The Influence of Water Vapor and Sulfur Dioxide on the Catalytic Decomposition of Nitrous Oxide

In a catalysts screening for the nitrous oxide decomposition, three groups of catalysts (metals on supports, hydrotalcites, and perovskites) were studied relating to their activity in the presence of vapor or sulfur dioxide, in the temperature range from 200 to 500 °C. It was found that the water vapor strongly inhibates the nitrous oxide decomposition at T = 200–400 °C. The sulfur dioxide poisons the catalysts, in particular the perovskites. The catalysts Rh‐ZrO₂ and Ex‐Co, Rh‐Al‐HTlc are potentially suitable for the nitrous oxide decomposition in exhaust gas at around T = 500 °C.     

Kinetics of Ozone Decomposition in Water

The kinetics of ozone decomposition in water were determined experimentally over a pH range of 0.45 to 10.2 and temperature range of 3.5 to 60°C in a batch reactor. These data were analyzed and compared with th e reanalyzed data from other investigators.     

Fe2O3/Al2O3 catalysts for the N2O decomposition in the nitric acid industry

Fe₂O₃ catalysts supported on Al₂O₃ were used to remove nitrous oxide from the nitric acid plant simulated process stream (containing O₂, NO and H₂O). Catalysts were prepared by the coprecipitation method and were characterized for their physico-chemical properties by BET, XRD, AFM and TPR analysis. A strong influence of the post-preparation heating conditions on the structural and catalytic properties of the catalysts has been evidenced. Laboratory tests revealed 95% conversion of N₂O at temperature 750 °C and a slight decrease in activity in the presence of H₂O and NO. The catalysts were inert towards decomposition of NO. The pilot-plant reactor and real plant studies (up to 3300 h time-on-stream) confirmed high activity and very good mechanical stability of the catalysts as well as no decomposition of nitric oxide.     

铁改性分子筛直接催化分解一氧化二氮

采用以离子交换法制备的Fe-ZSM-5、Fe-MCM-22和Fe-Beta分子筛催化剂,系统地考察了分子筛构型、酸性和酸中心分布对N2O直接催化分解的影响.采用N2吸附、红外光谱仪(FT-IR)、NH3程序升温脱附实验(NH3-TPD)、H2程序升温还原实验(H2-TPR)和原位漫反射红外光谱(in situ DRIFTS)等方法考察了铁离子负载量、Si与Al摩尔比和分子筛构型对N2O催化分解的影响.结果表明,价键补偿Fe3 离子是N2O分解的主要活性组分;分子筛活性随Si和Al摩尔比的减少和铁离子负载量的增加而增加;Fe-Beta分子筛的催化活性明显高于Fe-ZSM-5和Fe-MCM-22分子筛;分子筛酸性和酸中心分布影响铁离子的分布,从而导致不同构型分子筛催化分解N2O的活性具有明显差异.     

Chemical Kinetics of the Thermal Decomposition of NTO

The kinetics of thermal decomposition of 3‐nitro‐2,4‐dihydro‐3H‐1,2,4‐triazol‐5‐one (NTO) in the temperature interval from 200 °C to 260 °C was investigated using a glass Bourdon gauge. The overall decomposition reaction includes two distinct stages: the fast first‐order decomposition and the subsequent autocatalytic reaction. The importance of the first stage increases with increasing decomposition temperature and decreasing loading density of the Bourdon gauge (m/V). A period of preliminary heating, at a lower temperature, strongly influences the autocatalytic stage when the decomposition is carried out at a higher temperature. In the temperature domain 200–220 °C, the Arrhenius constants of the decomposition reaction are found to be close to the values usually observed for nitrocompounds: E=173 kJ/mol and log₁₀ k≈12.5 (s⁻¹). It is shown that a simple model of NTO decomposition based on an autocatalytic reaction of the m‐th order can describe the course of the decomposition at high temperature but the m number appears to be excessively high, up to 4. A new model of the decomposition is developed, including an initial monomolecular reaction, decomposition of the crystalline substance, and an autocatalytic reaction of NTO dissolved in liquid decomposition products. This model gives the common order of autocatalysis, m=1.     

Eu_2O_3/LDPE复合材料热性能及热氧分解动力学

通过热失重法、差示扫描量热法研究了氧化铕(Eu2O3)对低密度聚乙烯(LDPE)热氧分解行为的影响及复合材料的热分解动力学。结果表明:在添加Eu2O3后,LDPE在空气气氛下的热稳定性得到了提高;Eu2O3/LDPE复合材料的热氧分解反应为一级反应;Eu2O3的加入使得LDPE热氧分解表观活化能增大;添加Eu2O3并不会影响LDPE的氧化诱导期,说明Eu2O3对LDPE的热氧稳定机理与抗氧剂不同。     

Kinetics of Heterogeneous Catalytic Ozone Decomposition in Water on an Activated Carbon

Ozone decomposition in water in the presence of an activated carbon has been studied. Variables investigated were agitation speed, carbon particle size, temperature and pH. In all cases, the presence of activated carbon improved the ozone decomposition rate. Between pH 2 and 7 the ozone decomposition rate due to both the homogeneous and heterogeneous mechanisms hardly varied while a significant increase was noticed with increasing pH. A kinetic study based on a Langmuir-Hinselwood type mechanism for the heterogeneous surface reaction was undertaken. According to this mechanism the heterogeneous ozone decomposition kinetics can be simplified to follow a first order process. Fit of experimental results to the kinetic equations derived from the mechanism allowed for the determination of the apparent first order rate constants of the ozone surface heterogeneous reaction and adsorption equilibrium constants.     

Experimental Investigation on the Heterogeneous Kinetic Process of the Low Thermal Decomposition of Ammonium Perchlorate Particles

The thermal decomposition of ammonium perchlorate has been extensively studied in the past. Nevertheless, the various results published illustrate, on the one hand, significant differences regarding the influence of different parameters on the decomposition and on the other hand, a lack of useful quantitative laws to predict the thermal behaviour of this crystal under a range of conditions (temperature, duration of exposure, presence of confinement).     

Nitrous oxide as an oxidant for ethane oxydehydrogenation

Waste nitrous oxide was used as an oxidant for ethane oxydehydrogenation performed at the range of temperature from 350 to 450 °C over iron modified zeolite catalysts. Different zeolite matrices (zeolite ZSM-5 of different Si/Al ratio, H-Y, mordenite) modified with iron cations introduced into zeolite by means of ionic exchange were applied as catalysts for the reaction under study. Additionally, amorphous silica and alumina silica as well as silicalite of MFI structure were also used as a matrix for iron ions accommodation and they were tested for oxydehydrogenation reaction. It was found that only iron modified zeolites showed activity for reaction under study. Amorphous oxide supports and crystalline neutral silicalite modified with iron cations by means of impregnation were completely inactive for oxydehydrogenation reaction. The best catalytic performance was found on iron modified zeolites of MFI structure. The Si/Al ratio of the ZSM-5 matrix influenced the activity for ethane oxydehydrogenation reaction insignificantly. N₂O oxidant was partly utilized for ethane oxidation (towards ethene or carbon oxides), while some part of the oxidant was decomposed to nitrogen and oxygen. Performing the reaction at 450 °C resulted in a high ethene yield and complete N₂O removal.     

The impact of grassland ploughing on CO2 and N2O emissions in the Netherlands

The contribution of ploughing permanent grassland and leys to emissions of N₂O and CO₂ is not yet well known. In this paper, the contribution of ploughing permanent grassland and leys, including grassland renovation, to CO₂ and N₂O emissions and mitigation options are explored. Land use changes in the Netherlands during 1970–2020 are used as a case study. Three grassland management operations are defined: (i) conversion of permanent grassland to arable land and leys; (ii) rotations of leys with arable crops or bulbs; and (iii) grassland renovation. The Introductory Carbon Balance Model (ICBM) is modified to calculate C and N accumulation and release. Model calibration is based on ICBM parameters, soil organic N data and C to N ratios. IPCC emission factors are used to estimate N₂O-emissions. The model is validated with data from the Rothamsted Park Grass experiments. Conversion of permanent grassland to arable land, a ley arable rotation of 3 years ley and 3 years arable crops, and a ley bulb rotation of 6 years ley and one year bulbs, result in calculated N₂O and CO₂ emissions totalling 250, 150 and 30 ton CO₂-equivalents ha^–1, respectively. Most of this comes from CO₂. Emissions are very high directly after ploughing and decrease slowly over a period of more than 50 years. N₂O emissions in 3/3 ley arable rotation and 6/1 ley bulb rotation are 2.1 and 11.0 ton CO₂-equivalents ha^–1 year^–1, respectively. From each grassland renovation, N₂O emissions amount to 1.8 to 5.5 ton CO₂-equivalents ha^–1. The calculated total annual emissions caused by ploughing in the Netherlands range from 0.5 to 0.65 Mton CO₂-equivalents year^–1. Grassland renovation in spring offers realistic opportunities to lower the N₂O emissions. Developing appropriate combinations of ley, arable crops and bulbs, will reduce the need for conversion of permanent pasture. It will also decrease the rotational losses, due to a decreased proportion of leys in rotations. Also spatial policies are effective in reducing emissions of CO₂ and N₂O. Grassland ploughing contributes significantly to N₂O and CO₂ emissions. The conclusion can be drawn that total N₂O emissions are underestimated, because emissions from grassland ploughing are not taken into account. Specific emission factors and the development of mitigation options are required to account for the emissions and to realise a reduction of emissions due to the changes in grassland ploughing.     

Impact of different forms of N fertilizer on N2O emissions from intensive grassland

Nitrous oxide (N₂O) emissions were measured over two years from an intensively managed grassland site in the UK. Emissions from ammonium nitrate (AN) and urea (UR) were compared to those from urea modified by various inhibitors (a nitrification inhibitor, UR(N), a urease inhibitor, UR(U), and both inhibitors together, SU), as well as a controlled release urea (CR). N₂O fluxes varied through time and between treatments. The differences between the treatments were not consistent throughout the year. After the spring and early summer fertilizer applications, fluxes from AN plots were greater than fluxes from UR plots, e.g. the cumulative fluxes for one month after N application in June 1999 were 5.2 ± 1.1 kg N₂O-N ha^–1 from the AN plots, compared to 1.4 ± 1.0 kg N₂O-N ha^–1 from the UR plots. However, after the late summer application, there was no difference between the two treatments, e.g. cumulative fluxes for the month following N application in August 2000 were 3.3 ± 0.7 kg N₂O-N ha^–1 from the AN plots and 2.9 ± 1.1 kg N₂O-N ha^–1 from the UR plots. After all N applications, fluxes from the UR(N) plots were much less than those from either the AN or the UR plots, e.g. 0.2 ± 0.1 kg N₂O-N ha^–1 in June 1999 and 1.1 ± 0.3 kg N₂O-N ha^–1 in August 2000. Combining the results of this experiment with earlier work showed that there was a greater N₂O emission response to rainfall around the time of fertilizer application in the AN plots than in the UR plots. It was concluded that there is scope for reducing N₂O emissions from N-fertilized grassland by applying UR instead of AN to wet soils in cool conditions, e.g. when grass growth begins in spring. Applying UR with a nitrification inhibitor could cut emissions further.     

Estimates of the interannual variations of N2O emissions from agricultural soils in Canada

The DNDC model was used to estimate direct N₂O emissions from agricultural soils in Canada from 1970 to 1999. Simulations were carried out for three soil textures in seven soil groups, with two to four crop rotations within each soil group. Over the 30-year period, the average annual N₂O emission from agricultural soils in Canada was found to be 39.9 Gg N₂O–N, with a range from 20.0 to 77.0 Gg N₂O–N, and a general trend towards increasing N₂O emissions over time. The larger emissions are attributed to an increase in N-fertilizer application and perhaps to a trend in higher daily minimum temperatures. Annual estimates of N₂O emissions were variable, depending on timing of rainfall events and timing and duration of spring thaw events. We estimate, using DNDC, that emissions of N₂O in eastern Canada (Atlantic Provinces, Quebec, Ontario) were approximately 36% of the total emissions in Canada, though the area cropped represents 19% of the total. Over the 30-year period, the eastern Gleysolic soils had the largest average annual emissions of 2.47 kg N₂O–N ha^–1 y^–1 and soils of the dryer western Brown Chernozem had the smallest average emission of 0.54 kg N₂O–N ha^–1 y^–1. On average, for the seven soil groups, N₂O emissions during spring thaw were approximately 30% of total annual emissions. The average N₂O emissions estimates from 1990 to 1999 compared well with estimates for 1996 using the IPCC methodology, but unlike the IPCC methodology our modeling approach provides annual variations in N₂O emissions based on climatic differences.     

Zn, Al, Rh-mixed oxides derived from hydrotalcite-like compound and their catalytic properties for N2O decomposition

The catalytic decomposition of nitrous oxide was studied over Zn, Al, Rh-mixed oxides derived from hydrotalcite-like compounds (HTlc) as a precursor. The study showed that, when the Zn/Al atomic ratio was 3, the rate of ZnAlRh-HTlc for N₂O decomposition increased with Rh loading up to 1.4 wt% (4.55 × 10⁴ μmol g⁻¹ h⁻¹ at 400°C), and levels off with further increase in Rh loading. Analogous behavior was found in the presence of NO₂ and water. In the presence of 0.5% water, the activity decreased with decreasing Zn/Al ratio, whereas the activity for N₂O decomposition in the presence of 0.1% NO₂ reached a maximum when the Zn/Al ratio was 3. The observed catalytic activities were comparable to those of the reported catalysts in the presence of NO₂ and water.     

N2O and NO emissions from different N sources and under a range of soil water contents

Emissions of nitrous oxide (N₂O) and nitric oxide (NO) have been identified as one of the most important sources of atmospheric pollution from grasslands. Soils are major sources for the production of N₂O and NO, which are by-products or intermediate products of microbial nitrification and denitrification processes. Some studies have tried to evaluate the importance of denitrification or nitrification in the formation of N₂O or NO but there are few that have considered emissions of both gases as affected by a wide range of different factors. In this study, the importance of a number of factors (soil moisture, fertiliser type and temperature) was determined for N₂O and NO emissions. Nitrous oxide and NO evolution in time and the possibility of using the ratio NO:N₂O as an indicator for the processes involved were also explored. Dinitrogen (N₂) and ammonia (NH₃) emissions were estimated and a mass balance for N fluxes was performed. Nitrous oxide and NO were produced by nitrification and denitrification in soils fertilised with and by denitrification in soils fertilised with . Water content in the soil was the most important factor affecting N₂O and NO emissions. Our N₂O and NO data were fitted to quadratic (r=0.8) and negative exponential (r=0.7) equations, respectively. A long lag phase was observed for the N₂O emitted from soils fertilised with (denitrification), which was not observed for the soils fertilised with (nitrification) and was possibly due to a greater inhibiting effect of low temperatures on microbial activity controlling denitrification rather than on nitrification. The use of the NO:N₂O ratio as a possible indicator of denitrification or nitrification in the formation of N₂O and NO was discounted for soils fertilised with . The N mass balance indicated that about 50 kg N ha⁻¹ was immobilised by microorganisms and/or taken up by plant roots, and that most of the losses ocurred in wet soils (WFPS >60%) as N₂ and NH₃ losses (>55%).     

Kinetics of Organic Matter Removal in a Chemical Sequential Reactor (CSR)

The Chemical Sequential Reactor (CSR) can be considered as an advanced oxidation process able to treat wastewaters with ozone. Its operation involves a succession of acidic and alkaline pH conditions throughout continuous ozonation. The two oxidation mechanisms (direct reaction of molecular ozone and hydroxyl free radical reactions], coupled with carbon dioxide stripping, increase removal rates and ozone efficiency. Ozone efficiency is also maintained for longer periods.     

Decomposition of nitrous oxide over supported rhodium catalysts and dependency on feed gas composition

The catalytic decomposition of nitrous oxide to nitrogen and oxygen was studied overRh/ZnO, Rh/CeO₂, Rh/ZSM-5, CuZSM-5 and CoAlCO₃HT (hydrotalcite). The effects of metal loading and calcination conditions upon the catalytic performance were examined on Rh/ZnO. A 0.5 wt.% Rh/ZnO catalyst was found to be the most active catalyst, whose reaction rate was 4.0 × 10⁴ μmol(N₂O) · g⁻¹ · h⁻¹ under the conditions of 950 ppm N₂O and 5% O₂ at 300°C. The oxidized Rh/ZnO showed a higher activity than that calcined in a reducing atmosphere. The TEM and EDX observations revealed the formation of particles of ca. 50Åin diameter. They consisted of rhodium and zinc oxides as major and minor components, respectively. The activities of all these catalysts decreased when NO₂ and H₂O were added to the feed.     

Theoretical Analysis of N2O to N2 Conversion During the Catalytic Decomposition of NO by Cu-Zeolites

Catalytic reactions of N₂O in Cu-exchanged silica zeolites (ZSM-5) have been investigated theoretically using first-principles density functional theory (DFT). We consider four possible reaction paths for the production of N₂, including (i) ZCu+N₂OZCuO+N₂, (ii) ZCuO+N₂OZCuO₂+N₂, (iii) ZCu+NO+N₂OZCuNO₂+N₂ and (iv) ZCu+NO₂+N₂OZCuNO₃+N₂ (Z refers to zeolites). Reactions (i) and (iii) are found to be the most favorable, whereas reactions (ii) and (iv) have much larger barriers. The implication for N₂O reactions in non-selective reduction of NO by CO is also discussed.     

有机铝聚合物反应釜的放大设计

简述了有机铝聚合物的制备中试工艺,通过计算,确定了放大后反应釜的传热面积、搅拌类型、搅拌转速及搅拌功率.为方便加料位置的调整,专门设计了可旋转的加料管.试生产结果表明放大设计是可行的.     

Kinetics of the formation and decomposition of chlorination by-products in surface waters

The presence of organic chlorination by-products (CBPs) in drinking waters has caused great public health concerns. One of the most important factors affecting their formation during the disinfection procedure is reaction time. The kinetics of the formation of CBPs can be different for the different categories or species of compounds, depending also on the chlorine dose, organic matter content and the presence of bromide ion. Decomposition of some CBPs also occurs due to hydrolysis or reactions with residual chlorine. Therefore, the final concentrations of individual species of CBPs reaching the consumers’ tap may deviate from the predictions. The aim of the present investigation was the determination of formation or decomposition kinetics of CBPs during chlorination of natural waters. 24 CBPs were studied in chlorinated water from three different sources. Different speciation of CBPs and different formation rates were observed for different water quality regarding bromide ion presence and organic matter content. Decomposition of some CBPs occurred, specifically haloketones, BCA and DBA, after an initial formation step. The percentages of incorporation of chlorine and organic matter into CBPs indicated that other halogenated compounds not identified during the present study have also been formed during chlorination. The importance of chlorine dose for the formation of CBPs and for the incorporation of organic matter was highlighted. Moreover, linear correlations were observed between the concentrations of chloroform-MCA, chloroform-DCA and chloroform-TCA as well as between total THMs and total HAAs, in all waters studied.     

Towards a Revised Coefficient for Estimating N2O Emissions from Legumes

The Intergovernmental Panel on Climate Change (IPCC) standard methodology to conduct national inventories of soil N₂O emissions is based on default (or Tier I) emission factors for various sources. The objective of our study was to summarize recent N₂O flux data from agricultural legume crops to assess the emission factor associated with rhizobial nitrogen fixation. Average N₂O emissions from legumes are 1.0 kg N ha⁻¹ for annual crops, 1.8 kg N ha⁻¹ for pure forage crops and 0.4 kg N ha⁻¹ for grass legume mixes. These values are only slightly greater than background emissions from agricultural crops and are much lower that those predicted using 1996 IPCC methodology. These field flux measurements and other process-level studies offer little support for the use of an emission factor for biological N fixation (BNF) by legume crops equal to that for fertiliser N. We conclude that much of the increase in soil N₂O emissions in legume crops may be attributable to the N release from root exudates during the growing season and from decomposition of crop residues after harvest, rather than from BNF per se. Consequently, we propose that the biological fixation process itself be removed from the IPCC N₂O inventory methodology, and that N₂O emissions induced by the growth of legume crops be estimated solely as a function of crop residue decomposition using an estimate of above- and below-ground residue inputs, modified as necessary to reflect recent findings on N allocation.