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Conventional diesel engines will continue to hold a vital role in the heavy- and medium-duty markets for the transportation of goods along with many other uses. The ability to offset traditional diesel fuels with low-net-carbon biofuels could have a significant impact on reducing the carbon footprint of these vehicles. A prior study screened several hundred candidate biofuel blendstocks based on required diesel blendstock properties and identified 12 as the most promising. Eight representative biofuel blendstocks were blended at a 30% volumetric concentration with EPA certification ultra-low-sulfur diesel (ULSD) and were investigated for emissions and fuel efficiency performance. This study used a single cylinder engine (based on the Ford 6.7L engine) using Conventional Diesel Combustion (CDC), also known as Mixing Control Compression Ignition (MCCI). The density, cetane number, distillation curve and sooting tendency (using the yield sooting index method) of the fuels were measured.

Almost one-third of the fuel energy is wasted through the exhaust of a vehicle. An efficient waste heat recovery (WHR) process will undoubtedly lead to improved fuel efficiency and reduced greenhouse gases (GHG) emission. Currently, there are multiple WHR technologies that are being investigated by various entities in the auto industry. One relatively simple device to extract heat energy from the exhaust is a heat exchanger. Heat exchangers are used in some automotive applications to transfer heat from the hot exhaust gas to the colder coolant fluid to raise the coolant temperature. The warmer coolant fluid can be used for several purposes such as; faster heating of the engine’s lubrication oil and transmission fluids during cold starts, and faster cabin heating, which in turn, can potentially improve the overall engine efficiency and reduce exhaust emissions.

Sustained NOx reduction at low temperatures, especially in the 150-200 °C range, shares some similarities with the more commonly discussed cold-start challenge, however, poses a number of additional and distinct technical problems. In this project, we set a bold target of achieving and maintaining 90% NOx conversion at the SCR catalyst inlet temperature of 150 °C. This project is intended to push the boundaries of the existing technologies, while staying within the realm of realistic future practical implementation. In order to meet the resulting challenges at the levels of catalyst fundamentals, system components, and system integration, Cummins has partnered with the DOE, Johnson Matthey, and Pacific Northwest National Lab and initiated the Sustained Low-Temperature NOx Reduction program at the beginning of 2015 and completed in 2017.

Fuel cell vehicles are entering the automotive market with significant potential benefits to reduce harmful greenhouse emissions, facilitate energy security, and increase vehicle efficiency while providing customer expected driving range and fill times when compared to conventional vehicles. One of the challenges for successful commercialization of fuel cell vehicles is transitioning the on-board fuel system from liquid gasoline to compressed hydrogen gas. Storing high pressurized hydrogen requires a specialized structural pressure vessel, significantly different in function, size, and construction from a gasoline container. In comparison to a gasoline tank at near ambient pressures, OEMs have aligned to a nominal working pressure of 700 bar for hydrogen tanks in order to achieve the customer expected driving range of 300 miles.

We describe a study to identify potential biofuels that enable advanced spark ignition (SI) engine efficiency strategies to be pursued more aggressively. A list of potential biomass-derived blendstocks was developed. An online database of properties and characteristics of these bioblendstocks was created and populated. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a bioblendstock met the requirements for advanced SI engines. Criteria included melting point (or cloud point) < -10°C and boiling point (or T90) <165°C. Compounds insoluble or poorly soluble in hydrocarbon were eliminated from consideration, as were those known to cause corrosion (carboxylic acids or high acid number mixtures) and those with hazard classification as known or suspected carcinogens or reproductive toxins.

Urea-selective catalytic reduction (SCR) catalysts are the leading aftertreatment technology for diesel engines, but there are major challenges associated with meeting future NOx emission standards, especially under transient drive cycle conditions that include large swings in exhaust temperatures. Here we present a simplified, transient, one-dimensional integral model of NOx reduction by NH₃ on a commercial small-pore Cu-zeolite urea-SCR catalyst for which detailed kinetic parameters have not been published. The model was developed and validated using data acquired from bench reactor experiments on a monolith core, following a transient SCR reactor protocol. The protocol incorporates NH₃ storage, NH₃ oxidation, NO oxidation and three global SCR reactions under isothermal conditions, at three space velocities and at three NH₃/NOx ratios.

Although the urea-SCR technology exhibits high NO reduction efficiency over a wide range of temperatures among the lean NO reduction technologies, further improvement in low-temperature performance is required to meet the future emission standards and to lower the system cost. In order to improve the catalyst technologies and optimize the system performance, it is critical to understand the reaction mechanisms and catalyst behaviors with respect to operating conditions. Urea-SCR catalysts exhibit poor NO reduction performance at low-temperature operating conditions (T ≺ 150°C). We postulate that the poor performance is either due to NH₃ storage inhibition by species like hydrocarbons or due to competitive adsorption between NH₃ and other adsorbates such as H₂O and hydrocarbons in the exhaust stream. In this paper we attempt to develop one-dimensional models to characterize inhibition and competitive adsorption in Fe-zeolite-based urea-SCR catalysts based on bench reactor experiments.

Synergies between various catalytic converters such as SCR and DPF are vital to the success of an integrated aftertreatment system for simultaneous NO and particulate matter control in diesel engines. Several issues such as hydrocarbon poisoning, thermal aging and other coupled aftertreatment dynamics need to be addressed to develop an effective emission control system. This work is significant especially in an integrated DPF-SCR aftertreatment scenario where the SCR catalyst on the filter substrate is exposed to un-burnt diesel hydrocarbons during active regeneration of the particulate filter. This paper reports an experimental and modeling study to understand the effect of hydrocarbons on a Fe-zeolite urea-SCR catalyst. Several bench-reactor tests to understand the inhibition of NO oxidation, to characterize hydrocarbon storage and to investigate the impact of hydrocarbons on SCR reactions were conducted.

The Pacific Northwest National Laboratory (PNNL) and the Volpentest Hazardous Materials Management and Emergency Response (HAMMER) Training and Education Center are helping to prepare emergency responders and permitting/code enforcement officials for their respective roles in the gradual transition to the hydrogen economy. Safety will be a critical component of the anticipated hydrogen transition. Public confidence goes hand in hand with perceived safety to such an extent that, without it, the envisioned transition is unlikely to occur. Stakeholders and the public must be reassured that hydrogen, although very different from gasoline and other conventional fuels, is no more dangerous. Ensuring safety in the hydrogen infrastructure will require a suitably trained emergency response force for containing the inevitable incidents as they occur, coupled with knowledgeable code officials to ensure that such incidents are kept to a minimum.

A slipstream of exhaust from a Caterpillar 3126B engine was diverted into a plasma-catalytic NOx control system in the space velocity range of 7,000 to 100,000 hr-1. The stream was first fed through a non-thermal plasma that was formed in a coaxial cylinder dielectric barrier discharge reactor. Plasma treated gas was then passed over a catalyst bed held at constant temperature in the range of 573 to 773 K. Catalysts examined consisted of γ-alumina, indium-doped γ-alumina, and silver-doped γ-alumina. Road and rated load conditions resulted in engine out NOx levels of 250 - 600 ppm. The effects of hydrocarbon level, catalyst temperature, and space velocity are discussed where propene and in one case ultra-low sulfur diesel fuel (late cycle injection) were the reducing agents used for NOx reduction. Results showed NOx reduction in the range of 25 - 97% depending on engine operating conditions and management of the catalyst and slipstream conditions.

Brønsted acidity of solution ion-exchanged and solid-state exchanged zeolites was compared for NaY, BaY, CaY, NaX, and CaX zeolites. These materials were chosen because they all exhibit catalytic activity in SCR of NOx in combination with a non-thermal plasma. Brønsted acidity was characterized qualitatively with retinol as an indicator dye. Our results show that the solid-state exchange using a chloride salt creates zeolites with lower acidity than zeolites obtained by conventional solution ion-exchange. NO2 adsorption was also found to create a significant quantity of acid sites at room temperature and a slight increase in acidity at 200°C. We speculate that the acid sites created by NO2 adsorption, because of their vicinity to metal cation sites in the zeolite, may lead to preferential reactions that lead to NOx reduction. BaY made by solution ion-exchange and BaY made by solid-state exchange using a chloride salt were tested for NOx reduction in a plasma-catalyst reactor system.

This paper describes two independent studies on γ-alumina as a plasma-activated catalyst. γ-alumina (2.5 - 4.3 wt%) was coated onto the surface of mesoporous silica to determine the importance of aluminum surface coordination on NOx conversion in conjunction with nonthermal plasma. Results indicate that the presence of 5- and 6- fold aluminum coordination sites in γ-alumina could be a significant factor in the NOx reduction process. A second study examined the effect of changing the reducing agent on NOx conversion. Several hydrocarbons were examined including propene, propane, isooctane, methanol, and acetaldehyde. It is demonstrated that methanol was the most effective reducing agent of those tested for a plasma-facilitated reaction over γ-alumina.

The catalytic activity of selected materials (BaY and NaY zeolites, and γ-alumina) for selective NOx reduction in combination with a non-thermal plasma was investigated. Our studies suggest that aldehydes, formed during the plasma treatment of simulated diesel exhaust, are the important species for the reduction of NOx to N2. Indeed, all materials that are active in plasma-assisted catalysis were found to be very effective for the thermal reduction of NOx in the presence of aldehydes. For example, the thermal catalytic activity of a BaY zeolite with aldehydes gives 80-90% NOx removal at 250°C with 200ppm NOx at the inlet and a VHSV=12,000 h-1. The hydrocarbon reductants, n-octane and 1-propyl alcohol, have also shown high thermal catalytic activity for NOx removal over BaY, NaY and γ-alumina.

In the discharge-catalyst treatment of diesel exhaust the discharge chemistry is known to oxidize NO to NO2 as well as to produce partially oxidized hydrocarbons for the heterogeneous reduction step. We find NO2 to be much more easily reduced to N2 on our catalysts, as long as there is a sufficient supply of reductant present. Unfortunately we typically find that a fraction of the NO2 is only partially reduced back to NO. Since much of the original hydrocarbon survives both the plasma and our catalyst, a subsequent stage of plasma will oxidize NO back to NO2 while at the same time replenishing the supply of partially oxidized hydrocarbon for another stage of heterogeneous catalysis. We present experimental evidence illustrating the advantages of multi-step discharge-catalyst treatment of NOx in simulated diesel exhaust.

We present here a phenomenological analysis of a cascade of two-step discharge-catalyst reactors. That is, each step of the cascade consists of a discharge reactor in series with a catalyst bed. These reactors are intended for use in the reduction of tailpipe emission of NOx from diesel engines. The discharge oxidizes NO to NO2, and partially oxidizes HC. The NO2 then reacts on the catalyst bed with hydrocarbons and partially oxidized HCs and is reduced to N2. The cascade may be essential because the best catalysts for this purpose that we have also convert significant fractions of the NO2 back to NO. As we show, reprocessing the gas may not only be necessary, but may also result in energy savings and increased device reliability.

The Office of Heavy Vehicle Technologies supports research to enable high-efficiency diesel engines to meet future emissions regulations, thus clearing the way for their use in light trucks as well as continuing as the most efficient powerplant for freight-haulers. Compliance with Tier 2 emission regulations for light-duty vehicles will require effective exhaust emission controls (aftertreatment) for diesels in these applications. Diesel-powered heavy trucks face a similar situation for the 2007 regulations announced by EPA in December 2000. DOE laboratories are working with industry to improve emission control technologies in projects ranging from application of new diagnostics for elucidating key mechanisms, to development and evaluation of prototype devices. This paper provides an overview of these R&D efforts, with examples of key findings and developments.

Proposed vehicle emissions regulations for the near future have prompted automotive manufactures and component suppliers to focus heavily on developing more efficient exhaust aftertreatment devices to lower emissions from spark and compression ignition engines. One of the primary pollutants from lean-burn engines, especially from diesels, are oxides of nitrogen (NOx). Current three-way catalytic converters will not have adequate performance to meet future emission reduction requirements. Therefore, there is a need for researchers and engineers to develop efficient exhaust aftertreatment devices that will reduce NOx emissions from lean-burn engines. These devices must have very high conversion of NOx gases, be unaffected by exhaust-gas impurity such as sulfur, and have minimal impact on vehicle operations and fuel economy. An effective technology for NOx control that is currently receiving a lot of attention is a non-thermal plasma system.

NOx reduction efficiency in simulated lean exhaust conditions has been examined for three proprietary catalyst materials using a non-thermal plasma discharge as a pretreatment stage to the catalyst. Using propene as the reducing agent for selective catalytic reduction, 74% reduction of NOx has been observed in the presence of 20 ppm SO2. For sulfur-free simulated exhaust, 84% NOx reduction has been obtained. Results show that the impact of sulfur on the samples examined can vary widely from virtually no effect (< 5%) to more than 20% loss in activity depending on the catalyst. Any loss due to sulfur poisoning appears to be irreversible according to limited measurements on poisoned catalysts exposed to sulfur-free exhaust streams. Catalysts were tested over a temperature range of 473-773K, with the highest activity observed at 773K. Examination of this large temperature window has shown that the optimum C1:NOx ratio changes with temperature.

NOx reduction under simulated lean burn conditions was studied using a non-thermal plasma in combination with zeolite and alumina catalysts. The influence of temperature and plasma treatment on the catalytic performance was investigated. Zeolite catalyst B showed high activity in the 150-300°C temperature region. Alumina Catalyst D was most active at temperatures higher than 250°C. In addition, the alumina catalyst was effective in oxidation of aldehydes formed during plasma treatment of the reaction mixture. When the reaction was carried out over a catalyst bed consisting of separate layers of the zeolite and alumina catalysts, the catalyst temperature range for significant NOx reduction was expanded to 150-500°C.

A double dielectric barrier discharge reactor driven by an alternating voltage is a relatively simple approach to promote oxidation of NO to NO2 for subsequent reduction in a catalyst bed. The chemical performance of such a non-thermal plasma reactor is determined by its current and electric field behavior in the gap, and by the fraction of the current carried by electrons, because the key reactants which initiate the NO oxidation and accompanying chemical changes are produced there, mostly by electron impact. We have tried to determine by models and experiments the bounds on performance of double dielectric barrier reactors and guidelines for optimization. Models reported here predict chemical results from time-resolved applied voltage and series sense capacitor data.