Experimental and modeling study of the filtration and oxidation characteristics of a diesel oxidation catalyst and a catalyzed particulate filter

A diesel oxidation catalyst (DOC) with a catalyzed diesel particulate filter (CPF) is an effective exhaust aftertreatment device that reduces particulate emissions from diesel engines, and properly designed DOC-CPF systems provide passive regeneration of the filter by the oxidation of PM via thermal and NO2/temperature-assisted means under various vehicle duty cycles. However, controlling the backpressure on engines caused by the addition of the CPF to the exhaust system requires a good understanding of the filtration and oxidation processes taking place inside the filter as the deposition and oxidation of solid particulate matter (PM) change as functions of loading time. In order to understand the solid PM loading characteristics in the CPF, an experimental and modeling study was conducted using emissions data measured from the exhaust of a John Deere 6.8 liter, turbocharged and after-cooled engine with a low-pressure loop EGR system and a DOC-CPF system (or a CCRT® - Catalyzed Continuously Regenerating Trap®, as named by Johnson Matthey) in the exhaust system. A series of experiments were conducted to evaluate the performance of the DOC-only, CPF-only and DOC-CPF configurations at two engine speeds (2200 and 1650 rpm) and various loads on the engine ranging from 5 to 100% of maximum torque at both speeds. Pressure drop across the DOC and CPF, mass deposited in the CPF at the end of loading, upstream and downstream gaseous and particulate emissions, and particle size distributions were measured at different times during the experiments to characterize the pressure drop and filtration efficiency of the DOCCPF system as functions of loading time. Pressure drop characteristics measured experimentally across the DOC-CPF system showed a distinct deep-bed filtration region characterized by a non-linear pressure drop rise, followed by a transition region, and then by a cake-filtration region with steadily increasing pressure drop with loading time at engine load cases with CPF inlet temperatures less than 325 °C. At the engine load cases with CPF inlet temperatures greater than 360 °C, the deep-bed filtration region had a steep rise in pressure drop followed by a decrease in pressure drop (due to wall PM oxidation) in the cake filtration region. Filtration efficiencies observed during PM cake filtration were greater than 90% in all engine load cases. Two computer models, i.e., the MTU 1-D DOC model and the MTU 1-D 2-layer CPF model were developed and/or improved from existing models as part of this research and calibrated using the data obtained from these experiments. The 1-D DOC model employs a three-way catalytic reaction scheme for CO, HC and NO oxidation, and is used to predict CO, HC, NO and NO2 concentrations downstream of the DOC. Calibration results from the 1-D DOC model to experimental data at 2200 and 1650 rpm are presented. The 1-D 2-layer CPF model uses a ‘2-filters in series approach’ for filtration, PM deposition and oxidation in the PM cake and substrate wall via thermal (O2) and NO2/temperature-assisted mechanisms, and production of NO2 as the exhaust gas mixture passes through the CPF catalyst washcoat. Calibration results from the 1-D 2-layer CPF model to experimental data at 2200 rpm are presented. Comparisons of filtration and oxidation behavior of the CPF at sample load-cases in both configurations are also presented. The input parameters and selected results are also compared with a similar research work with an earlier version of the CCRT®, to compare and explain differences in the fundamental behavior of the CCRT® used in these two research studies. An analysis of the results from the calibrated CPF model suggests that pressure drop across the CPF depends mainly on PM loading and oxidation in the substrate wall, and also that the substrate wall initiates PM filtration and helps in forming a PM cake layer on the wall. After formation of the PM cake layer of about 1-2 µm on the wall, the PM cake becomes the primary filter and performs 98-99% of PM filtration. In all load cases, most of PM mass deposited was in the PM cake layer, and PM oxidation in the PM cake layer accounted for 95-99% of total PM mass oxidized during loading. Overall PM oxidation efficiency of the DOC-CPF device increased with increasing CPF inlet temperatures and NO2 flow rates, and was higher in the CCRT® configuration compared to the CPF-only configuration due to higher CPF inlet NO2 concentrations. Filtration efficiencies greater than 90% were observed within 90-100 minutes of loading time (starting with a clean filter) in all load cases, due to the fact that the PM cake on the substrate wall forms a very efficient filter. A good strategy for maintaining high filtration efficiency and low pressure drop of the device while performing active regeneration would be to clean the PM cake filter partially (i.e., by retaining a cake layer of 1-2 µm thickness on the substrate wall) and to completely oxidize the PM deposited in the substrate wall. The data presented support this strategy.

Comprehensive review and application of particle image velocimetry

For a fluid dynamics experimental flow measurement technique, particle image velocimetry (PIV) provides significant advantages over other measurement techniques in its field. In contrast to temperature and pressure based probe measurements or other laser diagnostic techniques including laser Doppler velocimetry (LDV) and phase Doppler particle analysis (PDPA), PIV is unique due to its whole field measurement capability, non-intrusive nature, and ability to collect a vast amount of experimental data in a short time frame providing both quantitative and qualitative insight. These properties make PIV a desirable measurement technique for studies encompassing a broad range of fluid dynamics applications. However, as an optical measurement technique, PIV also requires a substantial technical understanding and application experience to acquire consistent, reliable results. Both a technical understanding of particle image velocimetry and practical application experience are gained by applying a planar PIV system at Michigan Technological University’s Combustion Science Exploration Laboratory (CSEL) and Alternative Fuels Combustion Laboratory (AFCL). Here a PIV system was applied to non-reacting and reacting gaseous environments to make two component planar PIV as well as three component stereographic PIV flow field velocity measurements in conjunction with chemiluminescence imaging in the case of reacting flows. This thesis outlines near surface flow field characteristics in a tumble strip lined channel, three component velocity profiles of non-reacting and reacting swirled flow in a swirl stabilized lean condition premixed/prevaporized-fuel model gas turbine combustor operating on methane at 5-7 kW, and two component planar PIV measurements characterizing the AFCL’s 1.1 liter closed combustion chamber under dual fan driven turbulent mixing flow.

Nano-engineering of composite material via reactive mechanical alloying/milling (RMA/M)

Attempts to strengthen a chromium-modified titanium trialuminide by a combination of grain size refinement and dispersoid strengthening led to a new means to synthesize such materials. This Reactive Mechanical Alloying/Milling process uses in situ reactions between the metallic powders and elements from a process control agent and/or a gaseous environment to assemble a dispersed small hard particle phase within the matrix by a bottom-up approach. In the current research milled powders of the trialuminide alloy along with titanium carbide were produced. The amount of the carbide can be varied widely with simple processing changes and in this case the milling process created trialuminide grain sizes and carbide particles that are the smallest known from such a process. Characterization of these materials required the development of x-ray diffraction means to determine particle sizes by deconvoluting and synthesizing components of the complex multiphase diffraction patterns and to carry out whole pattern analysis to analyze the diffuse scattering that developed from larger than usual highly defective grain boundary regions. These identified regions provide an important mass transport capability in the processing and not only facilitate the alloy development, but add to the understanding of the mechanical alloying process. Consolidation of the milled powder that consisted of small crystallites of the alloy and dispersed carbide particles two nanometers in size formed a unique, somewhat coarsened, microstructure producing an ultra-high strength solid material composed of the chromium-modified titanium trialuminide alloy matrix with small platelets of the complex carbides Ti2AlC and Ti3AlC2. This synthesis process provides the unique ability to nano-engineer a wide variety of composite materials, or special alloys, and has shown the ability to be extended to a wide variety of metallic materials.

PROPERTIES AND STRUCTURES OF Li-N BASED HYDROGEN STORAGE MATERIALS

Traditional transportation fuel, petroleum, is limited and nonrenewable, and it also causes pollutions. Hydrogen is considered one of the best alternative fuels for transportation. The key issue for using hydrogen as fuel for transportation is hydrogen storage. Lithium nitride (Li3N) is an important material which can be used for hydrogen storage. The decompositions of lithium amide (LiNH2) and lithium imide (Li2NH) are important steps for hydrogen storage in Li3N. The effect of anions (e.g. Cl-) on the decomposition of LiNH2 has never been studied. Li3N can react with LiBr to form lithium nitride bromide Li13N4Br which has been proposed as solid electrolyte for batteries. The decompositions of LiNH2 and Li2NH with and without promoter were investigated by using temperature programmed decomposition (TPD) and X-ray diffraction (XRD) techniques. It was found that the decomposition of LiNH2 produced Li2NH and NH3 via two steps: LiNH2 into a stable intermediate species (Li1.5NH1.5) and then into Li2NH. The decomposition of Li2NH produced Li, N2 and H2 via two steps: Li2NH into an intermediate species --- Li4NH and then into Li. The kinetic analysis of Li2NH decomposition showed that the activation energies are 533.6 kJ/mol for the first step and 754.2 kJ/mol for the second step. Furthermore, XRD demonstrated that the Li4NH, which was generated in the decomposition of Li2NH, formed a solid solution with Li2NH. In the solid solution, Li4NH possesses a similar cubic structure as Li2NH. The lattice parameter of the cubic Li4NH is 0.5033nm. The decompositions of LiNH2 and Li2NH can be promoted by chloride ion (Cl-). The introduction of Cl- into LiNH2 resulted in the generation of a new NH3 peak at low temperature of 250 °C besides the original NH3 peak at 330 °C in TPD profiles. Furthermore, Cl- can decrease the decomposition temperature of Li2NH by about 110 °C. The degradation of Li3N was systematically investigated with techniques of XRD, Fourier transform infrared (FT-IR) spectroscopy, and UV-visible spectroscopy. It was found that O2 could not affect Li3N at room temperature. However, H2O in air can cause the degradation of Li3N due to the reaction between H2O and Li3N to LiOH. The produced LiOH can further react with CO2 in air to Li2CO3 at room temperature. Furthermore, it was revealed that Alfa-Li3N is more stable in air than Beta-Li3N. The chemical stability of Li13N4Br in air has been investigated by XRD, TPD-MS, and UV-vis absorption as a function of time. The aging process finally leads to the degradation of the Li13N4Br into Li2CO3, lithium bromite (LiBrO2) and the release of gaseous NH3. The reaction order n = 2.43 is the best fitting for the Li13N4Br degradation in air reaction. Li13N4Br energy gap was calculated to be 2.61 eV.

PRODUCTION OF BIOFUEL INTERMEDIATES FROM WOODY FEEDSTOCKS VIA FAST PYROLYSIS AND TORREFACTION

The main objective of this research was to investigate pyrolysis and torrefaction of forest biomass species using a micropyrolysis instrument. It was found that 30-45% of the original sample mass remained as bio-char in the pyrolysis temperature range of 500 - 700˚C for aspen, balsam, and switchgrass. The non-char mass was converted to gaseous and vapor products, of which 10-55% was water and syngas, 2-12% to acetic acid, 2-12% to hydroxypropanone, 1-3% to furaldehyde, and 5-15% to various phenolic compounds. In addition, several general trends in the evolution of gaseous species were indentified when woody feedstocks were pyrolyzed. With increasing temperature it was observed that: (1) the volume of gas produced increased, (2) the volume of CO2 decreased and the volumes of CO and CH4 increased, and (3) the rates of gas evolution increased. In the range of torrefaction temperature (200 - 300˚C), two mechanistic models were developed to predict the rates of CO2 and acetic acid product formation. The models fit the general trend of the experimental data well, but suggestions for future improvement were also noted. Finally, it was observed that using torrefaction as a pre-curser to pyrolysis improves the quality of bio-oil over traditional pyrolysis by reducing the acidity through removal of acetic acid, reducing the O/C ratio by removal of some oxygenated species, and removing a portion of the water.

AN EXPERIMENTAL INVESTIGATION INTO THE EFFECTS OF BIODIESEL BLENDS ON PARTICULATE MATTER OXIDATION IN A CATALYZED PARTICULATE FILTER DURING ACTIVE REGENERATION

Active regeneration experiments were carried out on a production 2007 Cummins 8.9L ISL engine and associated DOC and CPF aftertreatment system. The effects of SME biodiesel blends were investigated in this study in order to determine the PM oxidation kinetics associated with active regeneration, and to determine the effect of biodiesel on them. The experimental data from this study will also be used to calibrate the MTU-1D CPF model. Accurately predicting the PM mass retained in the CPF and the oxidation characteristics will provide the basis for computation in the ECU that will minimize the fuel penalty associated with active regeneration. An active regeneration test procedure was developed based on previous experimentation at MTU. During each experiment, the PM mass in the CPF is determined by weighing the filter at various phases. In addition, DOC and CPF pressure drop, particle size distribution, gaseous emissions, temperature, and PM concentration data are collected and recorded throughout each experiment. The experiments covered a range of CPF inlet temperatures using ULSD, B10, and B20 blends of biodiesel. The majority of the tests were performed at CPF PM loading of 2.2 g/L with in-cylinder dosing, although 4.1 g/L and a post-turbo dosing injector were also used. The PM oxidation characteristics at different test conditions were studied in order to determine the effects of biodiesel on PM oxidation during active regeneration. A PM reaction rate calculation method was developed to determine the global activation energy and the corresponding pre-exponential factor for all test fuels. The changing sum of the total flow resistance of the wall, cake, and channels was also determined as part of the data analysis process in order to check on the integrity of the data and to correct input data to be consistent with the expected trends of the resistance based on the engine conditions used in the test procedure. It was determined that increasing the percent biodiesel content in the test fuel tends to increase the PM reaction rate and the regeneration efficiency of fuel dosing, i.e., at a constant CPF inlet temperature, B20 test fuel resulted in the highest PM reaction rate and regeneration efficiency of fuel dosing. Increasing the CPF inlet temperature also increases PM reaction rate and regeneration efficiency of fuel dosing. Performing active regeneration with B20 as opposed to ULSD allows for a lower CPF temperature to be used to reach the same level of regeneration efficiency, or it allows for a shorter regeneration time at a constant CPF temperature, resulting in decreased fuel consumption for the engine during active regeneration in either scenario.

Nitrogen removal and sustainability of vertical flow constructed wetlands for small scale wastewater treatment

The challenge for wastewater professionals is to design and operate treatment processes that support human well being and are environmentally sensitive throughout the life-cycle. This research focuses on one technology for small-scale wastewater treatment: the vertical flow constructed wetland (VFCW), which is herein investigated for the capacity to remove ammonium and nitrate nitrogen from wastewater. Hydraulic regime and presence/absence of vegetation are the basis for a three-phase bench scale experiment to determine oxygen transfer and nitrogen fate in VFCWs. Results show that 90% NH4+-N removal is achieved in aerobic downflow columns, 60% NO3--N removal occurs in anaerobic upflow columns, and 60% removal of total nitrogen can be achieved in downflow-upflow in-series. The experimental results are studied further using a variably saturated flow and reactive transport model, which allows a mechanistic explanation of the fate and transport of oxygen and nitrogen. The model clarifies the mechanisms of oxygen transport and nitrogen consumption, and clarifies the need for readily biodegradable COD for denitrification. A VFCW is then compared to a horizontal flow constructed wetland (HFCW) for life cycle environmental impacts. High areal emissions of greenhouse gases from VFCWs compared to HFCWs are the driver for the study. The assessment shows that because a VFCW is only 25% of the volume of an HFCW designed for the same treatment quality, the VFCW has only 25-30% of HFCW impacts over 12 impact categories and 3 damage categories. Results show that impacts could be reduced by design improvements. Design recommendations are downflow wetlands for nitrification, upflow wetlands for denitrification, series wetlands for total nitrogen removal, hydraulic load of 142 L/m2d, 30 cm downflow wetland depth, 1.0 m upflow wetland depth, recycle, vegetation and medium-grained sand. These improvements will optimize nitrogen removal, minimize gaseous emissions, and reduce wetland material requirements, thus reducing environmental impact without sacrificing wastewater treatment quality.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.