Direct and Indirect Applications of Dielectric Barrier Discharge Plasma to Catalytic Reduction of Nitrogen Oxides from Exhaust Gas

Dielectric barrier discharge （DBD） plasma was utilized to oxidize NO contained in the exhaust gas to NO2, ultimately improve the selective catalytic reduction of nitrogen oxides （NOx）. In the one case, DBD was created directly in the exhaust gas （direct application）, and in the an other case, ozone produced by DBD was injected into the exhaust gas （indirect application）. A comparative study between such direct and indirect applications of DBD plasma was made in terms of the NOx removal efficiency and the energy consumption. The NO2 content in the exhaust gas was changed by the voltage applied to the DBD device （for direct application） or by the amount of ozone added to the exhaust gas （for indirect application）. In both cases, NO was easily oxidized to NO2, and the change in NO2 content largely affected the NOx removal performance of the catalytic reactor placed downstream, where both NO and NO2 were reduced to N2 in the presence of ammonia as the reducing agent. The experiments were primarily concerned with the effect of reaction temperature on the catalytic NOx reduction at various NO2 contents. The direct and indirect applications of DBD were found to remarkably improve the catalytic NOx reduction, especially at low temperatures.

Catalyst-Packed Non-Thermal Plasma Reactor for Removal of Nitrogen Oxides

A single-stage plasma-catalytic reactor in which catalytic materials werepacked was used to remove nitrogen oxides. The packing material was scoria being made of variousmetal oxides including Al_2O_3, MgO, TiO_2, etc. Scoria was able to act not only as dielectricpellets but also as a catalyst in the presence of reducing agent such as ethylene and ammonia.Without plasma discharge, scoria did not work well as a catalyst in the temperature range of 100 ℃to 200 ℃, showing less than 10% of NOx removal efficiency. When plasma is produced inside thereactor, the NOx removal efficiency could be increased to 60% in this temperature range.

A New Approach for Removal of Nitrogen Oxides from Synthetic Gas-streams under High Concentration of Oxygen in Biofilters

The potential of using denitrifying and nitrifying concurrent biofilters for the removal of nitrogen oxides from synthetic gas streams was studied under the condition of high oxygen concentration. It was found that more than 85% of nitric oxide was removed from synthetic combustion gas-streams which contained 20% oxygen and 350 μL/L NO, with a residence time of 60 seconds. In the process, it was found that the existing of oxygen showed no evident negative effect on the efficiency of nitrogen removal.

Removal of Nitrogen Oxides in Diesel Engine Exhaust by Plasma Assisted Molecular Sieves

This paper reports the studies conducted on removal of oxides ofnitrogen (NOx) from diesel engine exhaust using electrical dischargeplasma combined with adsorbing materials such as molecular sieves.This study is being reported for the first time. The exhaust is takenfrom a diesel engine of 6 kW under no load conditions. Thecharacteristic behavior of a pulse energized dielectric barrierdischarge reactor in the diesel exhaust treatment is reported. TheNOx removal was not significant (36/100) when the reactor without anypacking was used.

Simultaneous removal of ethanol, acetaldehyde and nitrogen oxides over V-Pd/γ-Al_2O_3-TiO_2 catalyst

V-Pd/γ-Al2O3-TiO2 catalysts with different vanadium contents were prepared by a combined sol-gel and impregnation method. X-ray diffraction （XRD）, N2 adsorption-desorption （BET）, X-ray photoelectron spectroscopy （XPS） and catalytic removal of ethanol, acetaldehyde and nitrogen oxides at low temperature （〈300 ？C） were used to assess the properties of the catalysts. The results showed that the sample with 1wt% vanadium exhibited an excellent catalytic performance for simultaneous removal of ethanol, acetaldehyde and nitrogen oxides. The conversions of ethanol, acetaldehyde and nitrogen oxides at 250 ？C were 100%, 74.4% and 98.7%, respectively. V-Pd/γ-Al2O3-TiO2 catalyst with 1 wt% vanadium showed the largest surface area and higher dispersion of vanadium oxide on the catalyst surface, and possessed a larger mole fraction of V4＋ species and unique PdO species on the surface, which can be attributed to the strong synergistic effect among palladium, vanadium and the carriers. The higher activity of V-Pd/γ-Al2O3-TiO2 catalyst is related to the V4＋ and Pd2＋ species on the surface, which might be favorable for the formation of active sites.

Selective catalytic reduction of nitrogen oxides over a modified silicoaluminophosphate commercial zeolite

Nitrogen oxides（NOx：NO,NO2）are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NOx.The regulations have been strengthened and to comply with them,one of the two methods commonly used is the selective catalytic reduction of NOxby NH3（NH3-SCR）,NH3being supplied by the in-situ hydrolysis of urea.Efficiency and durability of the catalyst for this process are highly required.Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800℃.In this study,very active catalysts for the NH3-SCR of NOxwere prepared by using a silicoaluminophosphate commercial zeolite as copper host structure.Characterizations by X-ray diffraction（XRD）,scanning electron microscopy（SEM）and temperature programmed desorption of ammonia（NH3-TPD）showed that this commercial zeolite was hydrothermally stable up to 850℃ and,was able to retain some structural properties up to950℃.After hydrothermal treatment at 850℃,the NOxreduction efficiency into NH3-SCR depends on the copper content.The catalyst with a copper content of 1.25 wt.%was the most active.The difference in activity was much more important when using NO than the fast NO/NO2reaction mixture.

Ground-high altitude joint detection of ozone and nitrogen oxides in urban areas of Beijing

Based on observational data of ozone （O3） and nitrogen oxide （NOx） mixing ratios on the ground and at high altitude in urban areas of Beijing during a period of six days in November 2011, the temporal and spatial characteristics of mixing ratios were analyzed. The major findings include： urban O3 mixing ratios are low and NOx mixing ratios are always high near the road in November. Vertical variations of the gases are significantly different in and above the planetary boundary layer. The mixing ratio of O3 is negatively correlated with that of NOx and they are positively correlated with air temperature, which is the main factor directly causing vertical variation of O3 and NOx mixing ratios at 600-2100 m altitude. The NOx mixing ratios elevated during the heating period, while the O3 mixing ratios decreased： these phenomena are more significant at high altitudes compared to lower altitudes. During November, air masses in the urban areas of Beijing are brought by northwesterly winds, which transport O3 and NOx at low mixing ratios. Due to Beijing＇s natural geographical location, northwest air currents arc beneficial to the dilution and dispersion of pollutants, which can result in lower O3 and NOx background values in the Beijing urban area.

A review on nitrogen transformation and conversion during coal pyrolysis and combustion based on quantum chemical calculation and experimental study

The emission of NOx during coal combustion contributes to the formation of acid rain and photochemical smog,which would seriously affect the quality of atmospheric environment.Therefore,the decrease of NOx is of great importance for improving the efficient utilization of coal.The present review comprehensively summarized the influence factors and mechanisms of migration and transformation of nitrogen during the coal pyrolysis and combustion based on experimental study and quantum chemical calculation.Firstly,in the process of pyrolysis:the occurrence state and transformation of nitrogen were concluded.The influence of temperature,atmosphere,heating rate and catalyst on formation of NOx precursor and nitrogen migration path at the molecular level were summarized;Secondly,during the process of combustion:the influence of temperature,ambient oxygen concentration,physical structure of coal char,catalyst on heterogeneous oxidation of char(N)were summarized;The effects of char surface properties,catalyst and ambient atmosphere on heterogeneous reduction of NOx were also concluded.Based on the quantum chemical calculation,the reaction path of heterogeneous oxidation of char-N and heterogeneous reduction of NOx were described in detail.Current studies focus more on the generation of HCN and NH3,but in order to reduce the pollution of NOx from the source,it is necessary to further improve the process conditions and the optimal formula of producing more N2 during pyrolysis,as well as clarify the path of the generation of N2.Experiments study and quantum chemistry calculation should be combined to complete the research of directional nitrogen reduction during pyrolysis and denitration during combustion.

Water Content Effect on Oxides Yield in Gas and Liquid Phase Using DBD Arrays in Mist Spray

Electric discharge in and in contact with water can accompany ultraviolet（UV）radiation and electron impact, which can generate a large number of active species such as hydroxyl radicals（OH）, oxygen radical（O）, ozone（O_3） and hydrogen peroxide（H_2O_2）. In this paper, a nonthermal plasma processing system was established by means of dielectric barrier discharge（DBD）arrays in water mist spray. The relationship between droplet size and water content was examined,and the effects of the concentrations of oxides in both treated water and gas were investigated under different water content and discharge time. The relative intensity of UV spectra from DBD in water mist was a function of water content. The concentrations of both O_3 and nitrogen dioxide（NO_2） in DBD room decreased with increasing water content. Moreover, the concentrations of H_2O_2, O_3 and nitrogen oxides（NOx） in treated water decreased with increasing water content,and all the ones enhanced after discharge. The experimental results were further analyzed by chemical reaction equations and commented by physical principles as much as possible. At last,the water containing phenol was tested in this system for the concentration from 100 mg/L to9.8 mg/L in a period of 35 min.

Roles of Metallic Oxides in the Elimination Reactions of NO

The catalytic effect of several metallic oxides(Fe2O3, Cr3O3 and Ni2O3) on elimination of NO has been studied in a flow type reactor, and the roles of metallic oxide in the elimination reactions of NO has also been discussed. The results show that in the system of NO-CO-CO2-N2, the catalytic reaction of NO/CO on the metallic oxide plays a leading role in NO elimination especially for Fe2O3 and Cr2O3 samples. However, Ni2O3 and its pre-reduced samples show extremely remarkable catalytic effect on direct decomposition of NO.

Gas-Phase Conversion of the U(VI), Sr, Mo, and Zr Oxides in Nitrating Atmosphere

The gas-phase conversion of U3O8, MoO3, SrO, and their mechanical mixtures, and also of ZrO2 into water-soluble compounds in the atmosphere of (NOx + vapor H2O) or HNO3 (vapor) was studied. In the course of gas-phase conversion, U3O8 and SrO transform into water-soluble compounds (nitrates, hydroxonitrates), whereas MoO3 and ZrO2 undergo no changes. The principal possibility of separating U from Mo and Zr by gas-phase conversion of the oxides in the atmosphere of (NOx + vapor H2O) or HNO3 (vapor) was demonstrated.

The effects of nitrogen fertilizer application on methane and nitrous oxide emission/uptake in Chinese croplands

The application of nitrogen（N） fertilizer to increase crop yields has a significant influence on soil methane（CH_4） and nitrous oxide（N_2O） emission/uptake.A meta-analysis was carried out on the effect of N application on（i） CH_4 emissions in rice paddies,（ii） CH_4 uptake in upland fields and（iii） N_2O emissions.The responses of CH_4 emissions to N application in rice paddies were highly variable and overall no effects were found.CH_4 emissions were stimulated at low N application rates（〈100 kg N ha^（-1）） but inhibited at high N rates（〉200 kg N ha^（-1）） as compared to no N fertilizer（control）.The response of CH_4 uptake to N application in upland fields was 15%lower than control,with a mean CH_4 uptake factor of-0.001 kg CH_4-C kg^（-1） N.The mean N_2O emission factors were 1.00 and 0.94%for maize（Zea mays） and wheat（Triticum aestivum）,respectively,but significantly lower for the rice（Oryza sativa）（0.51%）.Compared with controls,N addition overall increased global warming potential of CH_4 and N_2O emissions by 78%.Our result revealed that response of CH_4 emission to N input might depend on the CH_4concentration in rice paddy.The critical factors that affected CH_4 uptake and N_2O emission were N fertilizer application rate and the controls of CH_4 uptake and N_2O emission.The influences of application times,cropping systems and measurement frequency should all be considered when assessing CH_4 and N_2O emissions/uptake induced by N fertilizer.

Roles of Ceria on Copper and Manganese Oxides Catalyst——Adsorption of NO and CO

A microreactor system and TPD techniques were used to study the reaction kinetics of the CO+ NO reaction and the adsorption of CO,NO,CO_2 and N_2O over Cu-Mn-O(Ⅰ)and Cu-Mn-Ce-O(Ⅱ) catalysts.The results show that the catalytic activity of(Ⅱ)is higher than that of(Ⅰ)for the CO+NO reac- tion,and the higher the conversion of NO,the larger was the activity difference between(Ⅰ)and(Ⅱ).For (Ⅰ)the rate of NO elimination is dependent on the partial pressures of NO,CO,CO_2 with the kinetics or- ders of 0.48,0.56,0.08,respectively.The TPD study shows that the presence of Ce in(Ⅱ)may promote the adsorption of NO,CO on the surface,i.e.an increase of the coverage θ_(NO),θ_(CO),which result in a decrease of the hindrance of the reaction products.For CO_2 and N_2O the situation is in the opposite,the presence of Ce makes the θ_(CO)_2)and θ_(NO)on(Ⅱ)decrease,which weakens the inhibition of CO_2 for the reaction.

Nitrogen mobility,ammonia volatilization,and estimated leaching loss from long-term manure incorporation in red soil

Nitrogen（N） loss from fertilization in agricultural fields has an unavoidable negative impact on the environment and a better understanding of the major pathways can assist in developing the best management practices. The aim of this study was to evaluate the fate of N fertilizers applied to acidic red soil（Ferralic Cambisol） after 19 years of mineral（synthetic） and manure fertilizer treatments under a cropping system with wheat-maize rotations. Five field treatments were examined： control（CK）, chemical nitrogen and potash fertilizer（NK）, chemical nitrogen and phosphorus fertilizer（NP）, chemical nitrogen, phosphorus and potash fertilizer（NPK） and the NPK with manure（NPKM, 70% N from manure）. Based on the soil total N storage change in 0–100 cm depth, ammonia（NH_3） volatilization, nitrous oxide（N_2O） emission, N plant uptake, and the potential N leaching loss were estimated using a mass balance approach. In contrast to the NPKM, all mineral fertilizer treatments（NK, NP and NPK） showed increased nitrate（NO_3~–） concentration with increasing soil depth, indicating higher leaching potential. However, total NH_3 volatilization loss was much higher in the NPKM（19.7%） than other mineral fertilizer treatments（≤4.2%）. The N_2O emissions were generally low（0.2–0.9%, the highest from the NPKM）. Total gaseous loss accounted for 1.7, 3.3, 5.1, and 21.9% for NK, NP, NPK, and NPKM treatments, respectively. Estimated N leaching loss from the NPKM was only about 5% of the losses from mineral fertilizer treatments. All data demonstrated that manure incorporation improved soil productivity, increased yield, and reduced potential leaching, but with significantly higher NH_3 volatilization, which could be reduced by improving the application method. This study confirms that manure incorporationis an essential strategy in N fertilization management in upland red soil cropping system.

Relationship of Tumor Necrosis Factor-α and Nitrogen Oxide with Treatment of Frequent Relapse Nephrotic Syndrome by Shenkangling(肾康灵)Granule in Children

Objective: To observe the relationship of tumor necrosis factor-o (TNF-a) and nitrogen oxide (NO) with the treatment of frequent relapse nephrotic syndrome (FRNS) and to explore the patho-genesis of FRNS and the therapeutic mechanism of Shenkangling (肾康灵,SKL) Granule in children. Methods: Sixty children suffering from FRNS were randomly divided into the treated group and control group, 30 in each, and the other 30 healthy children were taken as healthy group. The patients were treated with prednisone for a long-term course, and those with no effect or partial effect shown were treated with additional Tripterygium or Cytoxan in the control group, while in the treated group patients were treated with prednisone and additional SKL. The two groups were compared as to their changes of TNF-a, NO before and after treatment, and the relapses after treatment. Results: The levels of TNF-a and NO in the sick children before treatment were markedly higher than those after treatment and normal group (P< 0. 01). The positive correlation between TNF-o of FRNS cases and relapse risk displayed more significance than that between the relapse of FRNS and NO. The difference between treated group and control group was significant (P<0. 01). Conclusion: TNF-a can be regarded as the monitoring parameter of the active phase in FRNS, and the higher the level, the more possible the relapse would occur. SKL could markedly reduce the relapse rate of FRNS in children.

Supported Manganese Oxide on Graphite Oxide: Catalytic Oxidation of Nitrogen Oxide in Waste Gas

The catalytic oxidation of nitrogen oxide( NO) from waste gas was investigated using advanced oxidation process based on sulfate radicals. The manganese oxide immobilized on graphene oxide( GO) can activate peroxymonosulfate( PMS) for the oxidation of NO in waste gas. The Mn3O4 / GO catalyst system was characterized via X-ray diffraction( XRD), Fourier transform infrared spectrocopy( FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy( XPS), energy dispersive X-ray spectroscopy( EDS),and scanning electron microscope( SEM).The results showed that Mn3O4 was distributed on GO. The Mn3O4 /GO catalyst system exhibited efficient activity for NO oxidation when the Mn3O4 /GO catalyst had an optimum Mn3O4 loading. In addition,the best catalytic oxidation could be achieved within 60 min with 0. 25 mmol /L Mn3 O4 /GO catalyst, and2 mmol /L PMS dosage at 25 ℃. The catalysts also exhibited stable performance after several rounds of regeneration. Therefore,the results may have significant technical implication for utilizing Mn3O4 /PMS to oxidize NO for offgas treatment.

An Experimental Observation of the Thermal Effects and NO Emissions during Dissociation and Oxidation of Ammonia in the Presence of a Bundle of Thermocouples in a Vertical Flow Reactor

Ammonia (NH3) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH3 concentrations (5%, 10%, and 15%) and reactor temperatures between 700 K and 1000 K. The thermal effects during both NH3 dissociation (endothermic) and oxidation (exothermic) were observed using a bundle of thermocouples positioned along the central axis of the quartz reactor, while the corresponding NH3 conversions and nitrogen oxides emissions were determined by analysing the gas composition of the reactor exit stream. A stronger endothermic effect, as indicated by a greater temperature drop during NH3 dissociation, was observed as the NH3 feed concentration and reactor temperature increased. During NH3 oxidation, a predominantly greater exothermic effect with increasing NH3 feed concentration and reactor temperature was also evident;however, it was apparent that NH3 dissociation occurred near the reactor inlet, preceding the downstream NH3 and H2 oxidation. For both NH3 dissociation and oxidation, NH3 conversion increased with increasing temperature and decreasing initial NH3 concentration. Significant levels of NOX emissions were observed during NH3 oxidation, which increased with increasing temperature. From the experimental results, it is speculated that the stainless-steel in the thermocouple bundle may have catalysed NH3 dissociation and thus changed the reaction chemistry during NH3 oxidation.

Estimation of Lightning-Generated NO_(x) in the Mainland of China Based on Cloud-to-Ground Lightning Location Data

Lightning-generated nitrogen oxides(LNO_(x))have a major influence on the atmosphere and global climate change.Therefore,it is of great importance to obtain a more accurate estimation of LNO_(x).The aim of this study is to provide a reference for the accurate estimation of the total LNO_(x) in the mainland of China based on cloud-to-ground lightning(CG)location data from 2014 to 2018.The energy of each CG flash was based on the number of return strokes per CG flash,the peak current of each return stroke,and the assumed CG breakdown voltage.The energy of intracloud lightning(IC)was based on the estimated frequencies of IC and the assumed energy of each IC flash.Combining the energy of lightning and the number of nitric oxide(NO)molecules produced by unit energy(ρno),the total LNO_(x) production in the mainland of China was determined.The LNO_(x) in the mainland of China estimated in this study is in the range(0.157-0.321)×10^(9) kg per year[Tg(N)yr-1],which is on the high end of other scholars’works.Negative cloud-to-ground lightning(NCG)flashes produce the most moles of NO_(x),while positive cloud-to-ground lightning(PCG)flashes produce the least total moles of NO_(x).The breakdown voltage of PCG is greater than that of IC or NCG,while the latter has a greater output of LNO_(x).

Optimization of decoupling combustion characteristics of coal briquettes and biomass pellets in household stoves

Burning coal briquettes or biomass pellets in household decoupling stoves is of significance to the reduction of residential pollutant emissions such as NO and CO. In order to make full use of the superiority of decoupling combustion technology, the household stoves should be specially designed and optimized to adapt to fuel types and combustion characteristics. Using numerical simulation and experimental validation, this study quantitatively clarified that the reducibility of devolatilization char plays an important role in the suppression of NO emission in the decoupling combustion of coal, while the reducibility of pyrolysis gases has a dominant effect on the reduction of NO in the decoupling combustion of biomass. An optimal parameter combination of throat height and grate angle was obtained for the simultaneous suppression of NO and CO emissions in the household decoupling stove burning coal briquettes. Two types of decoupling stoves were developed to enable the clean combustion of biomass pellets. The A-type biomass stove with a multi-pass smoke tunnel shows a better comprehensive NO and CO reduction effectiveness than the B-type biomass stove consisting of a two-stage grate structure and an S-shaped pyrolysis chamber. The optimal structural parameters provided references for the design and manufacture of commercial decoupling coal and biomass stoves.

Selective synthesis of nitrate from air using a plasma-driven gas-liquid relay reaction system

The direct oxidation of nitrogen is a potential pathway to achieving the zero-carbon-emission synthesis of nitric acid or nitrate, because it does not involve ammonia synthesis and additional ammonia oxidation processes. However, the slow kinetics of nitrogen oxidation and the difficult selective control of oxidation products hinder the development of this process. In this study, a plasma-driven gas-liquid relay reaction system was developed to overcome these limitations. A typical feature of this reaction system is that it can efficiently generate NO_x under plasma exposure;moreover, the specific anions in the absorption solution can be oxidized to strong oxidants capable of relay oxidation of low-valence nitrogen oxides. This feature allows for the deep oxidation of nitrogen, thus enabling the oxidation products of nitrogen to exist in high-valence states in the absorption solution. For experimental verification, we achieved the 100% selective synthesis of nitrate under plasma exposure, with air as the supply gas and a sodium sulfate solution as the absorption solution.