Evaluation of char combustion models: measurement and analysis of variability in char particle size and density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maloney, Daniel J; Monazam, Esmail R; Casleton, Kent H

Char samples representing a range of combustion conditions and extents of burnout were obtained from a well-characterized laminar flow combustion experiment. Individual particles from the parent coal and char samples were characterized to determine distributions in particle volume, mass, and density at different extent of burnout. The data were then compared with predictions from a comprehensive char combustion model referred to as the char burnout kinetics model (CBK). The data clearly reflect the particle- to-particle heterogeneity of the parent coal and show a significant broadening in the size and density distributions of the chars resulting from both devolatilization and combustion.more » Data for chars prepared in a lower oxygen content environment (6% oxygen by vol.) are consistent with zone II type combustion behavior where most of the combustion is occurring near the particle surface. At higher oxygen contents (12% by vol.), the data show indications of more burning occurring in the particle interior. The CBK model does a good job of predicting the general nature of the development of size and density distributions during burning but the input distribution of particle size and density is critical to obtaining good predictions. A significant reduction in particle size was observed to occur as a result of devolatilization. For comprehensive combustion models to provide accurate predictions, this size reduction phenomenon needs to be included in devolatilization models so that representative char distributions are carried through the calculations.« less

A comparison of simple global kinetic models for coal devolatilization with the CPD model

DOE PAGES

Richards, Andrew P.; Fletcher, Thomas H.

2016-08-01

Simulations of coal combustors and gasifiers generally cannot incorporate the complexities of advanced pyrolysis models, and hence there is interest in evaluating simpler models over ranges of temperature and heating rate that are applicable to the furnace of interest. In this paper, six different simple model forms are compared to predictions made by the Chemical Percolation Devolatilization (CPD) model. The model forms included three modified one-step models, a simple two-step model, and two new modified two-step models. These simple model forms were compared over a wide range of heating rates (5 × 10 3 to 10 6 K/s) at finalmore » temperatures up to 1600 K. Comparisons were made of total volatiles yield as a function of temperature, as well as the ultimate volatiles yield. Advantages and disadvantages for each simple model form are discussed. In conclusion, a modified two-step model with distributed activation energies seems to give the best agreement with CPD model predictions (with the fewest tunable parameters).« less

Kinetic analysis of manure pyrolysis and combustion processes.

PubMed

Fernandez-Lopez, M; Pedrosa-Castro, G J; Valverde, J L; Sanchez-Silva, L

2016-12-01

Due to the depletion of fossil fuel reserves and the environmental issues derived from their use, biomass seems to be an excellent source of renewable energy. In this work, the kinetics of the pyrolysis and combustion of three different biomass waste samples (two dairy manure samples before (Pre) and after (Dig R) anaerobic digestion and one swine manure sample (SW)) was studied by means of thermogravimetric analysis. In this work, three iso-conversional methods (Friedman, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS)) were compared with the Coats-Redfern method. The E a values of devolatilization stages were in the range of 152-170kJ/mol, 148-178kJ/mol and 156-209kJ/mol for samples Pre, Dig R and SW, respectively. Concerning combustion process, char oxidation stages showed lower E a values than that obtained for the combustion devolatilization stage, being in the range of 140-175kJ/mol, 178-199kJ/mol and 122-144kJ/mol for samples Pre, Dig R and SW, respectively. These results were practically the same for samples Pre and Dig R, which means that the kinetics of the thermochemical processes were not affected by anaerobic digestion. Finally, the distributed activation energy model (DAEM) and the pseudo-multi component stage model (PMSM) were applied to predict the weight loss curves of pyrolysis and combustion. DAEM was the best model that fitted the experimental data. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Chaotic Terrains of Mercury: A History of Large-Scale Crustal Devolatilization

NASA Astrophysics Data System (ADS)

Rodriguez, J. A. P.; Domingue, D. L.; Berman, D. C.; Kargel, J. S.; Baker, V. R.; Teodoro, L. F.; Banks, M.; Leonard, G.

2018-05-01

Approximately 400 million years after the Caloris basin impact, extensive collapse formed Mercury's chaotic terrains. Collapse likely resulted from regionally elevated heat flow devolatilizing crustal materials along NE and NW extensional faults.

Numerical investigation of slag formation in an entrained-flow gasifier

NASA Astrophysics Data System (ADS)

Zageris, G.; Geza, V.; Jakovics, A.

2018-05-01

A CFD mathematical model for an entrained-flow gasifier is constructed – the model of an actual gasifier is rendered in 3D and appropriately meshed. Then, the turbulent gas flow in the gasifier is modeled with the realizable k-ε approach, taking devolatilization, combustion and coal gasification in account. Various such simulations are conducted, obtaining results for different air inlet positions and by tracking particles of varying sizes undergoing devolatilization and gasification. The model identifies potential problematic zones where most particles collide with the gasifier walls, indicating risk regions where ash deposits could most likely form. In conclusion, effects on the formation of an ash layer of air inlet positioning and particle size allowed in the main gasifier tank are discussed, and viable solutions such as radial inlet positioning for decreasing the amount of undesirable deposits are proposed. We also conclude that the particular chemical reactions that take place inside the gasifier play a significant role in determining how slagging occurs inside a gasifier.

Impact-induced devolatilization of CaSO4 anhydrite and implications for K-T extinctions: Preliminary results

NASA Technical Reports Server (NTRS)

Tyburczy, James A.; Ahrens, Thomas J.

1993-01-01

The recent suggestions that the target area for the K-T bolide may have been a sulfate-rich evaporite and that the resulting sulfuric acid-rich aerosol was responsible for the subsequent cooling of the Earth and the resulting biological extinctions has prompted us to experimentally examine the impact-induced devolatization of the sulfate minerals anhydrite (CaSO4) and gypsum (CaSO4(2H2O)). Preliminary results for anhydrite are reported. Up to 42 GPa peak shock pressure, little or no devolatilization occurs, consistent with chemical thermodynamic calculations. Calculation of the influence of the partial pressure of the gas species on impact-induced devolatilization suggests that an even greater amount of sulfur than that proposed by Brett could have been released to the atmosphere by an impact into a sulfate-rich layer. Solid recovery, impact-induced devolatilization experiments were performed on the Caltech 20mm gun using vented, stainless steel sample assemblies.

Updraft Fixed Bed Gasification Aspen Plus Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

2007-09-27

The updraft fixed bed gasification model provides predictive modeling capabilities for updraft fixed bed gasifiers, when devolatilization data is available. The fixed bed model is constructed using Aspen Plus, process modeling software, coupled with a FORTRAN user kinetic subroutine. Current updraft gasification models created in Aspen Plus have limited predictive capabilities and must be "tuned" to reflect a generalized gas composition as specified in literature or by the gasifier manufacturer. This limits the applicability of the process model.

Comprehensive Model of Single Particle Pulverized Coal Combustion Extended to Oxy-Coal Conditions

DOE PAGES

Holland, Troy; Fletcher, Thomas H.

2017-02-22

Oxy-fired coal combustion is a promising potential carbon capture technology. Predictive CFD simulations are valuable tools in evaluating and deploying oxy-fuel and other carbon capture technologies either as retrofit technologies or for new construction. But, accurate predictive simulations require physically realistic submodels with low computational requirements. In particular, comprehensive char oxidation and gasification models have been developed that describe multiple reaction and diffusion processes. Our work extends a comprehensive char conversion code (CCK), which treats surface oxidation and gasification reactions as well as processes such as film diffusion, pore diffusion, ash encapsulation, and annealing. In this work several submodels inmore » the CCK code were updated with more realistic physics or otherwise extended to function in oxy-coal conditions. Improved submodels include the annealing model, the swelling model, the mode of burning parameter, and the kinetic model, as well as the addition of the chemical percolation devolatilization (CPD) model. We compare our results of the char combustion model to oxy-coal data, and further compared to parallel data sets near conventional conditions. A potential method to apply the detailed code in CFD work is given.« less

Comprehensive Model of Single Particle Pulverized Coal Combustion Extended to Oxy-Coal Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holland, Troy; Fletcher, Thomas H.

Oxy-fired coal combustion is a promising potential carbon capture technology. Predictive CFD simulations are valuable tools in evaluating and deploying oxy-fuel and other carbon capture technologies either as retrofit technologies or for new construction. But, accurate predictive simulations require physically realistic submodels with low computational requirements. In particular, comprehensive char oxidation and gasification models have been developed that describe multiple reaction and diffusion processes. Our work extends a comprehensive char conversion code (CCK), which treats surface oxidation and gasification reactions as well as processes such as film diffusion, pore diffusion, ash encapsulation, and annealing. In this work several submodels inmore » the CCK code were updated with more realistic physics or otherwise extended to function in oxy-coal conditions. Improved submodels include the annealing model, the swelling model, the mode of burning parameter, and the kinetic model, as well as the addition of the chemical percolation devolatilization (CPD) model. We compare our results of the char combustion model to oxy-coal data, and further compared to parallel data sets near conventional conditions. A potential method to apply the detailed code in CFD work is given.« less

A Mechanistic Investigation of Nitrogen Evolution and Corrosion with Oxy-Combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dale Tree; Andrew Mackrory; Thomas Fletcher

A premixed, staged, down-fired, pulverized coal reactor and a flat flame burner were used to study the evolution of nitrogen in coal contrasting differences in air and oxy-combustion. In the premixed reactor, the oxidizer was staged to produce a fuel rich zone followed by a burnout zone. The initial nominal fuel rich zone stoichiometric ratio (S.R.) of 0.85 selected produced higher NO reductions in the fuel rich region under oxy-combustion conditions. Air was found to be capable of similar NO reductions when the fuel rich zone was at a much lower S.R. of 0.65. At a S.R. of 0.85, oxy-combustionmore » was measured to have higher CO, unburned hydrocarbons, HCN and NH{sub 3} in the fuel rich region than air at the same S.R. There was no measured difference in the initial formation of NO. The data suggest devolatilization and initial NO formation is similar for the two oxidizers when flame temperatures are the same, but the higher CO{sub 2} leads to higher concentrations of CO and nitrogen reducing intermediates at a given equivalence ratio which increases the ability of the gas phase to reduce NO. These results are supported by flat flame burner experiments which show devolatilization of nitrogen from the coal and char to be similar for air and oxy-flame conditions at a given temperature. A model of premixed combustion containing devolatilization, char oxidation and detailed kinetics captures most of the trends seen in the data. The model suggests CO is high in oxy-combustion because of dissociation of CO{sub 2}. The model also predicts a fraction (up to 20%, dependent on S.R.) of NO in air combustion can be formed via thermal processes with the source being nitrogen from the air while in oxy-combustion equilibrium drives a reduction in NO of similar magnitude. The data confirm oxy-combustion is a superior oxidizer to air for NO control because NO reduction can be achieved at higher S.R. producing better char burnout in addition to NO from recirculated flue gas being reduced as it passes back through the flame.« less

Pyrolysis reaction models of waste tires: Application of Master-Plots method for energy conversion via devolatilization.

PubMed

Irmak Aslan, Dilan; Parthasarathy, Prakash; Goldfarb, Jillian L; Ceylan, Selim

2017-10-01

Land applied disposal of waste tires has far-reaching environmental, economic, and human health consequences. Pyrolysis represents a potential waste management solution, whereby the solid carbonaceous residue is heated in the absence of oxygen to produce liquid and gaseous fuels, and a solid char. The design of an efficient conversion unit requires information on the reaction kinetics of pyrolysis. This work is the first to probe the appropriate reaction model of waste tire pyrolysis. The average activation energy of pyrolysis was determined via iso-conversional methods over a mass fraction conversion range between 0.20 and 0.80 to be 162.8±23.2kJmol -1 . Using the Master Plots method, a reaction order of three was found to be the most suitable model to describe the pyrolytic decomposition. This suggests that the chemical reactions themselves (cracking, depolymerization, etc.), not diffusion or boundary layer interactions common with carbonaceous biomasses, are the rate-limiting steps in the pyrolytic decomposition of waste tires. Copyright © 2017 Elsevier Ltd. All rights reserved.

Numerical Simulation on Hydrodynamics and Combustion in a Circulating Fluidized Bed under O2/CO2 and Air Atmospheres

NASA Astrophysics Data System (ADS)

Zhou, W.; Zhao, C. S.; Duan, L. B.; Qu, C. R.; Lu, J. Y.; Chen, X. P.

Oxy-fuel circulating fluidized bed (CFB) combustion technology is in the stage of initial development for carbon capture and storage (CCS). Numerical simulation is helpful to better understanding the combustion process and will be significant for CFB scale-up. In this paper, a computational fluid dynamics (CFD) model was employed to simulate the hydrodynamics of gas-solid flow in a CFB riser based on the Eulerian-Granular multiphase model. The cold model predicted the main features of the complex gas-solid flow, including the cluster formation of the solid phase along the walls, the flow structure of up-flow in the core and downward flow in the annular region. Furthermore, coal devolatilization, char combustion and heat transfer were considered by coupling semi-empirical sub-models with CFD model to establish a comprehensive model. The gas compositions and temperature profiles were predicted and the outflow gas fractions are validated with the experimental data in air combustion. With the experimentally validated model being applied, the concentration and temperature distributions in O2/CO2 combustion were predicted. The model is useful for the further development of a comprehensive model including more sub-models, such as pollutant emissions, and better understanding the combustion process in furnace.

Effects of combustion temperature on PCDD/Fs formation in laboratory-scale fluidized-bed incineration.

PubMed

Hatanaka, T; Imagawa, T; Kitajima, A; Takeuchi, M

2001-12-15

Combustion experiments in a laboratory-scale fluidized-bed reactor were performed to elucidate the effects of combustion temperature on PCDD/Fs formation during incineration of model wastes with poly(vinyl chloride) or sodium chloride as a chlorine source and copper chloride as a catalyst. Each temperature of primary and secondary combustion zones in the reactor was set independently to 700, 800, and 900 degrees C using external electric heaters. The PCDD/Fs concentration is reduced as the temperature of the secondary combustion zone increases. It is effective to keep the temperature of the secondary combustion zone high enough to reduce their release during the waste incineration. On the other hand, as the temperature of the primary combustion zone rises, the PCDD/Fs concentration also increases. Lower temperature of the primary combustion zone results in less PCDD/Fs concentration in these experimental conditions. This result is probably related to the devolatilization rate of the solid waste in the primary combustion zone. The temperature decrease slows the devolatilization rate and promotes mixing of oxygen and volatile matters from the solid waste. This contributes to completing combustion reactions, resulting in reducing the PCDD/Fs concentration.

Measurement and modeling of advanced coal conversion processes, Volume II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solomon, P.R.; Serio, M.A.; Hamblen, D.G.

1993-06-01

A two dimensional, steady-state model for describing a variety of reactive and nonreactive flows, including pulverized coal combustion and gasification, is presented. The model, referred to as 93-PCGC-2 is applicable to cylindrical, axi-symmetric systems. Turbulence is accounted for in both the fluid mechanics equations and the combustion scheme. Radiation from gases, walls, and particles is taken into account using a discrete ordinates method. The particle phase is modeled in a lagrangian framework, such that mean paths of particle groups are followed. A new coal-general devolatilization submodel (FG-DVC) with coal swelling and char reactivity submodels has been added.

Sunflower shells utilization for energetic purposes in an integrated approach of energy crops: laboratory study pyrolysis and kinetics.

PubMed

Zabaniotou, A A; Kantarelis, E K; Theodoropoulos, D C

2008-05-01

Sunflower is a traditional crop which can be used for the production of bioenergy and liquid biofuels. A study of the pyrolytic behaviour of sunflower residues at temperatures from 300 to 600 degrees C has been carried out. The experiments were performed in a captive sample reactor under atmospheric pressure and helium as sweeping gas. The yields of the derived pyrolysis products were determined in relation to temperature, with constant sweeping gas flow of 50 cm3 min(-1) and heating rate of 40 degrees Cs(-1). The maximum gas yield of around 53 wt.% was obtained at 500 degrees C, whereas maximum oil yield of about 21 wt.% was obtained at 400 degrees C. A simple first order kinetic model has been applied for the devolatilization of biomass. Kinetic constants have been estimated: E=78.15 kJ mol(-1); k(0)=1.03 x 10(3)s(-1).

Causes of distal volcano-tectonic seismicity inferred from hydrothermal modeling

NASA Astrophysics Data System (ADS)

Coulon, C. A.; Hsieh, P. A.; White, R.; Lowenstern, J. B.; Ingebritsen, S. E.

2017-10-01

Distal volcano-tectonic (dVT) seismicity typically precedes eruption at long-dormant volcanoes by days to years. Precursory dVT seismicity may reflect magma-induced fluid-pressure pulses that intersect critically stressed faults. We explored this hypothesis using an open-source magmatic-hydrothermal code that simulates multiphase fluid and heat transport over the temperature range 0 to 1200 °C. We calculated fluid-pressure changes caused by a small (0.04 km3) intrusion and explored the effects of flow geometry (channelized vs. radial flow), magma devolatilization rates (0-15 kg/s), and intrusion depths (5 and 7.5 km, above and below the brittle-ductile transition). Magma and host-rock permeabilities were key controlling parameters and we tested a wide range of permeability (k) and permeability anisotropies (kh/kv), including k constant, k(z), k(T), and k(z, T, P) distributions, examining a total of 1600 realizations to explore the relevant parameter space. Propagation of potentially causal pressure changes (ΔP ≥ 0.1 bars) to the mean dVT location (6 km lateral distance, 6 km depth) was favored by channelized fluid flow, high devolatilization rates, and permeabilities similar to those found in geothermal reservoirs (k 10- 16 to 10- 13 m2). For channelized flow, magma-induced thermal pressurization alone can generate cases of Δ P ≥ 0.1 bars for all permeabilities in the range 10- 16 to 10- 13 m2, whereas in radial flow regimes thermal pressurization causes Δ P < 0.1 bars for all permeabilities. Changes in distal fluid pressure occurred before proximal pressure changes given modest anisotropies (kh/kv 10-100). Invoking k(z,T,P) and high, sustained devolatilization rates caused large dynamic fluctuations in k and P in the near-magma environment but had little effect on pressure changes at the distal dVT location. Intrusion below the brittle-ductile transition damps but does not prevent pressure transmission to the dVT site.

Characterization of fuels for second-generation PFBC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zevenhoven, C.A.P.; Hupa, M.

1997-12-31

In second-generation PFBC technology a solid fuel is partly converted in a devolatilization step (in a carbonizer) to produce a char and a pressurized fuel gas, followed by PFB combustion of the char. The fuel gas is led to the combustion chamber of a gas turbine after it is mixed with the PFBC off-gas, thus increasing the temperature at the inlet of the expansion turbine. Clearly, the optimization of the carbonizer design and operation is essential to the process. Detailed information on the behavior of solid fuels under pressurized conditions is, however, largely limited to steam and/or carbon dioxide gasificationmore » reactivities, obtained at a different combination of process parameters, such as temperature, pressure, heating rate, particle size and gas atmosphere. In the present work, the effect of temperature, pressure and heating rates on the yields of volatiles and char residue reactivity has been measured for a set of fuels ranging from bituminous coal to wood. Laboratory conditions were typical for the carbonizer and combustion reactors in a second-generation PFBC system. A pressurized thermogravimetric reactor (PTGR) operated at heating rates of around 250 K/s and a pressurized grid heater (PGH) operated at heating rates up to 3,000 K/s were used to analyze fuel devolatilization and char reactivity against carbon dioxide or steam at temperatures between 800 and 1,100 C, and 1, 10 or 25 bar total pressure. For comparison, a few experiments were repeated without a separate devolatilization step. The behavior of the various fuels were compared and related to proximate and ultimate fuel analysis. Several empirical, engineering equations are given. A simple 2-parameter model which separates intrinsic surface reactivity and physical, structure effects, very well describes the time-conversion data of the char. It was found that the fuel O/C molar ratio is a very good index for char reactivity, when the char O/C ratio itself is unknown.« less

A Chlorine-Centric Perspective on Fluid-Mediated Processes at Convergent Plate Boundaries

NASA Astrophysics Data System (ADS)

Selverstone, J.

2014-12-01

The release and migration of metamorphic fluids from subducting slabs into overlying mantle is widely recognized as a major mechanism in producing arc geochemical signatures and returning fluid-mobile elements to earth's crust and surface environments. Although the magnitudes of many geochemical fluxes are well constrained, the processes whereby mass transfer occurs in different portions of the subduction system are less well known. Chlorine stable isotopes provide a new perspective on some of these processes: Cl is hydrophilic, but decarbonation reactions favor Cl retention in minerals. Cl also shows less isotopic fractionation than other fluid-sensitive systems and may thus preserve evidence of specific fluid sources and/or fluid mixing events. Detailed studies of sedimentary sequences show that individual beds are isotopically homogeneous but large heterogeneities in δ37Cl exist across beds on a cm to m scale and vary as a function of depositional environment. Compositionally correlative medium-, high-, and ultrahigh-pressure metamorphic sequences in the Alps record decreases of 30-50% in Cl contents in the earliest stages of metamorphism, but little change thereafter. No statistically significant change in isotopic composition occurs during prograde metamorphism of individual horizons, and the same large degree of isotopic heterogeneity (up to 6‰) persists throughout the prograde devolatilization history of the rocks. Likewise, analysis of HP/UHP serpentinites and altered oceanic crust show that heterogeneous protolith compositions are preserved during transport to sub-arc depths, despite large-scale devolatilization. However, upward transport of rocks within the subduction channel results in highly localized interaction with isotopically distinct, Cl-bearing fluid packets. Overlying forearc wedge rocks also record heterogeneous and channelized interaction with distinct fluid components with different δ37Cl. Within-layer fluid compartmentalization during continuous devolatilization reactions must thus be reconciled with discontinuous, cross-layer fluid percolation out of the slab and into the wedge. The resulting implications of the chlorine data for recent mechanical models of slab-to-wedge fluid transport will be discussed.

Impact Cratering Calculations

NASA Technical Reports Server (NTRS)

Ahrens, Thomas J.

2001-01-01

This research is computational /theoretical and complements the Caltech experimental program. We have developed an understanding of the basic physical processes and produced computational models and implemented these into Eulerian and Lagrangian finite element codes. The key issues we have addressed include the conditions required for: faulting (strain localization), elastic moduli weakening, dynamic weakening (layering elastic instabilities and fluidization), bulking (creation of porosity at zero pressure) and compaction of pores, frictional melting (creation of pseudotachylytes), partial and selective devolatilization of materials (e.g. CaCO3, water/ice mixtures), and debris flows.

Pyrolytic Characteristics and Kinetics of Phragmites australis

PubMed Central

Zhao, Hui; Yan, Huaxiao; Zhang, Congwang; Liu, Xiaodong; Xue, Yanhui; Qiao, Yingyun; Tian, Yuanyu; Qin, Song

2011-01-01

The pyrolytic kinetics of Phragmites australis was investigated using thermogravimetric analysis (TGA) method with linear temperature programming process under an inert atmosphere. Kinetic expressions for the degradation rate in devolatilization and combustion steps have been obtained for P. australis with Dollimore method. The values of apparent activation energy, the most probable mechanism functions, and the corresponding preexponential factor were determined. The results show that the model agrees well with the experimental data and provide useful information for the design of pyrolytic processing system using P. australis as feedstock to produce biofuel. PMID:22007256

Simulation of fluidized bed coal combustors

NASA Technical Reports Server (NTRS)

Rajan, R.

1979-01-01

The many deficiencies of previous work on simulation of fluidized bed combustion (FBC) processes are presented. An attempt is made to reduce these deficiencies, and to formulate a comprehensive FBC model taking into account the following elements: (1) devolatilization of coal and the subsequent combustion of volatiles and residual char; (2) sulfur dioxide capture by limestone; (3) NOx release and reduction of NOx by char; (4) attrition and elutriation of char and limestone; (5) bubble hydrodynamics; (6) solids mixing; (7) heat transfer between gas and solid, and solid and heat exchange surfaces; and (8) freeboard reactions.

Causes of distal volcano-tectonic seismicity inferred from hydrothermal modeling

USGS Publications Warehouse

Coulon, Cecile A.; Hsieh, Paul A.; White, Randall A.; Lowenstern, Jacob B.; Ingebritsen, Steven E.

2017-01-01

Distal volcano-tectonic (dVT) seismicity typically precedes eruption at long-dormant volcanoes by days to years. Precursory dVT seismicity may reflect magma-induced fluid-pressure pulses that intersect critically stressed faults. We explored this hypothesis using an open-source magmatic-hydrothermal code that simulates multiphase fluid and heat transport over the temperature range 0 to 1200 °C. We calculated fluid-pressure changes caused by a small (0.04 km3) intrusion and explored the effects of flow geometry (channelized vs. radial flow), magma devolatilization rates (0–15 kg/s), and intrusion depths (5 and 7.5 km, above and below the brittle-ductile transition). Magma and host-rock permeabilities were key controlling parameters and we tested a wide range of permeability (k) and permeability anisotropies (kh/kv), including k constant, k(z), k(T), and k(z, T, P) distributions, examining a total of ~ 1600 realizations to explore the relevant parameter space. Propagation of potentially causal pressure changes (ΔP ≥ 0.1 bars) to the mean dVT location (6 km lateral distance, 6 km depth) was favored by channelized fluid flow, high devolatilization rates, and permeabilities similar to those found in geothermal reservoirs (k ~ 10− 16 to 10− 13 m2). For channelized flow, magma-induced thermal pressurization alone can generate cases of ∆ P ≥ 0.1 bars for all permeabilities in the range 10− 16 to 10− 13 m2, whereas in radial flow regimes thermal pressurization causes ∆ P < 0.1 bars for all permeabilities. Changes in distal fluid pressure occurred before proximal pressure changes given modest anisotropies (kh/kv ~ 10–100). Invoking k(z,T,P) and high, sustained devolatilization rates caused large dynamic fluctuations in k and P in the near-magma environment but had little effect on pressure changes at the distal dVT location. Intrusion below the brittle-ductile transition damps but does not prevent pressure transmission to the dVT site.

Lithospheric processes that enhance melting at rifts

NASA Astrophysics Data System (ADS)

Elkins-Tanton, L. T.; Furman, T.

2008-12-01

Continental rifts are commonly sites for mantle melting, whether in the form of ridge melting to create new oceanic crust, or as the locus of flood basalt activity, or in the long initial period of rifting before lavas evolve fully into MORBs. The high topography in the lithosphere-asthenosphere boundary under a rift creates mantle upwelling and adiabatic melting even in the absence of a plume. This geometry itself, however, is conducive to lithospheric instability on the sides of the rifts. Unstable lithosphere may founder into the mantle, producing more complex aesthenospheric convective patterns and additional opportunities to produce melt. Lithospheric instabilities can produce additional adiabatic melting in convection produced as they sink, and they may also devolatilize as they sink, introducing the possibility of flux melting to the rift environment. We call this process upside-down melting, since devolatilization and melting proceed as the foundering lithosphere sinks, rather than while rising, as in the more familiar adiabatic decompression melting. Both adiabatic melting and flux melting would take place along the edges of the rift and may even move magmatism outside the rift, as has been seen in Ethiopia. In volcanism postdating the flood basalts on and adjacent to the Ethiopian Plateau there is evidence for both lithospheric thinning and volatile enrichment in the magmas, potentially consistent with the upside-down melting model. Here we present a physical model for the conjunction of adiabatic decompression melting to produce new oceanic crust in the rift, while lithospheric gravitational instabilities drive both adiabatic and flux melting at its margins.

Development and numerical/experimental characterization of a lab-scale flat flame reactor allowing the analysis of pulverized solid fuel devolatilization and oxidation at high heating rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemaire, R., E-mail: romain.lemaire@mines-douai.fr; Menanteau, S.

2016-01-15

This paper deals with the thorough characterization of a new experimental test bench designed to study the devolatilization and oxidation of pulverized fuel particles in a wide range of operating conditions. This lab-scale facility is composed of a fuel feeding system, the functioning of which has been optimized by computational fluid dynamics. It allows delivering a constant and time-independent mass flow rate of fuel particles which are pneumatically transported to the central injector of a hybrid McKenna burner using a carrier gas stream that can be inert or oxidant depending on the targeted application. A premixed propane/air laminar flat flamemore » stabilized on the porous part of the burner is used to generate the hot gases insuring the heating of the central coal/carrier-gas jet with a thermal gradient similar to those found in industrial combustors (>10{sup 5} K/s). In the present work, results issued from numerical simulations performed a priori to characterize the velocity and temperature fields in the reaction chamber have been analyzed and confronted with experimental measurements carried out by coupling particle image velocimetry, thermocouple and two-color pyrometry measurements so as to validate the order of magnitude of the heating rate delivered by such a new test bench. Finally, the main features of the flat flame reactor we developed have been discussed with respect to those of another laboratory-scale system designed to study coal devolatilization at a high heating rate.« less

Development and numerical/experimental characterization of a lab-scale flat flame reactor allowing the analysis of pulverized solid fuel devolatilization and oxidation at high heating rates

NASA Astrophysics Data System (ADS)

Lemaire, R.; Menanteau, S.

2016-01-01

This paper deals with the thorough characterization of a new experimental test bench designed to study the devolatilization and oxidation of pulverized fuel particles in a wide range of operating conditions. This lab-scale facility is composed of a fuel feeding system, the functioning of which has been optimized by computational fluid dynamics. It allows delivering a constant and time-independent mass flow rate of fuel particles which are pneumatically transported to the central injector of a hybrid McKenna burner using a carrier gas stream that can be inert or oxidant depending on the targeted application. A premixed propane/air laminar flat flame stabilized on the porous part of the burner is used to generate the hot gases insuring the heating of the central coal/carrier-gas jet with a thermal gradient similar to those found in industrial combustors (>105 K/s). In the present work, results issued from numerical simulations performed a priori to characterize the velocity and temperature fields in the reaction chamber have been analyzed and confronted with experimental measurements carried out by coupling particle image velocimetry, thermocouple and two-color pyrometry measurements so as to validate the order of magnitude of the heating rate delivered by such a new test bench. Finally, the main features of the flat flame reactor we developed have been discussed with respect to those of another laboratory-scale system designed to study coal devolatilization at a high heating rate.

Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments

NASA Technical Reports Server (NTRS)

Bell, Mary S.

2009-01-01

The shock behavior of calcite and gypsum is important in understanding the Cretaceous/Tertiary event and other terrestrial impacts that contain evaporite sediments in their targets. Most interest focuses on issues of devolatilization to quantify the production of CO2 or SO2 to better understand their role in generating a temporary atmosphere and its effects on climate and biota [e.g., papers in 1,2,3,4]. Devolatilization of carbonate is also important because the dispersion and fragmentation of ejecta is strongly controlled by the expansion of large volumes of gas during the impact process as well [5,6]. Shock recovery experiments for calcite yield seemingly conflicting results: early experimental devolatilization studies [7,8,9] suggested that calcite was substantially outgassed at 30 GPa (> 50%). However, the recent petrographic work of [10,11,12] presented evidence that essentially intact calcite is recovered from 60 GPa experiments. [13] reported results of shock experiments on anhydrite, gypsum, and mixtures of those phases with silica. Their observations indicate little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another (preliminary) report of shock experiments on calcite, anhydrite, and gypsum, [14] observe calcite recrystallization when shock loaded at 61 GPa, only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa. [15] shock loaded anhydrite and quartz to a peak pressure of 60 GPa. All of the quartz grains were trans-formed to glass and the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggest that recrystallization of anhydrite grains is the result of a solid state transformation. [16] reanalyzed the calcite and anhydrite shock wave experiments of [17] using improved equations of state of porous materials and vaporized products. They determined the pressures for incipient and complete vaporization to be 32.5 and 122 GPa for anhydrite and 17.8 and 54.1 GPa for calcite, respectively, a factor of 2 to 3 lower than reported earlier by [17].

Modeling of the devolatilization kinetics during pyrolysis of grape residues.

PubMed

Fiori, Luca; Valbusa, Michele; Lorenzi, Denis; Fambri, Luca

2012-01-01

Thermo-gravimetric analysis (TGA) was performed on grape seeds, skins, stalks, marc, vine-branches, grape seed oil and grape seeds depleted of their oil. The TGA data was modeled through Gaussian, logistic and Miura-Maki distributed activation energy models (DAEMs) and a simpler two-parameter model. All DAEMs allowed an accurate prediction of the TGA data; however, the Miura-Maki model could not account for the complete range of conversion for some substrates, while the Gaussian and logistic DAEMs suffered from the interrelation between the pre-exponential factor k0 and the mean activation energy E0--an obstacle that can be overcome by fixing the value of k0 a priori. The results confirmed the capabilities of DAEMs but also highlighted some drawbacks in their application to certain thermodegradation experimental data. Copyright © 2011 Elsevier Ltd. All rights reserved.

Computational fluid dynamics assessment: Volume 1, Computer simulations of the METC (Morgantown Energy Technology Center) entrained-flow gasifier: Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Celik, I.; Chattree, M.

1988-07-01

An assessment of the theoretical and numerical aspects of the computer code, PCGC-2, is made; and the results of the application of this code to the Morgantown Energy Technology Center (METC) advanced gasification facility entrained-flow reactor, ''the gasifier,'' are presented. PCGC-2 is a code suitable for simulating pulverized coal combustion or gasification under axisymmetric (two-dimensional) flow conditions. The governing equations for the gas and particulate phase have been reviewed. The numerical procedure and the related programming difficulties have been elucidated. A single-particle model similar to the one used in PCGC-2 has been developed, programmed, and applied to some simple situationsmore » in order to gain insight to the physics of coal particle heat-up, devolatilization, and char oxidation processes. PCGC-2 was applied to the METC entrained-flow gasifier to study numerically the flash pyrolysis of coal, and gasification of coal with steam or carbon dioxide. The results from the simulations are compared with measurements. The gas and particle residence times, particle temperature, and mass component history were also calculated and the results were analyzed. The results provide useful information for understanding the fundamentals of coal gasification and for assessment of experimental results performed using the reactor considered. 69 refs., 35 figs., 23 tabs.« less

Witness of fluid-flow organization during high-pressure antigorite dehydration

NASA Astrophysics Data System (ADS)

López Sánchez-Vizcaíno, Vicente; Padrón-Navarta, José Alberto; Garrido, Carlos J.; Gómez-Pugnaire, María. Teresa

2010-05-01

The link between devolatilization reactions and fluid flow is crucial to unravel important geodynamic processes in subduction zones as deformation and element transfer is extremely controlled by the presence of water. At high confining pressure, significant fluid pressure gradients are expected in a reacting rock being dehydrated, because of its rather limited permeability [1]. Compactation-driven fluid flow seems to be an intrinsic mechanism occurring at devolatilization of viscolastic rocks. Nevertheless, and despite the important implications of this coupled deformation/fluid-migration mechanism for fluid transport, a conclusive confirmation of these processes by petrological and textural evidences in metamorphic terrains has been hampered by the scarcity of devolatilization fronts in the geological record. Evidences of high-pressure antigorite dehydration found at Cerro del Almirez (Betic Cordillera, Spain) [2] represent a noteworthy exception. Here, the transition between the hydrous protolith (antigorite serpentinite) and the prograde product assemblage (olivine + orthopyroxene + chlorite, chlorite harzburgite) is extremely well preserved and can be surveyed in detail. The maximum stability of the antigorite has been experimentally determined at ~680°C at 1.6-1.9 GPa [3]. Antigorite dehydration is accompanied by release of high amounts of high-pressure water-rich fluids (~ 9 wt.% fluid). Distinctive layers (up to 1 m thick) of transitional lithologies occur in between atg-serpentinite and chl-harburgite all along the devolatilization front, consisting of (1) chlorite-antigorite olivine-serpentinite, which gradually changes to (2) chlorite-antigorite-olivine-orthopyroxene serpentinite. These transitional lithologies are more massive and darker in color than atg-serpentinite and largely consist of coarse sized grains of antigorite and chlorite (250-500 μm). Antigorite in these assemblages is characterized by microstructural disorder features, which are lacking in antigorite far from the devolatilization front [4]. The sharp appearance of chlorite (Chl-in), crosscutting the serpentinite foliation, and coarsening of olivine define the upper limit of the transitional lithologies, whereas the lower limit (Atg-out) is gradational to chl-harzburgite. The modal increase of orthopyroxene is concomitant with the gradual disappearance of antigorite. The gradual disappearance of antigorite over short distances leads to the final prograde assemblage in the Chl-harzburgite with two contrasting textures: (1) coarse granular texture and (2) an intriguing spinifex-like texture (arborescent growth of centimeter-sized olivine and orthopyroxene). Both textures alternate at the meter to tens of meters scale over the entire massif. We interpret these textures as the result of contrasting pore fluid overpressure, reaction rates and fluid-flow organization shortly after the antigorite breakdown. These observations will be discussed on the frame of the reaction kinetic and the propagation of deformation associated to fluid pressure gradients. [1] Connolly, Journal of Geophysical Research 112 (B8), 18 (1997). [2] Trommsdorff, López Sánchez-Vizcaíno, Gómez-Pugnaire et al., Contrib Mineral Petr 132 (2), 139 (1998). [3] Padrón-Navarta, Hermann, Garrido et al., Contrib Mineral Petr 159 (1), 25 (2010). [4] Padrón-Navarta, López Sánchez-Vizcaíno, Garrido et al., Contrib Mineral Petr 156 (5), 679 (2008).

Evaluating the combustion reactivity of drop tube furnace and thermogravimetric analysis coal chars with a selection of metal additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katherine Le Manquais; Colin E. Snape; Ian McRobbie

Opportunities exist for effective coal combustion additives that can reduce the carbon content of pulverized fuel ash (PFA) to below 6%, thereby making it saleable for filler/building material applications without the need for postcombustion treatment. However, with only limited combustion data currently available for the multitude of potential additives, catalytic performance under pulverized fuel (PF) boiler conditions has received relatively little attention. This paper therefore compares the reactivity of catalyzed bituminous coal chars from thermogravimetric analysis (TGA) with those generated by devolatilization in a drop tube furnace (DTF). The principal aim was to explore the fundamental chemistry behind the chosenmore » additives' relative reactivities. Accordingly, all eight of the investigated additives increased the TGA burnout rate of the TGA and DTF chars, with most of the catalysts demonstrating consistent reactivity levels across chars from both devolatilization methods. Copper(I) chloride, silver chloride, and copper nitrate were thus identified as the most successful additives tested, but it proved difficult to establish a definitive reactivity ranking. This was largely due to the use of physical mixtures for catalyst dispersion, the relatively narrow selection of additives examined, and the inherent variability of the DTF chars. Nevertheless, one crucial exception to normal additive behavior was discovered, with copper(I) chloride perceptibly deactivating during devolatilization in the DTF, even though it remained the most effective catalyst tested. As a prolonged burnout at over 1000{sup o}C was required to replicate this deactivation effect on the TGA, the phenomenon could not be detected by typical testing procedures. Subsequently, a comprehensive TGA study showed no obvious relationship between the catalyst-induced reductions in the reaction's apparent activation energy and the samples recorded burnout rates.« less

Ammonium loss and nitrogen isotopic fractionation in biotite as a function of metamorphic grade in metapelites from western Maine, USA

NASA Astrophysics Data System (ADS)

Plessen, Birgit; Harlov, Daniel E.; Henry, Darrell; Guidotti, Charles V.

2010-08-01

Ammonium fixed in micas of metamorphic rocks is a sensitive indicator both of organic-inorganic interactions during diagenesis as well as of the devolatilization history and fluid/rock interaction during metamorphism. In this study, a collection of geochemically well-characterized biotite separates from a series of graphite-bearing Paleozoic greenschist- to upper amphibolite-facies metapelites, western Maine, USA, were analyzed for ammonium nitrogen ( NH4+-N) contents and isotopic composition (δ 15N NH4) using the HF-digestion distillation technique followed by the EA-IRMS technique. Biotite separates, sampled from 9 individual metamorphic zones, contain 3000 to 100 ppm NH4+-N with a wide range in δ 15N from +1.6‰ to +9.1‰. Average NH4+-N contents in biotite show a distinct decrease from about 2750 ppm for the lowest metamorphic grade (˜500 °C) down to 218 ppm for the highest metamorphic grade (˜685 °C). Decreasing abundances in NH4+ are inversely correlated in a linear fashion with increasing K + in biotite as a function of metamorphic grade and are interpreted as a devolatilization effect. Despite expected increasing δ 15N NH4 values in biotite with nitrogen loss, a significant decrease from the Garnet Zones to the Staurolite Zones was found, followed by an increase to the Sillimanite Zones. This pattern for δ 15N NH4 values in biotite inversely correlates with Mg/(Mg + Fe) ratios in biotite and is discussed in the framework of isotopic fractionation due to different exchange processes between NH4+-NH or NH4+-N, reflecting devolatilization history and redox conditions during metamorphism.

OXIDATION AND DEVOLATILIZATION OF NITROGEN IN COAL CHAR

EPA Science Inventory

The reactions of organically-bound nitrogen in coal char during combustion have been studied in a laboratory furnace using size-graded char particles prepared by the pyrolysis of a Montana lignite. The time-resolved variations of nitrogen-to-carbon ratio during char oxidation hav...

The Bulk Elemental Composition of any Terrestrial Planets in the Alpha Centauri System

NASA Astrophysics Data System (ADS)

Lineweaver, C. H.; Schonberger, B. F. G.; Robles, J. A.

2010-04-01

Based on the devolatilization patterns in the solar system, and on the differences in the chemical compositions of the Sun and Alpha Centauri, we make estimates of the chemical composition of any Earth-like planets in the Alpha Centauri system.

Coal Combustion Science quarterly progress report, April--June 1992. Task 1, Coal devolatilization: Task 2, Coal char combustion; Task 3, Fate of mineral matter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hardesty, D.R.; Hurt, R.H.; Baxter, L.L.

1992-09-01

The objective of this work is to support the Office of Fossil Energy in executing research on coal combustion science. This project consists of basic research on coal combustion that supports both the Pittsburgh Energy Technology Center (PETC) Direct Utilization Advanced Research and Technology Development Program, and the International Energy Agency (IEA) Coal Combustion Science Project. Specific tasks include: The characterization of the physical and chemical processes that constitute the early devolatilization phase of coal combustion: Characterization of the combustion behavior of selected coals under conditions relevant to industria pulverized coal-fired furnaces; and to establish a quantitative understanding of themore » mechanisms and rates of transformation, fragmentation, and deposition of mineral matter in coal combustion environments as a function of coal type, particle size and temperature, the initial forms and distributions of mineral species in the unreacted coal, and the local gas temperature and composition.« less

Is torrefaction of polysaccharides-rich biomass equivalent to carbonization of lignin-rich biomass?

PubMed

Bilgic, E; Yaman, S; Haykiri-Acma, H; Kucukbayrak, S

2016-01-01

Waste biomass species such as lignin-rich hazelnut shell (HS) and polysaccharides-rich sunflower seed shell (SSS) were subjected to torrefaction at 300°C and carbonization at 600°C under nitrogen. The structural variations in torrefied and carbonized biomasses were compared. Also, the burning characteristics under dry air and pure oxygen (oxy-combustion) conditions were investigated. It was concluded that the effects of carbonization on HS are almost comparable with the effects of torrefaction on SSS in terms of devolatilization and deoxygenation potentials and the increases in carbon content and the heating value. Consequently, it can be proposed that torrefaction does not provide efficient devolatilization from the lignin-rich biomass while it is relatively more efficient for polysaccharides-rich biomass. Heat-induced variations in biomass led to significant changes in the burning characteristics under both burning conditions. That is, low temperature reactivity of biomass reduced considerably and the burning shifted to higher temperatures with very high burning rates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Subduction-Zone Metamorphic Pathway for Deep Carbon Cycling: Evidence from the Italian Alps and the Tianshan

NASA Astrophysics Data System (ADS)

Bebout, G. E.; Collins, N.; Cook-Kollars, J.; Angiboust, S.; Agard, P.; Scambelluri, M.; John, T.; Kump, L. R.

2013-12-01

Depending on the magnitude of the poorly constrained C flux in ultramafic rocks, on a global basis, sediments and altered oceanic crust (AOC) together deliver 70-95% of the C currently entering subduction zones. We are investigating extents of retention and metamorphic release of C in deeply subducted AOC and carbonate-rich sediment represented by HP/UHP meta-ophiolitic and metasedimentary rocks in the Italian Alps and in the Tianshan. Study of metapelite devolatilization in the same W. Alps suite (Bebout et al., 2013, Chem. Geol.) provides a geochemical framework for study of C behavior along prograde P-T paths similar to those experienced in forearcs of most modern subduction margins. Study of veins in the Tianshan affords examination of C mobility in UHP fluids, in later stages as metabasaltic rocks were fragmented in the subduction channel. Our results for sediments and AOC indicate impressive retention of oxidized C (carbonate) and reduced C (variably metamorphosed organic matter) to depths approaching those beneath arc volcanic fronts. In metasedimentary rocks, extensive isotopic exchange between the oxidized and reduced C resulted in shifts in both reservoirs toward upper mantle compositions. Much of the carbonate in metabasalts has C and O isotopic compositions overlapping with those for carbonate in AOC, with some HP/UHP metamorphic veins showing greater influence of organic C signatures from metasedimentary rocks. Calculations of prograde devolatilization histories using Perple-X demonstrate that, in most forearcs, very little decarbonation occurs in the more carbonate-rich rocks unless they are flushed by H2O-rich fluids from an external source, for example, from the hydrated ultramafic section of subducting slabs (cf. Gorman et al., 2006; G3) or from more nearby rocks experiencing dehydration (e.g., metapelites). A comparison of the most recently published thermal models for modern subduction zones (van Keken et al., 2011, JGR) with calculated and experimentally determined phase relations indicates that significant C loss during devolatilization (and partial melting) should occur as subducting sections traverse depths beneath arcs. The extent of C mobility due to carbonate dissolution remains uncertain. On a global basis, imbalance between subducted C input and C return flux by magmatism (excluding ultramafic inputs, ~40×20% of subducted C return via arcs and ~80×20% by all magmatism; Bebout, 2013, Treat. Geochem.) indicates net modern C return to the mantle, perhaps a reversal of Archean net outgassing (despite more rapid subduction). Global C cycle models predict that relatively small (and geologically plausible) change in the subduction/volcanic C flux could significantly affect atmospheric CO2 levels and thus global climate.

Combustion properties of Kraft Black Liquors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frederick, W.J. Jr.; Hupa, M.

1993-04-01

In a previous study of the phenomena involved in the combustion of black liquor droplets a numerical model was developed. The model required certain black liquor specific combustion information which was then not currently available, and additional data were needed for evaluating the model. The overall objectives of the project reported here was to provide experimental data on key aspects of black liquor combustion, to interpret the data, and to put it into a form which would be useful for computational models for recovery boilers. The specific topics to be investigated were the volatiles and char carbon yields from pyrolysismore » of single black liquor droplets; a criterion for the onset of devolatilization and the accompanying rapid swelling; and the surface temperature of black liquor droplets during pyrolysis, combustion, and gasification. Additional information on the swelling characteristics of black liquor droplets was also obtained as part of the experiments conducted.« less

On the formation of granulites

USGS Publications Warehouse

Bohlen, S.R.

1991-01-01

The tectonic settings for the formation and evolution of regional granulite terranes and the lowermost continental crust can be deduced from pressure-temperature-time (P-T-time) paths and constrained by petrological and geophysical considerations. P-T conditions deduced for regional granulites require transient, average geothermal gradients of greater than 35??C km-1, implying minimum heat flow in excess of 100 mW m-2. Such high heat flow is probably caused by magmatic heating. Tectonic settings wherein such conditions are found include convergent plate margins, continental rifts, hot spots and at the margins of large, deep-seated batholiths. Cooling paths can be constrained by solid-solid and devolatilization equilibria and geophysical modelling. -from Author

Dynamical evidence regarding the relationship between asteroids and meteorites

NASA Technical Reports Server (NTRS)

Wetherill, G. W.

1978-01-01

Meteorites are fragments of small solar system bodies transferring into the vicinity of earth from the inner edge of the asteroid belt. Photometric measurements support an association between Apollo objects and chondritic meteorites. Dynamical arguments indicate that most Apollo objects are devolatilized comet residues, however; petrographic and cosmogonical reasons argue against this conclusion.

Hydrogen isotope investigation of amphibole and biotite phenocrysts in silicic magmas erupted at Lassen Volcanic Center, California

USGS Publications Warehouse

Underwood, S.J.; Feeley, T.C.; Clynne, M.A.

2012-01-01

Hydrogen isotope ratio, water content and Fe3 +/Fe2 + in coexisting amphibole and biotite phenocrysts in volcanic rocks can provide insight into shallow pre- and syn-eruptive magmatic processes such as vesiculation, and lava drainback with mixing into less devolatilized magma that erupts later in a volcanic sequence. We studied four ~ 35 ka and younger eruption sequences (i.e. Kings Creek, Lassen Peak, Chaos Crags, and 1915) at the Lassen Volcanic Center (LVC), California, where intrusion of crystal-rich silicic magma mushes by mafic magmas is inferred from the varying abundances of mafic magmatic inclusions (MMIs) in the silicic volcanic rocks. Types and relative proportions of reacted and unreacted hydrous phenocryst populations are evaluated with accompanying chemical and H isotope changes. Biotite phenocrysts were more susceptible to rehydration in older vesicular glassy volcanic rocks than coexisting amphibole phenocrysts. Biotite and magnesiohornblende phenocrysts toward the core of the Lassen Peak dome are extensively dehydroxylated and reacted from prolonged exposure to high temperature, low pressure, and higher fO2 conditions from post-emplacement cooling. In silicic volcanic rocks not affected by alteration, biotite phenocrysts are often relatively more dehydroxylated than are magnesiohornblende phenocrysts of similar size; this is likely due to the ca 10 times larger overall bulk H diffusion coefficient in biotite. A simplified model of dehydrogenation in hydrous phenocrysts above reaction closure temperature suggests that eruption and quench of magma ascended to the surface in a few hours is too short a time for substantial H loss from amphibole. In contrast, slowly ascended magma can have extremely dehydrogenated and possibly dehydrated biotite, relatively less dehydrogenated magnesiohornblende and reaction rims on both phases. Eruptive products containing the highest proportions of mottled dehydrogenated crystals could indicate that within a few days prior to eruption, degassed vesiculated magma or lava had drained back down the volcanic conduit and mixed with less devolatilized magma. The vesiculated magma contained hydrous phenocrysts with lattice damage, which locally raised the effective H diffusion coefficient by ca 10–100 × and resulted in increased mineral dehydrogenation. Remobilization of dacite magma mush by relatively more reduced mafic magma appears to have generated further fO2 variations in May 1915 as oxidized magma from shallow levels circulated to depths where dehydrogenation of hydrous phenocrysts began. The δDMagmatic H2O expressed in LVC acid hot springs is likely a mixture derived from devolatilized ascending mafic magmas and crystallizing silicic magma mush.

Comparison of the combustion reactivity of TGA and drop tube furnace chars from a bituminous coal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katherine Le Manquais; Colin Snape; Ian McRobbie

This paper compares the reactivity of chars generated in a drop tube furnace (DTF) to those from TGA. The implications of devolatilization temperature, heating rate and residence time are considered. For the smaller particle size ranges of the bituminous coal investigated (ATC), optimized devolatilization procedures were used to generate corresponding TGA burnout rates between the two char types. However, with fractions of >75 {mu}m, the DTF chars showed an increased burnout propensity when moving from combustion regime II to combustion regime III. Scanning electron microscope (SEM) images and internal surface areas indicate that this is because of incompatible char morphologies.more » Thus, while chars produced under the conditions of TGA pyrolysis strongly resemble raw coal and display an undeveloped pore network; the DTF chars are highly porous, extensively swollen and possess considerably larger internal surface areas. Subsequently, char burnout variability was quantified, with the reactivity distribution for the DTF samples found to be up to an order of magnitude more significant than for the TGA chars. This is attributed to a fluctuating devolatilization environment on the DTF. Finally, a TGA study observed a robust particle size based compensation effect for the TGA chars, with the relative reaction rates and activation energies demonstrating the presence of internal diffusion control. However this phenomenon was partly alleviated for the DTF chars, since their higher porosities reduce mass transfer restrictions. Moreover, it should be realized that DTF char fractions of <38 {mu}m, including those required to ensure true intrinsic control under the investigated burnout conditions, cannot be produced directly. This is because of bridging and sloughing in the DTF's screw-feeder. Instead, such samples must be created by grinding larger particles, which destroys the char's existing porosity. 60 refs., 9 figs., 5 tabs.« less

Chemical cleaning of coal by molten caustic leaching after pretreatment by low-temperature devolatilization

DOEpatents

Chriswell, Colin D.; Kaushik, Surender M.; Shah, Navin D.; Markuszewski, Richard

1989-08-22

Pretreatment of coal by devolatization at temperatures ranging from about 420.degree. C. to about 450.degree. C. for from about 10 minutes to about 30 minutes before leaching with molten caustic leads to a significant reduction in carbonate formation, greatly reducing the cost of cleaning coal on a per ton basis.

Characterization of bio-oil from induction-heating pyrolysis of food-processing sewage sludges using chromatographic analysis.

PubMed

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).

Contact metamorphism of black shales: global carbon cycle and climate perturbations

NASA Astrophysics Data System (ADS)

Aarnes, I.; Svensen, H.; Polteau, S.; Connolly, J. A. D.; Planke, S.

2009-04-01

There is an increasing interest in improving the understanding of past climate changes, as it can lead to a better understanding of future challenges related to global warming and anthropogenic release of greenhouse gases. The formation of Large Igneous Provinces (LIPs) and sill intrusions in volcanic basins correlate with global warming events and mass extinctions, e.g. the Karoo Basin, South Africa (~183 Ma), the Møre and Vøring Basins offshore Norway (~55 Ma), and the Tunguska Basin, Siberia (~252 Ma). The proxy records from these events suggest that rapid release of large amounts of isotopically 13C-depleted greenhouse gases (CO2 and methane) to the atmosphere. Organic matter stored in sedimentary rocks (e.g. black shale) represents a major carbon source. Large volumes of greenhouse gases may form by contact metamorphism of organic-rich sediments around sill intrusions associated with LIPs. The organic-rich Ecca Group forms the base of the Karoo sedimentary succession and contains thousands of degassing pipe structures rooted in contact aureoles around sill intrusions. Numerical and analogue modelling show that these piercement structures form during violent eruptions releasing the overpressure driven by dehydration and devolatilization metamorphic reactions. In this study we evaluate the aureole processes numerically in order to constrain the amount of gases formed in contact aureoles around sill intrusions, and the isotopic composition of those gases. The total organic carbon (TOC) in the shale and the intrusion thickness are the most important parameters controlling the amount of carbon gas that can trigger pipe formation and release into the atmosphere. . We model thermal cracking using a general kinetic approach, while dehydration reactions are modeled under the assumption of thermodynamic equilibrium. The theoretical approach is tested against borehole data from the Karoo Basin in South Africa (geochemical analyses, Rock-Eval pyrolysis, TOC, vitrinite reflectance and stable isotopes). Decreasing TOC content and increasing vitrinite reflectance with decreasing distance to the intrusive contact are signatures of thermogenic hydrocarbon formation. During high temperature metamorphism, formation of carbon gases is preferred over liquid hydrocarbons. However, only limited isotopic fractionation is occurring in the released carbon gases during increasing temperature. Increasing veining towards the contact of a 10 meter sill suggests that hydrocarbon formation in organic-rich aureoles leads to pressure buildup and fracturing of the aureole, even with small volumes. Our numerical model also shows that sill thicknesses in the order of 100 m are necessary to produce the pressure buildup in the contact aureole and subsequent venting. In addition, mineral dehydration and thermal stresses contribute to pore fluid pressure increase. We use our numerical model to predict the amount of fluids produced as response to thin (~10 meter) and thick (~100 meter) sills. The model provides us with important estimates of rate and duration of gas formation. The time-scale of subsurface gas formation is well within the time scale indicated by the proxy data. Results from isotope compositions demonstrate that the 2.8t/m2 of organic carbon escapes the contact aureole during devolatilization processes involving the generation of light carbon gases. The calculated isotopic composition of the carbon released is similar whether using the batch devolatilization or the Rayleigh distillation model, and ranges from the background values to 1-2 permil lighter values with decreasing distance from the contact. The extrapolation of our results to the portion of the sedimentary basin intruded by magma suggests that contact metamorphism of organic-rich sediments triggered a potential release of between 2000 to 10000 Gt of isotopically light carbon gas to the atmosphere. In conclusion, the amount and composition of methane that can be produced and vented from contact aureoles in the Karoo Basin during the Toarcian is within the same order of magnitude as required to explain global carbon isotope excursion and hence global warming.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenstreet, S.; Gladman, B.; Ngo, H.

While computing an improved near-Earth object (NEO) steady-state orbital distribution model, we discovered in the numerical integrations the unexpected production of retrograde orbits for asteroids that had originally exited from the accepted main-belt source regions. Our model indicates that {approx}0.1% (a factor of two uncertainty) of the steady-state NEO population (perihelion q < 1.3 AU) is on retrograde orbits. These rare outcomes typically happen when asteroid orbits flip to a retrograde configuration while in the 3:1 mean-motion resonance with Jupiter and then live for {approx}0.001 to 100 Myr. The model predicts, given the estimated near-Earth asteroid (NEA) population, that amore » few retrograde 0.1-1 km NEAs should exist. Currently, there are two known MPC NEOs with asteroidal designations on retrograde orbits which we therefore claim could be escaped asteroids instead of devolatilized comets. This retrograde NEA population may also answer a long-standing question in the meteoritical literature regarding the origin of high-strength, high-velocity meteoroids on retrograde orbits.« less

Filtering coal-derived oil through a filter media precoated with particles partially solubilized by said oil

DOEpatents

Rodgers, Billy R.; Edwards, Michael S.

1977-01-01

Solids such as char, ash, and refractory organic compounds are removed from coal-derived liquids from coal liquefaction processes by the pressure precoat filtration method using particles of 85-350 mesh material selected from the group of bituminous coal, anthracite coal, lignite, and devolatilized coals as precoat materials and as body feed to the unfiltered coal-derived liquid.

H2O and CO2 devolatilization in subduction zones: implications for the global water and carbon cycles (Invited)

NASA Astrophysics Data System (ADS)

van Keken, P. E.; Hacker, B. R.; Syracuse, E. M.; Abers, G. A.

2010-12-01

Subduction of sediments and altered oceanic crust functions as a major carbon sink. Upon subduction the carbon may be released by progressive metamorphic reactions, which can be strongly enhanced by free fluids. Quantification of the CO2 release from subducting slabs is important to determine the provenance of CO2 that is released by the volcanic arc and to constrain the flux of carbon to the deeper mantle. In recent work we used a global set of high resolution thermal models of subduction zones to predict the flux of H2O from the subducting slab (van Keken, Hacker, Syracuse, Abers, Subduction factory 4: Depth-dependent flux of H2O from subducting slabs worldwide, J. Geophys. Res., under review) which provides a new estimate of the dehydration efficiency of the global subducting system. It was found that mineralogically bound water can pass efficiently through old and fast subduction zones (such as in the western Pacific) but that warm subduction zones (such as Cascadia) see nearly complete dehydration of the subducting slab. The top of the slab is sufficiently hot in all subduction zones that the upper crust dehydrates significantly. The degree and depth of dehydration is highly diverse and strongly depends on (p,T) and bulk rock composition. On average about one third of subducted H2O reaches 240 km depth, carried principally and roughly equally in the gabbro and peridotite sections. The present-day global flux of H2O to the deep mantle translates to an addition of about one ocean mass over the age of the Earth. We extend the slab devolatilization work to carbon by providing an update to Gorman et al. (Geochem. Geophys. Geosyst, 2006), who quantified the effects of free fluids on CO2 release. The thermal conditions were based on three end-member subduction zones with linear interpolation to provide a global CO2 flux. We use the new high resolution and global set of models to provide higher resolution predictions for the provenance and pathways of CO2 release to the mantle wedge and a more robust prediction of the global CO2 flux in subduction.

Impact and collisional processes in the solar system

NASA Technical Reports Server (NTRS)

Ahrens, Thomas J.; Gazis, C.; Pepin, R.; Becker, R.; Cronin, R.; Tyburczy, J.; Tingle, T.; Duffy, T.; Rowan, L.

1991-01-01

As impact cratered terrains have been successively recognized on certain planets and planetary satellites, it has become clear that impact processes are important to the understanding of the accretion and evolution of all solid planets. The noble gases in the normalized atmospheric inventories of the planets and the normalized gas content of meteorites are grossly similar, but demonstrate differences from each other which are not understood. In order to study shock devolatilization of the candidate carrier phases which are principally thought to be carbonaceous or hydrocarbons in planetesimals, experiments were conducted on noble gase implantation in various carbons: carbon black, activated charcoal, graphite, and carbon glass. These were candidate starting materials for impact devolatilization experiments. Initial experiments were conducted on vitreous amorphous carbon samples which were synthesized under vapor saturated conditions using argon as the pressurizing medium. An amino acid and surface analysis by laser ionization analyses were performed on three samples of shocked Murchison meteorite. A first study was completed in which a series of shock loading experiments on a porous limestone and on a non-porous gabbro in one and three dimensions were performed. Also a series of recovery experiments were conducted in which shocked molten basalt a 1700 C is encapsulated in molybdenum containers and shock recovered from up to 6 GPa pressures.

Comparative Studies of the Pyrolytic and Kinetic Characteristics of Maize Straw and the Seaweed Ulva pertusa

PubMed Central

Ye, Naihao; Li, Demao; Chen, Limei; Zhang, Xiaowen; Xu, Dong

2010-01-01

Seaweed has attracted considerable attention as a potential biofuel feedstock. The pyrolytic and kinetic characteristics of maize straw and the seaweed Ulva pertusa were studied and compared using heating rates of 10, 30 and 50°C min−1 under an inert atmosphere. The activation energy, and pre-exponential factors were calculated by the Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Popescu methods. The kinetic mechanism was deduced by the Popescu method. The results indicate that there are three stages to the pyrolysis; dehydration, primary devolatilization and residual decomposition. There were significant differences in average activation energy, thermal stability, final residuals and reaction rates between the two materials. The primary devolatilization stage of U. pertusa can be described by the Avramic-Erofeev equation (n = 3), whereas that of maize straw can be described by the Mampel Power Law (n = 2). The average activation energy of maize straw and U. pertusa were 153.0 and 148.7 KJ mol−1, respectively. The pyrolysis process of U.pertusa would be easier than maize straw. And co-firing of the two biomass may be require less external heat input and improve process stability. There were minor kinetic compensation effects between the pre-exponential factors and the activation energy. PMID:20844751

Predicting properties of gas and solid streams by intrinsic kinetics of fast pyrolysis of wood

DOE PAGES

Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; ...

2015-12-12

Pyrolysis has the potential to create a biocrude oil from biomass sources that can be used as fuel or as feedstock for subsequent upgrading to hydrocarbon fuels or other chemicals. The product distribution/composition, however, is linked to the biomass source. This work investigates the products formed from pyrolysis of woody biomass with a previously developed chemical kinetics model. Different woody feedstocks reported in prior literature are placed on a common basis (moisture, ash, fixed carbon free) and normalized by initial elemental composition through ultimate analysis. Observed product distributions over the full devolatilization range are explored, reconstructed by the model, andmore » verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO 2), char, and condensable (oil, water) species. Elementary compositions of these streams are also investigated. As a result, close agreement between literature data, model predictions, and independent experimental data indicate that the proposed model/method is able to predict the ideal distribution from fast pyrolysis given reaction temperature, residence time, and feedstock composition.« less

Ab initio calculations and kinetic modeling of thermal conversion of methyl chloride: implications for gasification of biomass.

PubMed

Singla, Mallika; Rasmussen, Morten Lund; Hashemi, Hamid; Wu, Hao; Glarborg, Peter; Pelucchi, Matteo; Faravelli, Tiziano; Marshall, Paul

2018-04-25

Limitations in current hot gas cleaning methods for chlorine species from biomass gasification may be a challenge for end use such as gas turbines, engines, and fuel cells, all requiring very low levels of chlorine. During devolatilization of biomass, chlorine is released partly as methyl chloride. In the present work, the thermal conversion of CH3Cl under gasification conditions was investigated. A detailed chemical kinetic model for pyrolysis and oxidation of methyl chloride was developed and validated against selected experimental data from the literature. Key reactions of CH2Cl with O2 and C2H4 for which data are scarce were studied by ab initio methods. The model was used to analyze the fate of methyl chloride in gasification processes. The results indicate that CH3Cl emissions will be negligible for most gasification technologies, but could be a concern for fluidized bed gasifiers, in particular in low-temperature gasification. The present work illustrates how ab initio theory and chemical kinetic modeling can help to resolve emission issues for thermal processes in industrial scale.

Scrap tyre pyrolysis: Modified chemical percolation devolatilization (M-CPD) to describe the influence of pyrolysis conditions on product yields.

PubMed

Tan, Vincent; De Girolamo, Anthony; Hosseini, Tahereh; Alhesan, Jameel Aljariri; Zhang, Lian

2018-03-16

This paper attempts to develop a modified chemical percolation devolatilization (M-CPD) model that can include heat transfer, primary pyrolysis and the secondary cracking reactions of volatiles together to describe the pyrolysis of waste scrap tyre chip, as well as to examine the influence of operating conditions on the scrap tyre pyrolysis product yields. Such a study has yet to be conducted in the past, thereby leading to a large knowledge gap failing to understand the pyrolysis of the coarse feedstock appropriately. To validate the developed model, a number of operating parameters including reactor configurations, carrier gas compositions (argon and argon blended with CO 2 and/or steam), scrap tyre chip size (0.5-15.0 mm), terminal pyrolysis temperature (400-800 °C) and heating rate (10 °C/min and 110 °C/min) were examined in a lab-scale fixed-bed pyrolyser, with a particular focus on the secondary cracking extents of the liquid tar. Through both experimental investigation and modelling approach, it was found that significant secondary cracking extent occurred upon the increase in the feedstock size, heating rate and residence time. Upon the fast pyrolysis, the average temperature gap between the centres of the coarse particle and reactor wall could reach a maximum of 115 °C for the tyre chips of 6-15 mm. Consequently, its primary volatiles underwent the secondary cracking reaction at an overall extent of 17% at a terminal temperature of 600 °C and a fast heating rate of 110 °C/min. Consequently, the yield of light gases including methane was increased remarkably. The flow rate of inert carrier gas was also influential in the secondary cracking, in which a maximum tar yield (54 wt%) was reached at a carrier gas flow rate of 1.5  L/min. This indicates the occurrence of secondary cracking has been largely minimised. At a pyrolysis temperature of 600 °C, the addition of CO 2 in the carrier gas had an insignificant effect on the product yield distribution under the slow heating scheme. In contrast, the addition of steam resulted in a slight increase of carbon monoxide, presumably due to the occurrence of gasification reaction. Copyright © 2018 Elsevier Ltd. All rights reserved.

Impact induced dehydration of serpentine and the evolution of planetary atmospheres

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1982-01-01

Results of shock recovery experiments carried out on antigorite serpentine Mg3Si2O5(OH)4 are reported. The main objective of the present study is the determination of critical shock pressures for partial and complete dehydration of serpentine under shock loading. It is pointed out that serpentine and serpentine-like layer silicates are the major water-bearing phases in carbonaceous chondrites. It appears that these minerals, and a poorly defined cometary contribution, were the most likely water-bearing phases in accreting planetesimals which led to the formation of the terrestrial planets. The obtained results imply that the process of impact induced devolatilization of volatile bearing minerals during accretion is likely to have occurred on earth. The findings lend support to the model of a terrestrial atmosphere/hydrosphere forming during the later stages of accretion of the earth.

GIANT IMPACT: AN EFFICIENT MECHANISM FOR THE DEVOLATILIZATION OF SUPER-EARTHS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Shang-Fei; Hori, Yasunori; Lin, D. N. C.

Mini-Neptunes and volatile-poor super-Earths coexist on adjacent orbits in proximity to host stars such as Kepler-36 and Kepler-11. Several post-formation processes have been proposed for explaining the origin of the compositional diversity between neighboring planets: mass loss via stellar XUV irradiation, degassing of accreted material, and in situ accumulation of the disk gas. Close-in planets are also likely to experience giant impacts during the advanced stage of planet formation. This study examines the possibility of transforming volatile-rich super-Earths/mini-Neptunes into volatile-depleted super-Earths through giant impacts. We present the results of three-dimensional hydrodynamic simulations of giant impacts in the accretionary and disruptivemore » regimes. Target planets are modeled with a three-layered structure composed of an iron core, silicate mantle, and hydrogen/helium envelope. In the disruptive case, the giant impact can remove most of the H/He atmosphere immediately and homogenize the refractory material in the planetary interior. In the accretionary case, the planet is able to retain more than half of the original gaseous envelope, while a compositional gradient suppresses efficient heat transfer as the planetary interior undergoes double-diffusive convection. After the giant impact, a hot and inflated planet cools and contracts slowly. The extended atmosphere enhances the mass loss via both a Parker wind induced by thermal pressure and hydrodynamic escape driven by the stellar XUV irradiation. As a result, the entire gaseous envelope is expected to be lost due to the combination of those processes in both cases. Based on our results, we propose that Kepler-36b may have been significantly devolatilized by giant impacts, while a substantial fraction of Kepler-36c’s atmosphere may remain intact. Furthermore, the stochastic nature of giant impacts may account for the observed large dispersion in the mass–radius relationship of close-in super-Earths and mini-Neptunes (at least to some extent)« less

Elemental Mercury Diffusion Processes and Concentration at the Lunar Poles

NASA Technical Reports Server (NTRS)

Moxley, Frederick; Killen, Rosemary M.; Hurley, Dana M.

2011-01-01

In 2009, the Lyman Alpha Mapping Project (LAMP) spectrograph onboard the Lunar Reconnaissance Orbiter (LRO) spacecraft made the first detection of element mercury (Hg) vapor in the lunar exosphere after the Lunar Crater Observing and Sensing Satellite (LCROSS) Centaur rocket impacted into the Cabeus crater in the southern polar region of the Moon. The lunar regolith core samples from the Apollo missions determined that Hg had a devolatilized pattern with a concentration gradient increasing with depth, in addition to a layered pattern suggesting multiple episodes of burial and volatile loss. Hg migration on the lunar surface resulted in cold trapping at the poles. We have modeled the rate at which indigenous Hg is lost from the regolith through diffusion out of lunar grains. We secondly modeled the migration of Hg vapor in the exosphere and estimated the rate of cold-trapping at the poles using a Monte Carlo technique. The Hg vapor may be lost from the exosphere via ionization, Jeans escape, or re-impact into the surface causing reabsorption.

Experimental investigation of wood combustion in a fixed bed with hot air

DOE Office of Scientific and Technical Information (OSTI.GOV)

Markovic, Miladin, E-mail: m.markovic@utwente.nl; Bramer, Eddy A.; Brem, Gerrit

Highlights: • Upward combustion is a new combustion concept with ignition by hot primary air. • Upward combustion has three stages: short drying, rapid devolatilization and char combustion. • Variation of fuel moisture and inert content have little influence on the combustion. • Experimental comparison between conventional and upward combustion is presented. - Abstract: Waste combustion on a grate with energy recovery is an important pillar of municipal solid waste (MSW) management in the Netherlands. In MSW incinerators fresh waste stacked on a grate enters the combustion chamber, heats up by radiation from the flame above the layer and ignitionmore » occurs. Typically, the reaction zone starts at the top of the waste layer and propagates downwards, producing heat for drying and devolatilization of the fresh waste below it until the ignition front reaches the grate. The control of this process is mainly based on empiricism. MSW is a highly inhomogeneous fuel with continuous fluctuating moisture content, heating value and chemical composition. The resulting process fluctuations may cause process control difficulties, fouling and corrosion issues, extra maintenance, and unplanned stops. In the new concept the fuel layer is ignited by means of preheated air (T > 220 °C) from below without any external ignition source. As a result a combustion front will be formed close to the grate and will propagate upwards. That is why this approach is denoted by upward combustion. Experimental research has been carried out in a batch reactor with height of 4.55 m, an inner diameter of 200 mm and a fuel layer height up to 1 m. Due to a high quality two-layer insulation adiabatic conditions can be assumed. The primary air can be preheated up to 350 °C, and the secondary air is distributed via nozzles above the waste layer. During the experiments, temperatures along the height of the reactor, gas composition and total weight decrease are continuously monitored. The influence of the primary air speed, fuel moisture and inert content on the combustion characteristics (ignition rate, combustion rate, ignition front speed and temperature of the reaction zone) is evaluated. The upward combustion concept decouples the drying, devolatilization and burnout phase. In this way the moisture and inert content of the waste have almost no influence on the combustion process. In this paper an experimental comparison between conventional and reversed combustion is presented.« less

A kinetic study on the catalysis of KCl, K2SO4, and K2CO3 during oxy-biomass combustion.

PubMed

Deng, Shuanghui; Wang, Xuebin; Zhang, Jiaye; Liu, Zihan; Mikulčić, Hrvoje; Vujanović, Milan; Tan, Houzhang; Duić, Neven

2018-07-15

Biomass combustion under the oxy-fuel conditions (Oxy-biomass combustion) is one of the approaches achieving negative CO 2 emissions. KCl, K 2 CO 3 and K 2 SO 4 , as the major potassium species in biomass ash, can catalytically affect biomass combustion. In this paper, the catalysis of the representative potassium salts on oxy-biomass combustion was studied using a thermogravimetric analyzer (TGA). Effects of potassium salt types (KCl, K 2 CO 3 and K 2 SO 4 ), loading concentrations (0, 1, 3, 5, 8 wt%), replacing N 2 by CO 2 , and O 2 concentrations (5, 20, 30 vol%) on the catalysis degree were discussed. The comparison between TG-DTG curves of biomass combustion before and after water washing in both the 20%O 2 /80%N 2 and 20%O 2 /80%CO 2 atmospheres indicates that the water-soluble minerals in biomass play a role in promoting the devolatilization and accelerating the char-oxidation; and the replacement of N 2 by CO 2 inhibits the devolatilization and char-oxidation processes during oxy-biomass combustion. In the devolatilization stage, the catalysis degree of potassium monotonously increases with the increase of potassium salt loaded concentration. The catalysis degree order of the studied potassium salts is K 2 CO 3  > KCl > K 2 SO 4 . In the char-oxidation stage, with the increase of loading concentration the three kinds of potassium salts present inconsistent change tendencies of the catalysis degree. In the studied loading concentrations from 0 to 8 wt%, there is an optimal loading concentration for KCl and K 2 CO 3 , at 3 and 5 wt%, respectively; while for K 2 SO 4 , the catalysis degree on char-oxidation monotonically increases with the loading potassium concentration. For most studied conditions, regardless of the potassium salt types or the loading concentrations or the combustion stages, the catalysis degree in the O 2 /CO 2 atmosphere is stronger than that in the O 2 /N 2 atmosphere. The catalysis degree is also affected by the O 2 concentrations, and the lowest catalysis degree is generally around 20 vol% O 2 concentration. The kinetic parameters under the different studied conditions are finally obtained. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of torrefaction on structure and fast pyrolysis behavior of corncobs.

PubMed

Zheng, Anqing; Zhao, Zengli; Chang, Sheng; Huang, Zhen; Wang, Xiaobo; He, Fang; Li, Haibin

2013-01-01

Pretreatment of corncobs using torrefaction was conducted in an auger reactor at 250-300 °C and residence times of 10-60 min. The torrefied corncobs were fast pyrolyzed in a bubbling fluidized bed reactor at 470 °C to obtain high-quality bio-oil. The heating value and pH of the bio-oil improved when the torrefaction as pretreatment was applied; however, increasing bio-oil yield penalties were observed with increasing torrefaction severity. Fourier transform infrared Spectroscopy (FTIR) and quantitative solid (13)C nuclear magnetic resonance spectrometry (NMR) analysis of torrefied corncobs showed that the devolatilization, crosslinking and charring of corncobs during torrefaction could be responsible for the bio-oil yield penalties. Gas chromatography-mass spectrometry (GC-MS) analysis showed that the acetic acid and furfural contents of the bio-oil decreased with torrefaction temperature or residence time. The results showed that torrefaction is an effective method of pretreatment for improving bio-oil quality if the crosslinking and charring of biomass can be restricted. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermogravimetric-mass spectrometric analysis on combustion of lignocellulosic biomass.

PubMed

López-González, D; Fernandez-Lopez, M; Valverde, J L; Sanchez-Silva, L

2013-09-01

Combustion characteristics of biomass main components and three lignocellulosic biomass (fir wood, eucalyptus wood and pine bark) were investigated by thermogravimetric analysis coupled with mass spectrometry. The combustion of biomass was divided into two main steps, devolatilization and char oxidation stage. Heating rate effect was also studied. Generally, the higher the heating rate, the higher the decomposition temperature. Furthermore, the weight loss rate decreased due to particle temperature gradients. Combustion kinetics were studied. Models based on reaction order (Oi), nucleation (Ni) and diffusion (Di) achieved the best fitting to the experimental data. Cellulose oxidation presented the highest activation energies. CO, CO2 and H2O were the main components evolved from combustion. Additionally, light hydrocarbons (CH4 and C2H5) were also present. Finally, nitrogen compounds were in a higher proportion than sulfur compounds being released as primary amines and NOx. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pyrolytic and Kinetic Characteristics of the Thermal Decomposition of Perilla frutescens Polysaccharide

PubMed Central

Zhou, Quancheng; Sheng, Guihua

2012-01-01

The thermal decomposition of Perilla frutescens polysaccharide was examined by thermogravimetry, differential thermogravimetry, and differential thermal analysis. The results showed that the mass loss of the substance proceeded in three steps. The first stage can be attributed to the expulsion of the water from ambient temperature to 182°C. The second stage corresponded to devolatilization from 182°C to 439°C. The residue slowly degraded in the third stage. The weight loss in air is faster than that in nitrogen, because the oxygen in air accelerated the pyrolytic reaction speed reaction. The heating rate significantly affected the pyrolysis of the sample. Similar activation energies of the degradation process (210–211 kJ mol−1) were obtained by the FWO, KAS, and Popescu techniques. According to Popescu mechanism functions, the possible kinetic model was estimated to be Avrami–Erofeev 20 g(α) = [−ln(1–α)]4. PMID:23300715

The dilemma of the Jiaodong gold deposits: Are they unique?

USGS Publications Warehouse

Goldfarb, Richard J.; Santosh, M.

2013-01-01

The ca. 126–120 Ma Au deposits of the Jiaodong Peninsula, eastern China, define the country's largest gold province with an overall endowment estimated as >3000 t Au. The vein and disseminated ores are hosted by NE- to NNE-trending brittle normal faults that parallel the margins of ca. 165–150 Ma, deeply emplaced, lower crustal melt granites. The deposits are sited along the faults for many tens of kilometers and the larger orebodies are associated with dilatational jogs. Country rocks to the granites are Precambrian high-grade metamorphic rocks located on both sides of a Triassic suture between the North and South China blocks. During early Mesozoic convergent deformation, the ore-hosting structures developed as ductile thrust faults that were subsequently reactivated during Early Cretaceous “Yanshanian” intracontinental extensional deformation and associated gold formation.Classification of the gold deposits remains problematic. Many features resemble those typical of orogenic Au including the linear structural distribution of the deposits, mineralization style, ore and alteration assemblages, and ore fluid chemistry. However, Phanerozoic orogenic Au deposits are formed by prograde metamorphism of accreted oceanic rocks in Cordilleran-style orogens. The Jiaodong deposits, in contrast, formed within two Precambrian blocks approximately 2 billion years after devolatilization of the country rocks, and thus require a model that involves alternative fluid and metal sources for the ores. A widespread suite of ca. 130–123 Ma granodiorites overlaps temporally with the ores, but shows a poor spatial association with the deposits. Furthermore, the deposit distribution and mineralization style is atypical of ores formed from nearby magmas. The ore concentration requires fluid focusing during some type of sub-crustal thermal event, which could be broadly related to a combination of coeval lithospheric thinning, asthenospheric upwelling, paleo-Pacific plate subduction, and seismicity along the continental-scale Tan-Lu fault. Possible ore genesis scenarios include those where ore fluids were produced directly by the metamorphism of oceanic lithosphere and overlying sediment on the subducting paleo-Pacific slab, or by devolatilization of an enriched mantle wedge above the slab. Both the sulfur and gold could be sourced from either the oceanic sediments or the serpentinized mantle. A better understanding of the architecture of the paleo-Pacific slab during Early Cretaceous below the eastern margin of China is essential to determination of the validity of possible models.

Volatile transfer and recycling at convergent margins: Mass-balance and insights from high-P/T metamorphic rocks

NASA Astrophysics Data System (ADS)

Bebout, Gray E.

The efficiency with which volatiles are deeply subducted is governed by devolatilization histories and the geometries and mechanisms of fluid transport deep in subduction zones. Metamorphism along the forearc slab-mantle interface may prevent the deep subduction of many volatile components (e.g., H2O, Cs, B, N, perhaps As, Sb, and U) and result in their transport in fluids toward shallower reservoirs. The release, by devolatilization, and transport of such components toward the seafloor or into the forearc mantle wedge, could in part explain the imbalances between the estimated amounts of subducted volatiles and the amounts returned to Earth's surface. The proportion of the initially subducted volatile component that is retained in rocks subducted to depths greater than those beneath magmatic arcs (>100 km) is largely unknown, complicating assessments of deep mantle volatile budgets. Isotopic and trace element data and volatile contents for the Catalina Schist, the Franciscan Complex, and eclogite-facies complexes in the Alps (and elsewhere) provide insight into the nature and magnitude of fluid production and transport deep in subduction zones and into the possible effects of metamorphism on the compositions of subducting rocks. Compatibilities of the compositions of the subduction-related rocks and fluids with the isotopic and trace element compositions of various mantle-derived materials (igneous rocks, xenoliths, serpentinite seamounts) indicate the potential to trace the recycling of rock and fluid reservoirs chemically and isotopically fractionated during subduction-zone metamorphism.

Carbon dioxide released from subduction zones by fluid-mediated reactions

NASA Astrophysics Data System (ADS)

Ague, Jay J.; Nicolescu, Stefan

2014-05-01

The balance between the subduction of carbonate mineral-bearing rocks into Earth's mantle and the return of CO2 to the atmosphere by volcanic and metamorphic degassing is critical to the carbon cycle. Carbon is thought to be released from subducted rocks mostly by simple devolatilization reactions. However, these reactions will also retain large amounts of carbon within the subducting slab and have difficulty in accounting for the mass of CO2 emitted from volcanic arcs. Carbon release may therefore occur via fluid-induced dissolution of calcium carbonate. Here we use carbonate δ18O and δ13C systematics, combined with analyses of rock and fluid inclusion mineralogy and geochemistry, to investigate the alteration of the exhumed Eocene Cycladic subduction complex on the Syros and Tinos islands, Greece. We find that in marble rocks adjacent to two fluid conduits that were active during subduction, the abundance of calcium carbonate drastically decreases approaching the conduits, whereas silicate minerals increase. Up to 60-90% of the CO2 was released from the rocks--far greater than expected via simple devolatilization reactions. The δ18O of the carbonate minerals is 5-10 lighter than is typical for metamorphosed carbonate rocks, implying that isotopically light oxygen was transported by fluid infiltration from the surroundings. We suggest that fluid-mediated carbonate mineral removal, accompanied by silicate mineral precipitation, provides a mechanism for the release of enormous amounts of CO2 from subduction zones.

Comprehensive model for predicting elemental composition of coal pyrolysis products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ricahrds, Andrew P.; Shutt, Tim; Fletcher, Thomas H.

Large-scale coal combustion simulations depend highly on the accuracy and utility of the physical submodels used to describe the various physical behaviors of the system. Coal combustion simulations depend on the particle physics to predict product compositions, temperatures, energy outputs, and other useful information. The focus of this paper is to improve the accuracy of devolatilization submodels, to be used in conjunction with other particle physics models. Many large simulations today rely on inaccurate assumptions about particle compositions, including that the volatiles that are released during pyrolysis are of the same elemental composition as the char particle. Another common assumptionmore » is that the char particle can be approximated by pure carbon. These assumptions will lead to inaccuracies in the overall simulation. There are many factors that influence pyrolysis product composition, including parent coal composition, pyrolysis conditions (including particle temperature history and heating rate), and others. All of these factors are incorporated into the correlations to predict the elemental composition of the major pyrolysis products, including coal tar, char, and light gases.« less

Solution and shock-induced exsolution of argon in vitreous carbon

NASA Technical Reports Server (NTRS)

Gazis, Carey; Ahrens, Thomas J.

1991-01-01

To add to the knowledge of noble gas solution and exsolution in carbonaceus material, experiments were performed on vitreous carbon. Ar-rich vitreous carbon samples were prepared under vapor-saturated conditions using argon as the pressurizing medium. Solubility data were obtained for temperatures of 773 to 973 K and pressures of 250 to 1500 bars. Up to 7 wt pct Ar was dissolved in the carbon. The solubility data were compared to a thermodynamic model of argon atoms dissolving into a fixed population of 'holes' in the carbon. Two variations of the model yielded estimates of the enthalpy of solution of Ar in vitreous carbon equal to about -4700 cal/mole. Preliminary shock experiments showed that 28 percent of the total argon was released by driving 4 GPa shocks into the argon-rich carbon. It was demonstrated that shock-induced argon loss is not simply caused by the impact-induced diminution of grain size. The present value of shock pressure required for partial impact devolatilization of Ar from carbon is below the range (5-30 GPa) at which H2O is released from phyllosilicates.

Thermodynamic Parameterization of Subduction-Zone Devolatilization and Application to Quantify Carbon Fluxes from Slab

NASA Astrophysics Data System (ADS)

Tian, M.; Katz, R. F.; Rees Jones, D. W.; May, D.

2017-12-01

Compared with other plate-tectonic boundaries, subduction zones (SZ) host the most drastic mechanical, thermal, and chemical changes. The transport of carbon through this complex environment is crucial to mantle carbon budget but remains the subject of active debate. Synthesis of field studies suggests that carbon subducted with the incoming slab is almost completely returned to the surface environment [Kelemen and Manning, 2015], whereas thermodynamic modelling indicates that a significant portion of carbon is retained in the slab and descends into the deep mantle [Gorman et al., 2006]. To address this controversy and quantify the carbon fluxes within SZs, it is necessary to treat the chemistry of fluid/volatile-rock interaction and the mechanics of porous fluid/volatile migration in a consistent modelling framework. This requirement is met by coupling a thermodynamic parameterization of de/re-volatilization with a two-phase flow model of subduction zones. The two-phase system is assumed to comprise three chemical components: rock containing only non-volatile oxides, H2O and CO2; the fluid phase includes only the latter two. Perple_X is used to map out the binary subsystems rock+H2O and rock+CO2; the results are parameterised in terms of volatile partition coefficients as a function of pressure and temperature. In synthesising the binary subsystems to describe phase equilibria that incorporate all three components, a Margules coefficient is introduced to account for non-ideal mixing of CO2/H2O in the fluid, such that the partition coefficients depend further on bulk composition. This procedure is applied to representative compositions of sediment, MORB, and gabbro for the slab, and peridotite for the mantle. The derived parameterization of each rock type serves as a lightweight thermodynamic module interfaceable with two-phase flow models of SZs. We demonstrate the application of this thermodynamic module through a simple model of carbon flux with a prescribed flow direction through (and out of) the slab. This model allows us to evaluate the effects of flow path and lithology on carbon storage within the slab.

Combustion studies of coal derived solid fuels by thermogravimetric analysis. III. Correlation between burnout temperature and carbon combustion efficiency

USGS Publications Warehouse

Rostam-Abadi, M.; DeBarr, J.A.; Chen, W.T.

1990-01-01

Burning profiles of 35-53 ??m size fractions of an Illinois coal and three partially devolatilized coals prepared from the original coal were obtained using a thermogravimetric analyzer. The burning profile burnout temperatures were higher for lower volatile fuels and correlated well with carbon combustion efficiencies of the fuels when burned in a laboratory-scale laminar flow reactor. Fuels with higher burnout temperatures had lower carbon combustion efficiencies under various time-temperature conditions in the laboratory-scale reactor. ?? 1990.

Assessing the Role of Anhydrite in the KT Mass Extinction: Hints from Shock-loading Experiments

NASA Technical Reports Server (NTRS)

Skala, R.; Lnagenhorst, F.; Hoerz, F.

2004-01-01

Various killing mechanisms have been suggested to contribute to the mass extinctions at the KT boundary, including severe, global deterioration of the atmosphere and hydrosphere due to SO(x) released from heavily shocked, sulfate-bearing target rocks. The devolatilization of anhydrite is predominantly inferred from thermodynamic considerations and lacks experimental confirmation. To date, the experimentally determined shock behavior of anhydrite is limited to solid-state effects employing X-ray diffraction methods. The present report employs additional methods to characterize experimentally shocked anhydrite.

Ultra-Fast Laser Desorption/Laser Ionization Mass Spectrometry for the Organic Analysis of Stardust Sample Return

NASA Technical Reports Server (NTRS)

Clemett, Simon J.; McKay, David S.

2005-01-01

The STARDUST sample return capsule is anticipated to provide 500-1000 cometary particles 15 m in size. These were collected during the 340 km flyby of Comet P/Wild-2 and impacted the aerogel collection medium at a relative velocity of approx. 6.1 /kms. Hypervelocity impact studies suggest that some fraction of the original organic inventory of collected particles ought to remain intact, although there is likely to be a significant amount of devolatilization and disassociation of the lower mass organic fraction.

Conversion of raw carbonaceous fuels

DOEpatents

Cooper, John F [Oakland, CA

2007-08-07

Three configurations for an electrochemical cell are utilized to generate electric power from the reaction of oxygen or air with porous plates or particulates of carbon, arranged such that waste heat from the electrochemical cells is allowed to flow upwards through a storage chamber or port containing raw carbonaceous fuel. These configurations allow combining the separate processes of devolatilization, pyrolysis and electrochemical conversion of carbon to electric power into a single unit process, fed with raw fuel and exhausting high BTU gases, electric power, and substantially pure CO.sub.2 during operation.

Carbon monoxide detection of chemisorbed oxygen in coal and other carbonaceous materials

USGS Publications Warehouse

Hinckley, C.C.; Wiltowski, T.; Wiltowska, T.; Ellison, D.W.; Shiley, R.H.; Wu, L.

1990-01-01

The oxidation of carbon monoxide by mildly oxidized and devolatilized coal samples was studied thermogravimetrically. The oxidation was attributed to oxygen chemisorbed on inorganic components of the coals. The reaction of CO with pyrite producing carbonyl sulphide, OCS, accompanied the oxidation. A mechanism for CO oxidation is proposed in which active oxygen chemisorbed on the inorganic components of the coal directly oxidized CO to CO2, and facilitates the chemisorption of CO on the coal as carbonate. A factor, ?? = ( 11 14) [1 - ( Wn Wc)], was derived where Wn is the sample weight loss not attributed to OCS formation, and Wc is the estimated weight of evolved CO2. This quantity is proportional to the fraction of CO2 produced by the direct oxidation of CO, and was used to compare the coal samples studied. Samples of an Illinois No. 5 coal yielded average ?? values of 0.7 and those of an Illinois No. 6 coal yielded values of 0.6, indicating that in these cases, the majority of CO2 produced came from the direct oxidation of CO. The results obtained for the coal samples are compared with a selection of carbonaceous samples for which the proposed mechanism does not apply. ?? 1990.

Pore Fluid Extraction by Reactive Solitary Waves in 3-D

NASA Astrophysics Data System (ADS)

Omlin, Samuel; Malvoisin, Benjamin; Podladchikov, Yury Y.

2017-09-01

In the lower crust, viscous compaction is known to produce solitary porosity and fluid pressure waves. Metamorphic (de)volatilization reactions can also induce porosity changes in response to the propagating fluid pressure anomalies. Here we present results from high-resolution simulations using Graphic Processing Unit parallel processing with a model that includes both viscous (de)compaction and reaction-induced porosity changes. Reactive porosity waves propagate in a manner similar to viscous porosity waves, but through a different mechanism involving fluid release and trap in the solid by reaction. These waves self-generate from red noise or an ellipsoidal porosity anomaly with the same characteristic size and abandon their source region to propagate at constant velocity. Two waves traveling at different velocities pass through each other in a soliton-like fashion. Reactive porosity waves thus provide an additional mechanism for fluid extraction at shallow depths with implications for ore formation, diagenesis, metamorphic veins formation, and fluid extraction from subduction zones.

FeO and H-2O and the homogeneous accretion of the earth

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1983-01-01

Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting Earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

FeO and H2O and the homogeneous accretion of the earth

NASA Technical Reports Server (NTRS)

Lange, M. A.; Ahrens, T. J.

1984-01-01

Shock devolatilization recovery data for brunite (Mg(OH)2) shocked to 13 and 23 GPa are presented. These data combined with previous data for serpentine (Mg3Si2O5(OH)4) are used to constrain the minimum size terrestrial planet for which planetesimal infall will result in an impact generated water atmosphere. Assuming, in hydrous phyllosilicates, model calculations simulating the interaction of metallic iron with impact released free water on the surface of the accreting earth were carried out. It is assumed that the reaction of water with iron in the presence of enstatite is the prime source of the terrestrial FeO component of silicates and oxides. Lower and upper bounds on the terrestrial FeO budget are based on mantle FeO content and possible incorporation of FeO in the outer core. We demonstrate that the iron water reaction would resuit in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed.

Evolution of microstructure and elastic wave velocities in dehydrated gypsum samples

NASA Astrophysics Data System (ADS)

Milsch, Harald; Priegnitz, Mike

2012-12-01

We report on changes in P and S-wave velocities and rock microstructure induced by devolatilization reactions using gypsum as a reference analog material. Cylindrical samples of natural alabaster were dehydrated in air, at ambient pressure, and temperatures between 378 and 423 K. Dehydration did not proceed homogeneously but via a reaction front moving sample inwards separating an outer highly porous rim from the remaining gypsum which, above approximately 393 (±5) K, concurrently decomposed into hemihydrate. Overall porosity was observed to continuously increase with reaction progress from approximately 2% for fully hydrated samples to 30% for completely dehydrated ones. Concurrently, P and S-wave velocities linearly decreased with porosity from 5.2 and 2.7 km/s to 1.0 and 0.7 km/s, respectively. It is concluded that a linearized empirical Raymer-type model extended by a critical porosity term and based on the respective time dependent mineral and pore volumes reasonably replicates the P and S-wave data in relation to reaction progress and porosity.

Two-stage fixed-bed gasifier with selectable middle gas off-take point

DOEpatents

Strickland, Larry D.; Bissett, Larry A.

1992-01-01

A two-stage fixed bed coal gasifier wherein an annular region is in registry with a gasification zone underlying a devolatilization zone for extracting a side stream of high temperature substantially tar-free gas from the gasifier. A vertically displaceable skirt means is positioned within the gasifier to define the lower portion of the annular region so that vertical displacement of the skirt means positions the inlet into the annular region in a selected location within or in close proximity to the gasification zone for providing a positive control over the composition of the side stream gas.

Freeboard reactions in fluidized coal combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walsh, P.M.; Dutta, A.; Beer, J.M.

1984-05-11

The objective of this study was to determine the contribution of freeboard combustion to overall fixed carbon conversion during atmospheric pressure fluidized bed combustion of Kentucky No. 9 high volatile bituminous coal. The progress of the O/sub 2//char reaction in the freeboard was inferred from O/sub 2/ profiles determined by gas sampling. The rates of O/sub 2/ consumption were in good agreement with the O/sub 2//char rate expression of Sergeant and Smith (1973), except at the lowest temperature investigated (964 K). The discrepancy in this case might be due to catalysis of the O/sub 2//char reaction by lime, since thismore » was the first run of the series. Extrapolation of the O/sub 2/ profile to the bed surface using the rate expression of Sergeant and Smith showed that approximately all of the fixed carbon conversion could be accounted for by freeboard combustion. A simple model is proposed in which devolatilization, fragmentation, attrition, and volatile combustion are limited to the bed; with combustion of the finely ground char occurring only in the freeboard. This model predicts O/sub 2/ at the combustor outlet within 60% of the measured values, except in the low temperature/high lime case.« less

The Chemical Behavior of Fluids Released during Deep Subduction Based on Fluid Inclusions

NASA Astrophysics Data System (ADS)

Frezzotti, M. L.; Ferrando, S.

2014-12-01

We present a review of current research on fluid inclusions in (HP-) UHP metamorphic rocks that, combined with existing experimental research and thermodynamic models, allow us to investigate the chemical and physical properties of fluids released during deep subduction, their solvent and element transport capacity, and the subsequent implications for the element recycling in the mantle wedge. An impressive number of fluid inclusion studies indicate three main populations of fluid inclusions in HP and UHP metamorphic rocks: i) aqueous and/or non-polar gaseous fluid inclusions (FI), ii) multiphase solid inclusions (MSI), and iii) melt inclusions (MI). Chemical data from preserved fluid inclusions in rocks match with and implement "model" fluids by experiments and thermodynamics, revealing a continuity behind the extreme variations of physico-chemical properties of subduction-zone fluids. From fore-arc to sub-arc depths, fluids released by progressive devolatilization reactions from slab lithologies change from relatively diluted chloride-bearing aqueous solutions (± N2), mainly influenced by halide ligands, to (alkali) aluminosilicate-rich aqueous fluids, in which polymerization probably governs the solubility and transport of major (e.g., Si and Al) and trace elements (including C). Fluid inclusion data implement the petrological models explaining deep volatile liberation in subduction zones, and their flux into the mantle wedge.

Effect of H2O on the NO emission characteristics of pulverized coal during oxy-fuel combustion.

PubMed

Lei, Ming; Sun, Cen; Zou, Chan; Mi, Hang; Wang, Chunbo

2018-04-01

The NO emission characteristics of Datong bituminous coal and Yangquan anthracite in O 2 /H 2 O/CO 2 atmospheres were investigated by using a fixed-bed reactor system, and the emission characteristics were compared with the experimental results from O 2 /N 2 and O 2 /CO 2 atmospheres, especially at low O 2 concentrations and high temperatures. The results showed that NO emissions of pulverized coal in O 2 /CO 2 environments were less than those in the O 2 /N 2 environments, regardless of the O 2 concentration and the furnace temperature. Adding H 2 O decreased the possibility of reactions between the reductive groups (NH) and the oxygen radical during devolatilization, which led to a decrease in NO emissions at 1000 °C. However, as the furnace temperature increased, "additional" nitrogen precursors (HCN and NH 3 ) generated by enhanced char-H 2 O gasification were quickly oxidized to generate a large amount of NO during char oxidation that exceeded the amount of NO reduced by NH during devolatilization. Thus, the NO emissions in O 2 /CO 2 /H 2 O atmosphere were higher than those in O 2 /CO 2 atmosphere at a low O 2 concentration. However, as the O 2 concentration increased, the NO emissions in O 2 /CO 2 /H 2 O atmosphere became lower than those in O 2 /CO 2 atmosphere because the effect of H 2 O gasification became weaker. The NO emissions of Yangquan anthracite (YQ) were higher than those of DT, but the changing trend of YQ was similar to that of DT.

Kinetics of scrap tyre pyrolysis under vacuum conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Gartzen; Aguado, Roberto; Olazar, Martin

2009-10-15

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene-butadiene rubber) according to three successive steps. The latter method identifies themore » kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene-butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability. The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.« less

Kinetics of scrap tyre pyrolysis under vacuum conditions.

PubMed

Lopez, Gartzen; Aguado, Roberto; Olazar, Martín; Arabiourrutia, Miriam; Bilbao, Javier

2009-10-01

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene-butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12K in the reaction starting temperature. The kinetic constant at 503K for devolatilization of volatile additives at 0.25atm is 1.7 times higher than that at 1atm, and that corresponding to styrene-butadiene rubber at 723K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability. The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.

Intra-slab COH fluid fluxes evidenced by fluid-mediated decarbonation of lawsonite eclogite-facies altered oceanic metabasalts

NASA Astrophysics Data System (ADS)

Vitale Brovarone, Alberto; Chu, Xu; Martin, Laure; Ague, Jay J.; Monié, Patrick; Groppo, Chiara; Martinez, Isabelle; Chaduteau, Carine

2018-04-01

The interplay between the processes controlling the mobility of H2O and C-bearing species during subduction zone metamorphism exerts a critical control on plate tectonics and global volatile recycling. Here we present the first study on fresh, carbonate-bearing, lawsonite eclogite-facies metabasalts from Alpine Corsica, France, which reached the critical depths at which important devolatilization reactions occur in subducting slabs. The studied samples indicate that the evolution of oceanic crustal sequences subducted under present-day thermal regimes is dominated by localized fluid-rock interactions that are strongly controlled by the nature and extent of inherited (sub)seafloor hydrothermal processes, and by the possibility of deep fluids to be channelized along inherited or newly-formed discontinuities. Fluid channelization along inherited discontinuities controlled local rehydration and dehydration/decarbonation reactions and the stability of carbonate and silicate minerals at the blueschist-eclogite transition. Fluid-mediated decarbonation was driven by upward, up-temperature fluid flow in the inverted geothermal gradient of a subducting oceanic slab, a process that has not been documented in natural samples to date. We estimate that the observed fluid-rock reactions released 20-60 kg CO2 per m3 of rock (i.e. 0.7-2.1 wt% CO2), which is in line with the values predicted from decarbonation of metabasalts in open systems at these depths. Conversely, the estimated time-integrated fluid fluxes (20-50 t/m2) indicate that the amount of carbon transported by channelized fluid flow within the volcanic part of subducting oceanic plates is potentially much higher than previous numerical estimates, testifying to the percolation of C-bearing fluids resulting from devolatilization/dissolution processes operative in large reservoirs.

Hydromechanical Modeling of Fluid Flow in the Lower Crust

NASA Astrophysics Data System (ADS)

Connolly, J.

2011-12-01

The lower crust lies within an ambiguous rheological regime between the brittle upper crust and ductile sub-lithospheric mantle. This ambiguity has allowed two schools of thought to develop concerning the nature of fluid flow in the lower crust. The classical school holds that lower crustal rocks are inviscid and that any fluid generated by metamorphic devolatilization is squeezed out of rocks as rapidly as it is produced. According to this school, permeability is a dynamic property and fluid flow is upward. In contrast, the modern school uses concepts from upper crustal hydrology that presume implicitly, if not explicitly, that rocks are rigid or, at most, brittle. For the modern school, the details of crustal permeability determine fluid flow and as these details are poorly known almost anything is possible. Reality, to the extent that it is reflected by inference from field studies, offers some support to both schools. In particular, evidence of significant lateral and channelized fluid flow are consistent with flow in rigid media, while evidence for short (104 - 105 y) grain-scale fluid-rock interaction during much longer metamorphic events, suggests that reaction-generated grain-scale permeability is sealed rapidly by compaction; a phenomenon that is also essential to prevent extensive retrograde metamorphism. These observations provide a compelling argument for recognizing in conceptual models of lower crustal fluid flow that rocks are neither inviscid nor rigid, but compact by viscous mechanisms on a finite time-scale. This presentation will review the principle consequences of, and obstacles to, incorporating compaction in such models. The role of viscous compaction in the lower crust is extraordinarily uncertain, but ignoring this uncertainty in models of lower crustal fluid flow does not make the models any more certain. Models inevitably invoke an initial steady state hydraulic regime. This initial steady state is critical to model outcomes because it determines the compaction time and length scales and, thereby, the response of the system to perturbations. Unfortunately, because metamorphic devolatilization is the most probable source of lower crustal fluids, the assumption of an initial steady state leaves much to be desired. In truth, in the modeling of lower crustal fluid flow, less is known about the initial state than is known about possible perturbations to it, e.g., metamorphic fluid production. Compaction is a bad and good news story. The bad news is that local flow patterns may be influenced by unknowable details; the good news is that compaction-driven fluid flow has a tendency to self-organize. Self-organization eliminates the dependence on details that are present on spatial or temporal scales that are smaller than the compaction length and time scales. Porosity waves are the mechanism for this self-organization, through which dilational deformation is localized in time and space to create pathways for fluid expulsion. The resulting flow patterns are sensitive to material properties and initial state, thus, inversion of natural flow patterns offers the greatest hope for constraining the compaction scales. Knowledge of these scales is also important because they limit the influence of external forcings on flow patterns, e.g., a shear zone may induce lateral or downward fluid flow, but only on the compaction time and length scales.

Evaluation of agricultural residues pyrolysis under non-isothermal conditions: Thermal behaviors, kinetics, and thermodynamics.

PubMed

Chen, Jianbiao; Wang, Yanhong; Lang, Xuemei; Ren, Xiu'e; Fan, Shuanshi

2017-10-01

The thermal conversion characteristics, kinetics, and thermodynamics of agricultural residues, rape straw (RS) and wheat bran (WB), were investigated under non-isothermal conditions. TGA experiments showed that the pyrolysis characteristics of RS were quite different from those of WB. As reflected by the comprehensive devolatilization index, when the heating rate increased from 10 to 30Kmin -1 , the pyrolysis performance of RS and WB were improved 5.27 and 5.96 times, respectively. The kinetic triplets of the main pyrolysis process of agricultural residues were calculated by the Starink method and the integral master-plots method. Kinetic analysis results indicated that the most potential kinetic models for the pyrolysis of RS and WB were D 2 and F 2.7 , respectively. The thermodynamic parameters (ΔH, ΔG, and ΔS) were determined by the activated complex theory. The positive ΔH, positive ΔG, and negative ΔS at characteristic temperatures validated that the pyrolysis of agricultural residues was endothermic and non-spontaneous. Copyright © 2017 Elsevier Ltd. All rights reserved.

SILLi 1.0: a 1-D numerical tool quantifying the thermal effects of sill intrusions

NASA Astrophysics Data System (ADS)

Iyer, Karthik; Svensen, Henrik; Schmid, Daniel W.

2018-01-01

Igneous intrusions in sedimentary basins may have a profound effect on the thermal structure and physical properties of the hosting sedimentary rocks. These include mechanical effects such as deformation and uplift of sedimentary layers, generation of overpressure, mineral reactions and porosity evolution, and fracturing and vent formation following devolatilization reactions and the generation of CO2 and CH4. The gas generation and subsequent migration and venting may have contributed to several of the past climatic changes such as the end-Permian event and the Paleocene-Eocene Thermal Maximum. Additionally, the generation and expulsion of hydrocarbons and cracking of pre-existing oil reservoirs around a hot magmatic intrusion are of significant interest to the energy industry. In this paper, we present a user-friendly 1-D finite element method (FEM)-based tool, SILLi, which calculates the thermal effects of sill intrusions on the enclosing sedimentary stratigraphy. The model is accompanied by three case studies of sills emplaced in two different sedimentary basins, the Karoo Basin in South Africa and the Vøring Basin off the shore of Norway. An additional example includes emplacement of a dyke in a cooling pluton which forgoes sedimentation within a basin. Input data for the model are the present-day well log or sedimentary column with an Excel input file and include rock parameters such as thermal conductivity, total organic carbon (TOC) content, porosity and latent heats. The model accounts for sedimentation and burial based on a rate calculated by the sedimentary layer thickness and age. Erosion of the sedimentary column is also included to account for realistic basin evolution. Multiple sills can be emplaced within the system with varying ages. The emplacement of a sill occurs instantaneously. The model can be applied to volcanic sedimentary basins occurring globally. The model output includes the thermal evolution of the sedimentary column through time and the changes that take place following sill emplacement such as TOC changes, thermal maturity and the amount of organic and carbonate-derived CO2. The TOC and vitrinite results can be readily benchmarked within the tool to present-day values measured within the sedimentary column. This allows the user to determine the conditions required to obtain results that match observables and leads to a better understanding of metamorphic processes in sedimentary basins.

Comparison of RAGE Hydrocode Mars Impact Model Results to Scaling Law Predictions

NASA Astrophysics Data System (ADS)

Plesko, Catherine S.; Wohletz, K. H.; Coker, R. F.; Asphaug, E.; Gittings, M. L.

2007-10-01

Impact devolatilization has been proposed by Segura et al. (2002) and Carr (1996) as a mechanism for triggering sporadic, intense precipitation on Mars. We seek to examine this hypothesis, specifically to determine the lower bound on possible energy/size scales, and thus an upper bound on the frequency of such events. To do this, we employ various analytical and numerical modeling techniques including the RAGE hydrocode. RAGE (Baltrusaitis et al. 1996) is an Eulerian Hydrocode that runs in up to three dimensions and incorporates a variety of detailed equations of state including the temperature-based SESAME tables maintained by LANL. In order to validate RAGE hydrocode results at the scale of moderate to large asteroid impacts, we compare simplified models of vertical impacts of objects of diameter 10 -100 km into homogeneous basalt targets under Martian conditions to pressure scaling law predictions (Holsapple 1993, e.g. Tables 3-4) for the same scenario. Peak pressures are important to the volatile mobilization question (Stewart and Ahrens, 2005), thus it is of primary importance for planned future modeling efforts to confirm that pressures in RAGE are well behaved. Knowledge of the final crater geometry and the fate of ejecta are not required to understand our main question: to what depth and radius are subsurface volatiles are mobilized, for a given impact and target? This effort is supported by LANL/IGPP (CSP, RFC, KHW, MLG) and by NASA PG&G "Small Bodies and Planetary Collisions" (EA).

Numerical and experimental studies on effects of moisture content on combustion characteristics of simulated municipal solid wastes in a fixed bed.

PubMed

Sun, Rui; Ismail, Tamer M; Ren, Xiaohan; Abd El-Salam, M

2015-05-01

In order to reveal the features of the combustion process in the porous bed of a waste incinerator, a two-dimensional unsteady state model and experimental study were employed to investigate the combustion process in a fixed bed of municipal solid waste (MSW) on the combustion process in a fixed bed reactor. Conservation equations of the waste bed were implemented to describe the incineration process. The gas phase turbulence was modeled using the k-ε turbulent model and the particle phase was modeled using the kinetic theory of granular flow. The rate of moisture evaporation, devolatilization rate, and char burnout was calculated according to the waste property characters. The simulation results were then compared with experimental data for different moisture content of MSW, which shows that the incineration process of waste in the fixed bed is reasonably simulated. The simulation results of solid temperature, gas species and process rate in the bed are accordant with experimental data. Due to the high moisture content of fuel, moisture evaporation consumes a vast amount of heat, and the evaporation takes up most of the combustion time (about 2/3 of the whole combustion process). The whole bed combustion process reduces greatly as MSW moisture content increases. The experimental and simulation results provide direction for design and optimization of the fixed bed of MSW. Copyright © 2015 Elsevier Ltd. All rights reserved.

Pulverized coal burner

DOEpatents

Sivy, J.L.; Rodgers, L.W.; Koslosy, J.V.; LaRue, A.D.; Kaufman, K.C.; Sarv, H.

1998-11-03

A burner is described having lower emissions and lower unburned fuel losses by implementing a transition zone in a low NO{sub x} burner. The improved burner includes a pulverized fuel transport nozzle surrounded by the transition zone which shields the central oxygen-lean fuel devolatilization zone from the swirling secondary combustion air. The transition zone acts as a buffer between the primary and the secondary air streams to improve the control of near-burner mixing and flame stability by providing limited recirculation regions between primary and secondary air streams. These limited recirculation regions transport evolved NO{sub x} back towards the oxygen-lean fuel pyrolysis zone for reduction to molecular nitrogen. Alternate embodiments include natural gas and fuel oil firing. 8 figs.

Pulverized coal burner

DOEpatents

Sivy, Jennifer L.; Rodgers, Larry W.; Koslosy, John V.; LaRue, Albert D.; Kaufman, Keith C.; Sarv, Hamid

1998-01-01

A burner having lower emissions and lower unburned fuel losses by implementing a transition zone in a low NO.sub.x burner. The improved burner includes a pulverized fuel transport nozzle surrounded by the transition zone which shields the central oxygen-lean fuel devolatilization zone from the swirling secondary combustion air. The transition zone acts as a buffer between the primary and the secondary air streams to improve the control of near-burner mixing and flame stability by providing limited recirculation regions between primary and secondary air streams. These limited recirculation regions transport evolved NO.sub.x back towards the oxygen-lean fuel pyrolysis zone for reduction to molecular nitrogen. Alternate embodiments include natural gas and fuel oil firing.

Revised users manual, Pulverized Coal Gasification or Combustion: 2-dimensional (87-PCGC-2): Final report, Volume 2. [87-PCGC-2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, P.J.; Smoot, L.D.; Brewster, B.S.

1987-12-01

A two-dimensional, steady-state model for describing a variety of reactive and non-reactive flows, including pulverized coal combustion and gasification, is presented. Recent code revisions and additions are described. The model, referred to as 87-PCGC-2, is applicable to cylindrical axi-symmetric systems. Turbulence is accounted for in both the fluid mechanics equations and the combustion scheme. Radiation from gases, walls, and particles is taken into account using either a flux method or discrete ordinates method. The particle phase is modeled in a Lagrangian framework, such that mean paths of particle groups are followed. Several multi-step coal devolatilization schemes are included along withmore » a heterogeneous reaction scheme that allows for both diffusion and chemical reaction. Major gas-phase reactions are modeled assuming local instantaneous equilibrium, and thus the reaction rates are limited by the turbulent rate mixing. A NO/sub x/ finite rate chemistry submodel is included which integrates chemical kinetics and the statistics of the turbulence. The gas phase is described by elliptic partial differential equations that are solved by an iterative line-by-line technique. Under-relaxation is used to achieve numerical stability. The generalized nature of the model allows for calculation of isothermal fluid mechanicsgaseous combustion, droplet combustion, particulate combustion and various mixtures of the above, including combustion of coal-water and coal-oil slurries. Both combustion and gasification environments are permissible. User information and theory are presented, along with sample problems. 106 refs.« less

Tracing fluid transfer across subduction zones using iron and zinc stable isotopes

NASA Astrophysics Data System (ADS)

Williams, H. M.; Debret, B.; Pons, M. L.; Bouilhol, P.

2016-12-01

In subduction zones, serpentinite devolatilization within the downgoing slab and the fluids released play a fundamental role in volatile transfer as well as the redox evolution of the sub-arc mantle. Constraining subduction-related serpentinite devolatilisation is essential in order to better understand of the nature and composition of slab-derived fluids and fluid/rock interactions. Fe and Zn stable isotopes can trace fluid composition and speciation as isotope partitioning is driven by changes in oxidation state, coordination, and bonding environment. In the case of serpentinite devolatilisation, Fe isotope fractionation should reflect changes in Fe redox state and the formation of Fe-Cl- and SO42- complexes (Hill et al., GCA 2010); Zn isotope fractionation should be sensitive to complexation with CO32-, HS- and SO42- anions (Fujii et al., GCA 2011). We targeted samples from Western Alps ophiolite complexes, interpreted as remnants of serpentinized oceanic lithosphere metamorphosed and devolatilized during subduction (Hattori and Guillot, G3 2007; Debret et al., Chem. Geol. 2013). A striking negative correlation is present between bulk serpentinite Fe isotope composition and Fe3+/Fetot, with the highest grade samples displaying the heaviest Fe isotope compositions and lowest Fe3+/Fetot (Debret et al., Geology, 2016). The same samples also display a corresponding variation in Zn isotopes, with the highest grade samples displaying isotopically light compositions (Pons et al., in revision). The negative correlation between Fe and Zn isotopes and decrease in Fe3+/Fetot can explained by serpentinite sulfide breakdown and the release of fluids enriched in isotopically light Fe and heavy Zn sulphate complexes. The migration of these SOX-bearing fluids from the slab to the slab-mantle interface or mantle wedge has important implications for the redox evolution of the sub-arc mantle and the transport of metals from the subducting slab.

Entrained-flow gasification at elevated pressure: Volume 1: Final technical report, March 1, 1985-April 30,1987

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hedman, P.O.; Smoot, L.D.; Smith, P.J.

1987-10-15

The general purpose of this research program was to develop a basic understanding of the physical and chemical processes in entrained coal gasification and to use the results to improve and evaluate an entrained gasification computer model. The first task included the collection and analysis of in-situ gasifier data at elevated pressures with three coal types (North Dakota lignite, Wyoming subbituminous and Illinois bituminous), the design, construction, and testing of new coal/oxygen/steam injectors with a fourth coal type (Utah bituminous), the collection of supporting turbulent fluid dynamic (LDV) data from cold-flow studies, and the investigation of the feasibility of usingmore » laser-based (CARS) daignostic instruments to make measurements in coal flames. The second task included improvements to the two-dimensional gasifier submodels, tabulation and evaluation of new coal devolatilization and char oxidation data for predictions, fundamental studies of turbulent particle dispersion, the development of improved numerical methods, and validation of the comprehensive model through comparison of predictions with experimental results. The third task was to transfer technical advances to industry and to METC through technical seminars, production of a detailed data book, code placement, and publication of results. Research results for these three tasks are summarized briefly here and presented in detail in the body of the report and in supporting references. 202 refs., 73 figs., 23 tabs.« less

Numerical and experimental studies on effects of moisture content on combustion characteristics of simulated municipal solid wastes in a fixed bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Rui, E-mail: Sunsr@hit.edu.cn; Ismail, Tamer M., E-mail: temoil@aucegypt.edu; Ren, Xiaohan

Highlights: • The effects of moisture content on the burning process of MSW are investigated. • A two-dimensional mathematical model was built to simulate the combustion process. • Temperature distributions, process rates, gas species were measured and simulated. • The The conversion ratio of C/CO and N/NO in MSW are inverse to moisture content. - Abstract: In order to reveal the features of the combustion process in the porous bed of a waste incinerator, a two-dimensional unsteady state model and experimental study were employed to investigate the combustion process in a fixed bed of municipal solid waste (MSW) on themore » combustion process in a fixed bed reactor. Conservation equations of the waste bed were implemented to describe the incineration process. The gas phase turbulence was modeled using the k–ε turbulent model and the particle phase was modeled using the kinetic theory of granular flow. The rate of moisture evaporation, devolatilization rate, and char burnout was calculated according to the waste property characters. The simulation results were then compared with experimental data for different moisture content of MSW, which shows that the incineration process of waste in the fixed bed is reasonably simulated. The simulation results of solid temperature, gas species and process rate in the bed are accordant with experimental data. Due to the high moisture content of fuel, moisture evaporation consumes a vast amount of heat, and the evaporation takes up most of the combustion time (about 2/3 of the whole combustion process). The whole bed combustion process reduces greatly as MSW moisture content increases. The experimental and simulation results provide direction for design and optimization of the fixed bed of MSW.« less

Dehydration kinetics of shocked serpentine

NASA Technical Reports Server (NTRS)

Tyburczy, James A.; Ahrens, Thomas J.

1988-01-01

Experimental rates of dehydration of shocked and unshocked serpentine were determined using a differential scanning calorimetric technique. Dehydration rates in shocked serpentine are enhanced by orders of magnitude over corresponding rates in unshocked material, even though the impact experiments were carried out under conditions that inhibited direct impact-induced devolatilization. Extrapolation to temperatures of the Martian surface indicates that dehydration of shocked material would occur 20 to 30 orders of magnitude more rapidly than for unshocked serpentine. The results indicate that impacted planetary surfaces and associated atmospheres would reach chemical equilibrium much more quickly than calculations based on unshocked material would indicate, even during the earliest, coldest stages of accretion. Furthermore, it is suggested that chemical weathering of shocked planetary surfaces by solid-gas reactions would be sufficiently rapid that true equilibrium mineral assemblages should form.

Can the evolution of nitrogen cycle be traced by the N isotopic composition in mica?

NASA Astrophysics Data System (ADS)

Pinti, D. L.; Hashizume, K.

2011-12-01

A significant portion of nitrogen present in sedimentary rocks has a biological origin, trapped either in organic form, or as ammonium ion substituting potassium in mica. Mica might preserve biological N isotopic signatures (δ15N) in the geological record, allowing the evolution of the N cycle to be traced. However, diagenetic or metamorphic events can modify the pristine N isotopic signature leading to inaccurate interpretations. For example, devolatilization of the rock leads to a reduction in the N abundance and a contemporary increase of the δ15N because 14N escapes faster than 15N. We measured N isotopic compositions in whole rock, mica and feldspars separates from two Archean suites of cherts: 3.5 Ga Kitty's Gap and North Pole sequences in Pilbara, Western Australia and from the 3.45 Ga Hooggenoeg Fm, Barberton Greenstone Belt, South Africa. N was compared with the argon elemental and isotopic composition, because a relation between NH4+, which replaces K+ and radiogenic 40Ar*, which is produced by electron capture of K+ is expected. Both Pilbara and Barberton cherts show a clear correlation between N and 40Ar*, confirming the occurrence of a common speciation. K-Ar dating of the Hooggenoeg Formation mica and feldspars give ages of 2.1 and 1.1 Ga, respectively, indicating that loosely-bounded noble gas 40Ar* is lost from the host mineral during known metamorphic events. Observed correlations between 40Ar* and N suggests that nitrogen, although more strongly bounded as ammonium is also lost, possibly leading to isotopic fractionation. Measured δ15N values, however, are relatively constant (+8.1±0.6% for whole rock and +10.9±1.2% for mica) and do not display an inverse correlation with N abundances. This suggests either 1) that isotopic fractionation is not produced during N loss or; 2) that a process other than devolatilization fractionate N isotopes. Measured δ15N values are at levels far greater than those expected for Early Archean kerogens (0±2%) thus suggesting that fractionation took place but probably is induced by a process other than devolatilization. Step-combustion analyses of N and Ar from Kitty's Gap cherts reveals the presence of an inverse correlation between δ15N values and the 40Ar*/N ratios indicating mixing between two isotopically distinct components. The first, released at temperatures between 400° and 700° C from hydrous minerals, has a δ15N value close or below 0% and is accompanied by radiogenic Ar. The second, void of radiogenic Ar, is released at temperatures >800° C from anhydrous phases and has a δ15N value of +6 to +8%. The first component is likely ammonium replacing K in mica while the second is possibly ammonium adsorbed in-between negatively charged layers of clay minerals. Upon dehydration, the inter-layer site will be "closed", and loosely adsorbed cations are finally trapped in the mineral while noble gas Ar is lost. The higher δ15N in mica is possibly due either to (1) trapping of N representing a later (post-Archean) event, or; (2) fractionation of N with negative δ15N value due to partial release of N from the adsorption site. Mixing between different aliquots of these two components might possibly explain the observed N isotopic variability among micas in the Archean.

Sr-Nd-Pb Isotope Geochemistry of Melange Formation: Implications for Identification of Fluid Sources in the Mantle Wedge and the Arc

NASA Astrophysics Data System (ADS)

Bebout, G. E.; King, R. L.; Moriguti, T.; Nakamura, E.

2004-12-01

Paramount to our ability to decipher the behavior of fluids and melts within the mantle wedge and the overall subduction system are the chemical compositions of rocks adjacent to the slab-mantle interface. Profound metamorphic and metasomatic alteration of pre-subduction lithologies to form melange along the slab-mantle interface may yield rock types inheriting mixed chemical compositions of diverse pre-subduction lithologies. Early work on melange geochemistry indicates competitive effects between mechanical mixing, metasomatism by fluids or melts, and mineral stabilities imposed by the resulting bulk composition. We have explored the Sr-Nd-Pb isotope geochemistry of low- to high-grade melange zones in the Catalina Schist, CA, to address this crucial missing component in studies of subduction-zone mass flux. The Catalina Schist contains lawsonite-albite (LA), lawsonite-blueschist (LB), and amphibolite (AM) facies melange zones, all with mineralogy dominated by talc, chlorite, and Na-Ca amphiboles, with additional minerals such as micas, rutile, zircon, and apatite stabilized based on bulk sample chemistry. Major element compositions vary, from strongly ultramafic in the AM melange, to more crustal-like compositions (i.e., more reminiscent of basaltic to sedimentary protoliths) for LA and LB melange. However, initial Sr and Nd isotope ratios for all grades of melange are essentially indistinguishable, displaying a wide variation from 87Sr/86Sr=0.703-0.709 and ɛ Nd= +15 to -15. Covariations are generally negative, similar to that of the mantle array, but with some samples extending to higher Sr ratios at constant ɛ Nd that probably reflect inheritance of seawater Sr. No clear mixing relationships between 87Sr/86Sr and 1/Sr exist, suggesting either localized buffering of Sr isotope ratios or that mixing relations are obscured by secondary devolatilization. However, a clear mixing trend for Nd indicates two end-members, one a high-concentration, positive ɛ Nd source (AOC?), the other with low-concentration and negative ɛ Nd (devolatilized sediments?). Likewise, initial Pb isotope ratios for all grades of melange form a single array independent of rock type or inferred protolith. Melange matrix of the Catalina Schist preserves initial 206Pb/204Pb of 18.95-19.59, 207Pb/204Pb of 15.61-15.68, and 208Pb/204Pb of 37.85-39.05. Such elevated Pb ratios are typical of subducting oceanic sediments, but not of MORB-like oceanic crust or peridotites of the depleted mantle. The similarity of these initial ratios suggests pervasive alteration of Pb isotope signatures within diverse rock types by fluids during subduction. As Pb concentrations decline from LA/LB to AM melange, this suggests devolatilization of Pb from the ultramafic AM melange will transfer crustal-like Pb isotope ratios. Sr-Nd-Pb isotope systematics for arc volcanic rocks are commonly used as indicators of fluid sources from the subducting slab to the arc magma source region. Our results suggest such an assumption is extremely dangerous, as hybridization processes common to melange zones are more likely to occur along the slab-mantle interface than is preservation of a pre-subduction section. Such metamorphic mediation and buffering of "slab" compositions is essentially unknown, yet our data support an interpretation where these processes impart a fundamental control on the chemistry of fluids passed to the mantle wedge.

Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae

PubMed Central

Rowbotham, J. S.; Dyer, P. W.; Greenwell, H. C.; Selby, D.; Theodorou, M. K.

2013-01-01

Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

Sulfur degassing due to contact metamorphism during flood basalt eruptions

NASA Astrophysics Data System (ADS)

Yallup, Christine; Edmonds, Marie; Turchyn, Alexandra V.

2013-11-01

We present a study aimed at quantifying the potential for generating sulfur-rich gas emissions from the devolatilization of sediments accompanying sill emplacement during flood basalt eruptions. The potential contribution of sulfur-rich gases from sediments might augment substantially the magma-derived sulfur gases and hence impact regional and global climate. We demonstrate, from a detailed outcrop-scale study, that sulfur and total organic carbon have been devolatilized from shales immediately surrounding a 3-m thick dolerite sill on the Isle of Skye, Scotland. Localized partial melting occurred within a few centimetres of the contact in the shale, generating melt-filled cracks. Pyrite decomposed on heating within 80 cm of the contact, generating sulfur-rich gases (a mixture of H2S and SO2) and pyrrhotite. The pyrrhotite shows 32S enrichment, due to loss of 34S-enriched SO2. Further decomposition and oxidation of pyrrhotite resulted in hematite and/or magnetite within a few cm of the contact. Iron sulfates were produced during retrogressive cooling and oxidation within 20 cm of the contact. Decarbonation of the sediments due to heating is also observed, particularly along the upper contact of the sill, where increasing δ13C is consistent with loss of methane gas. The geochemical and mineralogical features observed in the shales are consistent with a short-lived intrusion, emplaced in <5 h. The dolerite magma contains pervasive pyrite and localized sulfur concentrations greater than the sulfur concentration at sulfide liquid saturation, consistent with addition of sulfur (perhaps from sediments) at a late stage. Our study provides evidence for desulfurization, as well as decarbonation, of shales adjacent to an igneous intrusion. The liberated fluids, rich in sulfur and carbon, are likely to be focused along regions of low pore fluid pressure along the margins of the sill. The sulfur gases liberated from the sediments would have augmented the sulfur dioxide (and hydrogen sulfide) yield of the eruption substantially, had they reached the surface. This enhancement of the magmatic sulfur budget has important implications for the climate impact of large flood basalt eruptions that erupt through thick, volatile-rich sedimentary sequences.

Experimental investigation of wood combustion in a fixed bed with hot air.

PubMed

Markovic, Miladin; Bramer, Eddy A; Brem, Gerrit

2014-01-01

Waste combustion on a grate with energy recovery is an important pillar of municipal solid waste (MSW) management in the Netherlands. In MSW incinerators fresh waste stacked on a grate enters the combustion chamber, heats up by radiation from the flame above the layer and ignition occurs. Typically, the reaction zone starts at the top of the waste layer and propagates downwards, producing heat for drying and devolatilization of the fresh waste below it until the ignition front reaches the grate. The control of this process is mainly based on empiricism. MSW is a highly inhomogeneous fuel with continuous fluctuating moisture content, heating value and chemical composition. The resulting process fluctuations may cause process control difficulties, fouling and corrosion issues, extra maintenance, and unplanned stops. In the new concept the fuel layer is ignited by means of preheated air (T>220 °C) from below without any external ignition source. As a result a combustion front will be formed close to the grate and will propagate upwards. That is why this approach is denoted by upward combustion. Experimental research has been carried out in a batch reactor with height of 4.55 m, an inner diameter of 200 mm and a fuel layer height up to 1m. Due to a high quality two-layer insulation adiabatic conditions can be assumed. The primary air can be preheated up to 350 °C, and the secondary air is distributed via nozzles above the waste layer. During the experiments, temperatures along the height of the reactor, gas composition and total weight decrease are continuously monitored. The influence of the primary air speed, fuel moisture and inert content on the combustion characteristics (ignition rate, combustion rate, ignition front speed and temperature of the reaction zone) is evaluated. The upward combustion concept decouples the drying, devolatilization and burnout phase. In this way the moisture and inert content of the waste have almost no influence on the combustion process. In this paper an experimental comparison between conventional and reversed combustion is presented. Copyright © 2013 Elsevier Ltd. All rights reserved.

Sulfate content of Europa's ocean and shell: evolutionary considerations and some geological and astrobiological implications.

PubMed

McKinnon, William B; Zolensky, Michael E

2003-01-01

Recent models for the origin of Jupiter indicate that the Galilean satellites were mostly derived from largely unprocessed solar nebula solids and planetesimals. In the jovian subnebula the solids that built Europa were first heated and then cooled, but the major effect was most likely partial or total devolatilization, and less likely to have been wholesale thermochemical reprocessing of rock + metal compositions (e.g., oxidation of Fe and hydration of silicates). Ocean formation and substantial alteration of interior rock by accreted water and ice would occur during and after accretion, but none of the formation models predicts or implies accretion of sulfates. Europa's primordial ocean was most likely sulfidic. After accretion and later radiogenic and tidal heating, the primordial ocean would have interacted hydrothermally with subjacent rock. It has been hypothesized that sulfides could be converted to sulfates if sufficient hydrogen was lost to space, but pressure effects and the impermeability of serpentinite imply that extraction of sulfate from thoroughly altered Europa-rock would have been inefficient (if indeed Mg sulfates formed at all). Permissive physical limits on the extent of alteration limit the sulfate concentration of Europa's evolved ocean to 10% by weight MgSO(4) or equivalent. Later oxidation of the deep interior of Europa may have also occurred because of water released by the breakdown of hydrated silicates, ultimately yielding S magma and/or SO(2) gas. Geological and astrobiological implications are considered.

Impact erosion of planetary atmospheres

NASA Astrophysics Data System (ADS)

Shuvalov, Valery

1999-06-01

The problem of planetary atmospheres evolution due to impacts of large cosmic bodies was investigated by Ahrens, O'Keefe, Cameron, Hunten and others. These studies were focused mainly on the atmosphere growth under impact devolatilization and atmosphere losses due to escape of high velocity ejecta. Most of the results concerning atmosphere erosion were based on assumption that atmosphere itself does not influence significantly on the ejecta evolution. However more detailed investigations show that atmospheric drag is important at least for 1-10km impactors. From the other hand the theory of large explosions in an exponential atmosphere is not applicable in the case under consideration because of the influence of a trail created during the body flight through the atmosphere. In the present study the problem of 1-10km asteroid impacts against the Earth is investigated with the use of multi-material hydrocode SOVA. This code is similar to the widely used CTH system and allows to model all stages of the impact (penetration into the atmosphere, collision with the ground surface covered by water basin, ejecta evolution). The air mass ejected from each altitude depending on impactor size and velocity is determined. Apart from the impacts into the present-day atmosphere, the erosion of the dense Proto-Atmosphere is also considered.

NANEX: Process design and optimization.

PubMed

Baumgartner, Ramona; Matić, Josip; Schrank, Simone; Laske, Stephan; Khinast, Johannes; Roblegg, Eva

2016-06-15

Previously, we introduced a one-step nano-extrusion (NANEX) process for transferring aqueous nano-suspensions into solid formulations directly in the liquid phase. Nano-suspensions were fed into molten polymers via a side-feeding device and excess water was eliminated via devolatilization. However, the drug content in nano-suspensions is restricted to 30 % (w/w), and obtaining sufficiently high drug loadings in the final formulation requires the processing of high water amounts and thus a fundamental process understanding. To this end, we investigated four polymers with different physicochemical characteristics (Kollidon(®) VA64, Eudragit(®) E PO, HPMCAS and PEG 20000) in terms of their maximum water uptake/removal capacity. Process parameters as throughput and screw speed were adapted and their effect on the mean residence time and filling degree was studied. Additionally, one-dimensional discretization modeling was performed to examine the complex interactions between the screw geometry and the process parameters during water addition/removal. It was established that polymers with a certain water miscibility/solubility can be manufactured via NANEX. Long residence times of the molten polymer in the extruder and low filling degrees in the degassing zone favored the addition/removal of significant amounts of water. The residual moisture content in the final extrudates was comparable to that of extrudates manufactured without water. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Characterization of Cracking Mechanisms of Carbon Anodes Used in Aluminum Industry by Optical Microscopy and Tomography

NASA Astrophysics Data System (ADS)

Amrani, Salah; Kocaefe, Duygu; Kocaefe, Yasar; Bhattacharyay, Dipankar; Bouazara, Mohamed; Morais, Brigitte

2016-10-01

The objective of this work is to understand the different mechanisms of crack formation in dense anodes used in the aluminum industry. The first approach used is based on the qualitative characterization of the surface cracks and the depth of these cracks. The second approach, which constitutes a quantitative characterization, is carried out by determining the distribution of the crack width along its length as well as the percentage of the surface containing cracks. A qualitative analysis of crack formation was also carried out using 3D tomography. It was observed that mixing and forming conditions have a significant effect on crack formation in green anodes. The devolatilization of pitch during baking causes the formation and propagation of cracks in baked anodes in which large particles control the direction of crack propagation.

Devolatilization Studies of Oil Palm Biomass for Torrefaction Process through Scanning Electron Microscopy

NASA Astrophysics Data System (ADS)

Daud, D.; Abd. Rahman, A.; Shamsuddin, A. H.

2016-03-01

In this work, palm oil biomass consisting of empty fruit bunch (EFB), mesocarp fibre and palm kernel shell (PKS) were chosen as raw material for torrefaction process. Torrefaction process was conducted at various temperatures of 240 °C, 270 °C and 300 °C with a residence time of 60 minutes. The morphology of the raw and torrefied biomass was then observed through Scanning Electron Microscopy (SEM) images. Also, through this experiment the correlation between the torrefaction temperatures with the volatile gases released were studied. From the observation, the morphology structure of the biomass exhibited inter-particle gaps due to the release of volatile gases and it is obviously seen more at higher temperatures. Moreover, the change of the biomass structure is influenced by the alteration of the lignocellulose biomass.

Co-pyrolysis behavior of fermentation residues with woody sawdust by thermogravimetric analysis and a vacuum reactor.

PubMed

Zheng, Yan; Zhang, Yimin; Xu, Jingna; Li, Xiayang; Charles Xu, Chunbao

2017-12-01

This study aimed at cost-effective utilization of fermentation residues (FR) from biogas project for bio-energy via co-pyrolysis of FR and woody sawdust (WS). In this study, a vacuum reactor was used to study the pyrolysis behaviors of individual and blend samples of FR and WS. Obvious synergistic effects were observed, resulting in a lower char yield but a higher gas yield. The presence of woody sawdust promoted the devolatilization of FR, and improved the syngas (H 2 and CO) content in the gaseous products. Compared to those of the char from pyrolysis of individual feedstock, co-pyrolysis of FR and WS in the vacuum reactor promoted the cracking reactions of large aromatic rings, enlarged the surface area and reduced the oxygenated groups of the resulted char. Copyright © 2017 Elsevier Ltd. All rights reserved.

Coal Combustion Science quarterly progress report, April--June 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hardesty, D.R.; Hurt, R.H.; Baxter, L.L.

1992-09-01

The objective of this work is to support the Office of Fossil Energy in executing research on coal combustion science. This project consists of basic research on coal combustion that supports both the Pittsburgh Energy Technology Center (PETC) Direct Utilization Advanced Research and Technology Development Program, and the International Energy Agency (IEA) Coal Combustion Science Project. Specific tasks include: The characterization of the physical and chemical processes that constitute the early devolatilization phase of coal combustion: Characterization of the combustion behavior of selected coals under conditions relevant to industria pulverized coal-fired furnaces; and to establish a quantitative understanding of themore » mechanisms and rates of transformation, fragmentation, and deposition of mineral matter in coal combustion environments as a function of coal type, particle size and temperature, the initial forms and distributions of mineral species in the unreacted coal, and the local gas temperature and composition.« less

Permeability of gypsum samples dehydrated in air

NASA Astrophysics Data System (ADS)

Milsch, Harald; Priegnitz, Mike; Blöcher, Guido

2011-09-01

We report on changes in rock permeability induced by devolatilization reactions using gypsum as a reference analog material. Cylindrical samples of natural alabaster were dehydrated in air (dry) for up to 800 h at ambient pressure and temperatures between 378 and 423 K. Subsequently, the reaction kinetics, so induced changes in porosity, and the concurrent evolution of sample permeability were constrained. Weighing the heated samples in predefined time intervals yielded the reaction progress where the stoichiometric mass balance indicated an ultimate and complete dehydration to anhydrite regardless of temperature. Porosity showed to continuously increase with reaction progress from approximately 2% to 30%, whilst the initial bulk volume remained unchanged. Within these limits permeability significantly increased with porosity by almost three orders of magnitude from approximately 7 × 10-19 m2 to 3 × 10-16 m2. We show that - when mechanical and hydraulic feedbacks can be excluded - permeability, reaction progress, and porosity are related unequivocally.

Pre-terrestrial origin of rust in the Nakhla meteorite

NASA Technical Reports Server (NTRS)

Wentworth, Susan J.; Gooding, James L.

1990-01-01

The authors present quantative elemental compositions and summarize textural evidence for the pre-terrestrial origin of rust on the Nakhla meteorite. The material in question is called 'rust' because its phase composition remains unknown. Compelling evidence for the pre-terrestrial origin of the rust is found in rust veins truncated by fusion crust and preserved as faults in sutured igneous crystals. Rust veins that approach the meteorite's fusion crust become discontinuous and exhibit vugs that suggest partial decrepitation; no veins that penetrate the fusion crust have been found. Because the rust probably contains volatile compounds, it is reasonable to expect that heating near the ablation surface (formed during atmospheric entry to Earth) would encourage devolatilization of the rust. Hence, the absence of rust veins in fusion crust and vugs in rust veins near fusion crust clearly imply that the rust existed in the meteorite before atmospheric entry.

Objectives and Capabilities of the Deep Space 2 (DS2) Evolved Water Experiment

NASA Astrophysics Data System (ADS)

Yen, A. S.; Murray, B.; Zent, A. P.

1999-09-01

The New Millennium Deep Space 2 (DS2) Mars Microprobes will impact the surface of Mars at a latitude of approximately 75 degrees South on December 3, 1999. The primary objective of this mission is to demonstrate penetrator technologies for future scientific applications. Nonetheless, measurements will be obtained with the goal of characterizing the atmospheric structure during entry as well as the penetrability, thermal conductivity, and water ice content of the polar layered terrains. In addition to demonstrating the ability to collect a subsurface sample, the evolved water experiment will test models of the south polar regions which indicate that water ice is stable at depths of 4 to 20 cm and greater [Paige and Keegan, 1994]. This prediction for the presence of ice is in contrast to atmospheric circulation models which suggest that water is irreversibly lost from southern latitudes and that the only extensive, permanent ice deposits are located in the northern hemisphere [Houben et al., 1997]. Furthermore, MOC images from the 1998 aerobraking phase suggest a rougher and perhaps more devolatilized surface than inferred from Viking and Mariner 9 data. Thus, the direct determination of the presence or absence of near-surface ice by the DS2 probes is important in the resolution of the fundamental questions about Mars regarding the global inventory of water and the climate history. In pursuit of these objectives, a 160 milliliter soil sample will be actively collected by a miniature drill and analyzed for water ice both thermally and spectroscopically. Specific capabilities and detection limits for the abundance of water ice will be presented at the meeting.

Nano-extrusion: a promising tool for continuous manufacturing of solid nano-formulations.

PubMed

Baumgartner, Ramona; Eitzlmayr, Andreas; Matsko, Nadejda; Tetyczka, Carolin; Khinast, Johannes; Roblegg, Eva

2014-12-30

Since more than 40% of today's drugs have low stability, poor solubility and/or limited ability to cross certain biological barriers, new platform technologies are required to address these challenges. This paper describes a novel continuous process that converts a stabilized aqueous nano-suspension into a solid oral formulation in a single step (i.e., the NANEX process) in order to improve the solubility of a model drug (phenytoin). Phenytoin nano-suspensions were prepared via media milling using different stabilizers. A stable nano-suspension was obtained using Tween(®) 80 as a stabilizer. The matrix material (Soluplus(®)) was gravimetrically fed into the hot melt extruder. The suspension was introduced through a side feeding device and mixed with the molten polymer to immediately devolatilize the water in the nano-suspension. Phenytoin nano-crystals were dispersed and embedded in the molten polymer. Investigation of the nano-extrudates via transmission electron microscopy and atomic force microscopy showed that the nano-crystals were embedded de-aggregated in the extrudates. Furthermore, no changes in the crystallinity (due to the mechanical and thermal stress) occurred. The dissolution studies confirmed that the prepared nano-extrudates increased the solubility of nano-crystalline phenytoin, regardless of the polymer. Our work demonstrates that NANEX represents a promising new platform technology in the design of novel drug delivery systems to improve drug performance. Copyright © 2014 Elsevier B.V. All rights reserved.

HIGH PRESSURE COAL COMBUSTION KINETICS PROJECT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chris Guenther; Bill Rogers

2001-09-15

The HPCCK project was initiated with a kickoff meeting held on June 12, 2001 in Morgantown, WV, which was attended by all project participants. SRI's existing g-RCFR reactor was reconfigured to a SRT-RCFR geometry (Task 1.1). This new design is suitable for performing the NBFZ experiments of Task 1.2. It was decided that the SRT-RCFR apparatus could be modified and used for the HPBO experiments. The purchase, assembly, and testing of required instrumentation and hardware is nearly complete (Task 1.1 and 1.2). Initial samples of PBR coal have been shipped from FWC to SRI (Task 1.1). The ECT device formore » coal flow measurements used at FWC will not be used in the SRI apparatus and a screw type feeder has been suggested instead (Task 5.1). NEA has completed a upgrade of an existing Fluent simulator for SRI's RCFR to a version that is suitable for interpreting results from tests in the NBFZ configuration (Task 1.3) this upgrade includes finite-rate submodels for devolatilization, secondary volatiles pyrolysis, volatiles combustion, and char oxidation. Plans for an enhanced version of CBK have been discussed and development of this enhanced version has begun (Task 2.5). A developmental framework for implementing pressure and oxygen effects on ash formation in an ash formation model (Task 3.3) has begun.« less

Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

NASA Astrophysics Data System (ADS)

Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

2008-02-01

Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10‰). Extrapolating the shock signature of the regrouped data to grains that experienced Martian meteorite-like shock pressures suggests that shock-induced water losses and hydrogen isotope enrichments could approach 1 wt.% H 2O and Δ D = + 100‰, respectively. If these values are valid, then impact shock effects could explain a substantial fraction of the low water contents and variable hydrogen isotope compositions of the Martian meteorite kaersutites.

Experimental Shock Transformation of Gypsum to Anhydrite: A New Low Pressure Regime Shock Indicator

NASA Technical Reports Server (NTRS)

Bell, Mary S.; Zolensky, Michael E.

2011-01-01

The shock behavior of gypsum is important in understanding the Cretaceous/Paleogene event and other terrestrial impacts that contain evaporite sediments in their targets (e.g., Mars Exploration Rover Spirit detected sulfate at Gusev crater, [1]). Most interest focuses on issues of devolatilization to quantify the production of SO2 to better understand its role in generating a temporary atmosphere and its effects on climate and biota [2,3]. Kondo and Ahrens [4] measured induced radiation emitted from single crystal gypsum shocked to 30 and 40 GPa. They observed greybody emission spectra corresponding to temperatures in the range of 3,000 to 4,000 K that are a factor of 2 to 10 times greater than calculated pressure-density energy equation of state temperatures (Hugoniot) and are high enough to melt gypsum. Chen et al. [5] reported results of shock experiments on anhydrite, gypsum, and mixtures of these phases with silica. Their observations indicated little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another report of shock experiments on calcite, anhydrite, and gypsum, Badjukov et al. [6] observed only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa but have not experimentally shocked gypsum in a step-wise manner to constrain possible incipient transformation effects. Schmitt and Hornemann [7] shock loaded anhydrite and quartz to a peak pressure of 60 GPa and report the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggested that recrystallization of anhydrite grains is the result of a solid-state transformation. They concluded that significant decomposition of anhydrite requires shock pressures higher than 60 GPa. Gupta et al. [8] reanalyzed the calcite and anhydrite shock wave experiments of Yang [9] using improved equations of state of porous materials and vaporized products. They determined the pressures for incipient and complete vaporization to be 32.5 and 122 GPa for anhydrite GPa which is a factor of 2 to 3 lower than reported earlier by Yang [9]. These studies are not in agreement regarding the onset of sulfate decomposition and documentation of shock effects in gypsum is incomplete.

Constitution of Drop-Tube-Generated Coal Chars from Vitrinite- and Inertinite-Rich South African Coals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Louw, Enette B.; Mitchell, Gareth D.; Wang, Juan

The structural transformations of coal and the resultant char morphologies are strongly dependent on the initial structure and degree of thermoplasticity achieved during coal-to-char transition. These are a function of petrographic composition, rank, particle size, and heating rate and strongly affect combustion behavior. This study compares the devolatilization and subsequent combustion behavior of an inertinite-rich (87.7% dmmf) and a vitrinite-rich (91.8% dmmf) South African coal, wet-screened to a narrow particle size distribution of 200 x 400 mesh. Pyrolysis chars were generated under rapid-heating conditions (104-105 °C/s) in a drop-tube reactor to closely resemble chars generated in pulverized combustion conditions. Themore » inertinite-rich coal took ~ 400 ms to devolatilize in the drop-tube, compared to only ~ 240 ms for the vitrinite-rich sample. The chemical and physical structure (the constitution) of the chars were investigated through a range of chemical, physical, and optical characteristics including the maceral differences, and high ash yields. To evaluate the combustion reactivity non-isothermal burn-out profiles were obtained through thermogravimetrical analyses (TGA) in air. The vitrinite-rich char had on average 20% higher reaction rates than the inertinite-rich char under the various combustion conditions. The char samples were de-ashed with HCl and HF acid which resulted in an increase in combustion reactivity. The maximum reaction rate of the high-ash (36% ash yield) inertinite-rich char increased with 80% after de-ashing. While the vitrinite-rich char with an ash yield of 15%, had a 20% increase in reactivity after de-ashing. The ash acted as a barrier, and the removal of ash most likely increased the access to reactive surface area. The chemical and physical structures of the chars were characterized through a range of different analytical techniques to quantify the factors contributing to reactivity differences. The morphologies of the chars were characterized with SEM and optical microscopy, while quantitative information on the ordered nature of chars was obtained through XRD on de-ashed chars. The inertinite-rich coal experienced limited fluidity during heat-treatment, resulting in slower devolatilization, limited growth in crystallite height (11.8 to 12.6Å), only rounding of particle edges, and producing > 40% of mixed-dense type chars. The vitrinite-char showed more significant structural transformations; producing mostly (80%) extensively swollen crassisphere, tenuisphere, and network-type chars, and XRD showed a large increase in crystallite height (4.3 to 11.7Å). Nitrogen adsorption and small-angle X-ray scattering (SAXS) were utilized to compare the nitrogen surface areas and pore size distributions. Both chars were mostly mesoporous but the inertinite-rich char had double the average pore size, which also resulted in a larger nitrogen surface area since nitrogen can only access surface areas in larger pores. The BET surface area was 3.9 and 2.7 m2/g for the inertinite- and vitrinite-rich chars respectively. SAXS data showed that the vitrinite-rich char had 60% higher frequencies of pores in the micropore range. Helium porosimetry indicated that the inertinite-rich coal and resultant char had higher densities than the vitrinite coal and char; 1.6 and 2.0 g/cm3, compared to 1.3 and 1.9 g/cm3 (dry basis). Non-isothermal TGA burnout profiles showed the inertinite-rich char had a burnout temperature of 680°C, slightly higher than the vitrinite-rich char’s 650 °C. This, along with the peak shape and position in the burnout profiles indicate that the vitrinite-rich char has a higher reactivity. The higher reactivity is due to a combination of factors likely including less organization, grater porosity and access to the reactive site, less ash blocking, and char morphology differences.« less

Iceless Icy Moons: Is the Nice Model In Trouble?

NASA Astrophysics Data System (ADS)

Dones, Henry C. Luke; Levison, H. F.

2012-05-01

Nimmo and Korycansky (2012; henceforth NK12) stated that if the outer Solar System underwent a Late Heavy Bombardment (LHB) in the Nice model, the mass striking the icy satellites at speeds up to tens of km/s would have vaporized so much ice that moons such as Mimas, Enceladus, and Miranda would have been devolatilized. NK12's possible explanations of this apparent discrepancy with observations include (1) the mass influx was a factor of 10 less than that in the Nice model; (2) the mass distribution of the impactors was top-heavy, so that luck might have saved some of the moons from suffering large, vapor-removing impacts; or (3) the inner moons formed after the LHB. NK12 calculated the mass influx onto the satellites from the lunar impact rate estimated by Gomes et al. (2005) and scaling factors calculated by Zahnle et al. (1998, 2003; also see Barr and Canup 2010). Production of vapor in hypervelocity impacts is calculated from Kraus et al. (2011). Our preliminary results show that there is about an order-of-magnitude uncertainty in the mass striking the satellites during the LHB, with NK12's estimate at the upper end of the range. We will discuss how the mass influx depends on the velocity and mass distributions of the impactors. The Nice model lives. We thank the NASA Lunar Science Institute (http://lunarscience.nasa.gov/) for support. Barr, A.C., Canup, R.M., Nature Geoscience 3, 164-167 (2010). Gomes, R., Levison, H.F., Tsiganis, K., Morbidelli, A., Nature 435, 466-469 (2005). Kraus, R.G., Senft, L.E., Stewart, S.T., Icarus 214, 724-738 (2011). Nimmo, F., Korycansky, D.G., Icarus, in press, http://www.sciencedirect.com/science/article/pii/S0019103512000310 (2012). Zahnle, K., Dones, L., Levison, H.F., Icarus 136, 202-222 (1998). Zahnle, K., Schenk, P., Levison, H.F., Dones, L., Icarus 163, 263-289 (2003).

Experimental and theoretical aspects of studying themodynamics and mass transport in polymer-solvent systems

NASA Astrophysics Data System (ADS)

Davis, Peter Kennedy

Mass transport and thermodynamics in polymer-solvent systems are two key areas of importance to the polymer industry. Numerous processes including polymerization reactors, membrane separations, foam production, devolatilization processes, film and coating drying, supercritical extractions, drug delivery, and even nano-technology require fundamental phase equilibria and diffusion information. Although such information is vital in equipment design and optimization, acquisition and modeling of these data are still in the research and development stages. This thesis is rather diverse as it addresses many realms of this broad research area. From high pressure to low pressure, experimental to theoretical, and infinite dilution to finite concentration, the thesis covers a wide range of topics that are of current importance to the industrial and academic polymer community. Chapter 1 discusses advances in the development of a new volumetric sorption pressure decay technique to make phase equilibrium and diffusion measurements in severe temperature-pressure environments. Chapter 2 provides the derivations and results of a new completely predictive Group Contribution Lattice Fluid Equation of State for multi-component polymer-solvent systems. The remaining four chapters demonstrate advances in the modeling of inverse gas chromatography (IGC) experiments. IGC has been used extensively of the last 50 years to make low pressure sorption and diffusion measurements at infinitely dilute and finite solvent concentrations. Chapter 3 proposes a new IGC experiment capable of obtaining ternary vapor-liquid equilibria in polymer-solvent-solvent systems. Also in that chapter, an extensive derivation is provided for a continuum model capable of describing the results of such an experiment. Chapter 4 presents new data collected on a packed column IGC experiment and a new model that can be used with those experimental data to obtain diffusion and partition coefficients. Chapter 5 addresses a rather controversial topic about IGC experiments near the polymer glass transition temperature. Using a new IGC model capable of describing both bulk absorption and surface adsorption, IGC behavior around the glass transition was able to be better understood. Finally, Chapter 6 presents an IGC model that can be used to separate bulk effects from surface effects in capillary column IGC experiments.

Decarbonation and carbonation processes in the slab and mantle wedge - insights from thermomechanical modeling

NASA Astrophysics Data System (ADS)

Gonzalez, C. M.; Gorczyk, W.; Connolly, J. A.; Gerya, T.; Hobbs, B. E.; Ord, A.

2013-12-01

Subduction zones offer one of the most geologically active and complex systems to investigate. They initiate a process in which crustal sediments are recycled, mantle heterogeneities arise, and mantle wedge refertilization occurs via slab derived volatiles and magma generation. Slab derived volatiles, consisting primarily of H2O - CO2 fluids, are especially critical in subduction evolution as they rheologically weaken the mantle wedge, decrease solidus temperatures, and rock-fluid interactions result in metasomatism. While the effects of H2O in these processes have been well studied in the past decades, CO2's role remains open for much scientific study. This is partly attributed to the sensitivity of decarbonation to the thermal gradient of the subduction zone, bulk compositions (sediments, basalts, peridotites) and redox state of the mantle. Here we show benchmarking results of a subduction scenario that implements carbonation-decarbonation reactions into a fully coupled petrological-thermomechanical numerical modeling code. We resolve stable mineralogy and extract rock properties via Perple_X at a resolution of 5°C and 25 MPa. The numerical technique employed is a characteristics-based marker-in-cell technique with conservative finite-differences that includes visco-elastic-plastic rheologies (I2ELVIS). The devolatilized fluids are tracked via markers that are either generated or consumed based on P-T conditions. The fluids are also allowed to freely advect within the velocity field. The hosts for CO2 in this system are computed via GLOSS average sediments (H2O: 7.29 wt% & CO2: 3.01 wt%), metabasalts ( H2O: 2.63 & CO2: 2.90 wt%), and ophicarbonates (H2O: 1.98 wt% & CO2: 5.00 wt%). Our results demonstrate the feasibility of applying this decarbonation-carbonation numerical method to a range of geodynamic scenarios that simulate the removal of CO2 from the subducting slab. Such applicable scenarios include sediment diapirism into the convecting wedge and better understanding the fate of carbonates beyond the subarc and consequent subduction into the deeper mantle within a fully coupled model framework. A case study where CO2 fluids are intimately connected to subduction and metasomatism of the mantle is in the Western Mediterranean in Italy. There, carbonate melts metasomatized the asthenosphere leading to a seismic low velocity zone associated with large scale mantle degassing in the region of approximately 70 Mt/year of CO2 [1]. This natural laboratory provides us with a present day example to help constrain the benchmarking process in order to refine our numerical techniques. [1] Frezzotti, Peccerillo, & Panza, 2009. Chemical Geology, 262(1-2), 108-120. doi: DOI 10.1016/j.chemgeo.2009.02.015

Kinetic studies on the reduction of iron ore nuggets by devolatilization of lean-grade coal

NASA Astrophysics Data System (ADS)

Biswas, Chanchal; Gupta, Prithviraj; De, Arnab; Chaudhuri, Mahua Ghosh; Dey, Rajib

2016-12-01

An isothermal kinetic study of a novel technique for reducing agglomerated iron ore by volatiles released by pyrolysis of lean-grade non-coking coal was carried out at temperature from 1050 to 1200°C for 10-120 min. The reduced samples were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and chemical analysis. A good degree of metallization and reduction was achieved. Gas diffusion through the solid was identified as the reaction-rate-controlling resistance; however, during the initial period, particularly at lower temperatures, resistance to interfacial chemical reaction was also significant, though not dominant. The apparent rate constant was observed to increase marginally with decreasing size of the particles constituting the nuggets. The apparent activation energy of reduction was estimated to be in the range from 49.640 to 51.220 kJ/mol and was not observed to be affected by the particle size. The sulfur and carbon contents in the reduced samples were also determined.

Characteristics of oily sludge combustion in circulating fluidized beds.

PubMed

Zhou, Lingsheng; Jiang, Xiumin; Liu, Jianguo

2009-10-15

Incineration of oily sludge in circulating fluidized beds may be an effective way for its management in some cases. The objective of the present paper is to investigate combustion characteristics of oily sludge, which would be helpful and useful for the design and simulation of a circulating fluidized bed. Firstly, the pyrolysis and combustion of oily sludge were studied through some thermal analyses, which included the thermogravimetric (TG) analysis and the differential thermal analytical (DTA) analysis. It was found that the combustion of oily sludge might be the combustion of its pyrolysis products. Secondly, an experiment for measuring of main components of the volatile from oily sludge pyrolysis was carried out. Some mathematic correlations about the compositions of volatile from oily sludge devolatilization were achieved from the experimental results. Finally, the combustion characteristics of oily sludge was studied in a lab-scale circulating fluidized bed, which could obtain some information about the location of release and combustion of the volatiles.

Chlorine Isotope Evidence for Syn-Subduction Modification of Serpentinites by Interaction with Sediment-Derived Fluid

NASA Astrophysics Data System (ADS)

Selverstone, J.; Sharp, Z. D.

2012-12-01

High-pressure serpentinites and rodingites and high- to ultrahigh-pressure metasedimentary rocks from the Aosta region, Italy, preserve strikingly different chlorine isotope compositions that can be used to constrain the nature of fluid-rock interactions during subduction. Serpentinites and rodingitized gabbroic dikes subducted to 70-80 km have bulk δ37Cl values between -1.6 and +0.9‰ (median= -0.5‰, n=26 plus 5 replicates; one amphibole-vein outlier at -2.9‰). Serpentinite δ37Cl values are positively correlated with Cr ± Cl contents (r2= 0.97 and 0.58) and negatively correlated with CaO (r2=0.72). BSE imaging and X-ray mapping reveal up to three generations of compositionally distinct serpentine and chlorite in single samples. The youngest generation, which is most abundant, has the lowest chlorine content. Three rodingite samples contain abundant texturally early fluid inclusions. These samples were finely crushed and leached in 18 MΩ H2O to extract water-soluble chlorides. The leachates, which are assumed to record the compositions of the fluid inclusions, have δ37Cl values that are 0.7-1.5‰ lower than the corresponding bulk rock values. Leachate from the outlier amph-magnesite vein is indistinguishable from the bulk value at -2.7‰. There is almost no overlap between the Cl isotope compositions of HP serp/rod samples and associated HP/UHP metasedimentary rocks. Calcmica schists, diamond-bearing Mn nodules, and impure marbles subducted to >130 km and calcmica schists and Mn crusts transported to 70-80 km have δ37Cl values between -4.5 and -1.5‰ (median= -2.7‰, n=25 plus 7 replicates; two outlier points at -0.5‰). Primary fluid inclusions in the diamondiferous samples contain carbonate- and silicate-bearing aqueous fluids with very low chloride contents (Frezzotti et al., 2011, Nature Geosci). Taken together, these data record a history of progressive modification of serpentinites and rodingites by mixing with low-δ37Cl, low-Cl, high-Ca fluids during subduction and metamorphism. Serpentinites with the highest Cr contents have Cl isotopic compositions identical to those of modern seafloor serpentinites (δ37Cl=0.2-0.6‰), consistent with primary serpentinization by seawater (e.g., Barnes et al. 2009, Lithos). Low-Cr serpentinites record significant interaction with a Ca-rich fluid that shifted the rocks to lower δ37Cl values and diluted the original Cr and Cl contents. The fluid was likely derived from continuous devolatilization reactions in associated low-δ37Cl, calcareous metasedimentary rocks. These data have important implications for models of subduction mass transfer associated with antigorite breakdown. If serpentinites are commonly modified by interaction with metasedimentary fluids prior to antigorite dehydration, chemical signatures imparted during deserpentinization will reflect the integrated history of fluid-rock interaction in the subduction channel rather than an endmember "serpentinite signature". The data further suggest that Cl may be hydrophobic in HP/UHP carbonate-bearing aqueous fluids, resulting in generation of low-Cl fluid during metamorphic devolatilization.

HIGH PRESSURE COAL COMBUSTON KINETICS PROJECT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stefano Orsino

As part of the U.S. Department of Energy (DoE) initiative to improve the efficiency of coal-fired power plants and reduce the pollution generated by these facilities, DOE has funded the High-Pressure Coal Combustion Kinetics (HPCCK) Projects. A series of laboratory experiments were conducted on selected pulverized coals at elevated pressures with the specific goals to provide new data for pressurized coal combustion that will help extend to high pressure and validate models for burnout, pollutant formation, and generate samples of solid combustion products for analyses to fill crucial gaps in knowledge of char morphology and fly ash formation. Two seriesmore » of high-pressure coal combustion experiments were performed using SRI's pressurized radiant coal flow reactor. The first series of tests characterized the near burner flame zone (NBFZ). Three coals were tested, two high volatile bituminous (Pittsburgh No.8 and Illinois No.6), and one sub-bituminous (Powder River Basin), at pressures of 1, 2, and 3 MPa (10, 20, and 30 atm). The second series of experiments, which covered high-pressure burnout (HPBO) conditions, utilized a range of substantially longer combustion residence times to produce char burnout levels from 50% to 100%. The same three coals were tested at 1, 2, and 3 MPa, as well as at 0.2 MPa. Tests were also conducted on Pittsburgh No.8 coal in CO2 entrainment gas at 0.2, 1, and 2 MPa to begin establishing a database of experiments relevant to carbon sequestration techniques. The HPBO test series included use of an impactor-type particle sampler to measure the particle size distribution of fly ash produced under complete burnout conditions. The collected data have been interpreted with the help of CFD and detailed kinetics simulation to extend and validate devolatilization, char combustion and pollutant model at elevated pressure. A global NOX production sub-model has been proposed. The submodel reproduces the performance of the detailed chemical reaction mechanism for the NBFZ tests.« less

Europa's Crust and Ocean: Origin, Composition, and the Prospects for Life

USGS Publications Warehouse

Kargel, J.S.; Kaye, J.Z.; Head, J. W.; Marion, G.M.; Sassen, R.; Crowley, J.K.; Ballesteros, O.P.; Grant, S.A.; Hogenboom, D.L.

2000-01-01

We have considered a wide array of scenarios for Europa's chemical evolution in an attempt to explain the presence of ice and hydrated materials on its surface and to understand the physical and chemical nature of any ocean that may lie below. We postulate that, following formation of the jovian system, the europan evolutionary sequence has as its major links: (a) initial carbonaceous chondrite rock, (b) global primordial aqueous differentiation and formation of an impure primordial hydrous crust, (c) brine evolution and intracrustal differentiation, (d) degassing of Europa's mantle and gas venting, (e) hydrothermal processes, and (f) chemical surface alteration. Our models were developed in the context of constraints provided by Galileo imaging, near infrared reflectance spectroscopy, and gravity and magnetometer data. Low-temperature aqueous differentiation from a carbonaceous CI or CM chondrite precursor, without further chemical processing, would result in a crust/ocean enriched in magnesium sulfate and sodium sulfate, consistent with Galileo spectroscopy. Within the bounds of this simple model, a wide range of possible layered structures may result; the final state depends on the details of intracrustal differentiation. Devolatilization of the rocky mantle and hydrothermal brine reactions could have produced very different ocean/crust compositions, e.g., an ocean/crust of sodium carbonate or sulfuric acid, or a crust containing abundant clathrate hydrates. Realistic chemical-physical evolution scenarios differ greatly in detailed predictions, but they generally call for a highly impure and chemically layered crust. Some of these models could lead also to lateral chemical heterogeneities by diapiric upwellings and/or cryovolcanism. We describe some plausible geological consequences of the physical-chemical structures predicted from these scenarios. These predicted consequences and observed aspects of Europa's geology may serve as a basis for further analys is and discrimination among several alternative scenarios. Most chemical pathways could support viable ecosystems based on analogy with the metabolic and physiological versatility of terrestrial microorganisms. ?? 2000 Academic Press.

Fluid-related inclusions in Alpine high-pressure peridotite reveal trace element recycling during subduction-zone dehydration of serpentinized mantle (Cima di Gagnone, Swiss Alps)

NASA Astrophysics Data System (ADS)

Scambelluri, Marco; Pettke, Thomas; Cannaò, Enrico

2015-11-01

Serpentinites release at sub-arc depths volatiles and several fluid-mobile trace elements found in arc magmas. Constraining element uptake in these rocks and defining the trace element composition of fluids released upon serpentinite dehydration can improve our understanding of mass transfer across subduction zones and to volcanic arcs. The eclogite-facies garnet metaperidotite and chlorite harzburgite bodies embedded in paragneiss of the subduction melange from Cima di Gagnone derive from serpentinized peridotite protoliths and are unique examples of ultramafic rocks that experienced subduction metasomatism and devolatilization. In these rocks, metamorphic olivine and garnet trap polyphase inclusions representing the fluid released during high-pressure breakdown of antigorite and chlorite. Combining major element mapping and laser-ablation ICP-MS bulk inclusion analysis, we characterize the mineral content of polyphase inclusions and quantify the fluid composition. Silicates, Cl-bearing phases, sulphides, carbonates, and oxides document post-entrapment mineral growth in the inclusions starting immediately after fluid entrapment. Compositional data reveal the presence of two different fluid types. The first (type A) records a fluid prominently enriched in fluid-mobile elements, with Cl, Cs, Pb, As, Sb concentrations up to 103 PM (primitive mantle), ∼102 PM Tl, Ba, while Rb, B, Sr, Li, U concentrations are of the order of 101 PM, and alkalis are ∼2 PM. The second fluid (type B) has considerably lower fluid-mobile element enrichments, but its enrichment patterns are comparable to type A fluid. Our data reveal multistage fluid uptake in these peridotite bodies, including selective element enrichment during seafloor alteration, followed by fluid-rock interaction along with subduction metamorphism in the plate interface melange. Here, infiltration of sediment-equilibrated fluid produced significant enrichment of the serpentinites in As, Sb, B, Pb, an enriched trace element pattern that was then transferred to the fluid released at greater depth upon serpentine dehydration (type A fluid). The type B fluid hosted by garnet may record the composition of the chlorite breakdown fluid released at even greater depth. The Gagnone study-case demonstrates that serpentinized peridotites acquire water and fluid-mobile elements during ocean floor hydration and through exchange with sediment-equilibrated fluids in the early subduction stages. Subsequent antigorite devolatilization at subarc depths delivers aqueous fluids to the mantle wedge that can be prominently enriched in sediment-derived components, potentially triggering arc magmatism without the need of concomitant dehydration/melting of metasediments or altered oceanic crust.

Fluidized bed combustion of pelletized biomass and waste-derived fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chirone, R.; Scala, F.; Solimene, R.

2008-10-15

The fluidized bed combustion of three pelletized biogenic fuels (sewage sludge, wood, and straw) has been investigated with a combination of experimental techniques. The fuels have been characterized from the standpoints of patterns and rates of fuel devolatilization and char burnout, extent of attrition and fragmentation, and their relevance to the fuel particle size distribution and the amount and size distribution of primary ash particles. Results highlight differences and similarities among the three fuels tested. The fuels were all characterized by limited primary fragmentation and relatively long devolatilization times, as compared with the time scale of particle dispersion away frommore » the fuel feeding ports in practical FBC. Both features are favorable to effective lateral distribution of volatile matter across the combustor cross section. The three fuels exhibited distinctively different char conversion patterns. The high-ash pelletized sludge burned according to the shrinking core conversion pattern with negligible occurrence of secondary fragmentation. The low-ash pelletized wood burned according to the shrinking particle conversion pattern with extensive occurrence of secondary fragmentation. The medium-ash pelletized straw yielded char particles with a hollow structure, resembling big cenospheres, characterized by a coherent inorganic outer layer strong enough to prevent particle fragmentation. Inert bed particles were permanently attached to the hollow pellets as they were incorporated into ash melts. Carbon elutriation rates were very small for all the fuels tested. For pelletized sludge and straw, this was mostly due to the shielding effect of the coherent ash skeleton. For the wood pellet, carbon attrition was extensive, but was largely counterbalanced by effective afterburning due to the large intrinsic reactivity of attrited char fines. The impact of carbon attrition on combustion efficiency was negligible for all the fuels tested. The size distribution of primary ash particles liberated upon complete carbon burnoff largely reflected the combustion pattern of each fuel. Primary ash particles of size nearly equal to that of the parent fuel were generated upon complete burnoff of the pelletized sludge. Nonetheless, secondary attrition of primary ash from pelletized sludge is large, to the point where generation of fine ash would be extensive over the typical residence time of bed ash in fluidized bed combustors. Very few and relatively fine primary ash particles were released after complete burnoff of wood pellets. Primary ash particles remaining after complete burnoff of pelletized straw had sizes and shapes that were largely controlled by the occurrence of ash agglomeration phenomena. (author)« less

Volatile (Li, B, F and Cl) mobility during amphibole breakdown in subduction zones

NASA Astrophysics Data System (ADS)

Debret, Baptiste; Koga, Kenneth T.; Cattani, Fanny; Nicollet, Christian; Van den Bleeken, Greg; Schwartz, Stephane

2016-02-01

Amphiboles are ubiquitous minerals in the altered oceanic crust. During subduction, their breakdown is governed by continuous reactions up to eclogitic facies conditions. Amphiboles thus contribute to slab-derived fluid throughout prograde metamorphism and continuously record information about volatile exchanges occurring between the slab and the mantle wedge. However, the fate of volatile elements and especially halogens, such as F and Cl, in amphibole during subduction is poorly constrained. We studied metagabbros from three different localities in the Western Alps: the Chenaillet ophiolite, the Queyras Schistes Lustrés and the Monviso meta-ophiolitic complexes. These samples record different metamorphic conditions, from greenschist to eclogite facies, and have interacted with different lithologies (e.g. sedimentary rocks, serpentinites) from their formation at mid-oceanic ridge, up to their devolatilization during subduction. In the oceanic crust, the initial halogen budget is mostly stored in magmatic amphibole (F = 300-7000 ppm; Cl = 20-1200 ppm) or in amphibole corona (F = 100-7000 ppm; Cl = 80-2000 ppm) and titanite (F = 200-1500 ppm; Cl < 200 ppm) formed during hydrothermal seafloor alteration. It is thus the fate of these phases that govern the halogen fluxes between the crust and the overlying mantle and/or the plate interface in subduction zones. Li and B are poorly stored in the oceanic crust (< 5 ppm). In subduction zones, prograde metamorphism of metagabbros is first marked by the crystallization of glaucophane at the expense of magmatic and amphibole coronas. This episode is accompanied with a decrease of halogen concentrations in amphiboles (< 200 ppm of F and Cl) suggesting that these elements can be transferred to the mantle wedge by fluids. In the Queyras Schistes Lustrés complex, the intense deformation and the abundant devolatilization of metasedimentary rocks produce large fluid flows that promote rock chemical hybridization (metasomatic mixing with hybrid composition between metasedimentary rock and metagabbro) at the metasedimentary rock/metagabbro contacts. Such fluid/rock interactions result in a strong addition of Li in glaucophane (up to 600 ppm) whereas halogen concentrations are unaffected. At eclogite facies conditions, metagabbros display low halogens concentrations (< 20 ppm of F and < 100 ppm of Cl) relative to altered oceanic crust (F = 40-650 ppm; Cl = 40-1400 ppm) suggesting that these elements are continuously released by fluids during the first 30-80 km of subduction whatever the tectonic environment (e.g. slab, plate interface) and the considered fluid/rock interactions.

Advanced modeling of nitrogen oxide emissions in circulating fluidized bed combustors: Parametric study of coal combustion and nitrogen compound chemistries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kilpinen, P.; Kallio, S.; Hupa, M.

1999-07-01

This paper describes work-in-progress aimed at developing an emission model for circulating fluidized bed combustors using detailed homogeneous and heterogeneous chemical kinetics. The main emphasis is on nitrogen oxides (NO{sub x}, N{sub 2}O) but also unburned gases (CO, C{sub x}H{sub y}) and sulfur dioxide (SO{sub 2}) will be investigated in the long run. The hydrodynamics is described by a 1.5-dimensional model where the riser is divided into three regions: a dense bubbling bed at the bottom, a vigorously mixed splash zone, and a transport zone. The two latter zones are horizontally split into a core region and an annular region.more » The solids circulation rate is calculated from the known solids inventory and the pressure and mass balances over the entire circulation loop. The solids are divided into classes according to size and type or particle. The model assumes instantaneous fuel devolatilization at the bottom and an even distribution of volatiles in the suspension phase of the dense bed. For addition of secondary air, a complete penetration and an instantaneous mixing with the combustor gases in the core region is assumed. The temperature distribution is assumed to be known, and no energy balance is solved. A comprehensive kinetic scheme of about 300 elementary gas-phase reactions is used to describe the homogeneous oxidation of the volatiles including both hydrocarbon and volatile-nitrogen components (NH{sub 3}, HCN). Heterogeneous char combustion to CO and CO{sub 2}, and char-nitrogen conversion to NO, N{sub 2}O, and N{sub 2} are described by a single particle model that includes 15 reaction steps given in the form of 6 net reaction paths. In the paper, the model is briefly described. A special emphasis is put on the evaluation of chemistry submodels. Modeling results on nitrogen oxides' formation are compared with measured concentration profiles in a 12 MW CFBC riser from literature. The importance of accurate chemistry description on predictions is illustrated by comparing modeling results using detailed kinetics to those obtained when hydrocarbon and volatile-nitrogen oxidation are described with empirical, global kinetic rate expressions from literature. Submodels that need further improvements are discussed.« less

Magmatism significantly alters the thermal structure of the wedge

NASA Astrophysics Data System (ADS)

Rees Jones, D. W.; Katz, R. F.; Rudge, J. F.; Tian, M.

2016-12-01

The temperature structure of the mantle wedge is typically modelled as a balance between thermal diffusion and advection by the solid mantle [e.g., 1]. The thermal state of the wedge promotes melting and melt transport in the natural system, but the thermal consequences of these processes have been neglected from previous models. We show that advective transport of sensible and latent heat by liquid magma can locally alter the temperature structure from canonical models by up to 200K. Liquids are liberated from the subducting slab by de-volatilization reactions. They trigger melting and become silicic en route to the surface, where they cause arc volcanism. These liquids transport heat advectively, and consume or supply latent heat as they melt or freeze. To analyse these effects, we parameterise melting in the presence of volatile species. We combine this with a one-dimensional "melting-column model," previously used to understand mid-ocean ridge volcanism. Our calculations highlight the thermal and chemical response to melt transport across the mantle wedge. Finally, we solve two-dimensional geodynamic models with a prescribed slab flux [2]. These models allow us to identify the most thermally significant fluxes of melt in the system. Perturbations of 200K are found at the base of the overriding lithosphere. This thermal signature of melt migration should be considered when interpreting heat flow, petrologic and seismic data [e.g., 3]. Such a thermal perturbation is likely to affect the chemistry of arc volcanoes, the solid mantle flow and, perhaps, the location of the volcanos themselves [4]. [1] van Keken, P. E., Currie, C., King, S. D., Behn, M. D., Cagnioncle, A., He, J., et al. (2008). A community benchmark for subduction zone modeling. PEPI, doi:10.1016/j.pepi.2008.04.015 [2] Wilson, C. R., Spiegelman, M., van Keken, P. E., & Hacker, B. R. (2014). Fluid flow in subduction zones: The role of solid rheology and compaction pressure. EPSL, doi:10.1016/j.epsl.2014.05.052 [3] Kelemen, P. B., Rilling, J., Parmentier, E., Mehl, L., & Hacker, B. (2004). Thermal structure due to solid-state flow in the mantle wedge beneath arcs. AGU Geophys. Mon. Ser., 138, 293-311 [4] England, P. C., Katz, R. F. (2010). Melting above the anhydrous solidus controls the location of volcanic arcs. Nature, doi:10.1038/nature09417

Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

NASA Astrophysics Data System (ADS)

Halder, S.; Fruehan, R. J.

2008-12-01

A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

Volatile Outputs From Subduction-Related Magmatism in the Oregon Cascades Estimated From Melt Inclusions, Spring Discharges, Heat Flow Data and Geochronology

NASA Astrophysics Data System (ADS)

Wallace, P.; Ruscitto, D.; Rowe, M.; Kent, A.

2008-12-01

Estimates of volatile fluxes provide a primary test for models of magmatism and volatile cycling during subduction in the endmember "hot and dry" Cascadia subduction zone, which is caused by slow convergence (4 cm/a) of the young (~10-12 Ma) Juan de Fuca plate with Western North America. Intra- arc rifting in the Central Oregon segment of the Cascade arc during the past 2 Ma has caused this region to have the highest mafic output along the arc. However, estimates of major volatile (H2O, CO2, S, Cl) fluxes and comparisons with other arcs (e.g. Central America) are not straightforward because there are no passively degassing volcanoes in the area. We estimate volatile outputs for the Central Oregon Cascades by combining data for olivine-hosted melt inclusions with regional heat flow (e.g. Ingebritsen, 1989; Blackwell,1990) and geochronological (Sherrod and Smith, 1990) studies. These flux estimates can be compared with those obtained from spring water studies (e.g. James, 1999; Hurwitz, 2005). This multidisciplinary approach allows us to more accurately constrain volatile fluxes, given that uncertainties in all methods are large and difficult to evaluate. Reported fluxes for Central Oregon springs are 3.4E5 CO2 and 1.5E4 Cl kg/yr/km of arc (James, 1999; Hurwitz, 2005). Melt inclusion data indicate primitive basaltic magmas in the Central Oregon Cascades have 1.0-3.5 wt% H2O, 800-1900 ppm S, and 300-1100 ppm Cl. Assuming global arc magma CO2 contents of ~1 wt% (Wallace, 2005), we estimate H2O/CO2 (1.0-3.5), S/CO2 (0.08-0.19), and Cl/CO2 (0.03-0.11) in magmas, which when combined with spring CO2 estimates, yield an H2O flux of 0.34-1.2E6, a S flux of 2.6-6.5E4, and a Cl flux of 1.0-3.7E4 kg/yr/km of arc. Alternatively, by combining melt inclusion data with magma flux estimates (14-38 km3/Myr/km of arc; Ingebritsen et al. 1989; Sherrod and Smith 1990) we estimate volatile fluxes for H2O: 0.39-5.4E6; S: 0.39-3.9E5; and Cl: 0.16- 2.3E5 kg/yr/km of arc. Given the uncertainties involved, these are highly consistent with the estimates based on spring data. For comparison, Central Oregon S and CO2 fluxes are 6-31% and 13-80%, respectively, of the fluxes estimated for the Central American arc on a kg/yr/km of arc basis (Sadofsky, 2008; Hilton, 1992). Comparison of Central Oregon volatile outputs with slab inputs (Ito, 1983; Hilton, 1992; Jarrard, 2003) suggests low recycling efficiencies via magmatism for H2O (3-26%) and S (1-7%) and more variable recycling efficiencies for CO2 (9-55%) and Cl (9-87%). Low volatile recycling efficiencies via magmatism are consistent with both the high temperatures estimated for the subducted slab beneath the Cascades and the presence of a shallow reservoir for early devolatilized material in the serpentinized forearc mantle wedge. Low but non-zero recycling efficiencies could indicate that 1) slab devolatilization beneath the forearc is incomplete and/or 2) downdragging of the serpentinized forearc mantle by corner flow in the mantle wedge is significant in this hot arc setting.

Modelisation et simulation de pyrolyse de pneus usages dans des reacteurs de laboratoire et industriel

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.

Coal desulfurization by chlorinolysis production and combustion test evaluation of product coals

NASA Technical Reports Server (NTRS)

Kalvinskas, J. J.; Daly, D.

1982-01-01

Laboratory-scale screening tests were carried out on coal from Harrison County, Ohio to establish chlorination and hydrodesulfurization conditions for the batch reactor production of chlorinolysis and chlorinolysis-hydrodesulfurized coals. In addition, three bituminous coals, were treated on the lab scale by the chlorinolysis process to provide 39 to 62% desulfurization. Two bituminous coals and one subbituminous coal were then produced in 11 to 15 pound lots as chlorinolysis and hydrodesulfurized coals. The chlorinolysis coals had a desulfurization of 29-69%, reductions in voltatiles and hydrogen. Hydrodesulfurization provided a much greater desulfurization (56-86%), reductions in volatiles and hydrogen. The three coals were combustion tested in the Penn State ""plane flame furnace'' to determine ignition and burning characteristics. All three coals burned well to completion as: raw coals, chlorinolysis processed coals, and hydrodesulfurized coals. The hydrodesulfurized coals experienced greater ignition delays and reduced burning rates than the other coals because of the reduced volatile content. It is thought that the increased open pore volume in the desulfurized-devolatilized coals compensates in part for the decreased volatiles effect on ignition and burning.

Pyrolysis and oxy-fuel combustion characteristics and kinetics of petrochemical wastewater sludge using thermogravimetric analysis.

PubMed

Chen, Jianbiao; Mu, Lin; Cai, Jingcheng; Yao, Pikai; Song, Xigeng; Yin, Hongchao; Li, Aimin

2015-12-01

The pyrolysis and oxy-fuel combustion characteristics of petrochemical wastewater sludge (PS) were studied in air (O2/N2) and oxy-fuel (O2/CO2) atmospheres using non-isothermal thermogravimetric analysis (TGA). Pyrolysis experiments showed that the weight loss profiles were almost similar up to 1050K in both N2 and CO2 atmospheres, while further weight loss took place in CO2 atmosphere at higher temperatures due to char-CO2 gasification. Compared with 20%O2/80%N2, the drying and devolatilization stage of PS were delayed in 20%O2/80%CO2 due to the differences in properties of the diluting gases. In oxy-fuel combustion experiments, with O2 concentration increasing, characteristic temperatures decreased, while characteristic combustion rates and combustion performance indexes increased. Kinetic analysis of PS decomposition under various atmospheres was performed using Coats-Redfern approach. The results indicated that, with O2 concentration increasing, the activation energies of Step 1 almost kept constant, while the values of subsequent three steps increased. Copyright © 2015 Elsevier Ltd. All rights reserved.

Combined different dehydration pretreatments and torrefaction to upgrade fuel properties of hybrid pennisetum (Pennisetum americanum ×P. purpureum).

PubMed

Yu, Yan; Wang, Guanghui; Bai, Xiaopeng; Liu, Jude; Wang, Decheng; Wang, Zhiqin

2018-05-16

Different dehydrating methods combined with torrefaction were investigated to find the underlying mechanism that how dehydration process influence the degree of hornification. Hybrid pennisetum was selected as the experiment material. Oven-dried sample (ODS), crushed dried sample (CDS), and sun-cured dried sample (SDS) were torrefied under the temperature of 275 °C and 300 °C with the duration time of 60 min. The results showed that, changes in elevated carbon content and higher heating value (HHV) and reduced oxygen content of SDS were the most obvious under identical torrefaction conditions. Fuel ratio of SDS was enhanced most under 300 °C. It also had the highest devolatilization index (D i ). The combination of sun-cured dried with torrefaction under 300 °C caused lowest degree of irreversible hornification happened during dehydrating process, and different hornification degrees caused by different dehydrating methods effect the enhancement of fuel properties of lignocellulosic biomass material. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of biomass pretreatment on upgrading of bio-oil: Comparison of dry and hydrothermal torrefaction.

PubMed

Xu, Xiwei; Tu, Ren; Sun, Yan; Li, Zhiyu; Jiang, Enchen

2018-08-01

The dry and hydrothermal torrefacation of on Camellia Shell (CS) was carried on three different devices- batch autoclave, quartz tube, and auger reactor. The torrefied bio-char products were investigated via TGA, elemental analysis and industrial analysis. Moreover, the pyrolysis and catalytic pyrolysis properties of torrefied bio-char were investigated. The results showed torrefaction significantly influenced the content of hemicellulose in CS. And hydrothermal torrefaction via batch autoclave and dry torrefaction via auger reactors promoted the hemicellulose to strip from the CS. Quartz tube and auger reactor were beneficial for devolatilization and improving heat value of torrefied bio-char. The result showed that the main products were phenols and acids. And hydrothermal torrefaction pretreatment effectively reduced the acids content from 34.5% to 13.2% and enriched the content of phenols (from 27.23% to 60.05%) in bio-oil due to the decreasing of hemicellulos in torrefied bio-char. And the catalyst had slight influence on the bio-oil distribution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pyrolysis of oil palm mesocarp fiber and palm frond in a slow-heating fixed-bed reactor: A comparative study.

PubMed

Kabir, G; Mohd Din, A T; Hameed, B H

2017-10-01

Oil palm mesocarp fiber (OPMF) and palm frond (PF) were respectively devolatilized by pyrolysis to OPMF-oil and PF-oil bio-oils and biochars, OPMF-char and PF-char in a slow-heating fixed-bed reactor. In particular, the OPMF-oil and PF-oil were produced to a maximum yield of 48wt% and 47wt% bio-oils at 550°C and 600°C, respectively. The high heating values (HHVs) of OPMF-oil and PF-oil were respectively found to be 23MJ/kg and 21MJ/kg, whereas 24.84MJ/kg and 24.15MJ/kg were for the corresponding biochar. The HHVs of the bio-oils and biochars are associated with low O/C ratios to be higher than those of the corresponding biomass. The Fourier transform infrared spectra and peak area ratios highlighted the effect of pyrolysis temperatures on the bio-oil compositions. The bio-oils are pervaded with numerous oxygenated carbonyl and aromatic compounds as suitable feedstocks for renewable fuels and chemicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geology and geochemistry of three sedimentary-rock-hosted disseminated gold deposits in Guizhou Province, People's Republic of China

USGS Publications Warehouse

Ashley, R.P.; Cunningham, C.G.; Bostick, N.H.; Dean, W.E.; Chou, I.-Ming

1991-01-01

Five sedimentary-rock-hosted disseminated gold deposits have been discovered since 1980 in southwestern Guizhou Province (PRC). Submicron-sized gold is disseminated in silty carbonate and carbonaceous shale host rocks of Permian and Triassic age. Arsenic, antimony, mercury, and thallium accompany the gold. Associated hydrothermal alteration resulted in decarbonatization of limestone, silicification, and argillization, and depletion of base metals, barium, and many other elements. Organic material occurs in most host rocks and ores. It was apparently devolatilized during a regional heating event that preceded hydrothermal activity, and thus was not mobilized during mineralization, and did not affect gold deposition. The geologic setting of the Guizhou deposits includes many features that are similar to those of sedimentary-rock-hosted deposits of the Great Basin, western United States. The heavy-element suite that accompanies gold is the same, but base metals are even scarcer in the Guizhou deposits than they are in U.S. deposits. The Guizhou deposits discovered to date are smaller than most U.S. deposits and have no known spatially associated igneous rocks. ?? 1991.

Chemistry of Earth's Putative Steam Atmosphere

NASA Astrophysics Data System (ADS)

Fegley, B.; Schaefer, L.

2007-12-01

The concept of a steam atmosphere generated by impact devolatilization of planetesimals accreted during Earth's formation is over 20 years old (Matsui and Abe, 1986; Lange and Ahrens, 1982). Surprisingly, with the possible exception of a few qualitative remarks, no one has critically assessed this scenario. We use thermochemical equilibrium and, where relevant, thermochemical kinetic calculations to model the chemistry of the "steam" atmosphere produced by impact volatilization of different types of accreting material. We present results for our nominal conditions (1500 K, total P = 100 bar). We also studied the effects of variable temperature and total pressure. The composition of the accreting material is modeled using average compositions of the Orgueil CI chondrite, the Murchison CM2 chondrite, the Allende CV3 chondrite, average ordinary (H, L, LL) chondrites, and average enstatite (EH, EL) chondrites. The major gases released from CI and CM chondritic material are H2O, CO2, H2, H2S, CO, CH4, and SO2 in decreasing order of abundance. About 10% of the atmosphere is CO2. The major gases released from CV chondritic material are CO2, H2O, CO, H2, and SO2 in decreasing order of abundance. About 20% of the total atmosphere is steam. The major gases released from average ordinary chondritic material are H2, CO, H2O, CO2, CH4, H2S, and N2 in decreasing order of abundance. The "steam" atmosphere is predominantly H2 + CO with steam being about 10% of the total atmosphere. The major gases released from EH chondritic material are H2, CO, H2O, CO2, N2, and CH4 in decreasing order of abundance. The "steam" atmosphere is predominantly H2 + CO with about 10% of the total atmosphere as steam. This work was supported by the NASA Astrobiology and Origins Programs.

Characterization of solid fuels at pressurized fluidized bed gasification conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zevenhoven, R.; Hupa, M.

1998-07-01

The gasification of co-gasification of solid fuel (coal, peat, wood) in air-blown fluidized bed gasifiers is receiving continued attention as an alternative to entrained flow gasifiers which in general are oxygen-blown. Fluidized bed gasification of wood and wood-waste at elevated pressures, and the so-called air-blown gasification cycle are examples of processes which are under development in Europe. based on complete or partial gasification of a solid fuel in a pressurized fluidized bed. At the same time, fuel characterization data for the combination of temperature, pressure and fuel particle heating rate that is encountered in fluidized bed gasification are very scarce.more » In this paper, quantitative data on the characterization of fuels for advanced combustion and gasification technologies based on fluidized beds are given, as a result from the authors participation in the JOULE 2 extension project on clean coal technology of the European community. Eleven solid fuels, ranging from coal via peat to wood, have been studied under typical fluidized bed gasification conditions: 800--1,000 C, 1--25 bar, fuel heating rate in the order of 100--1,000 C/s. Carbon dioxide was used as gasifying agent. A pressurized thermogravimetric reactor was used for the experiments. The results show that the solid residue yield after pyrolysis/devolatilization increases with pressure and decreases with temperature. For coal, the gasification reactivity of the char increases by a factor of 3 to 4 when pressurizing from 1 to 25 bar, for the younger fuels such as peat and wood, this effect is negligible. Several empirical engineering equations are given which relate the fuel performance to the process parameters and the proximate and chemical analyses of the fuel. A pressure maximum was found at which a maximum gasification reactivity occurs, for practically all fuels, and depending on temperature. It is shown that this can be explained and modeled using a Langmuir-Hinshelwood model.« less

Discriminating fluid source regions in orogenic gold deposits using B-isotopes

NASA Astrophysics Data System (ADS)

Lambert-Smith, James S.; Rocholl, Alexander; Treloar, Peter J.; Lawrence, David M.

2016-12-01

The genesis of orogenic gold deposits is commonly linked to hydrothermal ore fluids derived from metamorphic devolatilization reactions. However, there is considerable debate as to the ultimate source of these fluids and the metals they transport. Tourmaline is a common gangue mineral in orogenic gold deposits. It is stable over a very wide P-T range, demonstrates limited volume diffusion of major and trace elements and is the main host of B in most rock types. We have used texturally resolved B-isotope analysis by secondary ion mass spectrometry (SIMS) to identify multiple fluid sources within a single orogenic gold ore district. The Loulo Mining District in Mali, West Africa hosts several large orogenic gold ore bodies with complex fluid chemistry, associated with widespread pre-ore Na- and multi-stage B-metasomatism. The Gara deposit, as well as several smaller satellites, formed through partial mixing between a dilute aqueous-carbonic fluid and a hypersaline brine. Hydrothermal tourmaline occurs as a pre-ore phase in the matrix of tourmalinite units, which host mineralization in several ore bodies. Clasts of these tourmalinites occur in mineralized breccias. Disseminated hydrothermal and vein hosted tourmaline occur in textural sites which suggest growth during and after ore formation. Tourmalines show a large range in δ11B values from -3.5 to 19.8‰, which record a change in fluid source between paragenetic stages of tourmaline growth. Pre-mineralization tourmaline crystals show heavy δ11B values (8-19.8‰) and high X-site occupancy (Na ± Ca; 0.69-1 apfu) suggesting a marine evaporite source for hydrothermal fluids. Syn-mineralization and replacement phases show lighter δ11B values (-3.5 to 15.1‰) and lower X-site occupancy (0.62-0.88 apfu), suggesting a subsequent influx of more dilute fluids derived from devolatilization of marine carbonates and clastic metasediments. The large, overlapping range in isotopic compositions and a skew toward the opposing population in the δ11B data for both tourmaline groups reflects continual tourmaline growth throughout mineralization, which records the process of fluid mixing. A peak in δ11B values at ∼8‰ largely controlled by tourmalines of syn- to post-ore timing represents a mixture of the two isotopically distinct fluids. This paper demonstrates that B-isotopes in tourmaline can be instrumental in interpreting complex and dynamic hydrothermal systems. The importance of B as an integral constituent of orogenic ore forming fluids and as a gangue phase in orogenic gold deposits makes B-isotope analysis a powerful tool for testing the level of source region variability in these fluids, and by extension, that of metal sources.

Dynamics of fluid expulsion during high-pressure devolatilization of serpentinite in subduction settings: field, petrological and textural constraints from the Almirez ultramafic massif.

NASA Astrophysics Data System (ADS)

Garrido, C. J.; Padrón-Navarta, J. A.; López-Sánchez-Vizcaíno, V.; Gómez-Pugnaire, M. T.; Marchesi, C.; Tommasi, A.

2012-04-01

Our understanding of subduction zone processes is tightly connected to our knowledge of the cycling of volatiles in the Earth, namely the loci of devolatilization reactions and the fluid migration mechanism. The exact nature of fluid pathways at high-pressure conditions is poorly known and still highly speculative. Studies metamorphic terrains that record main dehydration reaction are, thus, an invaluable tool to decipher the mechanism for fluid expulsion. Among other dehydration reactions in subduction zones, the antigorite (Atg) breakdown is rather discontinuous, releases the largest amount of fluids (ca. 9 wt. %) and is considered to have important seismological implications. The antigorite dehydration front in the Cerro del Almirez (Betic Cordillera, Spain) offers, thus, an unique opportunity to investigate the dynamics of fluid expulsion through the study of micro- and macrotextures recorded in the prograde assemblage (chlorite harzburgite). Granoblastic texture are interspersed in decameter-sized domains with spinifex-like chl-harzburgite and were formed under similar P-T conditions (~1.6-1.9 GPa and 680-710°C). We ascribe these textures to shifts of the growth rate due to temporal and spatial fluctuations of the affinity of the Atg-breakdown reaction. These fluctuations are driven by cyclic variations of the excess fluid pressure which are ultimately controlled by the hydrodynamics of deserpentinization fluid expulsion. Crystallization at a low affinity of the reaction, correspondig to the granoblastic texture, may be attained if fluids are slowly drained out from the dehydration front. During the advancement of the dehydration front, overpressured domains are left behind preserving highly metastable Atg-serpentinite domains. Brittle failure results in a sudden drop of the fluid pressure, and a displacement of Atg equilibrium towards the prograde products that crystallizes at a high affinity of the reaction (spinifex-like texture). Evidences of brittle failure are found along grain-size reduction zones (GSRZ), a few mm to meters wide, which form roughly planar conjugate structures and crosscut the metamorphic texture. GSRZ are characterized by (1) sharp, irregular shapes and abrupt terminations contacts with undeformed metaperidotite, (2) an important reduction of the olivine grain size (60-250 µm), and (3) decrease in the opx modal amount. Analysis of olivine crystal-preferred orientations in GSRZ shows similar patterns, but a higher dispersion than in neighboring metaperidotite. These structures are interpreted as due to hydrofracturing allowing for the formation of high permeability channelways for overpressured fluids. This textural bimodality (granofels and Spinifex-like) and the record of brittle failure hence witnesses a unique example of the feedbacks between the cyclic dynamic of metamorphic fluid expulsion, the reaction rate and crystallisation of the Atg-dehydrating system.

The Dos and Don'ts of how to Build a Planet, Using the Moon as an Example

NASA Technical Reports Server (NTRS)

Jones, J. H.

2006-01-01

The bulk chemical compositions of planets may yield important clues concerning planetary origins. Failing that, bulk compositions are still important, in that they constrain calculation of planetary mineralogies and also constrain the petrogenesis of basaltic magmas. In the case of the Earth, there is little or no debate about the composition of the Earth's upper mantle. This is because our sample collections contain peridotitic xenoliths of that mantle. The most fertile of these are believed to have been little modified from their primary compositions. Using these samples and chondritic meteorites as a starting point, small perturbations on the compositions of existing samples allow useful reconstruction of the bulk silicate Earth (BSE). Elsewhere, I have argued that the next simplest case is the Eucrite Parent Body (EPB). Reconstructions based on Sc partitioning indicate that the EPB can be well approximated by a mixture of 20% eucrite and 80% equilibrium olivine. This leads to a parent body that is similar to CO (or devolatilized CM) chondrites. Partial melting experiments on CM chondrites confirm this model, because the residual solids in these experiments are dominated by olivine with minor pigonite [3]. The most difficult bodies to reconstruct are those that have undergone the most differentiation. Both the Moon and Mars may have passed through a magma ocean stage. In any event, lunar and martian basalts, unlike eucrites, were not derived from undifferentiated source regions. Reconstructions are primarily based on compositional trends within the basalts themselves with some critical assumptions: (i) Refractory lithophile elements (Ca, Al, REE, actinides) are presumed to be in chondritic relative abundances; and (ii) some major element ratio is believed to exist in a chondritic ratio (e.g., Mg/Si, Mg/Al). The most commonly used parameter is Mg/Si.

New evidence for long-distance fluid migration within the Earth's crust

NASA Astrophysics Data System (ADS)

Person, M.; Baumgartner, L.

1995-07-01

During the past decade, geologists have come to appreciate the interconnectedness of hydrologic, tectonic, thermal, and geochemical processes operating within the Earth's continental crust [Oliver, 1992]. This has led to a new geologically-based conceptual model of hydrology which is crustal-scale and is centered in plate tectonics theory (Fig. 1). From a geological perspective, the tectonic and thermal processes which drive plate motion are also responsible, either directly or indirectly, for inducing fluid motion across and through the continents. Supporting evidence for this emerging paradigm is based on observations of pervasive rock-water interactions associated with geologic processes as diverse as the chemical alteration of crustal rocks [Shelton et al, 1992; Elliott and Aronson, 1993; McManus and Hanor, 1993; Ague, 1991, 1994], devolatilization of minerals during burial and consequent metamorphism [Cox and Etheridge, 1989], the formation of energy and mineral deposits [Garven et al, 1993; and Cathles et al, 1993], remagnitization of ancient sedimentary rocks [McCabe and Elmore, 1989], the tectonic deformation of sedimentary basins [Oliver 1992, Ge and Garven, 1992], and the regulation of global climate [Caldeira et al, 1993, Kerrick and Caldeira, 1993, 1994]. This paper summarizes the many recent lines of theoretical, laboratory, and field evidence from diverse disciplines within the Earth Sciences supporting this emerging view of crustal-scale hydrology. Evidence for two types of long-distance fluid migration are highlighted: vertical pore water movement through crystalline rocks to depths greater than six km and lateral groundwater movement through sedimentary basins over hundereds of km. Also emphasized are the many driving mechanisms on fluid motion which are not typically considered in water quality and water supply investigations. Some geologic terms used in this paper, which may be unfamiliar to the reader, are defined in geologic dictionaries [American Geologic Institute, 1976].

Novel designs of fluidized bed combustors for low pollutant emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, W.; Bleek, C.M. van den; Dam-Johansen, K.

1995-12-31

It is known that NH{sub 3}, released during the devolatilization of fuel, is an important precursor for NO formation in fluidized bed combustors. On the other hand, NH{sub 3} may be used as a reducing agent in the thermal DeNO{sub x} process to reduce NO{sub x} emission levels. In this paper, a new concept of fluidized bed combustors is proposed based on the idea of in situ reduction of NO{sub x} by self-produced NH{sub 3} from fuel without lowering the sulfur capture level. This design is intended to separate the NH{sub 3} release process under reducing conditions from the charmore » combustion process under oxidizing conditions; this self-released NH{sub 3}, together with some combustibles, is mixed with gaseous combustion products in the upper part of the combustor for a further reduction of the NO{sub x} formed during combustion. Furthermore, the combustion of the combustibles may cause the temperature to rise in this upper zone and thereby reduce the emission of N{sub 2}O. The applications of this design to bubbling and circulating fluidized bed combustors are described and the mechanisms of the main reactions involved discussed.« less

Water inventories on Earth and Mars: Clues to atmosphere formation

NASA Technical Reports Server (NTRS)

Carr, M. H.

1992-01-01

Water is distributed differently on Earth and on Mars and the differences may have implications for the accretion of the two planets and the formation of their atmospheres. The Earth's mantle appears to contain at least several times the water content of the Martian mantle even accounting for differences in plate tectonics. One explanation is that the Earth's surface melted during accretion, as a result of development of a steam atmosphere, thereby allowing impact-devolitalized water at the surface to dissolve into the Earth's interior. In contrast, because of Mars' smaller size and greater distance from the Sun, the Martian surface may not have melted, so that the devolatilized water could not dissolve into the surface. A second possibility is suggested by the siderophile elements in the Earth's mantle, which indicates the Earth acquired a volatile-rich veneer after the core formed. Mars may have acquired a late volatile-rich veneer, but it did not get folded into the interior as with the Earth, but instead remained as a water rich veneer. This perception of Mars with a wet surface but dry interior is consistent with our knowledge of Mars' geologic history.

Oxygen isotope geochemistry of mafic phenocrysts in primitive mafic lavas from the southernmost Cascade Range, California

USGS Publications Warehouse

Underwood, Sandra J.; Clynne, Michael A.

2017-01-01

Previously reported whole-rock δ18O values (5.6–7.8‰) for primitive quaternary mafic lavas from the southernmost Cascades (SMC) are often elevated (up to 1‰) relative to δ18O values expected for mafic magmas in equilibrium with mantle peridotite. Olivine, clinopyroxene, and plagioclase crystals were separated from 29 geochemically well-characterized mafic lavas for δ18O measurements by laser fluorination to assess modification of the mantle sources by ancient and modern subducted components. Oxygen isotope values of olivine phenocrysts in calc-alkaline lavas and contemporaneous high alumina olivine tholeiitic (HAOT) lavas generally exceed depleted mantle olivine values (~4.9–5.3‰). Modern addition of up to 6 wt% slab-derived fluid from Gorda serpentinized peridotite dehydration (~15‰) or chlorite dehydration (~10‰) within the serpentinized peridotite can provide the 18O enrichment detected in olivine phenocrysts (δ18Oolivine = 5.3–6.3‰) in calc-alkaline mafic lavas, and elevate 18O in overlying mantle lithosphere, as well. Specifically, although HAOT δ18Oolivine values (5.5–5.7‰) may reflect partial melting in heterogeneous 18O enriched mantle source domains that developed during multiple subduction events associated with terrane accretion (e.g., <1 wt% of ~15‰ materials), an additional 18O enrichment of up to 2 wt% of 10–15‰ slab-derived hydrous fluids might be accommodated. The calc-alkaline primitive magmas appear to have experienced a continuous range of open system processes, which operate in the mantle and during rapid magma ascent to eruption, and occasionally post quench. Textural relationships and geochemistry of these lava samples are consistent with blends of mafic phenocrysts and degassed melts in varying states of 18O disequilibrium. In lenses of accumulated melt within peridotite near the base of the crust, coexisting olivine and clinopyroxene δ18O values probably are not at isotopic equilibrium because fluids introduced into the system perturbed the δ18Omelt values. A “sudden” melt extraction event interrupts 18O equilibration in phenocrysts and poorly mixed melt(s). Rapid ascent of volatile oversaturated primitive mafic magma through the crust appears to be accompanied by devolatilization and crystallization of anorthite-rich plagioclase with elevated δ18Oplag values. The (Sr/P)N values for the whole rock geochemistry are consistent with a 87Sr/86Sr ~0.7027 slab-derived fluid addition into the infertile peridotite source of magmas, and melt devolatilization is recorded in the mixture of disequilibrium δ18O values for the constituent phases of lavas. Morbidity of the Gorda Plate as it undergoes intense deformation from the spreading ridge to the trench is likely a key factor to developing the carrying capacity of hydrous fluids and mineral phases in the slab subducting into the SMC mantle.

Fluid and mass transfer into the cold mantle wedge of subduction zones: budgets and seismic constraints

NASA Astrophysics Data System (ADS)

Abers, G. A.; Hacker, B. R.; Van Keken, P. E.; Nakajima, J.; Kita, S.

2015-12-01

Dehydration of subducting plates should hydrate the shallow overlying mantle wedge where mantle is cold. In the shallow mantle wedge hydrous phases, notably serpentines, chlorite, brucite and talc should be stable to form a significant reservoir for H2O. Beneath this cold nose thermal models suggest only limited slab dehydration occurs at depths less than ca. 80 km except in warm subduction zones, but fluids may flow updip from deeper within the subducting plate to hydrate the shallow mantle. We estimate the total water storage capacity in cold noses, at temperatures where hydrous phases are stable, to be roughly 2-3% the mass of the global ocean. At modern subduction flux rates its full hydration could be achieved in 50-100 Ma if all subducting water devolatilized in the upper 100 km flows into the wedge; these estimates have at least a factor of two uncertainty. To investigate the extent to which wedge hydration actually occurs we compile and generate seismic images of forearc mantle regions. The compilation includes P- and S-velocity images with good sampling below the Moho and above the downgoing slab in forearcs, from active-source imaging, local earthquake tomography and receiver functions, while avoiding areas of complex tectonics. Well-resolved images exist for Cascadia, Alaska, the Andes, Central America, North Island New Zealand, and Japan. We compare the observed velocities to those predicted from thermal-petrologic models. Among these forearcs, Cascadia stands out as having upper-mantle seismic velocities lower than overriding crust, consistent with high (>50%) hydration. Most other forearcs show Vp close to 8.0 km/s and Vp/Vs of 1.73-1.80. We compare these observations to velocities predicted from thermal-mineralogical models. Velocities are slightly slower than expected for dry peridotite and allow 10-20% hydration, but also could also be explained as relict accreted rock, or delaminated, relaminated, or offscraped crustal material mixed with mantle. The absence of wholesale hydration of forearcs globally can be taken as evidence that most forearcs are too young to be substantially hydrated, that most subducted water bypasses the forearc and is released deeper, or that most fluid passing through the mantle nose does not react with the mantle.

Volatile-bearing phases in carbonaceous chondrites: Compositions, modal abundance, and reaction kinetics

NASA Technical Reports Server (NTRS)

Ganguly, Jibamitra

1990-01-01

The spectral and density characteristics of Phobos and Deimos (the two small natural satellites of Mars) strongly suggest that a significant fraction of the near-earth asteroids are made of carbonaceous chondrites, which are rich in volatile components and, thus, could serve as potential resources for propellants and life supporting systems in future planetary missions. However, in order to develop energy efficient engineering designs for the extraction of volatiles, knowledge of the nature and modal abundance of the minerals in which the volatiles are structurally bound and appropriate kinetic data on the rates of the devolatilization reactions is required. Theoretical calculations to predict the modal abundances and compositions of the major volatile-bearing and other mineral phases that could develop in the bulk compositions of C1 and C2 classes (the most volatile rich classes among the carbonaceous chondrites) were performed as functions of pressure and temperature. The rates of dehydration of talc at 585, 600, 637, and 670 C at P(total) = 1 bar were determine for the reaction: Talc = 3 enstatite + quartz + water. A scanning electron microscopic study was conducted to see if the relative abundance of phases can be determined on the basis of the spectral identification and x ray mapping. The results of this study and the other studies within the project are discussed.

Product distribution from pyrolysis of wood and agricultural residues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di Blasi, C.; Signorelli, G.; Di Russo, C.

1999-06-01

The pyrolysis characteristics of agricultural residues (wheat straw, olive husks, grape residues, and rice husks) and wood chips have been investigated on a bench scale. The experimental system establishes the conditions encountered by a thin (4 {times} 10{sup {minus}2} m diameter) packed bed of biomass particles suddenly exposed in a high-temperature environment, simulated by a radiant furnace. Product yields (gases, liquids, and char) and gas composition, measured for surface bed temperatures in the range 650--1000 K, reproduce trends already observed for wood. However, differences are quantitatively large. Pyrolysis of agricultural residues is always associated with much higher solid yields (upmore » to a factor of 2) and lower liquid yields. Differences are lower for the total gas, and approximate relationships exist among the ratios of the main gas species yields, indicating comparable activation energies for the corresponding apparent kinetics of formation. However, while the ratios are about the same for wood chips, rice husks, and straw, much lower values are shown by olive and grape residues. Large differences have also been found in the average values of the specific devolatilization rates. The fastest (up to factors of about 1.5 with respect to wood) have been observed for wheat straw and the slowest (up to factors of 2) for grape residues.« less

Formaldehyde and acetaldehyde emissions from residential wood combustion in Portugal

NASA Astrophysics Data System (ADS)

Cerqueira, Mário; Gomes, Luís; Tarelho, Luís; Pio, Casimiro

2013-06-01

A series of experiments were conducted to characterize formaldehyde and acetaldehyde emissions from residential combustion of common wood species growing in Portugal. Five types of wood were investigated: maritime pine (Pinus pinaster), eucalyptus (Eucalyptus globulus), cork oak (Quercus suber), holm oak (Quercus rotundifolia) and pyrenean oak (Quercus pyrenaica). Laboratory experiments were performed with a typical wood stove used for domestic heating in Portugal and operating under realistic home conditions. Aldehydes were sampled from diluted combustion flue gas using silica cartridges coated with 2,4-dinitrophenylhydrazine and analyzed by high performance liquid chromatography with diode array detection. The average formaldehyde to acetaldehyde concentration ratio (molar basis) in the stove flue gas was in the range of 2.1-2.9. Among the tested wood types, pyrenean oak produced the highest emissions for both formaldehyde and acetaldehyde: 1772 ± 649 and 1110 ± 454 mg kg-1 biomass burned (dry basis), respectively. By contrast, maritime pine produced the lowest emissions: 653 ± 151 and 371 ± 162 mg kg-1 biomass (dry basis) burned, respectively. Aldehydes were sampled separately during distinct periods of the holm oak wood combustion cycles. Significant variations in the flue gas concentrations were found, with higher values measured during the devolatilization stage than in the flaming and smoldering stages.

Integrated mild gasification processing at the Homer City Electric Power Generating Station site. Final report, July 1989--June 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Battista, J.J.; Zawadzki, E.A.

1993-07-01

A new process for the production of commercial grade coke, char, and carbon products has been evaluated by Penelec/NYSEG. The process, developed by Coal Technology Corporation, CTC, utilizes a unique screw reactor to produce a devolatilized char from a wide variety of coals for the production of commercial grade coke for use in blast furnaces, foundries, and other processes requiring high quality coke. This process is called the CTC Mild Gasification Process (MGP). The process economics are significantly enhanced by integrating the new technology into an existing power generating complex. Cost savings are realized by the coke producer, the cokemore » user, and the electric utility company. Site specific economic studies involving the Homer City Generating Station site in Western Pennsylvania, confirmed that an integrated MGP at the Homer City site, using coal fines produced at the Homer City Coal Preparation Plant, would reduce capital and operating costs significantly and would enable the HC Owners to eliminate thermal dryers, obtain low cost fuel in the form of combustible gases and liquids, and obtain lower cost replacement coal on the spot market. A previous report, identified as the Interim Report on the Project, details the technical and economic studies.« less

Temperature influence on the fast pyrolysis of manure samples: char, bio-oil and gases production

NASA Astrophysics Data System (ADS)

Fernandez-Lopez, Maria; Anastasakis, Kostas; De Jong, Wiebren; Valverde, Jose Luis; Sanchez-Silva, Luz

2017-11-01

Fast pyrolysis characterization of three dry manure samples was studied using a pyrolyzer. A heating rate of 600°C/s and a holding time of 10 s were selected to reproduce industrial conditions. The effect of the peak pyrolysis temperature (600, 800 and 1000°C) on the pyrolysis product yield and composition was evaluated. Char and bio-oil were gravimetrically quantified. Scanning electron microscopy (SEM) was used to analyse the char structure. H2, CH4, CO and CO2 were measured by means of gas chromatography (GC). A decrease in the char yield and an increase of the gas yield were observed when temperature increased. From 800°C on, it was observed that the char yield of samples Dig R and SW were constant, which indicated that the primary devolatilization reactions stopped. This fact was also corroborated by GC analysis. The bio-oil yield slightly increased with temperature, showing a maximum of 20.7 and 27.8 wt.% for samples Pre and SW, respectively, whereas sample Dig R showed a maximum yield of 16.5 wt.% at 800°C. CO2 and CO were the main released gases whereas H2 and CH4 production increased with temperature. Finally, an increase of char porosity was observed with temperature.

DESIGNING AN OPPORTUNITY FUEL WITH BIOMASS AND TIRE-DERIVED FUEL FOR COFIRING AT WILLOW ISLAND GENERATING STATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Payette; D. Tillman

During the period January 1, 2001-March 31, 2001, Allegheny Energy Supply Co., LLC (Allegheny) finalized the engineering of the Willow Island cofiring project, completed the fuel characterizations for both the Willow Island and Albright Generating Station projects, and initiated construction of both projects. Allegheny and its contractor, Foster Wheeler, selected appropriate fuel blends and issued purchase orders for all processing and mechanical equipment to be installed at both sites. This report summarizes the activities associated with the Designer Opportunity Fuel program, and demonstrations at Willow Island and Albright Generating Stations. The third quarter of the project involved completing the detailedmore » designs for the Willow Island Designer Fuel project. It also included complete characterization of the coal and biomass fuels being burned, focusing upon the following characteristics: proximate and ultimate analysis; higher heating value; carbon 13 nuclear magnetic resonance testing for aromaticity, number of aromatic carbons per cluster, and the structural characteristics of oxygen in the fuel; drop tube reactor testing for high temperature devolatilization kinetics and generation of fuel chars; thermogravimetric analyses (TGA) for char oxidation kinetics; and related testing. The construction at both sites commenced during this quarter, and was largely completed at the Albright Generating Station site.« less

Understanding Sulfur Systematics in Large Igneous Provinces Using Sulfur Isotopes

NASA Astrophysics Data System (ADS)

Novikova, S.; Edmonds, M.; Turchyn, A. V.; Maclennan, J.; Svensen, H.; Frost, D. J.; Yallup, C.

2013-12-01

The eruption of the Siberian Traps coincided with perhaps the greatest environmental catastrophe in Earth's history, at the Permo-Triassic boundary. The source and magnitude of the volatile emissions, including sulfur, associated with the eruption remain poorly understood yet were critical in forcing environmental change. Two of the primary questions are how much sulfur gases were emitted during the eruptions and from where they were sourced. Primary melts carry dissolved sulfur from the mantle. Magmas ponding in sills and ascending through dykes may also assimilate sulfur from country rocks, as well as heat the country rocks and generate fluids through contact metamorphism. If the magmas interacted thermally, for prolonged periods, with sulfur-rich country rocks then it is probable that the sulfur budget of these eruptions might have been augmented considerably. This is exactly what we have shown recently for a basaltic sill emplaced in oil shale that fed eruptions of the British Tertiary Province, where surrounding sediments showed extensive desulfurization (Yallup et al. Geoch. Cosmochim. Acta, online, 2013). In the current study sulfur isotopes and trace element abundances are used to discriminate sulfur sources and to model magmatic processes for a suite of Siberian Traps sill and lava samples. Our bulk rock and pyrite geochemical analyses illustrate clearly their high abundance of 34S over 32S. The high 34S/32S has been noted previously and linked to assimilation of sulfur from sediments but may alternatively be inherited from the mantle plume source. With the aim of investigating the sulfur isotopic signature in the melt prior to devolatilization, we use secondary ion mass spectrometry (SIMS), for which a specific set of glass standards was synthesised. In order to understand how sulfur isotopes fractionate during degassing we have also conducted a parallel study of well-characterized tephras from Kilauea Volcano, where sulfur degassing behavior is well known.

The elemental abundances (with uncertainties) of the most Earth-like planet

NASA Astrophysics Data System (ADS)

Wang, Haiyang S.; Lineweaver, Charles H.; Ireland, Trevor R.

2018-01-01

To first order, the Earth as well as other rocky planets in the Solar System and rocky exoplanets orbiting other stars, are refractory pieces of the stellar nebula out of which they formed. To estimate the chemical composition of rocky exoplanets based on their stellar hosts' elemental abundances, we need a better understanding of the devolatilization that produced the Earth. To quantify the chemical relationships between the Earth, the Sun and other bodies in the Solar System, the elemental abundances of the bulk Earth are required. The key to comparing Earth's composition with those of other objects is to have a determination of the bulk composition with an appropriate estimate of uncertainties. Here we present concordance estimates (with uncertainties) of the elemental abundances of the bulk Earth, which can be used in such studies. First we compile, combine and renormalize a large set of heterogeneous literature values of the primitive mantle (PM) and of the core. We then integrate standard radial density profiles of the Earth and renormalize them to the current best estimate for the mass of the Earth. Using estimates of the uncertainties in i) the density profiles, ii) the core-mantle boundary and iii) the inner core boundary, we employ standard error propagation to obtain a core mass fraction of 32.5 ± 0.3 wt%. Our bulk Earth abundances are the weighted sum of our concordance core abundances and concordance PM abundances. Unlike previous efforts, the uncertainty on the core mass fraction is propagated to the uncertainties on the bulk Earth elemental abundances. Our concordance estimates for the abundances of Mg, Sn, Br, B, Cd and Be are significantly lower than previous estimates of the bulk Earth. Our concordance estimates for the abundances of Na, K, Cl, Zn, Sr, F, Ga, Rb, Nb, Gd, Ta, He, Ar, and Kr are significantly higher. The uncertainties on our elemental abundances usefully calibrate the unresolved discrepancies between standard Earth models under various geochemical and geophysical assumptions.

Chondritic Mn/Na ratio and limited post-nebular volatile loss of the Earth

NASA Astrophysics Data System (ADS)

Siebert, Julien; Sossi, Paolo A.; Blanchard, Ingrid; Mahan, Brandon; Badro, James; Moynier, Frédéric

2018-03-01

The depletion pattern of volatile elements on Earth and other differentiated terrestrial bodies provides a unique insight as to the nature and origin of planetary building blocks. The processes responsible for the depletion of volatile elements range from the early incomplete condensation in the solar nebula to the late de-volatilization induced by heating and impacting during planetary accretion after the dispersion of the H2-rich nebular gas. Furthermore, as many volatile elements are also siderophile (metal-loving), it is often difficult to deconvolve the effect of volatility from core formation. With the notable exception of the Earth, all the differentiated terrestrial bodies for which we have samples have non-chondritic Mn/Na ratios, taken as a signature of post-nebular volatilization. The bulk silicate Earth (BSE) is unique in that its Mn/Na ratio is chondritic, which points to a nebular origin for the depletion; unless the Mn/Na in the BSE is not that of the bulk Earth (BE), and has been affected by core formation through the partitioning of Mn in Earth's core. Here we quantify the metal-silicate partitioning behavior of Mn at deep magma ocean pressure and temperature conditions directly applicable to core formation. The experiments show that Mn becomes more siderophile with increasing pressure and temperature. Modeling the partitioning of Mn during core formation by combining our results with previous data at lower P-T conditions, we show that the core likely contains a significant fraction (20 to 35%) of Earth's Mn budget. However, we show that the derived Mn/Na value of the bulk Earth still lies on the volatile-depleted end of a trend defined by chondritic meteorites in a Mn/Na vs Mn/Mg plot, which tend to higher Mn/Na with increasing volatile depletion. This suggests that the material that formed the Earth recorded similar chemical fractionation processes for moderately volatile elements as chondrites in the solar nebula, and experienced limited post nebular volatilization.

Textural Variations during Antigorite Dehydration as Markers for Fluid Release Mechanisms in Subduction Zones: Constrains from the Cerro del Almirez Ultramafic Massif (Betic Cordillera, SE Spain)

NASA Astrophysics Data System (ADS)

Dilissen, N. M.; Garrido, C. J.; Lopez Sanchez-Vizcaino, V.; Jabaloy-Sánchez, A.; Padrón-Navarta, J. A.

2015-12-01

Subduction zones are dynamic convergent plate boundaries associated with arc volcanism and earthquakes, which are believed to be controlled by fluids released during devolatilization reactions from the downgoing slab. The high-pressure breakdown of antigorite serpentinite to prograde chlorite-harzburgite is considered to be the most significant source of water in subduction zones. The Cerro del Almirez ultramafic massif (Betic Cordillera, SE Spain) is a unique exhumed subduction terrane that preserves this dehydration reaction as a sharp front. Chl-harzburgite in this massif displays two differentiated textures-granofels and spinifex-like- indicating that antigorite breakdown occurred at different overstepping of the dehydration reaction. Detailed mapping of textural variations in chl-harzburgite unveils a network of granofels and spinifex-like lenses. These lenses have triaxial ellipsoid shapes with average axial ratios of 16:7:1 and 19:8:1, respectively, with the shorter axis nearly perpendicular to the serpentine-out isograd, and the longest axis ranging from 23 to 190 meters. We calculated the volume of water release per lens using the modal amount of olivine according to the model reaction 1Atg = 4Clin + 6Fo + 6En + 15H2O. The growth time and water flux per lens was computed using experimental olivine growth rates for granular and dendritic, spinifex-like olivine. Preliminary results show that formation of spinifex and granofels lenses imply temporal variations of the volumetric water fluxes ranging from 0.12 to 0.02 m3m-2yr-1, respectively. If the time of formation of lenses is inversely proportional to its relative distance to the dehydration front, the 52m thick, chl-harzburgite lens network in Almirez records ca. 315 yrs of antigorite dehydration. Our results show that antigorite dehydration in subduction zones occurs in a highly non-steady regime with yearly to decadal variations of water fluxes that record variations in the dynamics of slab and fluid expulsion mechanisms.

Physical conditions on the early Earth

PubMed Central

Lunine, Jonathan I

2006-01-01

The formation of the Earth as a planet was a large stochastic process in which the rapid assembly of asteroidal-to-Mars-sized bodies was followed by a more extended period of growth through collisions of these objects, facilitated by the gravitational perturbations associated with Jupiter. The Earth's inventory of water and organic molecules may have come from diverse sources, not more than 10% roughly from comets, the rest from asteroidal precursors to chondritic bodies and possibly objects near Earth's orbit for which no representative class of meteorites exists today in laboratory collections. The final assembly of the Earth included a catastrophic impact with a Mars-sized body, ejecting mantle and crustal material to form the Moon, and also devolatilizing part of the Earth. A magma ocean and steam atmosphere (possibly with silica vapour) existed briefly in this period, but terrestrial surface waters were below the critical point within 100 million years after Earth's formation, and liquid water existed continuously on the surface within a few hundred million years. Organic material delivered by comets and asteroids would have survived, in part, this violent early period, but frequent impacts of remaining debris probably prevented the continuous habitability of the Earth for one to several hundred million years. Planetary analogues to or records of this early time when life began include Io (heat flow), Titan (organic chemistry) and Venus (remnant early granites). PMID:17008213

Carbon isotope geochemistry of graphite vein deposits from New Hampshire, U.S.A.

NASA Astrophysics Data System (ADS)

Rumble, Douglas, III; Hoering, Thomas C.

1986-06-01

Graphite veins of hydrothermal origin occur throughout central New Hampshire. Veins truncate sillimanite-grade, metasedimentary rocks of Early Devonian-Silurian age and range in size from microscopic to meters in thickness. In addition to graphite, veins may contain quartz, tourmaline, ilmenite, rutile, sillimanite, muscovite or chlorite. Vein mineralogy is generally compatible with wall rock mineral assemblages. Mineralization structures include wall-rock alteration zones, coxcomb graphite crystals on vein walls, and botryoidal, concentrically layered graphite-silicate nodules. The δ13C values of graphite in 14 deposits studied range from - 28%. (PDB) to - 9%. Veins whose textures give evidence of a single stage of mineralization have a narrow range of δ13C values (± 0.2%.). Other veins record successive episodes of graphite precipitation and have ranges of 3-6%. In one sample, adjacent layers of graphite differ by 3%. The wide range of δ13C may be explained by mixing carbon from two crustal reservoirs: biogenic, reduced carbon and carbonate. Precipitation of graphite results from mixing two or more aqueous fluids with different CO 2/CH 4 ratios. Parental fluids are produced by devolatilization during metamorphism. Water-rich fluids with CH4 > CO2 and low δ13C are derived from pelites that contained organic matter; whereas fluids with CO2 > CH4 and high δ13C come from siliceous carbonates.

Effects of igneous intrusion on microporosity and gas adsorption capacity of coals in the Haizi Mine, China.

PubMed

Jiang, Jingyu; Cheng, Yuanping

2014-01-01

This paper describes the effects of igneous intrusions on pore structure and adsorption capacity of the Permian coals in the Huaibei Coalfield, China. Twelve coal samples were obtained at different distances from a ~120 m extremely thick sill. Comparisons were made between unaltered and heat-affected coals using geochemical data, pore-fracture characteristics, and adsorption properties. Thermal alteration occurs down to ~1.3 × sill thickness. Approaching the sill, the vitrinite reflectance (R(o)) increased from 2.30% to 2.78%, forming devolatilization vacuoles and a fine mosaic texture. Volatile matter (VM) decreased from 17.6% to 10.0% and the moisture decreased from 3.0% to 1.6%. With decreasing distance to the sill, the micropore volumes initially increased from 0.0054 cm(3)/g to a maximum of 0.0146 cm(3)/g and then decreased to 0.0079 cm(3)/g. The results show that the thermal evolution of the sill obviously changed the coal geochemistry and increased the micropore volume and adsorption capacity of heat-affected coal (60-160 m from the sill) compared with the unaltered coals. The trap effect of the sill prevented the high-pressure gas from being released, forming gas pocket. Mining activities near the sill created a low pressure zone leading to the rapid accumulation of methane and gas outbursts in the Haizi Mine.

Combustion and Gasification Properties of Plastics Particles.

PubMed

Zevenhoven, Ron; Karlsson, Magnus; Hupa, Mikko; Frankenhaeuser, Martin

1997-08-01

The combustion and gasification behavior of the most common plastics is studied and compared with conventional fuels such as coal, peat, and wood. The aim is to give background data for finding the optimum conditions for co-combustion or co-gasification of a conventional fuel with a certain amount of plastic-derived fuel. Atmospheric or pressurized fluidized bed co-combustion of conventional fuels and plastics are considered to be promising future options. The plastics investigated were poly(ethylene) (PE), poly(propylene) (PP), poly(styrene) (PS), and poly(vinyl chloride) (PVC). Some of the samples had a print or color. The reference fuels were Polish bituminous coal, Finnish peat, and Finnish pine wood. PE, PP, and PS were found to burn like oil. The particles shrank to a droplet and burned completely during the pyrolysis stage, leaving no char. Printing and coloring left a small portion of ash. PVC was the only plastic that produced a carbonaceous residue, and its timescales for heating, devolatilization, and char burning were of the same order as those for peat and wood, and much shorter for the other plastics studied. An important result is that char from PVC contains less than 1% chlorine,99% hydrocarbon. The gasification rate of PVC char (at 1 bar and 25 bar) was of the same order as that of char from coal. Peat-char and wood-char were gasified an order of magnitude faster.

Physical conditions on the early Earth.

PubMed

Lunine, Jonathan I

2006-10-29

The formation of the Earth as a planet was a large stochastic process in which the rapid assembly of asteroidal-to-Mars-sized bodies was followed by a more extended period of growth through collisions of these objects, facilitated by the gravitational perturbations associated with Jupiter. The Earth's inventory of water and organic molecules may have come from diverse sources, not more than 10% roughly from comets, the rest from asteroidal precursors to chondritic bodies and possibly objects near Earth's orbit for which no representative class of meteorites exists today in laboratory collections. The final assembly of the Earth included a catastrophic impact with a Mars-sized body, ejecting mantle and crustal material to form the Moon, and also devolatilizing part of the Earth. A magma ocean and steam atmosphere (possibly with silica vapour) existed briefly in this period, but terrestrial surface waters were below the critical point within 100 million years after Earth's formation, and liquid water existed continuously on the surface within a few hundred million years. Organic material delivered by comets and asteroids would have survived, in part, this violent early period, but frequent impacts of remaining debris probably prevented the continuous habitability of the Earth for one to several hundred million years. Planetary analogues to or records of this early time when life began include Io (heat flow), Titan (organic chemistry) and Venus (remnant early granites).

Magmatic volatiles and the weathering of Mars

NASA Technical Reports Server (NTRS)

Clark, B. C.

1993-01-01

The sources for volatiles on Mars have been the subject of many hypotheses for exogenous influences including late accretion of volatile-enriched material, impact devolatilization to create massive early atmospheres, and even major bombardment by comets. However, the inventory of chemically active volatiles observable at the contemporary surface of Mars is consistent with domination by endogenous, subsequent planetary processes, viz., persistent magmatic outgassing. Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the geochemical similarities are such that the suite of gases emitted from Martian volcanic activity should include H2O, CO2, S-containing gases (e.g. H2S and/or SO2), and Cl-containing gases (e.g., Cl2 and/or HCl). H2O and CO2 exist in the atmosphere of Mars. Both are also present as surface condensates. However, spectroscopic observations of the Martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted, with upper limits of less than or equal to 10(exp -7) the abundance of CO2. Likewise, there is no evidence of polar condensates of compounds of these elements as there is for CO2 and H2O. Within the soil, on the other hand, there has been direct measurement of incorporated H2O and abundant compounds containing S and Cl. Barring some as yet implausible geochemical sequestering process, the S/Cl ratio of about 6:1 in Martian soils implies a limit of 5% on the contribution of matter of solarlike composition (e.g., carbonaceous chondrite or cometary material) to these volatiles. Hence, exogenous sources are minor or not yet observed. From analysis of elemental trends in Martian soils, it has been recently shown that a simple two-component model can satisfy the Viking in situ measurements. Component A includes Si and most or all the Al, Ca, Ti, and Fe. Component B, taken as 16 +/- 3% by weight of the total, contains S and most or all the Cl and Mg. These results constrain several models of Martian soil mineralogy but are consistent with a mixture of silicates (such as Fe-rich clays and accessory minerals and soluble salts). The overall element profile is notably like shergottites, with significant incorporation of chemically reactive atmospheric gases from magmatic degassing.

Properties and processing characteristics of low density carbon cloth phenolic composites

NASA Technical Reports Server (NTRS)

Wang, C. Jeff

1993-01-01

Ply-lift and pocketing are two critical anomalies of carbon cloth phenolic composites (CCPC) in rocket nozzle applications. Ply lift occurs at low temperatures when the A/P and in-plane permeabilities of the composite materials are still very low and in-plane porous paths are blocked. Pocketing occurs at elevated temperatures when in-plane permeability is reduced by the A/P compressive stress. The thermostructural response of CCPC in a rapid heating environment involves simultaneous heat, mass, and momentum transfer along with the degradation of phenolic resin in a multiphase system with temperature- and time-dependent material properties as well as dynamic processing conditions. Three temperature regions represent the consequent chemical reactions, material transformations, and property transitions, and provide a quick qualitative method for characterizing the thermostructural behavior of a CCPC. In order to optimize the FM5939 LDCCP (low density carbon cloth phenolic) for the nozzle performance required in the Advanced Solid Rocket Motor (ASRM) program, a fundamental study on LDCCP materials was conducted. The cured composite has a density of 1.0 +/- 0.5 gm/cc which includes 10 to 25 percent void volume. The weight percent of carbon microballoon is low (7-15 percent). However, they account for approximately one third of the volume and historically their percentages have not been controlled very tightly. In addition, the composite properties show no correlation with microballoon weight percent or fiber properties (e.g. fiber density or fiber moisture adsorption capacity). Test results concerning the ply-lift anomaly in the MNASA motor firings were: (1) Steeper ply angle (shorter path lenght) designs minimized/eliminated by lifting, (2) material with higher void volume ply lifted less frequently, (3) materials with high (greater than 9 percent) microballoon content had a higher rate of ply lifting, and (4) LDCCP materials failed at microballoon-resin interfaces. The objectives of this project are: (1) to investigate the effects of carbon microballoon and cabosil fillers as well as fiber heat treatment on plylift-related mechanical properties, (2) to develop a science-based thermostructural process model for the carbon phenolics. The model can be used in the future for the selection of the improved ASRM materials, (3) to develop the micro-failure mechanisms for the ply-lift initiation and propagation processes during the thermoelastic region of phenolic degradation, i.e. postcuring and devolatilization.

The late cretaceous Donlin Creek gold deposit, Southwestern Alaska: Controls on epizonal ore formation

USGS Publications Warehouse

Goldfarb, R.J.; Ayuso, R.; Miller, M.L.; Ebert, S.W.; Marsh, E.E.; Petsel, S.A.; Miller, L.D.; Bradley, D.; Johnson, Chad; McClelland, W.

2004-01-01

The Donlin Creek gold deposit, southwestern Alaska, has an indicated and inferred resource of approximately 25 million ounces (Moz) Au at a cutoff grade of 1.5 g/t. The ca. 70 Ma deposit is hosted in the Late Cretaceous Kuskokwim flysch basin, which developed in the back part of the are region of an active continental margin, on previously accreted oceanic terranes and continental fragments. A hypabyssal, mainly rhyolitic to rhyodacitic, and commonly porphyritic, 8- ?? 3-km dike complex, part of a regional ca. 77 to 58 Ma magmatic arc, formed a structurally competent host for the mineralization. This deposit is subdivided into about one dozen distinct prospects, most of which consist of dense quartz ?? carbonate veinlet networks that fill north-northeast-striking extensional fractures in the northeast-trending igneous rocks. The sulfide mineral assemblage is dominated by arsenopyrite, pyrite, and, typically younger, stibnite; gold is refractory within the arsenopyrite. Sericitization, carbonatization, and suffidation were the main alteration processes. Fluid inclusion studies of the quartz that hosts the resource indicate dominantly aqueous ore fluids with also about 3 to 7 mol percent CO2 ?? CH4 and a few tenths to a few mole percent NaCl + KCl. The gold-bearing fluids were mainly homogeneously trapped at approximately 275?? to 300??C and at depths of 1 to 2 km. Some of the younger stibnite may have been deposited by late-stage aqueous fluids at lower temperature. Measured ??18O values for the gold-bearing quartz range between 11 and 25 per mil; the estimated ??18O fluid values range from 7 to 12 per mil, suggesting a mainly crustally derived fluid. A broad range of measured ??D values for hydrothermal micas, between -150 and -80 per mil, is suggestive of a contribution from devolatilization of organic matter and/or minor amounts of mixing with meteoric fluids. Gold-associated hydrothermal sulfide minerals are characterized by ??34S values mainly between -16 and -10 per mil, with the sulfur derived from diagenetic pyrite and organic matter within ihe flysch basin. A smaller group of ??34S measurements, which shows values as depleted as -27 per mil, suggests a different local sulfur reservoir in the basin for the later hydrothermal episode dominated by stibnite. Initial ENd of -8.7 to -3.1 and 87Sr/86Sr measurements of 0.706 to 0.709 for the ore-hosting dikes also indicate a crustal reservoir for some of the Late Cretaceous magmatism. Overlapping lead isotope data for these intrusive rocks and for sulfide minerals suggest a crustal contribution for the lead in both. Copper- and gold-bearing stockwork veinlets in hornfels occur at Dome, a prospect located at the northern end of the Donlin Creek deposit. These stockworks are cut by the younger auriferous gold veins that define the main Donlin Creek gold mineralization. Highly saline, gas-rich, heterogeneously trapped fluids deposited the stockworks at temperatures approximately 100??C hotter than those of the main gold-forming event at Donlin Creek. The genetic relationship of the Dome prospect to the main Donlin Creek gold resource is equivocal. The epizonal Donlin Creek deposit shows affinities to the gold systems interpreted by various workers as orogenic or intrusion related; it shows important differences from typical epithermal and Carlin-like deposits. The ore-forming fluids were derived by either broad-scale metamorphic devolatilization above rising mantle melts or exsolution from a magma that was dominated by a significant flysch melt component. ??2004 by Economic Geology.

CO in Distantly Active Comets

NASA Astrophysics Data System (ADS)

Womack, M.; Sarid, G.; Wierzchos, K.

2017-03-01

The activity of most comets near the Sun is dominated by the sublimation of frozen water, the most abundant ice in comets. Some comets, however, are active well beyond the water-ice sublimation limit of ˜3 au. Three bodies dominate the observational record and modeling efforts for distantly active comets: the long-period comet C/1995 O1 (Hale-Bopp), and the short-period comets (with Centaur orbits) 29P/Schwassmann-Wachmann 1 and 2060 Chiron. We summarize what is known about these three objects with an emphasis on their gaseous comae. We calculate their CN/CO and CO2/CO production rate ratios from the literature and discuss implications, such as HCN and CO2 outgassing are not significant contributors to their comae. Using our own data we derive CO production rates, Q(CO), for all three objects to examine whether there is a correlation between gas production and different orbital histories and/or size. The CO measurements of Hale-Bopp (4-11 AU) and 29P are consistent with a nominal production rate of Q(CO) = 3.5 × 1029 r-2 superimposed with sporadic outbursts. The similarity of Hale-Bopp CO production rates for pre- and post-perihelion suggests that thermal inertia was not very important and therefore most of the activity is at or near the surface of the comet. We further examine the applicability of existing models in explaining the systematic behavior of our small sample. We find that orbital history does not appear to play a significant role in explaining 29P’s CO production rates. 29P outproduces Hale-Bopp at the same heliocentric distance, even though it has been subjected to much more solar heating. Previous modeling work on such objects predicts that 29P should have been devolatilized over a fresher comet like Hale-Bopp. This may point to 29P having a different orbital history than current models predict, with its current orbit acquired more recently. On the other hand, Chiron’s CO measurements are consistent with it being significantly depleted over its original state, perhaps due to increased radiogenic heating made possible by its much larger size or its higher processing due to orbital history. Observed spectral line profiles for several volatiles are consistent with the development and sublimation of icy grains in the coma at about 5-6 au for 29P and Hale-Bopp, and this is probably a common feature in distantly active comets, and an important source of volatiles for all comets within 5 au. In contrast, the narrow CO line profiles indicate a nuclear, and not extended, origin for CO beyond ˜4 au.

Effects of Igneous Intrusion on Microporosity and Gas Adsorption Capacity of Coals in the Haizi Mine, China

PubMed Central

2014-01-01

This paper describes the effects of igneous intrusions on pore structure and adsorption capacity of the Permian coals in the Huaibei Coalfield, China. Twelve coal samples were obtained at different distances from a ~120 m extremely thick sill. Comparisons were made between unaltered and heat-affected coals using geochemical data, pore-fracture characteristics, and adsorption properties. Thermal alteration occurs down to ~1.3 × sill thickness. Approaching the sill, the vitrinite reflectance (R o) increased from 2.30% to 2.78%, forming devolatilization vacuoles and a fine mosaic texture. Volatile matter (VM) decreased from 17.6% to 10.0% and the moisture decreased from 3.0% to 1.6%. With decreasing distance to the sill, the micropore volumes initially increased from 0.0054 cm3/g to a maximum of 0.0146 cm3/g and then decreased to 0.0079 cm3/g. The results show that the thermal evolution of the sill obviously changed the coal geochemistry and increased the micropore volume and adsorption capacity of heat-affected coal (60–160 m from the sill) compared with the unaltered coals. The trap effect of the sill prevented the high-pressure gas from being released, forming gas pocket. Mining activities near the sill created a low pressure zone leading to the rapid accumulation of methane and gas outbursts in the Haizi Mine. PMID:24723841

Shock vaporization and the accretion of the icy satellites of Jupiter and Saturn

NASA Technical Reports Server (NTRS)

Ahrens, T. J.; Okeefe, J. D.

1984-01-01

The role of impact vaporization acting during the formation of the Jovian and Saturnian satellites is examined in an attempt to explain the observed density in terms of composition of these rock and ice objects. A hypothesis is examined which states that the smaller satellites of Saturn having mean densities in the 1.1 to 1.4 Mg/cu m range represent primordial accreted planetesimal condensates formed in the proto-Jovian and Saturnian accretionary planetary discs. These densities are in the range expected for water-ice/silicate mixtures constrained in the solar values of O/Si and O/Mg atomic ratios. It is demonstrated that if the large satellites accreted from the same group of planetesimals which formed the small Saturnian satellites impact vaporization of water upon accretion in a porous regolith, at low H2O partial pressure, can account for the increase in mean planetesimal density from 1.6 Mg/cu m (43% H2O + 57% silicate) to a mean planetary density of 1.9 Mg/cu m for Ganymedean-sized water silicate objects. If impact volatilization of initially porous planetesimals is assumed, it can be demonstrated starting with planetesimals composed of 54% H2O and 40% silicate partial devolatilization upon accretion will yield a Ganymede-sized planet, having a radius of 2600 km and a density of 1.85 kg/cu m, similar to that of Ganymede, Callisto, and Titan.

Geology and origin of epigenetic lode gold deposits, Tintina Gold Province, Alaska and Yukon: Chapter A in Recent U.S. Geological Survey studies in the Tintina Gold Province, Alaska, United States, and Yukon, Canada--results of a 5-year project

USGS Publications Warehouse

Goldfarb, Richard J.; Marsh, Erin E.; Hart, Craig J.R.; Mair, John L.; Miller, Marti L.; Johnson, Craig; Gough, Larry P.; Day, Warren C.

2007-01-01

-rich and 18O-rich crustal fluids, most commonly of low salinity. The older group of ores includes the low-grade intrusion-related gold systems at Fort Knox near Fairbanks and those in Yukon, with fluids exsolved from fractionating melts at depths of 3 to 9 kilometers and forming a zoned sequence of auriferous mineralization styles extending outward to the surrounding metasedimentary country rocks. The causative plutons are products of potassic mafic magmas generated in the subcontinental lithospheric mantle that interacted with overlying lower to middle crust to generate the more felsic ore-related intrusions. In addition, the older ores include spatially associated, high-grade, shear-zonerelated orogenic gold deposits formed at the same depths from upward-migrating metamorphic fluids; the Pogo deposit is a relatively deep-seated example of such. The younger gold ores, restricted to southwestern Alaska, formed in unmetamorphosed sedimentary rocks of the Kuskokwim basin within 1 to 2 kilometers of the surface. Most of these deposits formed via fluid exsolution from shallowly emplaced, highly evolved igneous complexes generated mainly as mantle melts. However, the giant Donlin Creek orogenic gold deposit is a product of either metamorphic devolatilization deep in the basin or of a gold-bearing fluid released from a flysch-melt igneous body.

Uranium deposits at Shinarump Mesa and some adjacent areas in the Temple Mountain district, Emery County, Utah

USGS Publications Warehouse

Wyant, Donald G.

1953-01-01

Deposits of uraniferous hydrocarbons are associated with carnotite in the Shinarump conglomerate of Triassic age at Shinarump Mesa and adjacent areas of the Temple Mountain district in the San Rafael Swell of Emery County, Utah. The irregular ore bodies of carnotite-bearing sandstone are genetically related to lenticular uraniferous ore bodies containing disseminated asphaltitic and humic hydrocarbon in permeable sandstones and were localized indirectly by sedimentary controls. Nearly non-uraniferous bitumen commonly permeates the sandstones in the Shinarump conglomerate and the underlying Moekopi formation in the area. The ore deposits at Temple Mountain have been altered locally by hydrothermal solutions, and in other deposits throughout the area carnotite has been transported by ground and surface water. Uraniferous asphaltite is thought to be the non-volatile residue of an original weakly uraniferous crude oil that migrated into the San Rafael anticline; the ore metals concentrated in the asphaltite as the oil was devolatilized and polymerized. Carnotite is thought to have formed from the asphaltite by ground water leaching. It is concluded that additional study of the genesis of the asphaltitic uranium ores in the San Rafael Swell, of the processes by which the hydrocarbons interact and are modified (such as heat, polymerization, and hydrogenation under the influence of alpha-ray bombardment), of petroleum source beds, and of volcanic intrusive rocks of Tertiary age are of fundamental importance in the continuing study of the uranium deposits on the Colorado Plateau.

Intelligent Extruder

DOE Office of Scientific and Technical Information (OSTI.GOV)

AlperEker; Mark Giammattia; Paul Houpt

''Intelligent Extruder'' described in this report is a software system and associated support services for monitoring and control of compounding extruders to improve material quality, reduce waste and energy use, with minimal addition of new sensors or changes to the factory floor system components. Emphasis is on process improvements to the mixing, melting and de-volatilization of base resins, fillers, pigments, fire retardants and other additives in the :finishing'' stage of high value added engineering polymer materials. While GE Plastics materials were used for experimental studies throughout the program, the concepts and principles are broadly applicable to other manufacturers materials. Themore » project involved a joint collaboration among GE Global Research, GE Industrial Systems and Coperion Werner & Pleiderer, USA, a major manufacturer of compounding equipment. Scope of the program included development of a algorithms for monitoring process material viscosity without rheological sensors or generating waste streams, a novel detection scheme for rapid detection of process upsets and an adaptive feedback control system to compensate for process upsets where at line adjustments are feasible. Software algorithms were implemented and tested on a laboratory scale extruder (50 lb/hr) at GE Global Research and data from a production scale system (2000 lb/hr) at GE Plastics was used to validate the monitoring and detection software. Although not evaluated experimentally, a new concept for extruder process monitoring through estimation of high frequency drive torque without strain gauges is developed and demonstrated in simulation. A plan to commercialize the software system is outlined, but commercialization has not been completed.« less

40 CFR 1039.102 - What exhaust emission standards and phase-in allowances apply for my engines in model year 2014...

Code of Federal Regulations, 2014 CFR

2014-07-01

... Requirements § 1039.102 What exhaust emission standards and phase-in allowances apply for my engines in model year 2014 and earlier? The exhaust emission standards of this section apply for 2014 and earlier model years. See § 1039.101 for exhaust emission standards that apply to later model years. See 40 CFR 89.112...

40 CFR 1039.102 - What exhaust emission standards and phase-in allowances apply for my engines in model year 2014...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Requirements § 1039.102 What exhaust emission standards and phase-in allowances apply for my engines in model year 2014 and earlier? The exhaust emission standards of this section apply for 2014 and earlier model years. See § 1039.101 for exhaust emission standards that apply to later model years. See 40 CFR 89.112...

40 CFR 1039.102 - What exhaust emission standards and phase-in allowances apply for my engines in model year 2014...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Requirements § 1039.102 What exhaust emission standards and phase-in allowances apply for my engines in model year 2014 and earlier? The exhaust emission standards of this section apply for 2014 and earlier model years. See § 1039.101 for exhaust emission standards that apply to later model years. See 40 CFR 89.112...

40 CFR 1039.102 - What exhaust emission standards and phase-in allowances apply for my engines in model year 2014...

Code of Federal Regulations, 2012 CFR

2012-07-01

... Requirements § 1039.102 What exhaust emission standards and phase-in allowances apply for my engines in model year 2014 and earlier? The exhaust emission standards of this section apply for 2014 and earlier model years. See § 1039.101 for exhaust emission standards that apply to later model years. See 40 CFR 89.112...

Metal-saturated sulfide assemblages in NWA 2737: Evidence for impact-related sulfur devolatilization in Martian meteorites

NASA Astrophysics Data System (ADS)

Lorand, Jean-Pierre; Barrat, Jean-Alix; Chevrier, Vincent; Sautter, Violaine; Pont, Sylvain

2012-11-01