-Jun; Li, Wen-Wei; Jiang, Hong; Yu, Han-Qing
2017-05-10
Biomass is increasingly perceived as a renewable resource rather than as an organic solid waste today, as it can be converted to various chemicals, biofuels, and solid biochar using modern processes. In the past few years, pyrolysis has attracted growing interest as a promising versatile platform to convert biomass into valuable resources. However, an efficient and selective conversion process is still difficult to be realized due to the complex nature of biomass, which usually makes the products complicated. Furthermore, various contaminants and inorganic elements (e.g., heavy metals, nitrogen, phosphorus, sulfur, and chlorine) embodied in biomass may be transferred into pyrolysis products or released into the environment, arousing environmental pollution concerns. Understanding their behaviors in biomass pyrolysis is essential to optimizing the pyrolysis process for efficient resource recovery and less environmental pollution. However, there is no comprehensive review so far about the fates of chemical elements in biomass during its pyrolysis. Here, we provide a critical review about the fates of main chemical elements (C, H, O, N, P, Cl, S, and metals) in biomass during its pyrolysis. We overview the research advances about the emission, transformation, and distribution of elements in biomass pyrolysis, discuss the present challenges for resource-oriented conversion and pollution abatement, highlight the importance and significance of understanding the fate of elements during pyrolysis, and outlook the future development directions for process control. The review provides useful information for developing sustainable biomass pyrolysis processes with an improved efficiency and selectivity as well as minimized environmental impacts, and encourages more research efforts from the scientific communities of chemistry, the environment, and energy.
Effect of dry torrefaction on kinetics of catalytic pyrolysis of sugarcane bagasse
NASA Astrophysics Data System (ADS)
Daniyanto, Sutijan, Deendarlianto, Budiman, Arief
2015-12-01
Decreasing world reserve of fossil resources (i.e. petroleum oil, coal and natural gas) encourage discovery of renewable resources as subtitute for fossil resources. Biomass is one of the main natural renewable resources which is promising resource as alternate resources to meet the world's energy needs and raw material to produce chemical platform. Conversion of biomass, as source of energy, fuel and biochemical, is conducted using thermochemical process such as pyrolysis-gasification process. Pyrolysis step is an important step in the mechanism of pyrolysis - gasification of biomass. The objective of this study is to obtain the kinetic reaction of catalytic pyrolysis of dry torrified sugarcane bagasse which used Ca and Mg as catalysts. The model of kinetic reaction is interpreted using model n-order of single reaction equation of biomass. Rate of catalytic pyrolysis reaction depends on the weight of converted biomass into char and volatile matters. Based on TG/DTA analysis, rate of pyrolysis reaction is influenced by the composition of biomass (i.e. hemicellulose, cellulose and lignin) and inorganic component especially alkali and alkaline earth metallic (AAEM). From this study, it has found two equations rate of reaction of catalytic pyrolysis in sugarcane bagasse using catalysts Ca and Mg. First equation is equation of pyrolysis reaction in rapid zone of decomposition and the second equation is slow zone of decomposition. Value of order reaction for rapid decomposition is n > 1 and for slow decomposition is n<1. Constant and order of reactions for catalytic pyrolysis of dry-torrified sugarcane bagasse with presence of Ca tend to higher than that's of presence of Mg.
Lewan, M.D.; Ruble, T.E.
2002-01-01
This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 ??C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-US kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.
NASA Technical Reports Server (NTRS)
Devivar, Rodrigo
2014-01-01
The performance of a material is greatly influenced by its thermal and chemical properties. Analytical pyrolysis, when coupled to a GC-MS system, is a powerful technique that can unlock the thermal and chemical properties of almost any substance and provide vital information. At NASA, we depend on precise thermal analysis instrumentation for understanding aerospace travel. Our analytical techniques allow us to test materials in the laboratory prior to an actual field test; whether the field test is miles up in the sky or miles underground, the properties of any involved material must be fully studied and understood in the laboratory.
Dias, Pablo; Javimczik, Selene; Benevit, Mariana; Veit, Hugo
2017-02-01
Photovoltaic (PV) modules contain both valuable and hazardous materials, which makes its recycling meaningful economically and environmentally. In general, the recycling of PV modules starts with the removal of the polymeric ethylene-vinyl acetate (EVA) resin using pyrolysis, which assists in the recovery of materials such as silicon, copper and silver. The pyrolysis implementation, however, needs improvement given its importance. In this study, the polymers in the PV modules were characterized by Fourier transform infrared spectroscopy (FTIR) and the removal of the EVA resin using pyrolysis has been studied and optimized. The results revealed that 30min pyrolysis at 500°C removes >99% of the polymers present in photovoltaic modules. Moreover, the behavior of different particle size milled modules during the pyrolysis process was evaluated. It is shown that polymeric materials tend to remain at a larger particle size and thus, this fraction has the greatest mass loss during pyrolysis. A thermo gravimetric analysis (TGA) performed in all polymeric matter revealed the optimum pyrolysis temperature is around 500°C. Temperatures above 500°C continue to degrade matter, but mass loss rate is 6.25 times smaller. This study demonstrates the use of pyrolysis can remove >99% of the polymeric matter from PV modules, which assists the recycling of this hazardous waste and avoids its disposal. Copyright © 2016 Elsevier Ltd. All rights reserved.
National Aerospace Fuels Research Complex
2010-03-01
supercritical pyrolysis. 7 6. Representative chromatogram of low conversion stressed S-8 liquid product from supercritical pyrolysis on ECAT. 7 7...Representative chromatogram of very high conversion stressed S-8 liquid product from supercritical pyrolysis at UTRC. 9 8. Representative chromatogram...of stressed S-8 liquid product from supercritical pyrolysis at Louisiana State University. 9 9. GC-MS scanning total ion chromatograms of fuels
Catalytic pyrolysis characteristics of scrap printed circuit boards by TG-FTIR.
Zhao, Chunhu; Zhang, Xiaoping; Shi, Lin
2017-03-01
In the present work, pyrolysis and catalytic pyrolysis of waste printed circuit boards (WPCBs) was carried out in the coupling of Thermo Gravimetric Analysis and Fourier Transform Infrared Spectroscopy (TG-FTIR) under nitrogen atmosphere. The reaction temperature was increased from 30 to 700°C, while the heating rates were varied from 10 to 40°C/min. Experimental results show that the effect of catalyst on the WPCBs particles pyrolysis was significance. Compared with another two combustion-supporting agents (MgO, CaO), the whole pyrolysis process was optimized when the catalyst ZSM-5 was added into the WPCBs particles. The distributed activation energy model (DAEM) was used to analyze the kinetic parameters of the WPCBs pyrolysis. It was found that values of frequency factor (k 0 ) changed with different activation energy (E) values during pyrolysis process. The activation energy values range from 129.15 to 280.53kJ/mol, and the frequency factor values range from 9.02×10 10 to 4.21×10 22 s -1 . The generated major products for the catalytic pyrolysis of WPCBs were H 2 , CO 2 , CO, H 2 O, phenols and aromatics. Copyright © 2016 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Samolada, M.C.; Zabaniotou, A.A., E-mail: azampani@auth.gr
2014-02-15
Highlights: • The high output of MSS highlights the need for alternative routes of valorization. • Evaluation of 3 sludge-to-energy valorisation methods through SWOT analysis. • Pyrolysis is an energy and material recovery process resulting to ‘zero waste’. • Identification of challenges and barriers for MSS pyrolysis in Greece was investigated. • Adopters of pyrolysis systems face the challenge of finding new product markets. - Abstract: For a sustainable municipal sewage sludge management, not only the available technology, but also other parameters, such as policy regulations and socio-economic issues should be taken in account. In this study, the current statusmore » of both European and Greek Legislation on waste management, with a special insight in municipal sewage sludge, is presented. A SWOT analysis was further developed for comparison of pyrolysis with incineration and gasification and results are presented. Pyrolysis seems to be the optimal thermochemical treatment option compared to incineration and gasification. Sewage sludge pyrolysis is favorable for energy savings, material recovery and high added materials production, providing a ‘zero waste’ solution. Finally, identification of challenges and barriers for sewage sludge pyrolysis deployment in Greece was investigated.« less
Maliutina, Kristina; Tahmasebi, Arash; Yu, Jianglong
2018-05-01
Pressurized entrained-flow pyrolysis of Chlorella vulgaris microalgae was investigated. The impact of pressure on the yield and composition of pyrolysis products were studied. The results showed that the concentration of H 2 in bio-gas increased sharply with increasing pyrolysis pressure, while those of CO, CO 2 , CH 4 , and C 2 H 6 were dramatically decreased. The concentration of H 2 reached 88.01 vol% in bio-gas at 900 °C and 4 MPa. Higher pressures promoted the hydrogen transfer to bio-gas. The bio-oils derived from pressurized pyrolysis were rich in nitrogen-containing compounds and PAHs. The highest concentration of nitrogen-containing compounds in bio-oil was achieved at 800 °C and 1 MPa. Increasing pyrolysis pressure promoted the formation of nitrogen-containing compounds such as indole, quinoline, isoquinoline and phenanthridine. Higher pyrolysis pressures led to increased sphericity, enhanced swelling, and higher carbon order of bio-chars. Pressurized pyrolysis of biomass has a great potential for poly-generation of H 2 , nitrogen containing compounds and bio-char. Copyright © 2018 Elsevier Ltd. All rights reserved.
NASA Technical Reports Server (NTRS)
Breneman, W. C.; Cheung, H.; Farrier, E. G.; Morihara, H.
1977-01-01
A quartz fluid bed reactor capable of operating at temperatures of up to 1000 C was designed, constructed, and successfully operated. During a 30 minute experiment, silane was decomposed within the reactor with no pyrolysis occurring on the reactor wall or on the gas injection system. A hammer mill/roller-crusher system appeared to be the most practical method for producing seed material from bulk silicon. No measurable impurities were detected in the silicon powder produced by the free space reactor, using the cathode layer emission spectroscopic technique. Impurity concentration followed by emission spectroscopic examination of the residue indicated a total impurity level of 2 micrograms/gram. A pellet cast from this powder had an electrical resistivity of 35 to 45 ohm-cm and P-type conductivity.
NASA Astrophysics Data System (ADS)
Abdul-Hamead, Alaa A.
2018-05-01
In this article single and double nozzle (SN, DN) chemical spray pyrolysis techniques(CSP) proved that tin dioxide SnO2 thin film can be fabricated with different structures. SnO2 prepared from three different salts of tin with a concentration of 0.05 M, with thicknesses were about 0.2 ±0.02 µm. Microstructures inspections were achieved on films, beside optical transparency addition to the contact angle CA. The results show that films have tetragonal crystalline with different micro-structures, from sheet to rod and flower-like aggregates, by the variation of the used salts by DN more than SN, also the value of the CA of the prepared films varies with different structures, reaching its highest value for flower-like aggregates of about 130°. Finally, the optical transparency was different corresponding to the disparity in surfaces roughness and topography.
Synthesis of ZnO Hexagonal Micro Discs on Glass Substrates Using the Spray Pyrolysis Technique
NASA Astrophysics Data System (ADS)
Ikhmayies, Shadia J.; Zbib, Mohamad B.
2017-07-01
Zinc oxide (ZnO) is an important transparent conducting oxide of potential use in solar cells, electronics, photoelectronics, and sensors. In this work ZnO micro discs were synthesized in thin film form on glass substrates using the low cost spray pyrolysis method. The films were prepared from a precursor solution of ZnCl2 in distilled water at a substrate temperature of 300 ± 5°C. The as-synthesized samples were analyzed with x-ray diffraction, scanning electron microscopy, and x-ray energy dispersive spectroscopy (EDS). The morphology of the films showed randomly distributed micro discs of hexagonal shape. The EDS reports showed that the films contained Cl and Fe. Size analysis was performed using ImageJ software, where the average diameter was found to be 4.8 ± 0.9 μm, and the average thickness was found to be 254 ± 43 nm.
Transparent and conducting ZnO films grown by spray pyrolysis
NASA Astrophysics Data System (ADS)
Hadjeris, Lazhar; Herissi, Labidi; Badreddine Assouar, M.; Easwarakhanthan, Thomas; Bougdira, Jamal; Attaf, Nadhir; Salah Aida, M.
2009-03-01
ZnO films were prepared using the simple, flexible and cost-effective spray pyrolysis technique at different substrate temperatures and precursor molarity values. The films' structural, optical and electrical properties were investigated by x-ray diffraction, UV-VIS transmittance spectroscopy, profilometry and voltage-current-temperature (VIT) measurements. The films prepared at substrate temperatures above 400 °C appear better crystallized with (0 0 2) preferred orientation and exhibit higher visible transmittance (65-80%), higher electrical n-type semiconductor conductivity (10-50 (Ω cm)-1), lower activation energy (<0.35 eV) and smaller Urbach energy (80 meV). These results indicate that such sprayed ZnO films are chemically purer and have many fewer defects and less disorder owing to an almost complete chemical decomposition of the precursor droplets. ZnO films having desired optical and electrical properties for cheaper large-area solar cells may thus be tailored through the substrate temperature and the precursor molarity.
Li, Boyan; Ou, Longwen; Dang, Qi; Meyer, Pimphan; Jones, Susanne; Brown, Robert; Wright, Mark
2015-11-01
This study evaluates the techno-economic uncertainty in cost estimates for two emerging technologies for biofuel production: in situ and ex situ catalytic pyrolysis. The probability distributions for the minimum fuel-selling price (MFSP) indicate that in situ catalytic pyrolysis has an expected MFSP of $1.11 per liter with a standard deviation of 0.29, while the ex situ catalytic pyrolysis has a similar MFSP with a smaller deviation ($1.13 per liter and 0.21 respectively). These results suggest that a biorefinery based on ex situ catalytic pyrolysis could have a lower techno-economic uncertainty than in situ pyrolysis compensating for a slightly higher MFSP cost estimate. Analysis of how each parameter affects the NPV indicates that internal rate of return, feedstock price, total project investment, electricity price, biochar yield and bio-oil yield are parameters which have substantial impact on the MFSP for both in situ and ex situ catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.
Ferrera-Lorenzo, N; Fuente, E; Bermúdez, J M; Suárez-Ruiz, I; Ruiz, B
2014-01-01
A comparative study of the pyrolysis of a macroalgae industrial solid waste (algae meal) in an electrical conventional furnace and in a microwave furnace has been carried out. It was found that the chars obtained from both pyrolyses are similar and show good properties for performing as a solid bio-fuel and as a precursor of activated carbon. Bio-oils from conventional pyrolysis have a greater number of phenolic, pyrrole and alkane compounds whereas benzene and pyridine compounds are more predominant in microwave pyrolysis with a major presence of light compounds. The bio-gas fraction from microwave pyrolysis presents a much higher syngas content (H2+CO), and a lower CO2 and CH4 proportion than that obtained by conventional pyrolysis. Yields are similar for both treatments with a slightly higher gas yield in the case of microwave pyrolysis due to the fact that microwave heating favors heterogeneous reactions between the gases and the char. Copyright © 2013 Elsevier Ltd. All rights reserved.
Wei, Juntao; Gong, Yan; Guo, Qinghua; Ding, Lu; Wang, Fuchen; Yu, Guangsuo
2017-03-01
Physicochemical evolution (i.e. pore structure variation, carbon structure change and active AAEM transformation) during rice straw (RS) and Shenfu bituminous coal (SF) co-pyrolysis was quantitatively determined in this work. Moreover, the corresponding char gasification was conducted using a thermogravimetric analyzer (TGA) and relative reactivity was proposed to quantify the co-pyrolysis impact on co-gasification reactivity. The results showed that the development of pore structure in co-pyrolyzed chars was first inhibited and then enhanced with the decrease of SF proportion. The promotion effect of co-pyrolysis on order degree of co-pyrolyzed chars gradually weakened with increasing RS proportion. Co-pyrolysis mainly enhanced active K transformation in co-pyrolyzed chars and the promotion effect was alleviated with increasing RS proportion. The inhibition effect of co-pyrolysis on co-gasification reactivity weakened with increasing RS proportion and gasification temperature, which was mainly attributed to the combination of carbon structure evolution and active AAEM transformation in co-pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.
Investigating pyrolysis characteristics of moso bamboo through TG-FTIR and Py-GC/MS.
Liang, Fang; Wang, Ruijuan; Hongzhong, Xiang; Yang, Xiaomeng; Zhang, Tao; Hu, Wanhe; Mi, Bingbing; Liu, Zhijia
2018-05-01
This study was carried out to investigate pyrolysis characteristics of moso bamboo (Phyllostachys pubescens), including outer layer (OB), middle layer (MB) and inner layer (IB) and bamboo leaves (BL), through TG-FTIR and Py-GC/MS. The results showed that 70% of weight loss occurred at rapid pyrolysis stage with temperature of 200-400 °C. With increase in heating rate, pyrolysis process shifted toward higher temperature. IB, OB, MB and BL had a different activation energy at different conversion rates. BL had a higher activation energy than IB, OB and MB. The volatiles of bamboo was complicated with 2-30 of C atoms. IB, OB and MB mainly released benzofuran, hydroxyacetaldehyde and 2-Pentanone. BL released furan, acetic acid and phenol. The main pyrolysis products included H 2 O, CH 4 , CO 2 , CO, carboxylic acids, NO, NO 2 . Pyrolysis products of IB was the most and that of BL was the lowest. MB had the lowest pyrolysis temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.
Discernment of synergism in pyrolysis of biomass blends using thermogravimetric analysis.
Mallick, Debarshi; Poddar, Maneesh Kumar; Mahanta, Pinakeswar; Moholkar, Vijayanand S
2018-08-01
This study reports pyrolysis kinetics of biomass blends using isoconversional methods, viz. Friedman, FWO and KAS. Blends of three biomasses, viz. saw dust, bamboo dust and rice husk, were used. Extractives and volatiles in biomass and minerals in ash had marked influence on enhancement of reaction kinetics during co-pyrolysis, as indicated by reduction in activation energy and increase in decomposition intensity. Pyrolysis kinetics of saw dust and rice husk accelerated (positive synergy), while that of bamboo dust decelerated after blending (negative synergy). Predominant reaction mechanism of all biomass blends was 3-D diffusion in lower conversion range (α ≤ 0.5), while for α ≥ 0.5 pyrolysis followed random nucleation (or nucleation and growth mechanism). Higher reaction order for pyrolysis of blends of rice husk with saw dust and bamboo dust was attributed to catalytic effect of minerals in ash. Positive ΔH and ΔG was obtained for pyrolysis of all biomass blends. Copyright © 2018 Elsevier Ltd. All rights reserved.
Janković, Bojan
2011-10-01
The non-isothermal pyrolysis kinetics of Acetocell (the organosolv) and Lignoboost® (kraft) lignins, in an inert atmosphere, have been studied by thermogravimetric analysis. Using isoconversional analysis, it was concluded that the apparent activation energy for all lignins strongly depends on conversion, showing that the pyrolysis of lignins is not a single chemical process. It was identified that the pyrolysis process of Acetocell and Lignoboost® lignin takes place over three reaction steps, which was confirmed by appearance of the corresponding isokinetic relationships (IKR). It was found that major pyrolysis stage of both lignins is characterized by stilbene pyrolysis reactions, which were subsequently followed by decomposition reactions of products derived from the stilbene pyrolytic process. It was concluded that non-isothermal pyrolysis of Acetocell and Lignoboost® lignins can be best described by n-th (n>1) reaction order kinetics, using the Weibull mixture model (as distributed reactivity model) with alternating shape parameters. Copyright © 2011 Elsevier Ltd. All rights reserved.
[Influence of impurities on waste plastics pyrolysis: products and emissions].
Zhao, Lei; Wang, Zhong-Hui; Chen, De-Zhen; Ma, Xiao-Bo; Luan, Jian
2012-01-01
The study is aimed to evaluate the impact of impurities like food waste, paper, textile and especially soil on the pyrolysis of waste plastics. For this purpose, emissions, gas and liquid products from pyrolysis of waste plastics and impurities were studied, as well as the transfer of element N, Cl, S from the substrates to the pyrolysis products. It was found that the presence of food waste would reduce the heat value of pyrolysis oil to 27 MJ/kg and increase the moisture in the liquid products, therefore the food residue should be removed from waste plastics; and the soil, enhance the waste plastics' pyrolysis by improving the quality of gas and oil products. The presence of food residue, textile and paper leaded to higher gas emissions.
McGuigan, Megan; Waite, J Hunter; Imanaka, Hiroshi; Sacks, Richard D
2006-11-03
The reddish brown haze that surrounds Titan, Saturn's largest moon, is thought to consist of tholin-like organic aerosols. Tholins are complex materials of largely unknown structure. The very high peak capacity and structured chromatograms obtained from comprehensive two-dimensional GC (GC x GC) are attractive attributes for the characterization of tholin pyrolysis products. In this report, GC x GC with time-of-flight MS detection and a flash pyrolysis inlet is used to characterize tholin pyrolysis products. Identified pyrolysis products include low-molecular-weight nitriles, alkyl substituted pyrroles, linear and branched hydrocarbons, alkyl-substituted benzenes and PAH compounds. The pyrolysis of standards found in tholin pyrolysate showed that little alteration occurred and thus these structures are likely present in the tholin material.
Pyrolysis process for producing fuel gas
NASA Technical Reports Server (NTRS)
Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Wojtowicz, Marek A. (Inventor); Suuberg, Eric M. (Inventor)
2007-01-01
Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.
Methods for deoxygenating biomass-derived pyrolysis oil
Baird, Lance Awender; Brandvold, Timothy A.
2015-06-30
Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method for deoxygenating a biomass-derived pyrolysis oil comprising the steps of combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream is provided. The heated diluted pyoil feed stream has a feed temperature of about 150.degree. C. or greater. The heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.
NASA Astrophysics Data System (ADS)
Lanteigne, Jean-Remi
The present thesis covers an applied study on tire pyrolysis. The main objective is to develop tools to allow predicting the production and the quality of oil from tire pyrolysis. The first research objective consisted in modelling the kinetics of tires pyrolysis in a reactor, namely an industrial rotary drum operating in batch mode. A literature review performed later demonstrated that almost all kinetics models developed to represent tire pyrolysis could not represent the actual industrial process with enough accuracy. Among the families of kinetics models for pyrolysis, three have been identified: models with one single global reaction, models with multiple combined parallel reactions, and models with multiple parallel and series reactions. It was observed that these models show limitations. In the models with one single global reaction and with multiple parallels reactions, the production of each individual pyrolytic product cannot be predicted, but only for combined volatiles. Morevoer, the mass term in the kinetics refers to the final char weight (Winfinity) that varies with pyrolysis conditions, which yields less robust models. Also, despite the fact that models with multiple parallels and series reactions can predict the rate of production for each pyrolysis product, the selectivities are determined for operating temperatures instead of real mass temperatures, giving models for which parameters tuning is not adequate when used at the industrial scale. A new kinetics model has been developed, allowing predicting the rate of production of noncondensable gas, oil, and char from tire pyrolysis. The novelty of this model is the consideration of intrinsic selectivities for each product as a function of temperature. This hypothesis has been assumed valid considering that in the industrial pyrolysis process, pyrolysis kinetics is limiting. The developed model considers individual kinetics for each of the three pyrolytic products proportional to the global decomposition kinetics of pyrolysables. The simulation with data obtained in industrial operation showed the robustness of the model to predict with accuracy in transient regime, tires pyrolysis, with the help of model parameters obtained at laboratory scale, namely in regards of the trigger of production, the residence time of tires (dynamic production) and the amount of oil produced (cumulative yield). It is a novel way to model pyrolysis that could be extrapolated to new waste materials. The second objective of this doctoral research was to determine the evolution of specific tires specific heat during pyrolysis and the enthalpy of pyrolysis. The origin of this objective comes from a primary contradiction. With few exceptions, it is acknowledged that organic materials pyrolysis is globally an endothermic phenomenon. At the opposite, all experiments led with laboratory apparatuses such as DSC (Differential Scanning Calorimetry) showed exothermic peaks during dynamic experiments (constant heating rate). It has been confirmed by results obtained at the industrial scale, where no sign of exothermicity has been observed. The Hess Law has also confirmed these results, that globally, pyrolysis is indeed a completely endothermic process. An accurate energy balance is required to predict mass temperature during pyrolysis, this parameter being unbindable from kinetics. An advanced investigation of char first allowed demonstrating that specific heat of solids during pyrolysis decreases with increasing temperature until the weight loss peak is reached, around 400°C, and then starts increasing again. This observation, combined with the fact that the sample loses weight during pyrolysis is considered as the major cause of the apparition of an exothermic peak in laboratory scale experiments. That is, the control system of these apparatuses generates a bias and an unavoidable overheat of the samples producing this exothermic behavior. It would thus be an artifact. On the base of new data on the evolution of global specific heat during pyrolysis, a model of the energy balance has been developed at the industrial scale to determine the enthalpy of pyrolysis. The simulation has shown that a major part of the heat transferred to the pyrolized mass would make its temperature increase. Next, an enthalpy of pyrolysis dependent of weight loss was obtained. Finally, two other terms of enthalpy have been found, namely an enthalpy for the breakage of sulfur bridges and an enthalpy for the stabilization of char when conversion approaches completion. This research will have allowed establishing a novel general methodology to determine the enthalpy of pyrolysis. More particularly, new clarifications hasve been obtained in regards to the evolution of specific heat of solids during pyrolysis and new enthalpies of pyrolysis, all endothermic, could be obtained, in agreement with the theoretical expectations. The third research objective concerned the behavior of sulfur during tires pyrolysis. With as a premise that sulfur is an intrinsic contaminant of many types of waste, it is critical to clarify its fate during pyrolysis, in the present case for waste tires. It has been observed in the literature that some quantitative analyses had been presented, but generally, the mechanisms for the distribution of sulfur within the pyrolytic products remain unclear. Thus, it was then not possible to predict the transfer of sulfur to each of the tire pyrolysis products. The results taken form literature have been complemented with a series of TGA experiments followed by complete elemental analyses of the residual solids. Mass balances have been performed in order to characterize the distribution of elements within the three products (noncondensable gas, oil, and char). A novel parameter has been created during this research: the sulfur loss selectivity. This intrinsic selectivity is a prediction of the distribution of sulfur within the pyrolysis products as a function of temperature. Three phenomena has been identified that could affect the sulfur loss selectivity. First, the natural devolatilization of sulfur due to pyrolysis. Next, the sulfur devolatilization due to the desulfurization of the solid matrix by hydrogen and finally, the clustering of sulfur in the solid state due to metal sulfidation (zinc and iron). The results have shown that this selectivity reach a limit value of 1 when pyrolysis is limited by the kinetics and in the absence of metal. When the mass transfer is limiting at low temperature (<500°C) the selectivity will be greater than 1. At a temperature over 350°C with the presence of metals, the selectivity will be lower than 1. It is a useful tool for industrial pyrolysis processes, being a novel indicator for the distribution of contaminants during the pyrolysis of waste. A better comprehension of these mechanisms allows elaborating a better strategy when designing these industrial processes. For example, in light of this research, it could be preferable to pre-treat the tires at lower temperature to eliminate a significant part of sulfur before pyrolyzing them at high temperature. The resulting pyrolytic products would then necessitate a lighter purification post-treatment, being more efficient and more economical.
Methods for deoxygenating biomass-derived pyrolysis oil
Brandvold, Timothy A.
2015-07-14
Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method comprising the steps of diluting the biomass-derived pyrolysis oil with a phenolic-containing diluent to form a diluted pyoil-phenolic feed is provided. The diluted pyoil-phenolic feed is contacted with a deoxygenating catalyst in the presence of hydrogen at hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.
Xu, Gang; Zhang, You; Shao, Hongbo; Sun, Junna
2016-11-01
Phosphorus (P) recycling or reuse by pyrolyzing crop residue has recently elicited increased research interest. However, the effects of feedstock and pyrolysis conditions on P species have not been fully understood. Such knowledge is important in identifying the agronomic and environmental uses of biochar. Residues of three main Chinese agricultural crops and the biochars (produced at 300°C-600°C) derived from these crops were used to determine P transformations during pyrolysis. Hedley sequential fractionation and (31)P NMR analyses were used in the investigation. Our results showed that P transformation in biochar was significantly affected by pyrolysis temperature regardless of feedstock (Wheat straw, maize straw and peanut husk). Pyrolysis treatment transformed water soluble P into a labile (NaHCO3-Pi) or semi-labile pool (NaOH-Pi) and into a stable pool (Dil. HCl P and residual-P). At the same time, organic P was transformed into inorganic P fractions which was identified by the rapid decomposition of organic P detected with solution (31)P NMR. The P transformation during pyrolysis process suggested more stable P was formed at a higher pyrolysis temperature. This result was also evidenced by the presence of less soluble or stable P species, such as such as poly-P, crandallite (CaAl3(OH)5(PO4)2) and Wavellite (Al3(OH)3(PO4)2·5H2O), as detected by solid-state (31)P NMR in biochars formed at a higher pyrolysis temperature. Furthermore, a significant proportion of less soluble pyrophosphate was identified by solution (2%-35%) and solid-state (8%-53%) (31)P NMR, which was also responsible for the stable P forms at higher pyrolysis temperature although their solubility or stability requires further investigation. Results suggested that a relatively lower pyrolysis temperature retains P availability regardless of feedstock during pyrolysis process. Copyright © 2016. Published by Elsevier B.V.
Effect of temperature on pyrolysis product of empty fruit bunches
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rahman, Aizuddin Abdul; Sulaiman, Fauziah; Abdullah, Nurhayati
2015-04-24
Pyrolysis of empty fruit bunches (EFB) was performed in a fixed bed reactor equipped with liquid collecting system. Pyrolysis process was conducted by varying the terminal pyrolysis temperature from 300 to 500°C under heating rate of 10°C/min for at least 2 hours. Char yield was obtained highest at 300°C around 55.88 wt%, and started to decrease as temperature increase. The maximum yield of pyrolysis liquid was obtained around 54.75 wt% as pyrolysis temperature reach 450°C. For gas yield percentage, the yield gained as temperature was increased from 300 to 500°C, within the range between 8.44 to 19.32 wt%. The charmore » obtained at 400°C has great potential as an alternative solid fuel, due to its high heating value of 23.37 MJ/kg, low in volatile matter and ash content which are approximately around 40.32 and 11.12 wt%, respectively. The collected pyrolysis liquid within this temperature range found to have high water content of around 16.15 to 18.20 wt%. The high aqueous fraction seemed to cause the pyrolysis liquid to have low HHV which only ranging from 10.81 to 12.94 MJ/kg. These trends of results showed that necessary enhancement should be employ either on the raw biomass or pyrolysis products in order to approach at least the minimum quality of common hydrocarbon solid or liquid fuel. For energy production, both produced bio-char and pyrolysis liquid are considered as sustainable sources of bio-energy since they contained low amounts of nitrogen and sulphur, which are considered as environmental friendly solid and liquid fuel.« less
Chiang, Hung-Lung; Lin, Kuo-Hsiung; Lai, Nina; Shieh, Zhu-Xin
2014-05-15
Biosludge can be pyrolyzed to produce liquid oil as an alternative fuel. The content of five major elements, 22 trace elements and 16 PAHs was investigated in oven-dried raw material, pyrolysis residues and pyrolysis liquid products. Results indicated 39% carbon, 4.5% hydrogen, 4.2% nitrogen and 1.8% sulfur were in oven dried biosludge. Biosludge pyrolysis, carried out at temperatures from 400 to 800°C, corresponded to 34-14% weight in pyrolytic residues, 32-50% weight in liquid products and 31-40% weight in the gas phase. The carbon, hydrogen and nitrogen decreased and the sulfur content increased with an increase in the pyrolysis temperature at 400-800°C. NaP (2 rings) and AcPy (3 rings) were the major PAHs, contributing 86% of PAHs in oven-dried biosludge. After pyrolysis, the PAH content increased with the increase of pyrolysis temperature, which also results in a change in the PAH species profile. In pyrolysis liquid oil, NaP, AcPy, Flu and PA were the major species, and the content of the 16 PAHs ranged from 1.6 to 19 μg/ml at pyrolysis temperatures ranging from 400 to 800°C. Ca, Mg, Al, Fe and Zn were the dominant trace elements in the raw material and the pyrolysis residues. In addition, low toxic metal (Cd, V, Co, and Pb) content was found in the liquid oil, and its heat value was 7,800-9,500 kcal/kg, which means it can be considered as an alternative fuel. Copyright © 2014 Elsevier B.V. All rights reserved.
Liu, Guicai; Liao, Yanfen; Ma, Xiaoqian
2017-03-01
As important plastic blends in End-of-Life vehicles (ELV), pyrolysis profiles of ABS/PVC, ABS/PA6 and ABS/PC were investigated using thermogravimetric-Fourier transform infrared spectrometer (TG-FTIR). Also, CaCO 3 was added as plastic filler to discuss its effects on the pyrolysis of these plastics. The results showed that the interaction between ABS and PVC made PVC pyrolysis earlier and HCl emission slightly accelerated. The mixing of ABS and PA6 made their decomposition temperature closer, and ketones in PA6 pyrolysis products were reduced. The presence of ABS made PC pyrolysis earlier, and phenyl compounds in PC pyrolysis products could be transferred into alcohol or H 2 O. The interaction between ABS and other polymers in pyrolysis could be attributed to the intermolecular radical transfer, and free radicals from the polymer firstly decomposed led to a fast initiation the decomposition of the other polymer. As plastic filler, CaCO 3 promoted the thermal decomposition of PA6 and PC, and had no obvious effects on ABS and PVC pyrolysis process. Also, CaCO 3 made the pyrolysis products from PA6 and PC further decomposed into small-molecule compounds like CO 2 . The kinetics analysis showed that isoconversional method like Starink method was more suitable for these polymer blends. Starink method showed the average activation energy of ABS50/PVC50, ABS50/PA50 and ABS50/PC50 was 186.63kJ/mol, 239.61kJ/mol and 248.95kJ/mol, respectively, and the interaction among them could be reflected by the activation energy variation. Copyright © 2017 Elsevier Ltd. All rights reserved.
Chen, Shasha; Jia, Wanglu; Peng, Ping'an
2016-08-15
Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.
Tao, Dingyin; Zhang, Lihua; Shan, Yichu; Liang, Zhen; Zhang, Yukui
2011-01-01
High-performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS-MS) is regarded as one of the most powerful techniques for separation and identification of proteins. Recently, much effort has been made to improve the separation capacity, detection sensitivity, and analysis throughput of micro- and nano-HPLC, by increasing column length, reducing column internal diameter, and using integrated techniques. Development of HPLC columns has also been rapid, as a result of the use of submicrometer packing materials and monolithic columns. All these innovations result in clearly improved performance of micro- and nano-HPLC for proteome research.
Liquid Tunable Microlenses based on MEMS techniques
Zeng, Xuefeng; Jiang, Hongrui
2013-01-01
The recent rapid development in microlens technology has provided many opportunities for miniaturized optical systems, and has found a wide range of applications. Of these microlenses, tunable-focus microlenses are of special interest as their focal lengths can be tuned using micro-scale actuators integrated with the lens structure. Realization of such tunable microlens generally relies on the microelectromechanical system (MEMS) technologies. Here, we review the recent progress in tunable liquid microlenses. The underlying physics relevant to these microlenses are first discussed, followed by description of three main categories of tunable microlenses involving MEMS techniques, mechanically driven, electrically driven, and those integrated within microfluidic systems. PMID:24163480
Zhang, Huiyan; Xiao, Rui; Nie, Jianlong; Jin, Baosheng; Shao, Shanshan; Xiao, Guomin
2015-09-01
Catalytic co-pyrolysis of black-liquor lignin and waste plastics (polyethylene, PE; polypropylene PP; polystyrene, PS) was conducted in a fluidized bed. The effects of temperature, plastic to lignin ratio, catalyst and plastic types on product distributions were studied. Both aromatic and olefin yields increased with increasing PE proportion. Petrochemical yield of co-pyrolysis of PE and lignin was LOSA-1 > spent FCC > Gamma-Al2O3 > sand. The petrochemical yield with LOSA-1 is 43.9% which is more than two times of that without catalyst. The feedstock for co-pyrolysis with lignin is polystyrene > polyethylene > polypropylene. Catalytic co-pyrolysis of black-liquor lignin with PS produced the maximum aromatic yield (55.3%), while co-pyrolysis with PE produced the maximum olefin yield (13%). Copyright © 2015 Elsevier Ltd. All rights reserved.
Kinetic study of corn straw pyrolysis: comparison of two different three-pseudocomponent models.
Li, Zhengqi; Zhao, Wei; Meng, Baihong; Liu, Chunlong; Zhu, Qunyi; Zhao, Guangbo
2008-11-01
With heating rates of 20, 50 and 100 K min(-1), the thermal decomposition of corn straw samples (corn stalks skins, corn stalks cores, corn bracts and corn leaves) were studied using thermogravimetric analysis. The maximum pyrolysis rates increased with the heating rate increasing and the temperature at the peak pyrolysis rate also increased. Assuming the addition of three independent parallel reactions, corresponding to three pseudocomponents linked to the hemicellulose, cellulose and lignin, two different three-pseudocomponent models were used to simulate the corn straw pyrolysis. Model parameters of pyrolysis were given. It was found that the three-pseudocomponent model with n-order kinetics was more accurate than the model with first-order kinetics at most cases. It showed that the model with n-order kinetics was more accurate to describe the pyrolysis of the hemicellulose.
Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation
Dörsam, Stefan; Kirchhoff, Jennifer; Bigalke, Michael; Dahmen, Nicolaus; Syldatk, Christoph; Ochsenreither, Katrin
2016-01-01
Pyrolysis oil, a complex mixture of several organic compounds, produced during flash pyrolysis of organic lignocellulosic material was evaluated for its suitability as alternative carbon source for fungal growth and fermentation processes. Therefore several fungi from all phyla were screened for their tolerance toward pyrolysis oil. Additionally Aspergillus oryzae and Rhizopus delemar, both established organic acid producers, were chosen as model organisms to investigate the suitability of pyrolysis oil as carbon source in fungal production processes. It was observed that A. oryzae tolerates pyrolysis oil concentrations between 1 and 2% depending on growth phase or stationary production phase, respectively. To investigate possible reasons for the low tolerance level, eleven substances from pyrolysis oil including aldehydes, organic acids, small organic compounds and phenolic substances were selected and maximum concentrations still allowing growth and organic acid production were determined. Furthermore, effects of substances to malic acid production were analyzed and compounds were categorized regarding their properties in three groups of toxicity. To validate the results, further tests were also performed with R. delemar. For the first time it could be shown that small amounts of phenolic substances are beneficial for organic acid production and A. oryzae might be able to degrade isoeugenol. Regarding pyrolysis oil toxicity, 2-cyclopenten-1-on was identified as the most toxic compound for filamentous fungi; a substance never described for anti-fungal or any other toxic properties before and possibly responsible for the low fungal tolerance levels toward pyrolysis oil. PMID:28066378
Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation.
Dörsam, Stefan; Kirchhoff, Jennifer; Bigalke, Michael; Dahmen, Nicolaus; Syldatk, Christoph; Ochsenreither, Katrin
2016-01-01
Pyrolysis oil, a complex mixture of several organic compounds, produced during flash pyrolysis of organic lignocellulosic material was evaluated for its suitability as alternative carbon source for fungal growth and fermentation processes. Therefore several fungi from all phyla were screened for their tolerance toward pyrolysis oil. Additionally Aspergillus oryzae and Rhizopus delemar , both established organic acid producers, were chosen as model organisms to investigate the suitability of pyrolysis oil as carbon source in fungal production processes. It was observed that A. oryzae tolerates pyrolysis oil concentrations between 1 and 2% depending on growth phase or stationary production phase, respectively. To investigate possible reasons for the low tolerance level, eleven substances from pyrolysis oil including aldehydes, organic acids, small organic compounds and phenolic substances were selected and maximum concentrations still allowing growth and organic acid production were determined. Furthermore, effects of substances to malic acid production were analyzed and compounds were categorized regarding their properties in three groups of toxicity. To validate the results, further tests were also performed with R. delemar . For the first time it could be shown that small amounts of phenolic substances are beneficial for organic acid production and A. oryzae might be able to degrade isoeugenol. Regarding pyrolysis oil toxicity, 2-cyclopenten-1-on was identified as the most toxic compound for filamentous fungi; a substance never described for anti-fungal or any other toxic properties before and possibly responsible for the low fungal tolerance levels toward pyrolysis oil.
Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge.
Zhang, Jun; Zuo, Wei; Tian, Yu; Chen, Lin; Yin, Linlin; Zhang, Jie
2017-01-03
The sulfur distributions and evolution of sulfur-containing compounds in the char, tar and gas fractions were investigated during the microwave and conventional pyrolysis of sewage sludge. Increased accumulation of sulfur in the char and less production of H 2 S were obtained from microwave pyrolysis at higher temperatures (500-800 °C). Three similar conversion pathways were identified for the formation of H 2 S during microwave and conventional pyrolysis. The cracking of unstable mercaptan structure in the sludge contributed to the release of H 2 S below 300 °C. The decomposition of aliphatic-S compounds in the tars led to the formation of H 2 S (300-500 °C). The thermal decomposition of aromatic-S compounds in the tars generated H 2 S from 500 to 800 °C. However, the secondary decomposition of thiophene-S compounds took place only in conventional pyrolysis above 700 °C. Comparing the H 2 S contributions from microwave and conventional pyrolysis, the significant increase of H 2 S yields in conventional pyrolysis was mainly attributed to the decomposition of aromatic-S (increasing by 10.4%) and thiophene-S compounds (11.3%). Further investigation on the inhibition mechanism of H 2 S formation during microwave pyrolysis confirmed that, with the special heating characteristics and relative shorter residence time, microwave pyrolysis promoted the retention of H 2 S on CaO and inhibited the secondary cracking of thiophene-S compounds at higher temperatures.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Carpenter, Daniel; Westover, Tyler; Howe, Daniel
Here, we report here on an experimental study to produce refinery-ready fuel blendstocks via catalytic hydrodeoxygenation (upgrading) of pyrolysis oil using several biomass feedstocks and various blends. Blends were tested along with the pure materials to determine the effect of blending on product yields and qualities. Within experimental error, oil yields from fast pyrolysis and upgrading are shown to be linear functions of the blend components. Switchgrass exhibited lower fast pyrolysis and upgrading yields than the woody samples, which included clean pine, oriented strand board (OSB), and a mix of pinon and juniper (PJ). The notable exception was PJ, formore » which the poor upgrading yield of 18% was likely associated with the very high viscosity of the PJ fast pyrolysis oil (947 cp). The highest fast pyrolysis yield (54% dry basis) was obtained from clean pine, while the highest upgrading yield (50%) was obtained from a blend of 80% clean pine and 20% OSB (CP 8OSB 2). For switchgrass, reducing the fast pyrolysis temperature to 450 degrees C resulted in a significant increase to the pyrolysis oil yield and reduced hydrogen consumption during hydrotreating, but did not directly affect the hydrotreating oil yield. The water content of fast pyrolysis oils was also observed to increase linearly with the summed content of potassium and sodium, ranging from 21% for clean pine to 37% for switchgrass. Multiple linear regression models demonstrate that fast pyrolysis is strongly dependent upon the contents lignin and volatile matter as well as the sum of potassium and sodium.« less
Mechanical Behavior of Al-SiC Nanolaminate Composites Using Micro-Scale Testing Methods
NASA Astrophysics Data System (ADS)
Mayer, Carl Randolph
Nanolaminate composite materials consist of alternating layers of materials at the nanoscale (≤100 nm). Due to the nanometer scale thickness of their layers, these materials display unique and tailorable properties. This enables us to alter both mechanical attributes such as strength and wear properties, as well as functional characteristics such as biocompatibility, optical, and electronic properties. This dissertation focuses on understanding the mechanical behavior of the Al-SiC system. From a practical perspective, these materials exhibit a combination of high toughness and strength which is attractive for many applications. Scientifically, these materials are interesting due to the large elastic modulus mismatch between the layers. This, paired with the small layer thickness, allows a unique opportunity for scientists to study the plastic deformation of metals under extreme amounts of constraint. Previous studies are limited in scope and a more diverse range of mechanical characterization is required to understand both the advantages and limitations of these materials. One of the major challenges with testing these materials is that they are only able to be made in thicknesses on the order of micrometers so the testing methods are limited to small volume techniques. This work makes use of both microscale testing techniques from the literature as well as novel methodologies. Using these techniques we are able to gain insight into aspects of the material's mechanical behavior such as the effects of layer orientation, flaw dependent fracture, tension-compression asymmetry, fracture toughness as a function of layer thickness, and shear behavior as a function of layer thickness.
Assessing the functional mechanical properties of bioengineered organs with emphasis on the lung.
Suki, Béla
2014-09-01
Recently, an exciting new approach has emerged in regenerative medicine pushing the forefront of tissue engineering to create bioartificial organs. The basic idea is to create biological scaffolds made of extracellular matrix (ECM) that preserves the three-dimensional architecture of an entire organ. These scaffolds are then used as templates for functional tissue and organ reconstruction after re-seeding the structure with stem cells or appropriately differentiated cells. In order to make sure that these bioartificial organs will be able to function in the mechanical environment of the native tissue, it is imperative to fully characterize their mechanical properties and match them with those of the normal native organs. This mini-review briefly summarizes modern measurement techniques of mechanical function characterized mostly by the material or volumetric stiffness. Micro-scale and macro-scale techniques such as atomic force microscopy and the tissue strip stress-strain approach are discussed with emphasis on those that combine mechanical measurements with structural visualization. Proper micro-scale stiffness helps attachment and differentiation of cells in the bioartificial organ whereas macro-scale functionality is provided by the overall mechanical properties of the construct. Several approaches including failure mechanics are also described, which specifically probe the contributions of the main ECM components including collagen, elastin, and proteoglycans to organ level ECM function. Advantages, drawbacks, and possible pitfalls as well as interpretation of the data are given throughout. Finally, specific techniques to assess the functionality of the ECM of bioartificial lungs are separately discussed. © 2014 Wiley Periodicals, Inc.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lontio Fomekong, Roussin, E-mail: lonforou@yahoo.fr; Institut de la Matière Condensée et des Nanosciences, Université Catholique de Louvain, Croix du Sud 1, 1348 Louvain-La-Neuve; Kenfack Tsobnang, Patrice
2015-10-15
Nanoparticles of Ni{sub 1−x}Zn{sub x}O and Ni{sub 1−x}Zn{sub x}O/ZnO, which can be good candidates for selective gas sensors, were successfully obtained via a two-step synthetic route, in which the nickel zinc malonate precursor was first synthesized by co-precipitation from an aqueous solution, followed by pyrolysis in air at a relatively low temperature (~500 °C). The precursor was characterized by ICP-AES, FTIR and TG and the results indicate the molecular structure of the precursor to be compatible with Ni{sub 1−x}Zn{sub x}(OOCCH{sub 2}COO)·2H{sub 2}O. The decomposition product, characterized using various techniques (FTIR, XRD, ToF-SIMS, SEM, TEM and XPS), was established to bemore » a doped nickel oxide (Ni{sub 1−x}Zn{sub x}O for 0.01≤x≤0.1) and a composite material (Ni{sub 1−x}Zn{sub x}O/ZnO for 0.2≤x≤0.5). To elucidate the form in which the Zn is present in the NiO structure, three analytical techniques were employed: ToF-SIMS, XRD and XPS. While ToF SIMS provided a direct evidence of the presence of Zn in the NiO crystal structure, XRD showed that Zn actually substitutes Ni in the structure and XPS is a bit more specific by indicating that the Zn is present in the form of Zn{sup 2+} ions. - Highlights: • Coprecipitation synthesis of nickel zinc malonate single bath precursor was achieved. • The as synthesized precursors are an homogeneous mixture of nickel and zinc malonate. • XRD, ToF-SIMS, XPS, SEM and TEM was used to characterized decomposition products. • Ni{sub 1−x}Zn{sub x}O nanoparticles (0.01≤x≤0.1) formed after pyrolysis (~500 °C) of precursor. • Ni{sub 1−x}Zn{sub x}O/ZnO nanocomposite (0.2≤x≤0.5) formed after pyrolysis at 500 °C of precursor.« less
NASA Astrophysics Data System (ADS)
Eglinton, Timothy I.; Sinninghe Damsté, Jaap S.; Pool, Wim; de Leeuw, Jan W.; Eijk, Gert; Boon, Jaap J.
1992-04-01
This study describes the analysis of sulphur-containing products from Curie-point pyrolysis (Py) of eighty-five samples (kerogens, bitumen, and petroleum asphaltenes and coals) using gas chromatography (GC) in combination with sulphur-selective detection. Peak areas of approximately forty individual organic sulphur pyrolysis products (OSPP) were measured, and the results analysed with the aid of multivariate data reduction techniques (principal components analysis, (PCA)). The structural relationships proposed in an earlier publication ( SINNINGHE DAMSTé et al., 1989a) in which OSPP can be grouped according to common "carbon skeletons" are supported by PCA. The distribution of OSPP varies both as a function of kerogen type (as defined by elemental composition) and maturity, reflecting differences in the relative abundance of the various carbon skeleton types. Sulphur-containing products from Type I, Type II, and, to some extent, Type II-S kerogens are dominated by OSPP derived from "moieties" (i.e., discrete structural components within the macromolecule) possessing linear carbon skeletons, while coals and Type III kerogens give rise to higher relative abundances of OSPP with branched carbon skeletons. Type I kerogens are distinguished from Type II kerogens due to the type of linear carbon skeleton, the former yielding higher relative amounts of 2- n-alkylthiophenes and thiolanes and the latter 2,5-di-substituted sulphur-containing products. Products from sulphur-rich (Type II-S) kerogens differ by higher relative abundances of OSPP derived from precursors with isoprenoid and/or steroidal side-chain carbon skeletons, and by higher absolute abundances of all OSPP. Petroleum and, to a lesser extent, bitumen asphaltenes give rise to OSPP with longer carbon skeletons than do kerogens or coals. This observation supports the models proposed by SINNINGHE DAMSTé et al. (1990a) in which sulphur-containing moieties in asphaltenes are bound by fewer intermolecular bridges (i.e., are less extensively cross-linked) and, consequently, more readily yield longer chain products on pyrolysis. From these observations, we suggest that Py-GC in combination with PCA provides useful information concerning the chemical nature of organically bound sulphur in geomacromolecules. This information can be rationalised based on carbon skeleton relationships established for low molecular weight organic sulphur compounds, and in terms of kerogen type and overall sulphur content
Microscale vortex laser with controlled topological charge
NASA Astrophysics Data System (ADS)
Wang, Xing-Yuan; Chen, Hua-Zhou; Li, Ying; Li, Bo; Ma, Ren-Min
2016-12-01
A microscale vortex laser is a new type of coherent light source with small footprint that can directly generate vector vortex beams. However, a microscale laser with controlled topological charge, which is crucial for virtually any of its application, is still unrevealed. Here we present a microscale vortex laser with controlled topological charge. The vortex laser eigenmode was synthesized in a metamaterial engineered non-Hermitian micro-ring cavity system at exceptional point. We also show that the vortex laser cavity can operate at exceptional point stably to lase under optical pumping. The microscale vortex laser with controlled topological charge can serve as a unique and general building block for next-generation photonic integrated circuits and coherent vortex beam sources. The method we used here can be employed to generate lasing eigenmode with other complex functionalities. Project supported by the “Youth 1000 Talent Plan” Fund, Ministry of Education of China (Grant No. 201421) and the National Natural Science Foundation of China (Grant Nos. 11574012 and 61521004).
Emerging Technologies for Assembly of Microscale Hydrogels
Kavaz, Doga; Demirel, Melik C.; Demirci, Utkan
2013-01-01
Assembly of cell encapsulating building blocks (i.e., microscale hydrogels) has significant applications in areas including regenerative medicine, tissue engineering, and cell-based in vitro assays for pharmaceutical research and drug discovery. Inspired by the repeating functional units observed in native tissues and biological systems (e.g., the lobule in liver, the nephron in kidney), assembly technologies aim to generate complex tissue structures by organizing microscale building blocks. Novel assembly technologies enable fabrication of engineered tissue constructs with controlled properties including tunable microarchitectural and predefined compositional features. Recent advances in micro- and nano-scale technologies have enabled engineering of microgel based three dimensional (3D) constructs. There is a need for high-throughput and scalable methods to assemble microscale units with a complex 3D micro-architecture. Emerging assembly methods include novel technologies based on microfluidics, acoustic and magnetic fields, nanotextured surfaces, and surface tension. In this review, we survey emerging microscale hydrogel assembly methods offering rapid, scalable microgel assembly in 3D, and provide future perspectives and discuss potential applications. PMID:23184717
2008-09-01
Infiltration (CVI), Chemical Vapor Deposition (CVD) and polymer impregnation/ pyrolysis (PIP) [5:20, 32]. The SiC fibers currently... composite was infiltrated with a mixture of polymer , filler particles and solvent. During pyrolysis under nitrogen at temperatures > 1000 °C, the...using polymer infiltration and pyrolysis (PIP) method. Polymer infiltration and pyrolysis processing method allows near-net-shape molding and
Computational Studies of Pyrolysis and Upgrading of Bio-oils: Virtual Special Issue
Xiong, Qingang; Robichaud, David J.
2017-03-23
As research activities continue, our understanding of biomass pyrolysis has been significantly elevated and we sought to arrange this Virtual Special Issue (VSI) in ACS Sustainable Chemistry & Engineering to report recent progress on computational and experimental studies of biomass pyrolysis. Beyond highlighting the five national laboratories' advancements, prestigious researchers in the field of biomass pyrolysis have been invited to report their most recent activities.
Reaction mechanisms in cellulose pyrolysis: a literature review
DOE Office of Scientific and Technical Information (OSTI.GOV)
Molton, P.M.; Demmitt, T.F.
1977-08-01
A bibliographic review of 195 references is presented outlining the history of the research into the mechanisms of cellulose pyrolysis. Topics discussed are: initial product identification, mechanism of initial formation of levoglucosan, from cellulose and from related compounds, decomposition of cellulose to other compounds, formation of aromatics, pyrolysis of levoglucosan, crosslinking of cellulose, pyrolytic reactions of cellulose derivatives, and the effects of inorganic salts on the pyrolysis mechanism. (JSR)
On-Line Analysis and Kinetic Behavior of Arsenic Release during Coal Combustion and Pyrolysis.
Shen, Fenghua; Liu, Jing; Zhang, Zhen; Dai, Jinxin
2015-11-17
The kinetic behavior of arsenic (As) release during coal combustion and pyrolysis in a fluidized bed was investigated by applying an on-line analysis system of trace elements in flue gas. This system, based on inductively coupled plasma optical emission spectroscopy (ICP-OES), was developed to measure trace elements concentrations in flue gas quantitatively and continuously. Obvious variations of arsenic concentration in flue gas were observed during coal combustion and pyrolysis, indicating strong influences of atmosphere and temperature on arsenic release behavior. Kinetic laws governing the arsenic release during coal combustion and pyrolysis were determined based on the results of instantaneous arsenic concentration in flue gas. A second-order kinetic law was determined for arsenic release during coal combustion, and the arsenic release during coal pyrolysis followed a fourth-order kinetic law. The results showed that the arsenic release rate during coal pyrolysis was faster than that during coal combustion. Thermodynamic calculations were carried out to identify the forms of arsenic in vapor and solid phases during coal combustion and pyrolysis, respectively. Ca3(AsO4)2 and Ca(AsO2)2 are the possible species resulting from As-Ca interaction during coal combustion. Ca(AsO2)2 is the most probable species during coal pyrolysis.
Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang
2015-02-06
This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250-300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes.
Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang
2015-01-01
This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250–300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes. PMID:25656294
Gaurh, Pramendra; Pramanik, Hiralal
2018-01-01
A new and innovative approach was adopted to increase the yield of aromatics like, benzene, toluene and xylene (BTX) in the catalytic pyrolysis of waste polyethylene (PE). The BTX content was significantly increased due to effective interaction between catalystZSM-5 and target molecules i.e., lower paraffins within the reactor. The thermal and catalytic pyrolysis both were performed in a specially designed semi-batch reactor at the temperature range of 500 °C-800 °C. Catalytic pyrolysis were performed in three different phases within the reactor batch by batch systematically, keeping the catalyst in A type- vapor phase, B type- liquid phase and C type- vapor and liquid phase (multiphase), respectively. Total aromatics (BTX) of 6.54 wt% was obtained for thermal pyrolysis at a temperature of 700 °C. In contrary, for the catalytic pyrolysis A, B and C types reactor arrangement, the aromatic (BTX) contents were progressively increased, nearly 6 times from 6.54 wt% (thermal pyrolysis) to 35.06 wt% for C-type/multiphase (liquid and vapor phase). The pyrolysis oil were characterized using GC-FID, FT-IR, ASTM distillation and carbon residue test to evaluate its end use and aromatic content. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Travis, Jonathan
The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films is presented as a method for enabling non-conductive, but possibly electrochemically active materials, to be used for electrochemical applications.
Pyrolysis processing for solid waste resource recovery
NASA Technical Reports Server (NTRS)
Wojtowicz, Marek A. (Inventor); Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Suuberg, Eric M. (Inventor)
2007-01-01
Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.
Concentration-response data on toxicity of pyrolysis gases from some natural and synthetic polymers
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Huttlinger, N. V.
1978-01-01
Concentration-response data are presented on the toxic effects of the pyrolysis gases from some natural and synthetic polymers, using the toxicity screening test method developed at the University of San Francisco. The pyrolysis gases from wool, red oak, Douglas fir, polycaprolactam, polyether sulfone, polyaryl sulfone, and polyphenylene sulfide appeared to exhibit the concentration-response relationships commonly encountered in toxicology. Carbon monoxide seemed to be an important toxicant in the pyrolysis gases from red oak, Douglas fir, and polycaprolactam, but did not appear to have been the principal toxicant in the pyrolysis gases from polyether sulfone and polyphenylene sulfide.
Good coupling for the multiscale patch scheme on systems with microscale heterogeneity
NASA Astrophysics Data System (ADS)
Bunder, J. E.; Roberts, A. J.; Kevrekidis, I. G.
2017-05-01
Computational simulation of microscale detailed systems is frequently only feasible over spatial domains much smaller than the macroscale of interest. The 'equation-free' methodology couples many small patches of microscale computations across space to empower efficient computational simulation over macroscale domains of interest. Motivated by molecular or agent simulations, we analyse the performance of various coupling schemes for patches when the microscale is inherently 'rough'. As a canonical problem in this universality class, we systematically analyse the case of heterogeneous diffusion on a lattice. Computer algebra explores how the dynamics of coupled patches predict the large scale emergent macroscale dynamics of the computational scheme. We determine good design for the coupling of patches by comparing the macroscale predictions from patch dynamics with the emergent macroscale on the entire domain, thus minimising the computational error of the multiscale modelling. The minimal error on the macroscale is obtained when the coupling utilises averaging regions which are between a third and a half of the patch. Moreover, when the symmetry of the inter-patch coupling matches that of the underlying microscale structure, patch dynamics predicts the desired macroscale dynamics to any specified order of error. The results confirm that the patch scheme is useful for macroscale computational simulation of a range of systems with microscale heterogeneity.
Microwave-assisted co-pyrolysis of brown coal and corn stover for oil production.
Zhang, Yaning; Fan, Liangliang; Liu, Shiyu; Zhou, Nan; Ding, Kuan; Peng, Peng; Anderson, Erik; Addy, Min; Cheng, Yanling; Liu, Yuhuan; Li, Bingxi; Snyder, John; Chen, Paul; Ruan, Roger
2018-07-01
The controversial synergistic effect between brown coal and biomass during co-pyrolysis deserves further investigation. This study detailed the oil production from microwave-assisted co-pyrolysis of brown coal (BC) and corn stover (CS) at different CS/BC ratios (0, 0.33, 0.50, 0.67, and 1) and pyrolysis temperatures (500, 550, and 600 °C). The results showed that a higher CS/BC ratio resulted in higher oil yield, and a higher pyrolysis temperature increased oil yield for brown coal and coal/corn mixtures. Corn stover and brown coal showed different pyrolysis characteristics, and positive synergistic effect on oil yield was observed only at CS/BC ratio of 0.33 and pyrolysis temperature of 600 °C. Oils from brown coal mainly included hydrocarbons and phenols whereas oils from corn stover and coal/corn mixtures were dominated by ketones, phenols, and aldehydes. Positive synergistic effects were observed for ketones, aldehydes, acids, and esters whereas negative synergistic effects for hydrocarbons, phenols and alcohols. Copyright © 2018 Elsevier Ltd. All rights reserved.
Weng, Jun-Jie; Liu, Yue-Xi; Zhu, Ya-Nan; Pan, Yang; Tian, Zhen-Yu
2017-11-01
With the aim to support the experimental tests in a circulating fluidized bed pilot plant, the pyrolysis processes of coal, corn, and coal-corn blend have been studied with an online pyrolysis photoionization time-of-flight mass spectrometry (Py-PI-TOFMS). The mass spectra at different temperatures (300-800°C) as well as time-evolved profiles of selected species were measured. The pyrolysis products such as alkanes, alkenes, phenols, aromatics, as well as nitrogen- and sulfur-containing species were detected. As temperature rises, the relative ion intensities of high molecular weight products tend to decrease, while those of aromatics increase significantly. During the co-pyrolysis, coal can promote the reaction temperature of cellulose in corn. Time-evolved profiles demonstrate that coal can affect pyrolysis rate of cellulose, hemicellulose, and lignin of corn in blend. This work shows that Py-PI-TOFMS is a powerful approach to permit a better understanding of the mechanisms underlying the co-pyrolysis of coal and biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Boyan; Ou, Longwen; Dang, Qi
This study evaluates the techno-economic uncertainty in cost estimates for two emerging biorefinery technologies for biofuel production: in situ and ex situ catalytic pyrolysis. Stochastic simulations based on process and economic parameter distributions are applied to calculate biorefinery performance and production costs. The probability distributions for the minimum fuel-selling price (MFSP) indicate that in situ catalytic pyrolysis has an expected MFSP of $4.20 per gallon with a standard deviation of 1.15, while the ex situ catalytic pyrolysis has a similar MFSP with a smaller deviation ($4.27 per gallon and 0.79 respectively). These results suggest that a biorefinery based on exmore » situ catalytic pyrolysis could have a lower techno-economic risk than in situ pyrolysis despite a slightly higher MFSP cost estimate. Analysis of how each parameter affects the NPV indicates that internal rate of return, feedstock price, total project investment, electricity price, biochar yield and bio-oil yield are significant parameters which have substantial impact on the MFSP for both in situ and ex situ catalytic pyrolysis.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ben, Haoxi; Huang, Fang; Li, Liwei
2015-09-09
The pyrolysis of whole biomass—pine wood and bark—with mordenite (M), beta (β) and Y zeolites has been examined at 600°C. The GPC results indicated that the pyrolysis oils upgraded by Y and β zeolites have a very low average molecular weight range (70–170 g mol –1). Several NMR methods have been employed to characterize the whole portion of pyrolysis products. After the use of these two zeolites (Y and β), the two main products from the pyrolysis of cellulose—levoglucosan and HMF—were eliminated; this indicates a significant deoxygenation process. When a mixture of zeolites (Y and M) was used, the upgradedmore » pyrolysis oil exhibited advantages provided by both zeolites; this pyrolysis oil represents a biofuel precursor that has a very low average molecular weight and a relatively low acidity. Finally, this study opens up a new way to upgrade pyrolysis oils by employing mixtures of different functional zeolites to produce biofuel/biochemical precursors from whole biomass.« less
Wang, Yuxin; He, Tao; Liu, Kaituo; Wu, Jinhu; Fang, Yunming
2012-03-01
Compared hydrodeoxygenation experimental studies of both model compounds and real bio-oil derived from biomass fast pyrolysis and catalytic pyrolysis was carried out over two different supported Pt catalysts. For the model compounds, the deoxygenation degree of dibenzofuran was higher than that of cresol and guaiacol over both Pt/Al(2)O(3) and the newly developed Pt supported on mesoporous zeolite (Pt/MZ-5) catalyst, and the deoxygenation degree of cresol over Pt/MZ-5 was higher than that over Pt/Al(2)O(3). The results indicated that hydrodeoxygenation become much easier upon oxygen reduction. Similar to model compounds study, the hydrodeoxygenation of the real bio-oil derived from catalytic pyrolysis was much easier than that from fast pyrolysis over both Pt catalysts, and the Pt/MZ-5 again shows much higher deoxygenation ability than Pt/Al(2)O(3). Clearly synergy between catalytic pyrolysis and bio-oil hydro-processing was found in this paper and this finding will lead an advanced biofuel production pathway in the future. Copyright © 2012 Elsevier Ltd. All rights reserved.
Gong, Xiaomin; Huang, Danlian; Liu, Yunguo; Zeng, Guangming; Wang, Rongzhong; Wei, Jingjing; Huang, Chao; Xu, Piao; Wan, Jia; Zhang, Chen
2018-04-01
This study aimed to investigate the effect of pyrolysis on the stabilization of heavy metals in plant residues obtained after phytoremediation. Ramie residues, being collected after phytoremediation of metal contaminated sediments, were pyrolyzed at different temperatures (300-700 °C). Results indicated that pyrolysis was effective in the stabilization of Cd, Cr, Zn, Cu, and Pb in ramie residues by converting the acid-soluble fraction of metals into residual form and decreasing the TCLP-leachable metal contents. Meanwhile, the reutilization potential of using the pyrolysis products generated from ramie residues obtained after phytoremediation as sorbents was investigated. Adsorption experiments results revealed that the pyrolysis products presented excellent ability to adsorb methylene blue (MB) with a maximum adsorption capacity of 259.27 mg/g. This study demonstrated that pyrolysis could be used as an efficient alternative method for stabilizing heavy metals in plant residues obtained after phytoremediation, and their pyrolysis products could be reutilized for dye adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.