Emission of Toxic HCN During NOx Removal by Ammonia SCR in the Exhaust of Lean‐Burn Natural Gas Engines

Reducing greenhouse gas and pollutant emissions is one of the most stringent priorities of our society to minimize their dramatic effects on health and environment. Natural gas (NG) engines, in particular at lean conditions, emit less CO₂ in comparison to combustion engines operated with liquid fuels but NG engines still require emission control devices for NO_x removal. Using state‐of‐the‐art technologies for selective catalytic reduction (SCR) of NO_x with NH₃, we evaluated the interplay of the reducing agent NH₃ and formaldehyde, which is always present in the exhaust of NG engines. Our results show that a significant amount of highly toxic hydrogen cyanide (HCN) is formed. All catalysts tested partially convert formaldehyde to HCOOH and CO. Additionally, they form secondary emissions of HCN due to catalytic reactions of formaldehyde and its oxidation intermediates with NH₃. With the present components of the exhaust gas aftertreatment system the HCN emissions are not efficiently converted to non‐polluting gases. The development of more advanced catalyst formulations with improved oxidation activity is mandatory to solve this novel critical issue.     

Recent lean NOx catalyst technologies for automobile exhaust control

The current status of our development work on lean NO_x catalysts for application to future gasoline and diesel engines is described. As a result of further improvements in fuel economy, the temperature of exhaust gas will be lower and there will be smaller quantities of hydrocarbons (HCs) in the exhaust of future engines. Therefore, it is necessary to improve the activity of lean NO_x catalysts at lower temperatures and achieve higher selectivity of the NO_x–HC reaction. Utilizing precious metal catalysts is one effective way of improving catalyst activity at lower temperatures, and HC adsorption and reforming are two key technologies for improving the catalyst selectivity for the NO_x–HC reaction.     

Chemie im Motor: Verbrennungsmotoren versus Brennstoffzelle und Elektromotor

This article draws a bow from the fundamentals of the flame chemistry to combustion in engines. Aspects of radical chemistry, pollutant formation and combustion are highlighted. Concepts of current and future internal combustion engines are presented. A main focus lies on pollutant formation and reduction (CO₂, CO, NO_x, HC and soot). Finally, a vision of the future role of the internal combustion engine with respect to fuel cell and electrical engine is outlined.     

Recent lean NOx catalyst technologies for automobile exhaust control

The current status of our development work on lean NO_x catalysts for application to future gasoline and diesel engines is described. As a result of further improvements in fuel economy, the temperature of exhaust gas will be lower and there will be smaller quantities of hydrocarbons (HCs) in the exhaust of future engines. Therefore, it is necessary to improve the activity of lean NO_x catalysts at lower temperatures and achieve higher selectivity of the NO_x–HC reaction. Utilizing precious metal catalysts is one effective way of improving catalyst activity at lower temperatures, and HC adsorption and reforming are two key technologies for improving the catalyst selectivity for the NO_x–HC reaction.     

A New Spark Plug to Improve the Performances of Combustion Engines: Study and Analysis of Unburned Exhaust Gases

The ignition sparks provided by the conventional spark plug do not always ensure a fast and complete combustion of the hydrocarbon-air mixture. For this reason, we offer a new type of plug with a double spark using two simultaneous discharges generated by a pulsed high voltage-power supply. This work presents the comparison of two spark plugs, a classical one and a double spark plug, by analyzing the unburned hydrocarbon gases from the exhaust pipe of the engine. For a first gasoline engine, we measure the oxygen concentration in the exhaust gases with a lambda probe and the unburned hydrocarbon by the use of GC–MS coupled with SPME extraction technique. We can observe a clear decrease of total unburned hydrocarbon (THC). For a second motor test bench, powered with propane, we complete measures in function of air/fuel ratio of the THC, NO_x, CO₂ and CO. These results confirm that we obtained a better combustion especially for leaner mixtures.     

Physicochemical properties of ceramic tape involving Ca<Subscript>0.05</Subscript> Ba<Subscript>0.95</Subscript> Ce<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3</Subscript> as an electrolyte designed for electrolyte-supported solid oxide fuel cells (IT-SOFCs)

Energetic materials such as a mixture of guanidine nitrate (GN)/basic copper nitrate (BCN) are used as gas generators in automotive airbag systems. However, at the time of the airbag inflation, the gas generators release toxic combustion gases such as CO, NH₃, and NO_x. In this study, we investigated the combustion and thermal decomposition behaviors of GN/BCN mixture, focusing primarily on their exhaust gas composition. As a result, when the exhaust gas of the combustion under constant pressure in an inert gas stream was analyzed using a detection tube, the amount of NO_x (mainly NO) yielded greater decrease with increasing atmospheric pressure as compared to the amounts of CO and NH₃. Thus, provided GN/BCN is ignited in a closed container, a large amount of NO_x is presumed to have been released during the initial stage of combustion, which yielded comparatively low pressure. Results of the thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy (TG/DSC/FTIR) indicated that the GN/BCN mixture caused endothermic decomposition at 170 °C and exothermic decomposition at 208 °C, which was accompanied by 66% mass loss. The decomposition gases, CO₂, N₂O, and H₂O, were detected via FTIR spectrum. Because N₂O was not detected in the combustion gas, it was suggested that the detected N₂O was generated at a low temperature and decomposed in high-temperature combustion.     

Recent Development of Technology in Scale-up of Plasma Reactors for Environmental and Energy Applications

To date, numerous studies have investigated the aftertreatment of exhaust gases from fossil-fueled combustors and combustion engines by plasmas as an environmental plasma application. Owing to the high power requirements of environmental plasma, it is difficult to use the plasma alone for aftertreatment; hence, a hybrid process that combines plasma processing with other techniques is required to reduce the overall power consumption. In developing countries, low-cost plasma hybrid processing has attracted considerable attention as an alternative to the selective catalytic reduction NO_x decomposition (De-NO_x) method and wet lime–gypsum SO_x decomposition method. Moreover, reduced catalytic activity can be enhanced by the plasma because of the decreased exhaust gas temperature, owing to the increased combustion efficiency. This paper reviews studies on successful air pollutant decomposition processes using the plasma chemical process with scale-up reactors. First, experimental techniques and block diagrams of various environmental plasma systems are presented. Subsequently, real-world systems of scale-up plasma reactors are described in detail. Several experimental results suggest that the hybrid treatment of particulate matter and dry De-NO_x is very promising from the viewpoint of energy consumption and material recycling. CO₂ treatment is a very important direction for future work in environmental plasma.

     

Pilot-Scale Aftertreatment Using Nonthermal Plasma Reduction of Adsorbed NOx in Marine Diesel-Engine Exhaust Gas

Regulations governing marine diesel engine NO_x emissions have recently become more stringent. As it is difficult to fulfill these requirements by combustion improvements alone, effective aftertreatment technologies are needed to achieve efficient NO_x reductions. In this study, we develop an effective NO_x-reduction aftertreatment system for a marine diesel engine that employs combined nonthermal plasma (NTP) and adsorption. Compared with selective catalytic reduction, the proposed technology offers the advantages of not requiring a urea solution or harmful heavy-metal catalysts and low operating temperatures of less than 150 °C. The NO_x reduction comprises repeated adsorption and desorption flow processes using NTP combined with NO_x adsorbents made of MnO_x–CuO. High concentrations of NO_x are treated by NTP after NO_x adsorption and desorption, and this aftertreatment system demonstrates excellent energy efficiencies of 161 g(NO₂)/kWh, which fulfills the most recent International Maritime Organization emission NO_x standards in the Tier II–III regulations for 2016 and requires only 4.3 % of the engine output power.     

Total Diesel Emission Control Technology Using Ozone Injection and Plasma Desorption

An innovative total diesel emission control system for diesel particulate and NOx simultaneous reduction is proposed. In this system, the plasma reactor is located outside the emission exhaust pipe and activated gas induced from ozone activated by the plasma is injected into the exhaust pipe. On the other hand, the NOx reduction is achieved using oxygen-poor nonthermal plasma desorption. The concentration of oxygen can be changed either by controlling the incineration state of the engine or by injecting oxygen-poor gas. Experiments are carried out for the emission of small diesel engine generator and high performance is demonstrated. The effective or apparent required plasma energy can be decreased further using this system because of the periodic or intermittent application of the plasma. In the present study, the excellent reduction energy efficiencies of 6.6 g/kWh for PM and 16 g (NO₂)/kWh for NOx are achieved.     

Sulfur impact on diesel emission control- A review

The effect of sulfur on diesel emission control is reviewed in this paper. Diesel exhaust differs from that of petrol engine exhaust in two major characteristics. Firstly, diesel exhaust contains a far higher amount of particulate matter, and secondly, the exhaust is far leaner, that is, far more oxidizing than a typical exhaust from petrol engines. Under these conditions, the conventional three-way catalysts are not effective in reducing NO_x . Emission from diesel engines is a complex phenomenon. The composition, the properties and the amount of these emissions depend on strictly technical parameters such as engine design and engine operation characteristics and on fuel and lube oil composition. Diesel fuel contains a small amount of sulfur which has an adverse effect even on the raw particulate emissions. The investigations on the effect of sulfur on hydrocarbons, CO and NO_x abatement in diesel exhaust gas is reviewed together with the newest technologies to avoid catalyst deactivation by unwanted SO₂ reactions.     

Effects of Magnetic Nanofluid Fuel Combustion on the Performance and Emission Characteristics

Although the compression ignition engines are a significant source of power, their detrimental emissions create considerable problems to the environment as well as to humans. The objective of the present experimental investigation is to examine the effects of the magnetic nanofluid fuels on combustion performance characteristics and exhaust emissions. In this regard, the Fe₃O₄ nanoparticles dispersed in the diesel fuel with the nanoparticle concentrations of 0.4 and 0.8 vol% were employed for combustion in a single-cylinder, direct-injection diesel engine. After a series of experiments, it was demonstrated that the nanoparticle additives, even at very low concentrations, have considerable influence in diesel engine characteristics. Furthermore, the results indicated that the nanofluid fuel with nanoparticle concentration of 0.4 vol% shows better combustion characteristics in comparison with that of 0.8 vol%. Based on the experimental results, NO _x and SO₂ emissions dramatically reduce, while CO emissions and smoke opacity noticeably increase with increasing the dosing level of nanoparticles.     

Rhenium- and ruthenium-containing catalysts for neutralization of automobile exhaust

The rhenium- and ruthenium-containing catalysts are active in the oxidation of CH _x and CO and in the reduction of NO _x . Comparative testing of catalyst samples under laboratory conditions and on an engine stand demonstrated that these catalysts outperform the known commercial catalysts in the neutralization of exhaust gas from automotive gasoline engines. It is, therefore, possible to completely replace expensive Rh and partially replace Pt and Pd with cheaper components—Re and Rh—in the manufacturing of catalytic converters.     

From Chemical Kinetics to Streamer Corona Reactor and Voltage Pulse Generator

This paper discusses the global chemical kinetics of corona plasma-induced chemical reactions for pollution control. If there are no significant radical termination reactions, the pollution removal linearly depends on the corona energy density and/or the energy yield is a constant. If linear radical termination reactions play a dominant role, the removal rate shows experimental functions in terms of the corona energy density. If the radical concentration is significantly affected by nonlinear termination reactions, the removal rate depends on the square root of the corona energy density. These characteristics are also discussed with examples of VOC_s and NO_x removal and multiple processing. Moreover, this paper also discusses how to match a corona plasma reactor with a voltage pulse generator in order to increase the total energy efficiency. For a given corona reactor, a minimum peak voltage is found for matching a voltage pulse generator. Optimized relationship between the voltage rise time, the output impedance of a voltage pulse generator, and the stray capacitance of a corona reactor is presented. As an example, the paper discusses a 5.0-kW hybrid corona nonthermal plasma system for NO_x removal from exhaust gases.     

少量CeO2的添加对Pd/La-Al2O3密偶催化剂三效性能的影响

以La改性的Al₂O₃为载体,采用共吸附浸渍法制备了一系列不同CeO₂含量的单Pd密偶催化剂,并对其进行了表征. PdO_x和CeO₂之间的强相互作用改善了Pd⁰再氧化为PdO的能力,同时增强了反应条件下硝酸盐,亚硝酸盐和异氰酸盐在载体上的吸附. 因此适量CeO₂的添加明显改善了新鲜催化剂对HC和NO_x的催化性能,且当CeO₂添加量为2%时催化效果最佳. Pd-Ce界面上PdO_x和CeO₂间强相互作用也使得PdO_x物种在高温时仍能以小颗粒的形式分散在载体上,从而显著地提高催化剂的热稳定性. 经1100 ℃高温老化后,CeO₂ （2%-4%）的存在明显拓宽了HC和NO_x的操作窗口,这对于提高单Pd密偶催化剂在汽车尾气处理上的催化性能有重要意义.     

By-Products NOx Control and Performance Improvement of a Packed-Bed Nonthermal Plasma Reactor

NO_x are main toxic by-products in the effluent gas whendecomposing volatile organic compounds in air by a packed-bed plasmareactor. Several types of materials such as 13X zeolite, BaTiO₃and Pd/Pt catalysts have been selected to be packed in the reactor, andmethane decomposition and NOx by-products in discharged gases areinvestigated at different range of reaction temperature and dischargeenergy density at atmospheric pressure. The ratios of methane decompositionpercentage/NO_x concentration are used to assess these packed bedmaterials and reaction conditions. The results show that usingPd/-Al₂O₃ with lower percentage Pd as packedbed, and discharging with lower discharge density at higher reactiontemperature can reduce NO_x output effectively and greatly improveperformance of the reactor.     

Highly selective NOx reduction for diesel engine exhaust via an electrochemical system

It is challenging to reduce the nitrogen oxides (NO_x) in diesel engine exhaust due to the inhibiting effect of excess oxygen. In this study, a novel electrochemical deNO_x system was developed, which eliminated the need for additional reducing materials or a sophisticated controlling system as used in current diesel after-treatment techniques. The electrochemical system consisted of an electrochemical cell modified with NO_x adsorbents and a diesel oxidation catalyst placed upstream of the cell. The system offers highly selective NO_x reduction and a strong resistance to oxygen interference with almost zero emission of secondary pollutants.     

Kinetics of nitric oxide oxidation

Nitrogen oxides are nowadays a subject of global concern. Several types of nitrogen oxides exist in the environment: N₂O, NO, NO₂, N₂O₃, N₂O₄, N₂O₅. The abbreviation NO _x usually relates to nitric oxide NO, nitrogen dioxide NO₂, and nitrous oxide N₂O. The first two are harmful pollutants for both environment and human health, whereas the third is one of the greenhouse gases. Implementation of stringent NO _x emission regulations requires the development of new NO _x removal technologies from exhaust gases. One of many proposals for NO _x emission reduction is the application of an oxidizing agent which would transform NO _x to higher nitrogen oxides with higher solubility in water. The main objective of the paper was to present the rate constant of nitric oxide oxidation, determined in our studies.     

Effects of equivalence and fuel ratios on combustion characteristics of an RCCI engine fueled with methane/n-heptane blend

Rising fuel costs and efforts for reducing greenhouse gases have led researchers to propose optimized models of combustion which have high efficiency and low emissions. Reactivity controlled compression ignition (RCCI) engines are attractive due to their high efficiency and low NO_x and soot emissions over a wide range of operating conditions. In this study, methane and n-heptane are used as low and high reactive fuels, respectively, to create suitable fuel stratification within the cylinder. Modeling is carried out by AVL FIRE coupled with a chemical kinetics solver to investigate the effects of fuel ratio, initial temperature and equivalence ratio on the combustion performance and emission characteristics. Methane/n-heptane ratios are varied according to the energy ratio of each fuel while total input energy and total equivalence ratios are fixed. By increasing methane energy ratio from 65% to 85% in the constant intake temperature and pressure, the mixture Octane number increases, which would lead to an increase in ignition delay up to 5 crank angles. As a result, IMEP would be enhanced and also NO_x emission decreases because of lower combustion temperature. By increasing intake temperature, the maximum in-cylinder pressure, heat release rate and NO_x emission would increase significantly while soot emission decreases, and also ringing intensity increases up to 10%. On the other hand, increasing intake temperature reduces volumetric efficiency; as a result, IMEP is reduced by 11%. Also by increasing equivalence ratio from 0.35 to 0.55 in a constant energy ratio, noticeable growth in the maximum amount of pressure and temperature could be achieved; consequently, NO_x emission would increase significantly, IMEP increases by 43%, and ISFC decreases by 30%. The results indicate that these parameters have significant effects on the heavy-duty RCCI engine performance and emissions.

     

CeO2-ZrO2-La2O3-Al2O3 composite oxide and its supported palladium catalyst for the treatment of exhaust of natural gas engined vehicles

Composite supports CeO2-ZrO2-Al2O3 (CZA) and CeO2-ZrO2-Al2O3-La2O3 (CZALa) were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles (NGVs) operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction (XRD) and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperature-programmed reduction (H2-TPR) and oxygen storage capacity (OSC) measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Catalytic activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. They also have significant potential in industrial application because of their high performance and low cost.     

Surface,Interface and Structure Optimization of Metal-Organic Frameworks: Towards Efficient Resourceful Conversion of Industrial Waste Gases

Industrial waste gas emissions from fossil fuel over-exploitation have aroused great attention in modern society. Recently, metal-organic frameworks (MOFs) have been developed in the capture and catalytic conversion of industrial exhaust gases such as SO₂, H₂S, NO_x, CO₂, CO, etc. Based on these resourceful conversion applications, in this review, we summarize the crucial role of the surface, interface, and structure optimization of MOFs for performance enhancement. The main points include (1) adsorption enhancement of target molecules by surface functional modification, (2) promotion of catalytic reaction kinetics through enhanced coupling in interfaces, and (3) adaptive matching of guest molecules by structural and pore size modulation. We expect that this review will provide valuable references and illumination for the design and development of MOF and related materials with excellent exhaust gas treatment performance.