Hydrogen separation from the H2/N2 mixture by using a single and multi-stage inorganic membrane

The separation characteristics of hydrogen from a gas mixture were investigated by using a single and two-stage inorganic membrane. Three palladium impregnated membranes were prepared by using the sol-gel, hydrolysis, and soaking-and-vapor deposition (SVD) techniques. A two-stage gas separation system without a recycling stream was constructed to see how much the hydrogen separation factor would be increased. Numerical simulation for the separation system was conducted to predict the separation behavior for the multi-stage separation system and to determine the optimal operating conditions at which the highest separation factor is obtained. Gas separation through each prepared membrane was achieved mainly by Knudsen diffusion. The real separation factor for the H₂/ N₂ mixture was increased with the pressure difference and temperature for a single stage, respectively. For the twostage separation system, there was a maximum point at which the highest separation factor was obtained and the real hydrogen separation factor for H₂/N₂ mixture was increased about 40 % compared with a single stage separation. The numerical simulation for the single and two-stage separation system was in a good agreement with the experimental results. By numerical simulation for the three-stage separation system, which has a recycle stream and three membranes that have the same permeability and hydrogen selectivity near to the Knudsen value, it is clear that the hydrogen separation factors for H₂/N₂ mixture are increased from 1.8 to 3.65 and hydrogen can be concentrated up to about 80 %. The separation factors increased with increasing recycle ratio. Optimal operating conditions exist at which the maximum real separation factor for the gas mixture can be obtained for three-stage gas separation and they can be predicted successfully by numerical simulation.     

Emissions of N2O from Scottish agricultural soils, as a function of fertilizer N

Potato fields and cut (ungrazed) grassland in SE Scotland gave greater annual N₂O emissions per ha (1.0–3.2 kg N₂O–N ha^-1) than spring barley or winter wheat fields (0.3–0.8 kg N₂O–N ha^-1), but in terms of emission per unit of N applied the order was potatoes > barley > grass > wheat. On the arable land, especially the potato fields, a large part of the emissions occurred after harvest.When the grassland data were combined with those for 2 years' earlier work at the same site, the mean emission over 3 years, for fertilization with ammonium nitrate, was 2.24 kg N₂O–N ha^-1 (0.62% of the N applied). Also, a very strong relationship between N₂O emission and soil nitrate content was found for the grassland, provided the water-filled pore space was > 70%. Significant relationships were also found between the emissions from potato fields and the soil mineral N content, with the added feature that the emission per unit of soil mineral N was an order of magnitude larger after harvest than before, possibly due to the effect of labile organic residues on denitrification.Generally the emissions measured were lower, as a function of the N applied, than those used as the basis for the current value adopted by IPCC, possibly because spring/early summer temperatures in SE Scotland are lower than those where the other data were obtained. The role of other factors contributing to emissions, e.g. winter freeze–thaw events and green manure inputs, are discussed, together with the possible implications of future increases in nitrogen fertilizer use in the tropics.     

Application of O3 and O3/H2O2 as post-treatment processes for color removal in swine wastewater from a membrane filtration system

This study was aimed to evaluate the use of ozone (O₃) alone and peroxone (a combination of ozone and hydrogen peroxide; O₃/H₂O₂) as post-treatment processes for color removal in swine wastewater from a membrane filtration system. Results showed that the application of ozone-alone process or the peroxone process could reduce both capital and operating costs compared to reverse osmosis (RO) treatment. Of the two oxidation processes, the ozone-alone process was the most effective for treating nanofiltration (NF)-filtered wastewater, while the peroxone process was the most effective for treating ultrafiltration (UF)-filtered wastewater.     

Syngas production from H2O and CO2 over Zn particles in a packed‐bed reactor

The solar thermochemical production of H₂ and CO (syngas) from H₂O and CO₂ is examined via a two‐step cycle based on Zn/ZnO redox reactions. The first, endothermic step is the thermolysis of the ZnO driven by concentrated solar energy. The second, nonsolar step is the exothermic reaction of Zn with a mixture of H₂O and CO₂ yielding syngas and ZnO; the latter is recycled to the first step. A series of experimental runs of the second step was carried out in a packed‐bed reactor where ZnO particles provided an effective inert support for preventing sintering and enabling simple and complete recycling to the first, solar step. Experimentation was performed for Zn mass fractions in the range of 33–67 wt % Zn‐ZnO, and inlet gas concentrations in the range 0–75% H₂O–CO₂, yielding molar Zn‐to‐ZnO conversions up to 91%. A 25 wt % Zn‐ZnO sample mixture produced from the solar thermolysis of ZnO was tested in the same reactor setup and exhibited high reactivity and conversions up to 96%. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

炭分子筛上氧、氮吸附特性的实验测定

针对BF型炭分子筛孔结构的特点,利用双分散孔结构吸附模型,采用色谱扰动-应答方法,对微孔扩散控制传质机理进行了实验认定,测定了O2的吸附平衡常数K、扩散时间常数Dc/rc2以及O2、N2两组分常温下的吸附等温线.     

Decolorization and Modeling of Synthetic Wastewater Using O3 and H2O2/O3 Processes

This research deals with the decolorization of synthetic wastewater, prepared with the acid 1:2 metal-complex textile dye C.I. Acid Blue 193, using the ozonation (O₃) and H₂O₂/O₃ processes. To minimize the number of experiments, they were performed using the 2^k factorial design. Five influential parameters were examined: initial dye concentration, ozone flow rate, initial pH value, decolorization time and H₂O₂ addition. The decolorization efficiency was 95% in 20 minutes (pH = 7; O₃ flow rate of 2 g/L.h) and a higher increase in the toxicity after the ozonation process (39%) indicates the formation of carcinogenic by-products. According to the variance test analysis, the initial dye concentration, the ozone flow rate, the initial pH value and the decolorization time and their first- and second-order interactions are significant, while the H₂O₂ addition was not important with respect to the discussed range. With the help of these significant factors a regression model was constructed and the adequacy of the model was checked. The obtained regression polynomial was used to model the relation between the absorbance and the influential parameters by fitting the response surface. This response surface may be used to predict the absorbance result from a set of influential parameters, or it can be rearranged in such a way as to predict the set of process decolorization parameters necessary to reduce the absorbance of wastewater with the given initial dye concentration, below the prescribed limit. It is also shown that the 2^k factorial design can be suitable for predicting the operating expenses of the ozonation.     

H2,CO,N2,O2和CH4在碳膜中的扩散

Diffusion of pure H2,CO,N2,O2and CH4 gases through nanoporous carbon membrane is investigated by carrying out non-equilibrium molecular dynamics(NEMD)simulations.The flux,transport diflusivity and acti-vation energy for the pure gases diffusing through carbon membranes with various pore widths were investigated.The simulation results reveal that transport diffusivity increases with temperature and pore width.and its values port diflusivities are comparablc With that of Rao and Sircar(J.Membr.Sci.,1996).indicating the NEMD simula-tion method iS a good toO]for predicting the transport diflusivities for gases in porous materialS.which iS always difficult to be accurately measured by experiments.     

Use of O3 and O3/H2O2 for degradation of organic matter from Bayer liquor towards new resource management: Kinetic and mechanism

Since the quality of bauxite resources has decreased and the organic carbon content has increased, different approaches are explored to remove the organic matter in alumina production. Advanced oxidative processes (AOPs) represent a possibility since they are widely used as an alternative for treating wastewaters to degrade organic pollutant molecules and in hydrometallurgy processes. For this reason, the goal of the project was the ozonation of Bayer liquor for organic matter removal. The ozone concentration was evaluated over time, as well as the H₂O₂ concentration and temperature. Results showed that the total organic carbon (TOC) removal achieved 19% in the most optimized condition with a kinetic rate of 0.0157 h⁻¹ –21.9 mg/L O₃, 0.05 mol/L H₂O₂ at 80°C. The colour of the liquor changed from dark brown to white-yellow, indicating that the size of the organic compounds had decreased. Also, 95.4% of degraded TOC formed CO₂, and almost 50% of the organic matter was oxalate compounds. The energy required for ozone production versus removed organic matter demonstrated that the technique proposed might be technically and economically feasible to be applied in the Bayer process. The study demonstrates the application of AOP in an extremely alkaline condition.     

Electrochemical reduction of high pressure CO2 at a Cu electrode in cold methanol

The electrochemical reduction of high pressure CO₂ with a Cu electrode in cold methanol was investigated. A high pressure stainless steel vessel, with a divided H-type glass cell, was employed. The main products from CO₂ by the electrochemical reduction were methane, ethylene, carbon monoxide and formic acid. In the electrolysis of high pressure CO₂ at low temperature, the reduction products were formed in the order of carbon monoxide, methane, formic acid and ethylene. The best current efficiency of methane was of 20% at −3.0 V. The maximum partial current density for CO₂ reduction was approximately 15 mA cm⁻². The partial current density ratio of CO₂ reduction and hydrogen evolution, i(CO₂)/i(H₂), was more than 2.6 at potentials more positive than −3.0 V. This work can contribute to the large-scale manufacturing of fuel gases from readily available and inexpensive raw materials, CO₂-saturated methanol from industrial absorbers (the Rectisol process).     

Electrochemical promotion of NO reduction by C2H4 in 10% O2 using a monolithic electropromoted reactor with Rh/YSZ/Pt elements

The reduction of NO by C₂H₄ in high excess of O₂ and temperatures 200−300 °C was investigated using a monolithic electropromoted reactor (MEPR) with twenty-two Rh/YSZ/Pt parallel plate elements. It was found that at 220–240 °C and 10% O₂ the selective catalytic reduction (SCR) of NO can be electropromoted by 450% with near 100% selectivity to N₂ and Λ_NO values up to 2.4. The corresponding rate enhancement ratio of complete C₂H₄ oxidation is up to 900% with Faradaic efficiency, , values up to 350. The system appears promising for practical applications.     

Effect of chemical fertilizer form on N2O, NO and NO2 fluxes from Andisol field

N₂O, NO and NO₂ fluxes from an Andosol soil in Japan after fertilization were measured 6 times per day for 10 months from June 1997 to April 1998 with a fully automated flux monitoring system in lysimeters. Three nitrogen chemical fertilizers were applied to the soil–calcium nitrate (NI), controlled-release urea (CU), and controlled-release calcium nitrate (CN), and also no nitrogen fertilizer (NN). The total amount of nitrogen applied was 15 g N m^–2 in the first and the second cultivation period of Chinese vegetable. In the first measuremnt period of 89 days, the total N₂O emissions from NI, CN, CU, and NN were 18.4, 16.3, 48.7, and 9.60 mgN m^–2, respectively. The total NO emissions from NI, CN, CU, and NN were 48.4, 33.7, 149, and 13.7 mgN m^–2, respectively. In the second measurement period of 53 days, the total N₂O emissions from NI, CN, and CU were 9.66, 7.23, and 20.6 mgN m^–2, respectively. The total NO emissions from NI, CN, and CU were 24.7, 2.60 and 34.2 mgN m^–2, respectively. The total N₂O emission from CU was significantly higher than CN. In the third cultivation period, all plots were applied with 10 g N m^–2 of ammonium phosphate (AP) and winter barley was cultivated. In the third measurement period of 155 days, the total N₂O and NO emissions were 9.02 mgN m^–2 and 10.2 mgN m^–2, respectively. N₂O and NO peaks were observed just after the fertilization for 30 days and 15 days, respectively. N₂O, NO and NO₂ fluxes for the year were estimated to be 38.6 81.5, 48.2 181, and –24.8 to –39.3 mgN m^–2, respectively. NO₂ was absorbed in all the plots, and a negative correlation was found between NO₂ flux and the NO₂ concentration just after the chamber closed. NO was absorbed in the winter period, and a negative correlation was found between NO flux and the NO concentration just after the chamber closed. A diurnal pattern was observed in N₂O and NO fluxes in the summer, similar to air and soil temperature. We could find a negative relationship between flux ratio of NO-N to N₂O-N and water-filled pore space (WFPS), and a positive relationship between NO-N and N₂O-N fluxes and temperature. Q₁₀ values were 3.1 for N₂O and 8.7 for NO between 530 °C.     

Ozone Formation from the Reaction Of O2-Activated N2 Molecules and a New Type of Ozone Generator with Fine Wire Electrode

Experiments using an ozone generator which has a fine steel wire electrode are described. Various conditions of the wire electrode ozone generator such as wire diameter, volume density of wire electrode, applied voltage and the effects of SF₆ addition also are reported. The efficiency of the wire electrode ozone generator in air exceeded that of the usual ozone generator for 0.1 mm wire diameter and 0.156 g cm^?3 volume density of wire over the entire range of applied voltage. This efficiency increases by adding 0.08% SF₆ in air. Increase of ozone and NOX formation in the air ozone generator can be explained by the reactions of O₂ and activated N₂.     

Quantification of N-losses as NH3, NO, and N2O and N2 from fertilized maize fields in southwestern France

Emissions of nitrogen compounds (NO, NH₃, N₂O and N₂) from heavily fertilized (280 kg(N) ha^-1) and irrigated maize fields were studied over an annual cultivation cycle in southwestern France. NO and N₂O emissions were measured by chamber techniques throughout the year. During fertilization and maize growth periods, chamber measurements were intensified and complemented by flux-gradient micrometeorological measurements of NO_x and NH₃. The two methods used, Bowen ratio and a simplified aerodynamical techniques, agree quite well and quantify NO_x and NH₃ flux variations during the period of intense emission which followed fertilizer application. Over a yearly cycle, nitrogen loss in the form of NH₃, NO and N₂O were calculated using micrometeorological flux measurements and emission algorithms calibrated with field data (chambers). The soil denitrification potential represented by the ratio N₂O/(N₂O+N₂) was measured in the laboratory to calculate potential total gaseous nitrogen loss. Taking into account all uncertainties, the total N loss into the atmosphere represents 30 to 110 kg(N) ha^-1 with about less than 1% as NH₃, 40% as NO, 14% as N₂O and 46% as N₂. This is in agreement with the agronomic nitrogen budget based on the N fertilizer input and soil furniture and, on the N-output by crops and crop residues, which displays a net imbalance of 50 to 100 kg(N) ha^-1.     

35℃氨存在条件下NaCl-Na2SO4-H2O三元体系相图的测定

通过实验测定了35℃氨存在条件下NaCl-Na2SO4-H2O三元体系溶解度数据，并绘制了该体系的相图，以卤水氨法提硝工艺进行了初步探索。     

Experimental Study and Mathematical Modeling of NO Removal Using the UV/H2O2 Advanced Oxidation Process

An experimental study on NO removal via UV/H₂O₂ process was conducted in a semi‐continuous bubble‐column reactor and the effect of some operation parameters including NO initial concentration and gas flow rates on removal efficiency was investigated. Applying UV light increased the efficiency significantly. The steady‐state removal efficiency was found to be higher at the lower gas flow rates. The bubble size as an important factor in mass transfer calculations and modeling procedure was determined at different gas flow rates using bubble photographs and image processing technique. In the ranges of flow rates studied here, the gas flow rate had no significant effect on the bubble diameter. A mathematical model was developed to describe the NO removal process. The model predictions were compared with existing experimental data, confirming a good agreement of the data.     

Effects of deep application of urea on NO and N2O emissions from an Andisol

A modeling study revealed that the depth of nitric oxide (NO) production in soil is crucial for its flux, while that of nitrous oxide (N₂O) is not. To verify this result, laboratory experiments with soil columns classified as Andisol (Hydric Hapludand) were conducted, with changing the depth of urea application, at 0–0.1 or 0.1–0.2 m. All the NO concentration profiles in soil exhibited a sharp peak at each fertilized layer within 5 days of fertilizer application. NO concentration in soil decreased abruptly as the distance from the fertilized layer increased. These findings imply that NO is produced mainly within the fertilized layer, but does not diffuse widely in the soil columns, because of rapid NO uptake within the soil. As a result, the NO flux from soil columns fertilized at 0.1–0.2 m depth over the 48-day study period was reduced to almost the same rate as that of the unfertilized one. The total NO emissions from soil columns unfertilized and fertilized at 0–0.1 and 0.1–0.2 m depth were 0.02, 1.39 (± 0.05) and 0.05 (± 0.03) kg N ha^–1, respectively, suggesting that NO emission derived from N fertilizer could be reduced to 2% by shifting the depth of fertilizer application by 0.1 m. On the other hand, soil N₂O concentration profiles exhibited a gentler peak, because of the lower uptake by soil. N₂O fluxes were affected more by the soil conditions, e.g. soil water content, than the distance between fertilized depth and soil surface. The total N₂O emissions from soil columns unfertilized and fertilized at 0–0.1 and 0.1–0.2 m were 0.02, 0.16 (± 0.03) and 0.25 (± 0.04) kg N ha^–1, respectively.     

Conversions of fuel-N,volatile-N,and char-N to NO and N2O during combustion of a single coal particle in O2/N2 and O2/H2O at low temperature

Oxy-steam combustion is a promising next-generation combustion technology. Conversions of fuel-N, volatile-N, and char-N to NO and N₂O during combustion of a single coal particle in O₂/N₂ and O₂/H₂O were studied in a tube reactor at low temperature. In O₂/N₂, NO reaches the maximum value in the devolatilization stage and N₂O reaches the maximum value in the char combustion stage. In O₂/H₂O, both NO and N₂O reach the maximum values in the char combustion stage. The total conversion ratios of fuel-N to NO and N₂O in O₂/N₂ are obviously higher than those in O₂/H₂O, due to the reduction of H₂O on NO and N₂O. Temperature changes the trade-off between NO and N₂O. In O₂/N₂ and O₂/H₂O, the conversion ratios of fuel-N, volatile-N, and char-N to NO increase with increasing temperature, and those to N₂O show the opposite trends. The conversion ratios of fuel-N, volatile-N, and char-N to NO reach the maximum values at < O₂ > = 30 vol% in O₂/N₂. In O₂/H₂O, the conversion ratios of fuel-N and char-N to NO reach the maximum values at < O₂ > = 30 vol%, and the conversion ratio of volatile-N to NO shows a slightly increasing trend with increasing oxygen concentration. The conversion ratios of fuel-N, volatile-N, and char-N to N₂O decrease with increasing oxygen concentration in both atmospheres. A higher coal rank has higher conversion ratios of fuel-N to NO and N₂O. Anthracite coal exhibits the highest conversion ratios of fuel-N, volatile-N, and char-N to NO and N₂O in both atmospheres. This work is to develop efficient ways to understand and control NO and N₂O emissions for a clean and sustainable atmosphere.     

Enrichment of 41K isotope in potassium formed on and in a rhenium electrode during plasma electrolysis in K2CO3/H2O and K2CO3/D2O solutions

It was found that potassium forms on rhenium electrodes during plasma electrolysis in K₂CO₃/H₂O and K₂CO₃/D₂O solutions, and the new potassium has unnatural isotopic ratios. The isotope ⁴¹K increases from the natural abundance, 6.7%, to as much as 32–37%. The percentage of ⁴¹K in the potassium contamination in a rhenium electrode before electrolysis was close to the natural isotopic abundance (6.7%). This result suggests that the ⁴¹K was enriched by some unknown process connected with a vigorous discharge of plasma electrolysis.     

Catalytic reduction of N2O with CH4 and C3H6 over Ag–Rh/Al2O3 bimetallic catalyst in the presence of oxygen

A study of nitrous oxide (N₂O) reduction with methane (CH₄) and propene (C₃H₆) in the presence of oxygen (5%) over Ag/Al₂O₃, Rh/Al₂O₃ and Ag–Rh/Al₂O₃ catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry     

污水微生物脱氮过程中N2O产生机理及影响因素研究进展

产生于生物脱氮过程的N₂O是一种强效的温室气体并会导致臭氧层破坏。本文综述了污水脱氮过程中N₂O的产生机理及影响因素。羟胺氧化和AOB反硝化是硝化过程产生N₂O两种主要路径,诸如溶解氧、氨氮和亚硝酸盐等因素主要通过影响微生物的活动或酶的活性而间接影响硝化过程中N₂O的产生。反硝化过程是N₂O的另一重要产生来源,其N₂O生成量的多少与N₂O酶有直接关系,而溶解氧、有机碳源和亚硝酸盐等因素会影响反硝化过程中N₂O酶的活性。目前新型脱氮工艺也成为N₂O的潜在来源,但其N₂O产生机理还有待深入研究。尽管N₂O释放与周围环境变化密切相关,但本质原因还是由于微生物的作用及酶活性受到影响所致。文章最后指出污水生物脱氮过程中N₂O产量控制与减量化策略是今后研究的主要方向,并给出了几点建议。