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At least 163 records · Page 9

Across‐model spread and shrinking in predicting peatland carbon dynamics under global change

Abstract Large across‐model spread in simulating land carbon (C) dynamics has been ubiquitously demonstrated in model intercomparison projects (MIPs), and became a major impediment in advancing climate change prediction. Thus, it is imperative to identify underlying sources of the spread. Here, we used a novel matrix approach to analytically pin down the sources of across‐model spread in transient peatland C dynamics in response to a factorial combination of two atmospheric CO 2 levels and five temperature levels. We developed a matrix‐based MIP by converting the C cycle module of eight land models (i.e., TEM, CENTURY4, DALEC2, TECO, FBDC, CASA, CLM4.5 and ORCHIDEE) into eight matrix models. While the model average of ecosystem C storage was comparable to the measurement, the simulation differed largely among models, mainly due to inter‐model difference in baseline C residence time. Models generally overestimated net ecosystem production (NEP), with a large spread that was mainly attributed to inter‐model difference in environmental scalar. Based on the sources of spreads identified, we sequentially standardized model parameters to shrink simulated ecosystem C storage and NEP to almost none. Models generally captured the observed negative response of NEP to warming, but differed largely in the magnitude of response, due to differences in baseline C residence time and temperature sensitivity of decomposition. While there was a lack of response of NEP to elevated CO 2 (eCO 2 ) concentrations in the measurements, simulated NEP responded positively to eCO 2 concentrations in most models, due to the positive responses of simulated net primary production. Our study used one case study in Minnesota peatland to demonstrate that the sources of across‐model spreads in simulating transient C dynamics can be precisely traced to model structures and parameters, regardless of their complexity, given the protocol that all the matrix models were driven by the same gross primary production and environmental variables.

Hou, Enqing↗

Global Simulation of Atmospheric Mercury Concentrations and Deposition Fluxes

Results from a numerical model of the global emissions, transport, chemistry, and deposition of mercury (Hg) in the atmosphere are presented. Hg (in the form of Hg(O) and Hg(II)) is emitted into the atmosphere from natural and anthropogenic sources (estimated to be 4000 and 2100 Mg/ yr, respectively). It is distributed between gaseous, aqueous and particulate phases. Removal of Hg from the atmosphere occurs via dry deposition and wet deposition, which are calculated by the model to be 3300 and 2800 Mg/ yr, respectively. Deposition on land surfaces accounts for 47% of total global deposition. The simulated Hg ambient surface concentrations and deposition fluxes to the Earth's surface are consistent with available observations. Observed spatial and seasonal trends are reproduced by the model, although larger spatial variations are observed in Hg(O) surface concentrations than are predicted by the model. The calculated atmospheric residence time of Hg is -1.7 years. Chemical transformations between Hg(O) and HG(II) have a strong influence on Hg deposition patterns because HG(II) is removed faster than Hg(O). Oxidation of Hg(O) to HG(II) occurs primarily in the gas phase, whereas HG(II) reduction to Hg(O) occurs solely in the aqueous phase. Our model results indicated that in the absence of the aqueous reactions the atmospheric residence time of Hg is reduced to 1.2 from 1.7 years and the Hg surface concentration is -25% lower because of the absence of the HG(II) reduction pathway. This result suggests that aqueous chemistry is an essential component of the atmospheric cycling of Hg.

Shia, Run-Lie↗

Scaling of silicon nanoparticle growth in low temperature flowing plasmas

Low temperature plasmas are an emerging method to synthesize high quality nanoparticles (NPs). An established and successful technique to produce NPs is using a capacitively coupled plasma (CCP) in cylindrical geometry. Although a robust synthesis technique, optimizing or specifying NP properties using CCPs, is challenging. In this paper, results from a computational investigation for the growth of silicon NPs in flowing inductively coupled plasmas (ICPs) using Ar/SiH 4 gas mixtures of up to a few Torr are discussed. ICPs produce more locally constrained and quiescent plasma potentials. These positive plasma potentials produce an electrostatic trap for negatively charged NPs, which can significantly extend the residence time of NPs in the plasma, which in turn provides a controllable period for particle growth. The computational platforms used in this study consist of a two-dimensional plasma hydrodynamics model, a three-dimensional nanoparticle growth and trajectory tracking model, and a molecular dynamics simulation for deriving reactive sticking coefficients of silane radicals on Si NPs. Trends for the nanoparticle growth as a function of SiH 4 inlet fraction, gas residence time, energy deposition per particle, pressure, and reactor diameter are discussed. The general path for particle synthesis is the trapping of small NPs in the positive electrostatic potential, followed by entrainment in the gas flow upon reaching a critical particle size. Optimizing or controlling NP synthesis then depends on the spatial distribution of plasma potential, the density of growth species, and the relative time that particles spend in the electrostatic trap and flowing through higher densities of growth species upon leaving the trap.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Effect of anode ring arrangement on the spectroscopic characteristics of the NASA Lewis Bumpy Torus plasma

The modified Penning discharge in the NASA Lewis Bumpy Torus is normally produced by an anode ring at high voltage in each of the 12 magnetic mirror midplanes. For this investigation, the plasma was run with 12, 6, 3, and 1 anode rings. When 3 anode rings were used, the spectroscopically determined relative electron density and mean ion residence time increased by factors of 10 and 5, respectively, in one mode of operation. The discharge is observed to uniformly fill all bumps around the torus regardless of the anode arrangement and number. A plasma density on axis of 100 billion per cu cm is estimated for the 3-anode case in one mode of operation based on an observed discharge current to ion loss rate correlation and a measured mean ion residence time of .5 msec.

Richardson, R. W.↗

Effect of anode ring arrangement on the spectroscopic characteristics of the NASA Lewis bumpy torus plasma

The modified Penning discharge in the NASA Lewis Bumpy Torus is normally produced by an anode ring at high voltage in each of the 12 magnetic mirror midplanes. For this investigation, the plasma was run with 12, 6, 3, and 1 anode rings. When 3 anode rings were used, the spectroscopically determined relative electron density and mean ion residence time increase by factors of 10 and 5, respectively, in one mode of operation. The discharge is observed to uniformly fill all bumps around the torus regardless of the anode arrangement and number. A plasma density on axis of 10 to the 11th power cm/3 is estimated for the 3 anode case in one mode of operation based on an observed discharge current to ion loss rate correlation and a measured mean ion residence time of .5 msec.

Richardson, R. W.↗

Smoke-Point Properties of Non-Buoyant Round Laminar Jet Diffusion Flames

The laminar smoke-point properties of non-buoyant round laminar jet diffusion flames were studied emphasizing results from long-duration (100-230 s) experiments at microgravity carried out in orbit aboard the space shuttle Columbia. Experimental conditions included ethylene- and propane-fueled flames burning in still air at an ambient temperature of 300 K, pressures of 35-130 kPa, jet exit diameters of 1.6 and 2.7 mm, jet exit velocities of 170-690 mm/s, jet exit Reynolds numbers of 46-172, characteristic flame residence times of 40-302 ms, and luminous flame lengths of 15-63 mm. Contrary to the normal-gravity laminar smoke point, in microgravity, the onset of laminar smoke-point conditions involved two flame configurations: closed-tip flames with soot emissions along the flame axis and open-tip flames with soot emissions from an annular ring about the flame axis. Open-tip flames were observed at large characteristic flame residence times with the onset of soot emissions associated with radiative quenching near the flame tip: nevertheless, unified correlations of laminar smoke-point properties were obtained that included both flame configurations. Flame lengths at laminar smoke-point conditions were well correlated in terms of a corrected fuel flow rate suggested by a simplified analysis of flame shape. The present steady and non-buoyant flames emitted soot more readily than non-buoyant flames in earlier tests using ground-based microgravity facilities and than buoyant flames at normal gravity, as a result of reduced effects of unsteadiness, flame disturbances, and buoyant motion. For example, present measurements of laminar smoke-point flame lengths at comparable conditions were up to 2.3 times shorter than ground-based microgravity measurements and up to 6.4 times shorter than buoyant flame measurements. Finally, present laminar smoke-point flame lengths were roughly inversely proportional to pressure to a degree that is a somewhat smaller than observed during earlier tests both at microgravity (using ground-based facilities) and at normal gravity.

Urban, D. L.↗

Smoke-Point Properties of Nonbuoyant Round Laminar Jet Diffusion Flames

The laminar smoke-point properties of non-buoyant round laminar jet diffusion flames were studied emphasizing results from long-duration (100-230 s) experiments at microgravity carried out in orbit aboard the space shuttle Columbia. Experimental conditions included ethylene- and propane-fueled flames burning in still air at an ambient temperature of 300 K, pressures of 35-130 kPa, jet exit diameters of 1.6 and 2.7 mm, jet exit velocities of 170-690 mm/s, jet exit Reynolds numbers of 46-172, characteristic flame residence times of 40-302 ms, and luminous flame lengths of 15-63 mm. Contrary to the normal-gravity laminar smoke point, in microgravity the onset of laminar smoke-point conditions involved two flame configurations: closed-tip flames with soot emissions along the flame axis and open-tip flames with soot emissions from an annular ring about the flame axis. Open-tip flames were observed at large characteristic flame residence times with the onset of soot emissions associated with radiative quenching near the flame tip: nevertheless, unified correlations of laminar smoke-point properties were obtained that included both flame configurations. Flame lengths at laminar smoke-point conditions were well correlated in terms of a corrected fuel flow rate suggested by a simplified analysis of flame shape. The present steady and nonbuoyant flames emitted soot more readily than non-buoyant flames in earlier tests using ground-based microgravity facilities and than buoyant flames at normal gravity, as a result of reduced effects of unsteadiness, flame disturbances, and buoyant motion. For example, present measurements of laminar smokepoint flame lengths at comparable conditions were up to 2.3 times shorter than ground-based microgravity measurements and up to 6.4 times shorter than buoyant flame measurements. Finally, present laminar smoke-point flame lengths were roughly inversely proportional to pressure to a degree that is a somewhat smaller than observed during earlier tests both at microgravity (using ground-based facilities) and at normal gravity,

Urban, D. L.↗

Transient cycling of nitrogen, organic carbon and oxygen within the free-flowing Columbia River corridor: Linking exposure time dependent biogeochemical reactions to river stage fluctuations (Final project report)

The objective of this project was to develop next-generation techniques for representing the transformations of complex reaction networks like those impacting transient river-corridors, then apply them to develop upscaling tools. The project contributed significantly to the development of Lagrangian “mass transfer particle tracking” (MTPT) tools that are the first numerical framework that explicitly separates mixing and spreading processes; a crucial distinction for accurate representations of reaction rates across scales. The MTPT approach uses an operator splitting scheme where physical transport processes are simulated using classical random walk methods and each particle is treated as a “container” that carries with it any number of chemical species. Mixing between particles is simulated using a colocation-probability based mass transfer kernel and reactions are evaluated on each particle after mixing. The method is stable, accurate, and also allows the explicit modeling of residence time distributions of the individual containers of mass. The MTPT scheme allowed us to explore several research questions related to reactive transport in river corridors and complex reaction networks. We found that it is possible to quantify the exposure time distributions (ETDs) of reactants and that this does suggest some pathways to upscaling. However, comparable approximations can be obtained using simplified (reduced dimensionality) MTPT simulations in less time with similar uncertainty, so development of extensive ETD-based methods was not productive. The major findings are that i) the MTPT schemes are robust and highly accurate across a range of arbitrarily complex reactions, ii) the methods can be efficiently parallelized and the parallel performance characteristics of MTPT are predictable, and iii) the MTPT tools allow simultaneous tracking of residence time. The development of these research tools into efficient software packages continues. The methods are already available to the community because open-source, working examples have been included with all publications.

54 ENVIRONMENTAL SCIENCES↗

Computational fluid dynamics analysis of char conversion in Sandia’s pressurized entrained flow reactor

Design and analysis of practical reactors utilizing solid feedstocks rely on reaction rate parameters that are typically generated in lab-scale reactors. Evaluation of the reaction rate information often relies on assumptions of uniform temperature, velocity, and species distributions in the reactor, in lieu of detailed measurements that provide local information. This assumption might be a source of substantial error, since reactor designs can impose significant inhomogeneities, leading to data misinterpretation. Spatially resolved reactor simulations help understand the key processes within the reactor and support the identification of severe variations of temperature, velocity, and species distributions. In this work, Sandia’s pressurized entrained flow reactor is modeled to identify inhomogeneities in the reaction zone. Tracer particles are tracked through the reactor to estimate the residence times and burnout ratio of introduced coal char particles in gasifying environments. The results reveal a complex mixing environment for the cool gas and particles entering the reactor along the centerline and the main high-speed hot gas reactor flow. Furthermore, the computational fluid dynamics (CFD) results show that flow asymmetries are introduced through the use of a horizontal gas pre-heating section that connects to the vertical reactor tube. Computed particle temperatures and residence times in the reactor differ substantially from the idealized plug flow conditions typically evoked in interpreting experimental measurements. Furthermore, experimental measurements and CFD analysis of heat flow through porous refractory insulation suggest that for the investigated conditions (1350 °C, <20 atm), the thermal conductivity of the insulation does not increase substantially with increasing pressure.

47 OTHER INSTRUMENTATION↗

Single-Atom Nickel Dispersed on Mo 2 TiC 2 T x MXene for Upcycling of Polyolefins via Catalytic Hydropyrolysis for Fuels and Lubricants

Plastic waste has been a major social and environmental problem. Chemical upcycling of plastic waste into transportation fuels or lubricant oil has emerged as an attractive and promising approach to convert plastic waste into valuable products. However, conventional catalyst systems often require high-pressure hydrogen, prolonged residence time, and the use of noble metal catalysts. Here, we present zero-valent nickel single atoms on Mo-based MXenes (Ni/Mo 2 TiC 2 T x ) for effective hydrogenation of polyolefins. In situ spectroscopic and microscopic characterizations demonstrate the formation of Ni–Mo and Ni–C bonds at a low Ni loading, resulting in the formation of dispersed intercalated Ni atoms. The catalysts were then employed to convert polyethylene into fuels and lubricant molecules under atmospheric hydrogen pressure, short vapor residence time (τ < 1 s), and mild reaction temperature (300 °C). We further demonstrated the possibility of tuning the Ni structure by changing the Ni loading, attributed to the strong metal–support interactions (MSIs) with the Mo 2 TiC 2 T x support. Under optimized conditions, 22.5 C% gasoline, 12.0 C% diesel, 19.2 C% jet fuel (JP-8), and 37.4 C% lubricant were produced over 0.5% Ni/Mo 2 TiC 2 T x . This work highlights the potential of utilizing MSIs of Mo 2 TiC 2 T x MXenes to synthesize single-atom catalysts (SACs) for upcycling plastic waste into higher-value products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low NOx Heavy Fuel Combustor Concept Program

The development of the technology required to operate an industrial gas turbine combustion system on minimally processed, heavy petroleum or residual fuels having high levels of fuel-bound nitrogen (FBN) while producing acceptable levels of exhaust emissions is discussed. Three combustor concepts were designed and fabricated. Three fuels were supplied for the combustor test demonstrations: a typical middle distillate fuel, a heavy residual fuel, and a synthetic coal-derived fuel. The primary concept was an air staged, variable-geometry combustor designed to produce low emissions from fuels having high levels of FBN. This combustor used a long residence time, fuel-rich primary combustion zone followed by a quick-quench air mixer to rapidly dilute the fuel rich products for the fuel-lean final burnout of the fuel. This combustor, called the rich quench lean (RQL) combustor, was extensively tested using each fuel over the entire power range of the model 570 K engine. Also, a series of parameteric tests was conducted to determine the combustor's sensitivity to rich-zone equivalence ratio, lean-zone equivalence ratio, rich-zone residence time, and overall system pressure drop. Minimum nitrogen oxide emissions were measured at 50 to 55 ppmv at maximum continuous power for all three fuels. Smoke was less than a 10 SAE smoke number.

Novick, A. S.↗

Non‐OH‐driven liquid‐phase chemistry in water microdroplets

Abstract Water microdroplets containing organic and fluorinated compounds, such as formate, perfluorooctanoic acid (PFOA) and triflic acid, were exposed to a radiofrequency glow discharge plasma with a droplet residence time on the order of milliseconds. Triflic acid remained unaffected by any plasma condition while >75% decomposition of formate and PFOA could be achieved. In situ hydroxyl (OH)‐laser‐induced fluorescence measurements near the droplets confirmed that the conversion was independent of the OH flux to the droplet. A series of control experiments suggest that the contribution of vacuum UV photons in such decomposition of aqueous compounds can be significant for He and He + 17% Ar plasmas and can also explain unexpected decomposition trends as a function of droplet residence time in the plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The effect of fuel sprays on emissions from a gas turbine combustor

A research gas turbine combustor which allows for independent control of drop size, fuel/air ratio, air inlet temperature, pressure, reference velocity, and residence time has been used to study the influence of fuel spray characteristics on primary zone emissions. Local concentrations of oxides of nitrogen, carbon monoxide and unburned hydrocarbons at various locations in the flow, local gas temperature, gas velocity, and the turbulence intensity (measured with laser velocimetry) are obtained. A comprehensive data analysis program to compute the local fuel/air ratio and the sum of the mole fractions of the species present confirms the validity of the emissions data. Increasing drop size is correlated with an increase in unburned hydrocarbons, while increasing residence time is associated with sharp decreases in hydrocarbons and carbon monoxide and an increase in oxides of nitrogen.

Nicholls, J. A.↗

Heat Loss Effects on Emissions in an NH 3 RRQL Combustor

Ammonia (NH 3 ) is a carbon-free energy carrier with an infrastructure for production, storage, and distribution. There is interest in direct NH 3 combustion, but managing pollutant emissions is a key challenge, particularly nitric oxides (NO x ) due to the fuel-bound nitrogen atom, nitrous oxide (N 2 O), which is a potent greenhouse gas, and unburned NH 3 , which is harmful to humans and the environment. Rich staged combustor concepts with extended primary residence times (τ res,primary ), like Rich-Relax- Quick-mix-Lean (RRQL), offer a viable pathway for direct NH 3 combustion with low levels of NO x formation. However, minimizing secondary emissions such as N 2 O and unburned NH 3 and hydrogen (H 2 ) remains a critical challenge. Prior atmospheric-pressure studies have demonstrated that RRQL operation with sufficiently long τ res,primary enables substantial NO x relaxation and promotes NH 3 cracking to H 2 , if heat losses from the relaxation stage are limited. However, the combined influence of elevated pressure and long residence time on RRQL performance has not been explored. The present work examines RRQL operation at pressures up to 5 bar and elevated τ res,primary . Exhaust measurements of NO x , NH 3 , and N 2 O are used to quantify the extent of NO x relaxation and NH 3 cracking under nonadiabatic conditions. To contextualize and quantify the effects of heat losses in the experimental data, chemical reactor networks (CRNs) incorporating prescribed heat loss rates are employed to assess the sensitivity of emissions to thermal losses in the relaxation stage. Collectively, the results demonstrate that management and quantification of heat losses are essential to preserve NO x relaxation and limit NH 3 and N 2 O emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Autoignition in a premixing-prevaporizing fuel duct using 3 different fuel injection systems at inlet air temperatures to 1250 K

Conditions were determined in a continuous-flow, premixing-prevaporizing duct at which autoignition occurred. Test conditions were representative of an advanced, regenerative-cycle, automotive gas turbine. The test conditions inlet air temperatures from 600 to 1250 K (a vitiated preheater was used), pressures from 170 to 600 kPa, air velocities of 10 to 30 m/sec, equivalence ratios from 0.3 to 1.0, mixing lengths from 10 to 60 cm, and residence times of 2 to 100 ms. The fuel was diesel number 2. The duct was insulated and had an inside diameter of 12 cm. Three different fuel injection systems were used: One was a single simplex pressure atomizer, and the other two were multiple-source injectors. The data obtained with the simplex and one of the multiple-source injectors agreed satisfactorily with the references and correlated with an Arrenhius expression. The data obtained with the other multiple source injector, which used multiple cones to improve the fuel-air distribution, did not correlate well with residence time.

Tacina, R. R.↗

Autogenous acid production using a regulated bio-oxidation method for economical recovery of REEs and critical metals from coal-based resources

Acid is a necessary component for the successful leaching of minerals containing REEs (rare earth elements) and other sources. Pyrite (FeS2), which is present in REE containing minerals, can be used to produce acid. Pyrite is utilized as a source to create ferric sulfate and sulfuric acid in the presence of A. Ferroxidans. Such microorganism-based bio-oxidation necessitates the establishment of optimal conditions for continual acid production. For efficient acid generation, additional optimization was done by varying residence time, solid percentage, and airflow rate. A step-by-step analysis and associated details are offered in this work, which used pyrite to create acid for leaching. For the bio-oxidation of pyrite with varying purity, an automated bioreactor was used. Scanning electron microscopy with energy-dispersive X-ray spectroscopy was used to examine the morphology and elemental content of bioleaching sediments. Eh and pH measurements were continuously done to ensure healthy operation of the bioreactors. The analysis suggested that, the Eh value in the range of ∼ 640–680 mV, pH range of ∼ 1.3–1.5 and residence time of 4–6 days with 6% solid feed are favorable conditions of operation.

99 GENERAL AND MISCELLANEOUS↗

On Soot Inception in Nonpremixed Flames and the Effects of Flame Structure

A simplified three-step model of soot inception has been employed with high activation energy asymptotics to study soot inception in nonpremixed counterflow systems with emphasis on understanding the effects of hydrodynamics and transport. The resulting scheme yields three zones: (1) a fuel oxidation zone wherein the fuel and oxidizer react to form product as well as a radical R, (e.g., H), (2) a soot/precursor formation zone where the radical R reacts with fuel to form "soot/precursor" S, and (3) a soot/precursor consumption zone where S reacts with the oxidizer to form product. The kinetic scheme, although greatly simplified, allows the coupling between soot inception and flame structure to be assessed. The results yield flame temperature, flame location, and a soot/precursor index S(sub I) as functions of Damkohler number for S formation. The soot/precursor index indicates the amount of S at the boundary of the formation region. The flame temperature indirectly indicates the total amount of S integrated over the formation region because as S is formed less heat release is available. The results show that unlike oxidation reactions, an extinction turning-point behavior does not exist for soot. Instead, the total amount of S slowly decreases with decreasing Damkohler number (increasing strain rate), which is consistent with counterflow flame experiments. When the Lewis number of the radical is decreased from unity, the total S reduces due to reduced residence time for the radical in the soot formation region. Similarly, when the Lewis number of the soot/precursor is increased from unity the amount of S increases for all Damkohler numbers. In addition to studying fuel-air (low stoichiometric mixture fraction) flames, the air-side nitrogen was substituted into the fuel, yielding diluted fuel-oxygen (high stoichiometric mixture fraction) flames with the same flame temperature as the fuel - air flames. The relative flame locations were different however, and, consistent with counterflow flame experiments, this difference was found to dramatically reduce the total amount of S generated because the change in stoichiometric mixture fraction affects residence times, temperatures and concentrations in the soot/precursor formation and consumption zones. Furthermore, while the soot/precursor consumption reaction had a negligible effect on the soot process for fuel-air flames it was very important to diluted fuel - oxygen flames.

Chao, B. H.↗

Catalytic Bio-crude Production in a Novel, Short-Contact Time Reactor

RTI has developed a catalytic fast pyrolysis (CFP) process to produce biomass-based hydrocarbon replacement fuels. From a technology perspective, this advanced biofuels process produces liquid transportation fuels that can leverage capital expenditures in the existing petroleum distribution infrastructure. From a business perspective, this technology does not face potential market limitations caused by oxygenate blend limitations for light duty vehicle applications. A promising catalyst has been developed with excellent potential for deoxygenation to produce a hydrocarbon-rich biocrude that is more suitable for upgrading with traditional hydroprocessing technology. The role of the catalyst is to control the chemistry during biomass pyrolysis to produce a biocrude in a single step that has lower oxygen content and is more thermally stable than conventional biomass fast pyrolysis oil. Catalyst properties are optimized to minimize gas and coke production and improve catalytic deoxygenation and biocrude yields. Results from this project have demonstrated that biocrudes from catalytic fast pyrolysis contain <20 wt% oxygen, with the organic fraction as low as 12% oxygen. These oxygen numbers are > 50% lower compared to traditional fast pyrolysis oils. The biocrude produced from our CFP process can be upgraded to gasoline range hydrocarbons. A very conservative approach for upgrading included a preliminary stabilization step followed by a hydroprocessing step. The oxygen content in the upgraded product was decreased by 97% (to less than 3wt %) from the oxygen content of the biocrude sample. Additionally, the acid content was reduced by 99% from the acid content of the biocrude sample. In an optimized integrated process, the CFP step and the hydroprocessing (upgrading) step need to be carefully balanced to maximize the input biomass energy that is recovered in the finished biofuels. Hydrogen utilization and carbon recovery during both catalytic biomass pyrolysis and biocrude upgrading need to be optimized to maximize energy recovery in the finished biofuel. A nominal 1 ton per day (TPD) catalytic biomass pyrolysis system was designed based on the laboratory experimental data. The system was designed to achieve the short residence times (0.5–2 sec) and high heat transfer rates required for maximum liquid biocrude yields while optimizing process integration to maintain catalyst activity by continuous regeneration. The catalytic biomass pyrolysis reactor is a continuously circulating single-loop transport reactor design that is flexible enough to allow sensitivity studies around temperature, residence time, biomass feed rate, and catalyst-to-biomass ratio (i.e., catalyst circulation rate) for process optimization. For a nominal 100 lb/hr feed rate of dry biomass, the products include ~25 lb/hr char and coke, ~20 lb/hr permanent gases, and ~55 lb/hr condensable vapors. Pyrolysis temperatures are 350–600°C, and the system is operated close to ambient pressure. Production of the catalyst developed within the project was scaled up to provide enough material (200kg) for bench-scale testing. The 1TPD bench-scale unit was fabricated, installed and commissioned with this project. Biocrude samples from wood were produced in this unit with the CFP catalyst with material balance > 90%. The intermediate biocrude yields and chemical composition compare well with previous laboratory results and a hydroprocessing strategy for upgrading the resulting biocrude was developed. The experimental results obtained within this project were used to develop a process model for a 2000 TPD commercial facility. Detailed flow sheets were developed for all major unit operations in the process and provided a basis for an economic analysis to develop capital and operating costs. Estimates of the biofuel production costs were used to develop internal rates of return for the yields and compositions measured for the current state of technology at the end of this project and for the yields anticipated for an optimized (nth plant) scenario as additional process improvements are made.

09 BIOMASS FUELS↗