北京市国庆期间SO_2、CO、NO_x与O_3的监测与分析

于2001年国庆期间对北京市大气污染物SO2、CO、NOx与O3进行了连续监测,分析了各污染物浓度的变化特点及污染物之间的关系,评价了监测期间北京市的空气质量状况。结果表明:SO2、CO、NOx、O3体积分数均有明显的日变化特征。SO2体积分数日变化特征与冬季采暖期相比差异较大;NOx、CO体积分数的日变化趋势相近,低值区均出现在白天11:00～17:00;O3体积分数日变化特征显著,最大值出现在午后14:00左右,局地光化学反应生成是白天低层O3的主要来源。由相关性分析可知,O3与NOx呈负相关,相关系数为-0.53;CO与NOx呈正相关,相关系数为0.85。     

ANN–GA approach for predictive modeling and optimization of NOx emission in a tangentially fired boiler

An artificial neural network (ANN) and genetic algorithm (GA) approach to predict NOx emission of a 210 MW capacity pulverized coal-fired boiler and combustion parameter optimization to reduce NOx emission in flue gas, is proposed. The effects of oxygen concentration in flue gas, coal properties, coal flow, boiler load, air distribution scheme, flue gas outlet temperature, and nozzle tilt were studied. The data collected from parametric field experiments was used to build a feed-forward back-propagation neural net. The coal combustion parameters were used as inputs and NOx emission as outputs of the model. The ANN model was developed for full load conditions and its predicted values were verified with the actual values. The algebraic equation containing weights and biases of the trained net was used as fitness function in GA. The genetic search was used to find the optimum level of input operating conditions corresponding to low NOx emission. The results proved that the proposed approach could be used for generating feasible operating conditions.     

Effects of sodium modification, different reductants and SO(2) on NO reduction by Rh/Al(2)O(3) catalysts at excess O(2) conditions

Although many catalysts of NO reduction have been developed, the presence of excess O(2) and SO(2) significantly inhibits their performance when they are used to treat the incineration flue gas. To solve such problem, this study prepared new Rh/Al(2)O(3) catalysts and investigated the effects of Na modification, SO(2) and different reductants. Experimental results indicated that the average removal efficiency of NO at such high O(2) concentrations exceeded 80% when the Rh/Al(2)O(3) catalysts were used. CO was a better reductant than C(3)H(6) and the best concentration ratio of reductant/NO was equal to 1. Adding Na to modify Rh/Al(2)O(3) catalysts significantly enhanced the removal efficiency of NO from 80 to 99% at 250-300 degrees C, especially at relative high SO(2) concentrations. Unfortunately, Rh-Na/Al(2)O(3) catalysts do not have long-time activities for NO reduction, possibly because of the formation of NaNO(3). Both Rh/Al(2)O(3) and Rh-Na/Al(2)O(3) catalysts have good performance for NO reduction, they can feasibly be used to reduce NO in the flue gas from waste incineration.     

Photodegradation of direct yellow-12 using UV/H2O2/Fe2+

A detailed investigation of photodegradation of direct yellow-12 (DY12) using UV/H(2)O(2)/Fe(2+) has been carried out in a photochemical reactor. Experiments studied degradation as a function of concentration, decolorization and reduction in chemical oxygen demand (COD). The effect of operating parameters, such as UV, pH, amount of Fenton's reagent (H(2)O(2) and FeSO(4)), and amount of DY12 dye has also been determined. It has been observed that simultaneous utilization of UV irradiation with Fenton's reagent increases the degradation rate of DY12 dye. The dye quickly losses its color and there is an appreciable decrease in COD value, indicating that the dissolved organic have been oxidized. The kinetics of degradation of the dye in dilute aqueous solutions follows pseudo-first order kinetics. Final products detected at the end of the reaction include NO(3)(-), NO(2)(-), N(2)O, NO(2), SO(2), CO(2) and CO. Results indicate that dye degradation is dependent upon pH, UV-intensity, concentration of Fenton's reagent and dye. Acidic pH has been found to be more suitable in comparison to neutral and alkaline. The optimum concentration of Fenton's reagent (H(2)O(2)/Fe(2+)) was found as 1500/500 mg l(-1) for 50 mg l(-1) DY12 dye in water at pH 4. The results indicate that the treatment of DY12 dye wastewater with UV/Fe(2+)/H(2)O(2) system is efficient.     

Nano-structured gold catalysts supported on CeO2 and CeO2-Al2O3 for NOx reduction by CO: effect of catalyst pretreatment and feed composition

Gold catalysts supported on ceria and ceria-alumina were studied in NOx reduction by CO. Gold was loaded using deposition-precipitation method. The ceria-alumina (20 wt% alumina) support was synthesized by co-precipitation. The average size of gold and ceria nano-particles was bellow 10 nm. It was established that the type of pretreatment do not have a substantial effect on the catalytic activity. The presence of O2 in the feed leads to a high conversion of CO to CO2 but no NO conversion was registered. Both NO and CO conversion was increased adding H2 to the feed. The catalytic activity became higher upon adding higher amount of H2. Supplementary to the main reaction parallel reactions took place. Bellow 200 degrees C N2O formation and at 250 degrees C and above the NH3 formation was detected. At around 200 degrees C it was established 100% selectivity to N2. The addition of water to the feed influenced positively the CO conversion and did not influence negatively the conversion of NO. The selectivity to N2 at around 200 degrees C remained 100% independent of the presence of moisture. Alumina in the mixed support prevents the sintering of both gold and ceria nano-particles. The results obtained make the catalysts containing gold supported on ceria-alumina promising for practical application.     

Gliding arc plasma processing of CO2 conversion

Conversion of carbon dioxide (CO2) using gliding arc plasma was performed. The research was done to investigate the effect of variation of total gas flow rates and addition of auxiliary gases--N2, O2, air, water--to the CO2 conversion process. This system shows higher power efficiency than other nonthermal plasma methods. Experiment results indicate the conversion of CO2 reaches 18% at total gas flow rate of 0.8 L/min and produces CO and O2 as the main gaseous products. Among auxiliary gases, only N2 gives positive effect on CO2 conversion and the power efficiency at N2 concentration of 95% and total gas flow rate of 2 L/min increases about three times compared to pure CO2 process.     

A dual-use of DBD plasma for simultaneous NO(x) and SO(2) removal from coal-combustion flue gas

Dielectric barrier discharge (DBD) was investigated for the simultaneous removal of NO(x) and SO(2) from flue gas in a coal-combustion power plant. The DBD equipment was used in either a mode where flue gas was directed through the discharge zone (direct oxidation), or a mode where produced ozonized air was injected in the flue gas stream (indirect oxidation). Removal efficiencies of SO(2) and NO for both methods were measured and compared. Oxidation of NO is more efficient in the indirect oxidation, while oxidation of SO(2) is more efficient in the direct oxidation. Addition of NH(3), has lead to efficient removal of SO(2), due to thermal reaction, and has also enhanced NO removal due to heterogeneous reactions on the surface of ammonium salt aerosols. In the direct oxidation, concentration of CO increased significantly, while it maintained its level in the indirect oxidation.     

Nb-Re-W/Ti无毒催化剂的脱硝性能研究

为满足大气污染治理的严格要求,改进商用V_2O_5-WO_3/TiO_2脱硝催化剂有毒的弊端,提高催化剂的脱硝效率,本文采用挤出成型法制备蜂窝状Nb-Re-W/Ti(Re=Pr,Nd)无毒催化剂,在模拟烟气脱硝试验装置上进行脱硝活性测试,利用XPS和H2-TPR等表征手段对催化剂进行分析,就Nb和稀土元素的负载量对催化剂脱硝性能的影响进行探讨.研究结果表明:Nb-W/Ti催化剂中Nb最佳负载量为2.8%,最佳反应温度为350℃,NOx转化率最高可以达到95%;当Nb负载量为1.1%时,分别加入1.5%Pr和2.0%Nd后,催化剂的脱硝效率均能达到98%以上.     

微油点火燃烧器一级燃烧室点火性能试验研究

试验研究了不同一次风速和煤粉质量分数条件下微油点火燃烧器一级燃烧室的点火性能.研究结果表明,燃烧室中心温度随一次风速和煤粉质量分数的增加,呈先降低后增加的趋势;燃烧室中心线上的CO体积分数随一次风速的增加而增大,但随煤粉质量分数的增加而减小;燃烧室出口中心处的NOx体积分数随一次风速和煤粉浓度的增加则均呈现上升趋势.     

N2O removal in N2 or air by ArF excimer laser photolysis at atmospheric pressure

A photochemical process is proposed as a new efficient N(2)O removal technique in N(2) or air at atmospheric pressure and room temperature without using any catalysts. N(2)O diluted in N(2) or air was decomposed into N(2), O(2), and NO by using a 193 nm ArF excimer laser. The maximum conversion of N(2)O in N(2)O/N(2) or N(2)O/N(2)/O(2) mixtures was 93% at a laser power of 136 mJ, a repetition frequency of 5 Hz, and an irradiation time of 30 min. The formation ratios of N(2):O(2):NO in N(2)O/N(2) and N(2)O/N(2)/O(2) mixtures were 64:31:5.1% and 60:27:13%, respectively. The decomposition mechanism of N(2)O under 193 nm photolysis was discussed by comparing experimental data with calculated model using known photochemical and gas kinetic data.     

The atmospheric signature of carbon capture and storage

Compared with other industrial processes, carbon capture and storage (CCS) will have an unusual impact on atmospheric composition by reducing the CO(2) released from fossil-fuel combustion plants, but not reducing the associated O(2) loss. CO(2) that leaks into the air from below-ground CCS sites will also be unusual in lacking the O(2) deficit normally associated with typical land CO(2) sources, such as from combustion or ecosystem exchanges. CCS may also produce distinct isotopic changes in atmospheric CO(2). Using simple models and calculations, we estimate the impact of CCS or leakage on regional atmospheric composition. We also estimate the possible impact on global atmospheric composition, assuming that the technology is widely adopted. Because of its unique signature, CCS may be especially amenable to monitoring, both regionally and globally, using atmospheric observing systems. Measurements of the O(2)/N(2) ratio and the CO(2) concentration in the proximity of a CCS site may allow detection of point leaks of the order of 1000 ton CO(2) yr(-1) from a CCS reservoir up to 1 km from the source. Measurements of O(2)/N(2) and CO(2) in background air from a global network may allow quantification of global and hemispheric capture rates from CCS to the order of ±0.4 Pg C yr(-1).     

Suppression of methane/coal dust deflagration flame propagation by CO2/fly ash as a flue gas layer

To reveal the suppression characteristics of methane/coal dust deflagration flame propagation by the flue gas loading in local zones. The suppression experiments of flue gas layer (CO₂ and fly ash) with different thicknesses and fly ash concentrations were conducted in semi-open vertical combustion pipe. The flue gas layer was produced by self-designed flue gas layer generator. Flame propagation characteristics which including the flame image, velocity, the ion current and temperature were recorded by the high-speed photography, the ion current probe and the thermocouple. The residues after coal dust deflagration were characterized by FTIR (Fourier transform infrared spectroscopy). The results show that the flue gas layer has a significant suppression on deflagration flame propagation. With the increasing of flue gas layer thickness and fly ash concentration, the flame velocity, height, temperature and the ion current gradually decreases, and the suppression effect was enhanced. The asphyxiation of CO₂, heat absorption and insulation of fly ash were mainly methods for the suppression of coal dust deflagration flame.     

Photodegradation of 17beta-estradiol in water by UV-vis/Fe(III)/H2O2 system

Photodegradation of 17beta-estradiol (E2) in aqueous solutions by UV-vis/Fe(III)/H(2)O(2) system, namely Photo-Fenton system, was preliminarily investigated under a 250 W metal halide lamp (lambda > or = 313 nm). The influences of initial pH value, initial concentration of H(2)O(2) and E2 on photodegradation efficiency of E2 were discussed and the amount of CO(2) produced by the photodegradation reaction was measured. The results indicates that E2 could be decomposed efficiently in UV-vis/Fe(III)/H(2)O(2) system. Under the condition of 10.0 micromol L(-1) Fe(III), 1000 micromol L(-1) H(2)O(2) and pH 3.0, the degradation efficiency of 18.4 micromol L(-1) E2 reach 75.2% after the irradiation of 160 min. Over the range of pH 3.0-6.0, the higher acidity, the higher the degradation efficiency of E2 and initial reaction rate are. The degradation efficiency of E2 increases with increasing of initial concentration of H(2)O(2) and with decreasing of initial concentration of E2. The E2 mineralization efficiency increases with reaction time but the mineralization efficiency was lower. When the initial concentration of Fe(III) and H(2)O(2) were 10.0 and 1000 micromol L(-1), respectively, the mineralization efficiency of 18.4 micromol L(-1) E2 solution with pH 3.0 was only 21.6% after 160 min irradiation. It is suggested that the mineralization occurred probably only at aromatic ring.     

Preparation and application of granular ZnO/Al2O3 catalyst for the removal of hazardous trichloroethylene

Trichloroethylene (TCE) is a volatile and nerve-toxic liquid, which is widely used in many industries as an organic solvent. Without proper treatment, it will be volatilized into the atmosphere easily and hazardous to the human health and the environment. This study tries to prepare granular ZnO/Al(2)O(3) catalyst by a modified oil-drop sol-gel process incorporated the incipient wetness impregnation method and estimates its performance on the catalytic decomposition of TCE. The effects of different preparation and operation conditions are also investigated. Experimental results show that the granular ZnO/Al(2)O(3) catalyst has good catalytic performance on TCE decomposition and the conversion of TCE is 98%. ZnO/Al(2)O(3)(N) catalyst has better performance than ZnO/Al(2)O(3)(O) at high temperature. Five percent of active metal concentration and 550 degrees C calcination temperature are the better and economic preparation conditions, and the optimum operation temperature and space velocity are 450 degrees C and 18,000 h(-1), respectively. The conversions of TCE are similar and all higher than 90% as the oxygen concentration in feed gas is higher than 5%. By Fourier transform infrared spectrography (FT-IR) analyses, the major reaction products in the catalytic decomposition of TCE are HCl and CO(2). The Brunauer-Emmett-Teller (BET) surface areas of catalysts are significantly decreased as the calcination temperature is higher than 550 degrees C due to the sintering of catalyst materials, as well as the reaction temperature is higher than 150 degrees C due to the accumulations of reaction residues on the surfaces of catalysts. These results are also demonstrated by the results of scanning electron micrography (SEM) and energy disperse spectrography (EDS).     

Mn-Cu-La/TiO_2低温催化剂催化还原氮氧化物性能研究

采用浸渍法制备了Mn-Cu-La/TiO2催化剂,研究了其组分配比、焙烧温度等制备条件和NO进口浓度、空速、O2含量、NH3/NO摩尔比等操作条件对Mn-Cu-La/TiO2上NH3低温还原NO活性的影响;探讨了H2O、SO2对Mn-Cu-La/TiO2活性的影响.结果表明,该催化剂具有很好的低温SCR活性,空速为10 000h-1,反应温度为150℃下时NO转化率接近99.6%.180℃下同时通SO2、H2O后的360min内,活性始终保持在95%以上;单独通入SO2时,该催化剂较容易中毒;单独通入体积分数10%的H2O对催化剂活性基本没有影响,转化率始终保持在98%以上.     

Combustion of agro-waste with coal in a fluidized bed

In this study, a review of the studies done on the co-combustion of some agro-waste in a bubbling fluidized bed combustor (BFBC) having an inside diameter of 102 mm and a height of 900 mm is given. The agro-waste used to investigate the co-combustion characteristics were peach and apricot stones produced as a waste from the fruit juice industry, and olive cake produced as a waste from the olive oil industry. These are typical wastes for a Mediterranean country. A lignite coal was used for co-combustion. On-line concentrations of O₂, CO, CO₂, SO₂, NO _x and total hydrocarbons (C _m H _n ) were measured in the flue gas during combustion experiments. Variations of emissions of various pollutants were studied by changing the operating parameters (excess air ratio, fluidization velocity and fuel feed rate). Temperature distribution along the bed was measured with thermocouples. Emissions were also monitored from the exhaust. Various combinations of coal and biomass mixtures were tested. During the combustion tests, it was observed that the volatile matter from the biomass quickly volatilizes and mostly burns in the freeboard. The temperature profiles along the bed and the freeboard also confirmed this phenomenon. It was found that as the volatile matter of the biomass increases, combustion takes place more in the freeboard region. Better combustion conditions occur at higher excess air ratios. The results showed that co-combustion with these three proposed biomasses lowers the SO₂ and NO _x emissions considerably. CO and hydrocarbon emissions are lower at the higher excess air ratios.     

Aspen Plus-based simulation of a cement calciner and optimization analysis of air pollutants emission

The cement industry is a typical high energy consumption and heavy pollution industry, in which amounts of CO₂, NO, NO₂, and SO₂ discharge from the pre-calciner kiln system and cause severe greenhouse and acid rain effects. Meanwhile, reasonable division of the combustion environment in the calciner is the main method to control the formation of pollutant gases. In this article, a calciner process model in Aspen Plus is proposed based on the combustion mechanism analysis of the Dual Combustion and Denitration calciner (DD-calciner) and verified by industrial data. Then, for a concrete DD-calciner, the article studies the effects of the flow rate of coal and tertiary air on flue gas compositions and effects of the staging combustion technology on the NO _x , SO₂, and CO concentrations in the flue gas. Through comparing the model results with the relevant environmental standards, the optimization analysis for staging combustion parameters of the calciner is done, and the result shows that when the proportion of tertiary air entering the pyrolysis and combustion zone is controlled within the range of 57–65.52% (0.89 < α < 1.004), all the gas pollutants emit within accepted standards simultaneously. The calciner process model outlined in this article describes the key processes of the physical and chemical reactions in the calciner. It can be used to study the key operation and design parameters which influence the flue gas constituents, so as to provide data support for determining the pollutant emission reduction plan of the cement industries with a view to reduce air pollutant emission.     

锰基催化剂低温选择催化还原处理NOx的研究现状与展望

锰基催化剂具有较高的催化活性,且成本低,在选择性催化还原(SCR)尾气中的NO_x领域具有广阔应用前景。介绍了锰基低温SCR催化剂处理NO_x的最新进展。锰基催化剂可分为两类:锰氧化物催化剂和锰基掺杂过渡金属氧化物催化剂。针对锰氧化物催化剂,主要分析了锰的氧化价态、结晶形态、比表面积以及形态学对催化效果的影响;对于锰基掺杂过渡金属氧化物催化剂,重点分析了掺杂物对催化剂的催化能力、催化温度范围、N_2的选择性和抗SO_2、H_2O毒化能力的影响。最后在总结全文的基础上,展望了锰基催化剂的应用前景。     

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.     

Inhibition of PCDD/F and PCB formation in co-combustion

Co-combustion of coal-solid waste mixtures in pilot and laboratory-scale combustors with emphasis on monitoring of toxic chlorinated hydrocarbon emissions such as polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) and polychlorinated biphenyls (PCB) is elaborated. The objective of the work is to investigate the so-called primary measures technique. Twenty different thermally resistant inorganic compounds were added directly to the fuel as inhibitors of PCDD/F formation. The fuel-types used in this study included lignite coal, pre-treated municipal solid waste and polyvinyl chloride (PVC). Principle component analysis (PCA) provides the basis for a feasible discussion about the efficiency of 20 inhibitors on PCDD/F and PCB formation. The study showed that the metal oxides group investigated had no inhibitory effect. Although the single N- and S-containing compounds, used as additives for the type of lignite coal, solid waste and PVC fuel, are not very effective as inhibitors, all other N- and S-containing substances are capable to strongly reduce PCDD/F and PCB flue gas emission. The most effective inhibitors are (NH(4))(2)SO(4) and (NH(4))(2)S(2)O(3). (NH(4))(2)SO(4) present at 3% of the fuel can reduce the PCDD/F emissions to 90%. Its low cost and high efficiency favour them as useful for full-scale combustion units.