Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process

The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000ppm methane and 0.051gmin(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.     

A review of the catalysts used in the reduction of NO by CO for gas purification

The reduction of NO by the CO produced by incomplete combustion in the flue gas can remove CO and NO simultaneously and economically. However, there are some problems and challenges in the industrial application which limit the application of this process. In this work, noble metal catalysts and transition metal catalysts used in the reduction of NO by CO in recent years are systematically reviewed, emphasizing the research progress on Ir-based catalysts and Cu-based catalysts with prospective applications. The effects of catalyst support, additives, pretreatment methods, and physicochemical properties of catalysts on catalytic activity are summarized. In addition, the effects of atmosphere conditions on the catalytic activity are discussed. Several kinds of reaction mechanisms are proposed for noble metal catalysts and transition metal catalysts. Ir-based catalysts have an excellent activity for NO reduction by CO in the presence of O₂. Cu-based bimetallic catalysts show better catalytic performance in the absence of O₂, in that the adsorption and dissociation of NO can occur on both oxygen vacancies and metal sites. Finally, the potential problems existing in the application of the reduction of NO by CO in industrial flue gas are analyzed and some promising solutions are put forward through this review.

     

Urea as a PCDD/F inhibitor in municipal waste incineration

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at approximately 730 degrees C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Urea as a PCDD/F Inhibitor in Municipal Waste Incineration

ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from municipal waste incineration have been widely studied because of their extensive toxicity, and many efforts have been made to restrict their emissions. Although a number of chemical compounds have been shown in laboratory-scale tests to inhibit the formation of PCDD/Fs, few have been tested in pilot- or full-scale plants. This work evaluates the effect of urea as a PCDD/F inhibitor in a pilot-scale incinerator that uses refuse-derived fuel (RDF). The decomposition of urea under the test conditions was also studied using detailed kinetic modeling. An aqueous solution of urea was injected into the flue gas stream after the furnace at ~730 °C, with varied urea concentrations and flue gas residence times used between the furnace and the sampling point. The results demonstrate that urea can successfully inhibit PCDD/F formation in waste incineration if concentrations and injection points are properly adjusted. The kinetic model showed that urea can be rapidly decomposed under appropriate flue gas conditions, indicating that in addition to the urea molecule itself, decomposition products of urea can also be responsible for the reduction of PCDD/F production during incineration.     

Application of fluidized bed combustion to industrial waste treatment

Landfill and sea-dumping appear to be on their way out as acceptable methods for the disposal of untreated industrial wastes in Taiwan. Recently, there has been interest in the application of fluidized bed technology to waste incineration for efficient energy utilization and environmental protection. A pilot fluidized bed combustion system was used to investigate the incineration performance and parametric test for the waste from an industrial park. According to the experimental results, the appropriate operating conditions, including temperatures of 800-840 degrees C, aeration rates of U(0)/Um(f)-2.0 or so, and on-bed feeding, were recommended to treat such waste. The emissions of SO(x), NO(x) and CO in flue gas meet the ROC-EPA regulation.     

Computational modelling of NOx removal by selective non-catalytic reduction

This paper presents the results of computational kinetic modelling of the removal of nitrogen oxides (NO_x) from flue gases by selective non-catalytic reduction (SNCR) process using urea as a reducing agent. CHEMKIN and SENKIN computer codes were used with latest reaction mechanism parameters for simulated conditions in an isothermal plug flow reactor. Flue gas initial conditions were simulated as 70 litres/min propane containing 500 ppm background NO_x. A range of molar ratios was studied at optimum temperature. Carbon monoxide and hydrogen were investigated as potential enhancers to lower the temperature window. The modelling results suggested that the optimum temperature for peak reduction was around 1075°C with optimum molar ratios of 1.5. Hydrogen was found to be an efficient enhancer. The optimum residence time was found to be about 80 milliseconds.     

Acceleration of the Fe(III)EDTA(-) reduction rate in BioDeNO(x) reactors by dosing electron mediating compounds

BioDeNO(x), a novel technique to remove NO(x) from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N(2). Besides NO reduction, high rate biological Fe(III)EDTA(-) reduction is a crucial factor for a succesful application of the BioDeNO(x) technology, as it determines the Fe(II)EDTA(2-) concentration in the scrubber liquor and thus the efficiency of NO removal from the gas phase. This paper investigates the mechanism and kinetics of biological Fe(III)EDTA(-) reduction by unadapted anaerobic methanogenic sludge and BioDeNO(x) reactor mixed liquor. The influence of different electron donors, electron mediating compounds and CaSO(3) on the Fe(III)EDTA(-) reduction rate was determined in batch experiments (21mM Fe(III)EDTA(-), 55 degrees C, pH 7.2+/-0.2). The Fe(III)EDTA(-) reduction rate depended on the type of electron donor, the highest rate (13.9mMh(-1)) was observed with glucose, followed by ethanol, acetate and hydrogen. Fe(III)EDTA(-) reduction occurred at a relatively slow (4.1mMh(-1)) rate with methanol as the electron donor. Small amounts (0.5mM) of sulfide, cysteine or elemental sulfur accelerated the Fe(III)EDTA(-) reduction. The amount of iron reduced significantly exceeded the amount that can be formed by the chemical reaction of sulfide with Fe(III)EDTA(-), suggesting that the Fe(III)EDTA(-) reduction was accelerated via an auto-catalytic process with an unidentified electron mediating compound, presumably polysulfides, formed out of the sulfur additives. Using ethanol as electron donor, the specific Fe(III)EDTA(-) reduction rate was linearly related to the amount of sulfide supplied. CaSO(3) (0.5-100mM) inhibited Fe(III)EDTA(-) reduction, probably because SO(3)(2-) scavenged the electron mediating compound.     

Effects of water vapor pretreatment time and reaction temperature on CO(2) capture characteristics of a sodium-based solid sorbent in a bubbling fluidized-bed reactor

CO(2) capture from flue gas using a sodium-based solid sorbent was investigated in a bubbling fluidized-bed reactor. Carbonation and regeneration temperature on CO(2) removal was determined. The extent of the chemical reactivity after carbonation or regeneration was characterized via (13)C NMR. In addition, the physical properties of the sorbent such as pore size, pore volume, and surface area after carbonation or regeneration were measured by gas adsorption method (BET). With water vapor pretreatment, near complete CO(2) removal was initially achieved and maintained for about 1-2min at 50 degrees C with 2s gas residence time, while without proper water vapor pretreatment CO(2) removal abruptly decreased from the beginning. Carbonation was effective at the lower temperature over the 50-70 degrees C temperature range, while regeneration more effective at the higher temperature over the 135-300 degrees C temperature range. To maintain the initial 90% CO(2) removal, it would be necessary to keep the regeneration temperature higher than about 135 degrees C. The results obtained in this study can be used as basic data for designing and operating a large scale CO(2) capture process with two fluidized-bed reactors.     

降低FCC再生烟气NOx排放助剂的实验室评价

通过采用ACE装置与烟气NOx分析仪器联用的实验室评价方法,可在更接近实际催化裂化反应-再生过程的条件下,评价助剂对再生烟气中NOx的催化转化性能,同时还可考察助剂的加入对催化裂化产品分布的影响。采用该方法对几种降NOx助剂的性能进行了评价,结果表明,在催化剂体系中含有Pt基CO助燃剂的情况下,加入4％的RDNO;助剂后,烟气NOx降低幅度约30％～40％,且催化裂化产品分布基本不受影响。     

H2O2溶液同时脱硫脱硝实验研究

二氧化硫和氮氧化物是电厂产生的主要大气污染物,研究焦点越来越集中在在一个反应器内实现同时脱硫脱硝。实验以H2O溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,实验结果表明：H2O浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱除率影响显著,pH、氧含量对脱硝率影响不大。在整个实验范围内脱硫效率总是保持在98．5％以上,脱硝效率最高达到67．4％。     

尿素/高锰酸钾湿法烟气脱氮的试验研究

采用高锰酸钾和尿素配制成不同浓度的吸收溶液,在填有金属鲍尔环的管式吸收反应器中,对模拟烟气进行湿法烟气脱氮的研究。试验结果表明,用尿素和高锰酸钾配制成的吸收液进行湿法烟气脱氮,可以高效地脱除模拟烟气中的氮氧化物,高锰酸钾含量的增加可以显著提高脱氮效率,是决定脱氮效率高低的重要因素,在尿素和高锰酸钾含量分别为5%和0.60g/L时可以达到91.5%的平均脱氮效率;尿素含量、吸收液有效柱高和外加的SO2气体均对脱氮效率产生不同程度的影响。     

尿素/三乙醇胺吸收烟气NO_x的实验研究

以尿素作为吸收液,与NOx反应生成N2和CO2,脱除烟气中的氮氧化物。以一套双级串连的填料塔为主体反应器,分别对气速、液气比、反应物浓度、添加剂浓度和反应温度等参数对尿素溶液吸收NOx反应的影响进行了实验研究,获得了优化实验工况,研究结果显示,在气速为0.1 m/s、液气比为16 L/m3、三乙醇胺为0.01%（质量比）、尿素浓度为13%（质量比）工况下,反应温度为30~70℃,脱硝总效率可达50%以上,且随着NOx体积分数增加而提高。     

K2Cr2O7溶液同时脱硫脱硝实验研究

采用K2Cr2O7溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,考察多种因素对SO2脱除率(即脱硫率)和NO脱除率(即脱硝率)的影响。实验结果表明:K2Cr2O7浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱硫率、脱硝率影响显著;当烟气流量为0.4L/min,气相中O2体积分数为6%,SO2体积分数为0.09%,NO体积分数为0.100%,K2Cr2O7摩尔浓度为10mmol/L,反应温度为40℃时,脱硫率、脱硝率分别达到100%和64.3%。     

Reduction of combustion by-products in WTE plants: O2 enrichment of underfire air in the MARTIN SYNCOM process

The SYNCOM process involves oxygen enrichment of underfire air, recirculation of flue gas and a combustion control system using infrared thermography of the waste layer on the grate. At the demonstration plant in Coburg, operational reliability and plant availability using SYNCOM could be proven under real disposal conditions with a waste throughput of 7 t/h. Oxygen enrichment of the underfire air promotes the destruction of pollutants due to the high oxygen partial pressures and temperatures. This is then reflected in very low residual amounts of organic combustion by-products in the bottom ash and flue gas from the SYNCOM unit. The flue gas concentrations of organic pollutants are reduced, as compared with conventional operation, by over 35% (for CO, total hydrocarbons and PCDD/F) at the boiler outlet. As the flue gas flow is reduced by oxygen enrichment and flue gas recirculation, the resulting reduction in terms of kg of pollutant per Mg of waste is even higher. In the bottom ash, the level of organic residues is reduced, by 45% in the case of loss on ignition and by 55% in the case of TOC and dioxins (I-TE of PCDD/F). This is due to the higher oxygen partial pressures and the fuel bed temperature which is increased by 135 to 1200 degrees C. Other important features of the process include more intense sintering and thus improved immobilization of the bottom ash, as well as reduced flue gas and fly ash flows.     

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs.     

Evaluation of NO(x) flue gas analyzers for accuracy and their applicability for low-concentration measurements

The requirements of the Texas State Implementation Plan of the U.S. Clean Air Act for the Houston-Galveston Ozone Nonattainment Area stipulate large reductions in oxides of nitrogen (NO(x)) emissions. A large number of sources at Dow Chemical Co. sites within the nonattainment area may require the addition of continuous emission monitoring systems (CEMS) for online analysis of NO(x), CO, and O2. At the outset of this work, it was not known whether the analyzers could accurately measure NO(x) as low as 2 ppm. Therefore, NO(x) CEMS analyzers from five different companies were evaluated for their ability to reliably measure NO(x) in the 2-20 ppm range. Testing was performed with a laboratory apparatus that accurately simulated different mixtures of flue gas and, on a limited basis, simulated a dual-train sampling system on a gas turbine. The results indicate that this method is a reasonable approach for analyzer testing and reveal important technical performance aspects for accurate NO(x) measurements. Several commercial analyzers, if installed in a CEMS application with sampling conditioning components similar to those used in this study, can meet the U.S. Environmental Protection Agency's measurement data quality requirements for accuracy.     

Kinetics of carbon degradation and PCDD/PCDF formation on MSWI fly ash

The native carbon oxidation and PolyChloroDibenzo-p-Dioxins and PolyChloroDibenzoFurans, PCDD/F, formation were simultaneously studied at different temperatures (230-350 degrees C) and times (0-1440 min) in order to establish a direct correlation between the disappearance of the reagent and the formation of the products. The kinetic runs were conducted in an experimental set up where conditions were chosen to gain information on the role of fly ash deposits in cold zones of municipal solid waste incinerators in PCDD/F formation reaction. The carbon oxidation measured as the decrease of total organic carbon of fly ash was in agreement with the carbon evolved as sum of CO and CO(2). The carbon mass balance indicated an increase in the efficiency of carbon conversion in CO and CO(2) with temperature. The CO and CO(2) formation was the result of two parallel pseudo first order reactions thus giving significant information about the reaction mechanism. PCDD/F formation as a function of temperature showed that the maximum formation was achieved in a narrow range around 280 degrees C; the time effect at 280 degrees C was a progressive formation increase at least up to 900 min. The PCDF:PCDD molar ratio increased with temperature and time, and the most abundant homologues were HxCDD, HpCDD, OCDD for PCDD, and HxCDF, HpCDF within PCDF. These experimental results supported the hypothesis that the formation mechanism was the de novo synthesis.     

The importance of the location of sodium chlorite application in a multipollutant flue gas cleaning system

In this study, removing sulfur dioxide (SO2), nitrogen oxides (NO(x)), and mercury (Hg) from simulated flue gas was investigated in two laboratory-sized bubbling reactors that simulated an oxidizing reactor (where the NO and Hg(0) oxidation reactions are expected to occur) and a wet limestone scrubber, respectively. A sodium chlorite solution was used as the oxidizing agent. The sodium chlorite solution was an effective additive that enhanced the NO(x), Hg, and SO2 capture from the flue gas. Furthermore, it was discovered that the location of the sodium chlorite application (before, in, or after the wet scrubber) greatly influences which pollutants are removed and the amount removed. This effect is related to the chemical conditions (pH, absence/presence of particular gases) that are present at different positions throughout the flue gas cleaning system profile. The research results indicated that there is a potential to achieve nearly zero SO2, NO(x), and Hg emissions (complete SO2, NO, and Hg removals and -90% of NO(x) absorption from initial values of 1500 ppmv of SO2, 200 ppmv of NO(x), and 206 microg/m3 of Hg(0)) from the flue gas when sodium chlorite was applied before the wet limestone scrubber. However applying the oxidizer after the wet limestone scrubber was the most effective configuration for Hg and NO(x) control for extremely low chlorite concentrations (below 0.002 M) and therefore appears to be the best configuration for Hg control or as an additional step in NO(x) recleaning (after other NO(x) control facilities). The multipollutant scrubber, into which the chlorite was injected simultaneously with the calcium carbonate slurry, appeared to be the least expensive solution (when consider only capital cost), but exhibited the lowest NO(x) absorption at -50%. The bench-scale test results presented can be used to develop performance predictions for a full- or pilot-scale multipollutant flue gas cleaning system equipped with wet flue gas desulfurization scrubber.     

燃煤锅炉烟气NOx污染等离子体治理技术

燃煤锅炉烟气NOx污染治理技术种类较多.本文综合评述了各种烟气NOx污染等离子体治理技术,重点介绍了电晕放电脱除烟气中NOx的最新研究成果.对燃煤锅炉烟气NOx污染治理技术的研究和开发具有实用价值.