Synthesis of a chabazite-supported copper catalyst with full mesopores for selective catalytic reduction of nitrogen oxides at low temperature

A series of meso‐microporous copper‐supporting chabazite molecular sieve（CuSAPO‐34） catalysts with excellent performance in low‐temperature ammonia selective catalytic reduction（NH3‐SCR）have been synthesized via a one‐pot hydrothermal crystallization method. The physicochemical properties of the catalysts were characterized by scanning electron microscopy, transmission electron microscopy, N2 adsorption‐desorption measurements, X‐ray diffraction, 27 Al magic angle spinning nuclear magnetic resonance, diffuse reflectance ultraviolet‐visible spectroscopy, inductively coupled plasma‐atomic emission spectroscopy, X‐ray photoelectron spectroscopy, temperature‐programmed reduction measurements, and electron paramagnetic resonance analysis. The formation of micro‐mesopores in the Cu‐SAPO‐34 catalysts decreases diffusion resistance and greatly improves the accessibility of reactants to catalytic active sites. The main active sites for NH3‐SCR reaction are the isolated Cu^2＋ species displaced into the ellipsoidal cavity of the Cu‐SAPO‐34 catalysts.

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.

STUDIES ON TBP-NO_x——A NEW OXIDIZING AGENT PREPARED FROM NITROGEN OXIDES

Nitrogen oxides(NO_2 and NO)are absorbed by tributyl phosphorate(TBP)to fom a new complex mixture of TBP-NO_x. which is used as a selective oddizing agent to oxidize benzylalcohols to corresponding sldehydes or ketones In high yield. In the reaction process, nitrogen oxides are llberated mildly and mainly reduced to nitrogen, while tributyl phosphorate is recovered end recycled.

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.

Indoor Nitrogen Oxides Occurrence, Modeling and Prediction

Outdoor air quality, building materials, HVAC （Heating, Ventilation, Air Conditioning） systems and people activity are important factors in human exposition of polluted indoor air. The degree of signification varies in dependence on pollution character and its sources. Buildings eliminate significantly people exposition of outdoor pollutants, but on the other hand, buildings are significant source of indoor pollution. The contamination of indoor air is largely from the use of gas for heating and cooking appliances. A comprehensive analysis of indoor air pollution by nitrogen oxides shows that the extent of indoor air pollution and consequent exposure varies as a result of many factors mainly the differing dislribution of appliances and their level of use. This study aims to formulate a mathematical model for the production of nitrogen oxides indoors. The physical processes that determine the concentrations of indoor nitrogen oxides as a function of outdoor concentrations, indoor emission rates and building characteristics have been mathematically described. The mathematical model developed has been parameterized for typical Slovak residences. The modeling of the occurrence of indoor nitrogen oxides and verification of the model is presented in this paper.

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.

Multi-Pollutant Formation and Control in Pressurized Oxy-Combustion:SO_(x),NO_(x),Particulate Matter,and Mercury

Oxy-combustion is a promising carbon-capture technology,but atmospheric-pressure oxy-combustion has a relatively low net efficiency,limiting its application in power plants.In pressurized oxycombustion(POC),the boiler,air separation unit,flue gas recirculation unit,and CO_(2)purification and compression unit are all operated at elevated pressure;this makes the process more efficient,with many advantages over atmospheric pressure,such as low NO_(x)emissions,a smaller boiler size,and more.POC is also more promising for industrial application and has attracted widespread research interest in recent years.It can produce high-pressure CO_(2)with a purity of approximately 95%,which can be used directly for enhanced oil recovery or geo-sequestration.However,the pollutant emissions must meet the standards for carbon capture,storage,and utilization.Because of the high oxygen and moisture concentrations in POC,the formation of acids via the oxidation and solution of SO_(x)and NO_(x)can be increased,causing the corrosion of pipelines and equipment.Furthermore,particulate matter(PM)and mercury emissions can harm the environment and human health.The main distinction between pressurized and atmospheric-pressure oxy-combustion is the former’s elevated pressure;thus,the effect of this pressure on the pollutants emitted from POC—including SO_(x),NO_(x),PM,and mercury—must be understood,and effective control methodologies must be incorporated to control the formation of these pollutants.This paper reviews recent advances in research on SO_(x),NO_(x),PM,and mercury formation and control in POC systems that can aid in pollutant control in such systems.

Calculations and Sensitivity Analysis of Chlorine-,NO_(x)-,and Bromine-Depleting Cycles of Stratospheric Ozone

This paper presents an engineering system approach using a 2D model of conservation of mass to study the dynamics of ozone and concerned chemical species in the stratosphere.By considering all fourteen photolysis,ozone-generating,and-depleting chemical reactions,the model calculated the transient,spatial changes of ozone under different physical-chemical-radiative conditions.Validation against the measured data demonstrated good accuracy,close match of our model with the observed ozone concentrations at both 20°S and 90°N locations.The deviation in the average concentration was less than 1% and in ozone profiles less than 17%.The impacts of various chlorine-(Cl),nitrogen oxides-(NO_(x)),and bromine-(Br)depleting cycles on ozone concentrations and distribution were investigated.The chlorine catalytic depleting cycle was found to exhibit the most significant impact on ozone dynamics,confirming the key role of chlorine in the problem of ozone depletion.Sensitivity analysis was conducted with levels of 25%,50%,100%,200%,and 400% of the baseline value.The combined cycles(Cl+NO_(x)+Br)showed the most significant influence on ozone behavior.The total ozone abundance above the South Pole could decrease by a small 3%,from 281 DU(Dubson Units)to 273 DU for the 25% level,or by a huge thinning of 60%to 114 DU for the 400% concentration level.When the level of chlorine gases increased beyond 200%,it would cause ozone depletion to a level of ozone hole(below 220 DU).The 2D Ozone Model presented in this paper demonstrates robustness,convenience,efficiency,and executability for analyzing complex ozone phenomena in the stratosphere.

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.

Nitrosation Reaction Without Nitrogen Oxide Waste Gas Emission and Its Engineering Practice

The gas-liquid phase equilibrium is used in controlling the nitrosation reaction process. Decomposition of nitrous acid and oxidation side reaction.are suppressed in a closed reaction system. The system pressure is used as the criterion of the end of reaction, avoiding excessive feeding and reducing＇the decomposition＇of nitrous acid. The head space of the reactor is used as the gas buffer, stabilizing the feeding fluctuations and inhibiting the side reaction, decomposition of nitrous acid. Nitrogen oxide concentration is controlled at the minimum level.Thus the zero release ofnitrogen ox!de waste gas can be achieved without using any absorption process.

Dynamic model for predicting nitrogen oxide concentration at outlet of selective catalytic reduction denitrification system based on kernel extreme learning machine

To solve the increasing model complexity due to several input variables and large correlations under variable load conditions,a dynamic modeling method combining a kernel extreme learning machine(KELM)and principal component analysis(PCA)was proposed and applied to the prediction of nitrogen oxide(NO_(x))concentration at the outlet of a selective catalytic reduction(SCR)denitrification system.First,PCA is applied to the feature information extraction of input data,and the current and previous sequence values of the extracted information are used as the inputs of the KELM model to reflect the dynamic characteristics of the NO_(x)concentration at the SCR outlet.Then,the model takes the historical data of the NO_(x)concentration at the SCR outlet as the model input to improve its accuracy.Finally,an optimization algorithm is used to determine the optimal parameters of the model.Compared with the Gaussian process regression,long short-term memory,and convolutional neural network models,the prediction errors are reduced by approximately 78.4%,67.6%,and 59.3%,respectively.The results indicate that the proposed dynamic model structure is reliable and can accurately predict NO_(x)concentrations at the outlet of the SCR system.

Experimental Study on Ammonia Co-Firing with Coal for Carbon Reduction in the Boiler of a 300-MW Coal-Fired Power Station

To reduce CO_(2) emissions from coal-fired power plants,the development of low-carbon or carbon-free fuel combustion technologies has become urgent.As a new zero-carbon fuel,ammonia(NH_(3))can be used to address the storage and transportation issues of hydrogen energy.Since it is not feasible to completely replace coal with ammonia in the short term,the development of ammonia-coal co-combustion technology at the current stage is a fast and feasible approach to reduce CO_(2) emissions from coal-fired power plants.This study focuses on modifying the boiler and installing two layers of eight pure-ammonia burners in a 300-MW coal-fired power plant to achieve ammonia-coal co-combustion at proportions ranging from 20%to 10%(by heat ratio)at loads of 180-to 300-MW,respectively.The results show that,during ammonia-coal co-combustion in a 300-MW coal-fired power plant,there was a more significant change in NO_(x) emissions at the furnace outlet compared with that under pure-coal combustion as the boiler oxygen levels varied.Moreover,ammonia burners located in the middle part of the main combustion zone exhibited a better high-temperature reduction performance than those located in the upper part of the main combustion zone.Under all ammonia co-combustion conditions,the NH_(3) concentration at the furnace outlet remained below 1 parts per million(ppm).Compared with that under pure-coal conditions,the thermal efficiency of the boiler slightly decreased(by 0.12%-0.38%)under different loads when ammonia co-combustion reached 15 t·h^(-1).Ammonia co-combustion in coal-fired power plants is a potentially feasible technology route for carbon reduction.

Analyzing the surface passivity effect of germanium oxynitride:a comprehensive approach through first principles simulation and interface state density

High-purity germanium(HPGe)detectors,which are used for direct dark matter detection,have the advantages of a low threshold and excellent energy resolution.The surface passivation of HPGe has become crucial for achieving an extremely low energy threshold.In this study,first-principles simulations,passivation film preparation,and metal oxide semiconductor(MOS)capacitor characterization were combined to study surface passivation.Theoretical calculations of the energy band structure of the -H,-OH,and -NH_(2) passivation groups on the surface of Ge were performed,and the interface state density and potential with five different passivation groups with N/O atomic ratios were accurately analyzed to obtain a stable surface state.Based on the theoretical calculation results,the surface passivation layers of the Ge_(2)ON_(2) film were prepared via magnetron sputtering in accordance with the optimum atomic ratio structure.The microstructure,C-V,and I-V electrical properties of the layers,and the passivation effect of the Al/Ge_(2)ON_(2)/Ge MOS were characterized to test the interface state density.The mean interface state density obtained by the Terman method was 8.4×10^(11) cm^(-2) eV^(-1).The processing of germanium oxynitrogen passivation films is expected to be used in direct dark matter detection of the HPGe detector surface passivation technology to reduce the detector leakage currents.

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.

Review of Denitrogenation of Algae Biocrude Produced by Hydrothermal Liquefaction

Recently, algae biocrude has drawn considerable attention as algae are considered to be one of the major fuel feedstocks of the future. Based on some impressive results achieved under appropriate conditions, the algae hydrothermal liquefaction (HTL) process has proven to be energy efficient. However, the HTL of biocrude is characterized by a high nitrogen content, which prevents its use in the field of transportation due to the associated nitrogen oxide emissions. Despite this toxicity, few research efforts have focused on the denitrogenation of algae biocrude. In this study, we review the effect of different strain-specific operation parameters and process upgrades with respect to the nitrogen content of biocrude. To achieve denitrogenation, chemical engineering may be required, although some improvements in biocrude properties have been achieved in a number of process upgrades. The use of similar successful pathways has the potential to improve the field of HTL biocrude denitrogenation. These methods, including the adsorptive and extractive denitrogenations of fossil fuels and the hydrodenitrogenation of the main nitrogen compounds, are helpful for developing a better understanding of the potential of denitrogenation for algae HTL biocrude. We also recommend the use of some available catalysts and corresponding operation parameters to promote continued research on denitrogenation. © 2017, The Author(s).

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.