半焦负载钙和铁催化还原NO的研究

用浸渍法制备负载Ca和Fe的褐煤半焦,采用程序升温和恒温法在石英固定床反应器上于常压反应条件下研究了NO-半焦催化还原反应.研究发现,Ca和Fe对半焦还原NO的反应具有催化作用,其中Fe的催化作用强于Ca;热处理温度升高,Ca的催化作用降低,但热处理温度的变化基本不影响Fe的催化活性;CO和O₂气氛可以促进NO的还原,温度升高CO和O₂的促进作用减小.     

柴油表征燃料在高浓度CO2氛围下燃烧机理的分析

为研究高浓度CO₂在高温高压情况下对柴油燃烧特性的影响,提出了柴油表征燃料在CO₂/O₂氛围下的燃烧反应机理.通过量子化学计算了化学反应路径并对反应路径进行分析,最后进行柴油表征燃料燃烧的仿真.通过搭建定容燃烧弹试验台架和可视化系统进行试验与仿真分析,结果表明：在50% CO₂+50% O₂氛围下,对仿真与实验的火焰燃烧极限长度和火焰纵截面面积进行对比,最小误差分别为0.39%和0.64%,最大误差分别为8.54%和4.94%,说明此机理适用于高浓度CO₂氛围下柴油燃烧特性的研究;CO₂的化学效应在柴油表征燃料燃烧时具有促进作用,CO₂在2600 K时发生热解,热解产物CO与H自由基等发生反应可以生成着火促进剂·OH;柴油在50% CO₂+50% O₂、43% CO₂+57% O₂和35% CO₂+65% O₂氛围下的燃烧效率比空气氛围分别提高了28.2%、30.4%和33.3%.     

焦炭流化床燃烧条件下氧化亚氮生成途径的实验研究

在小型电加热流化床实验台上对一种无烟煤焦炭燃烧过程中氧化亚氮生成途径进行了实验研究。实验结果表明，HCN的气相氧化反应和NO与焦炭表面多相反应均为N2O的来源。HCN的析出是焦炭脱挥发分的结果，制焦温度越高，HCN的生成机会越小，HCN的氧化反应在N2O生成过程中作用越小，这时，NO和焦炭表面的多相应主导着N2O的生成。     

柴油/甲醇组合燃烧发动机的氮氧化物排放研究

在增压共轨发动机上采用柴油/甲醇组合燃烧(DMCC)方式进行了氮氧化物排放特性研究.对DMCC模式下NO x、NO、NO2等排放与纯柴油模式的对比分析表明:DMCC模式下的NO x排放比原机模式平均下降10%以上,NO平均下降幅度超过40%;采用DMCC模式后,NO2排放量都有明显大幅度的升高,并且NO2/NO比值呈现显著增大,平均高达100%以上.     

Thermal behaviors, combustion mechanisms, evolved gasses, and ash analysis of spent potlining for a hazardous waste management

An unavoidable but reusable waste so as to enhance a more circular waste utilization has been spent potlining (SPL) generated by the aluminum industry. The combustion mechanisms, evolved gasses, and ash properties of SPL were characterized dynamically in response to the elevated temperature and heating rates. Differential scanning calorimetric (DSC) results indicated an exothermic reaction behavior probably able to meet the energy needs of various industrial applications. The reaction mechanisms for the SPL combustion were best described using the 1.5-, 3- and 2.5-order reaction models. Fluoride volatilization rate of the flue gas was estimated at 2.24%. The SPL combustion emitted CO₂, HNCO, NO, and NO₂ but SO_x. The joint optimization of remaining mass, derivative thermogravimetry, and derivative DSC was achieved with the optimal temperature and heating rate combination of 783.5°C, and 5 °C/min, respectively. Interaction between temperature and heating rate exerted the strongest and weakest impact on DSC and remaining mass, respectively. The fluorine mainly as the formation of substantial NaF and CaF₂ in the residual ash. Besides, the composition and effect of environment of residual solid were evaluated. The ash slagging tendency and its mineral deposition mechanisms were elucidated in terms of turning SPL waste into a benign input to a circular waste utilization.     

流化床内焦炭对N2O和NO生成和分解的影响

在小型流化床试验上进行了焦炭的燃烧试验，研究焦炭颗粒和氧化钙对Ｎ２Ｏ和ＮＯ的分解反应，焦炭颗粒对Ｎ２Ｏ还原分解速率比ＮＯ快，氧化钙对Ｎ２Ｏ分解有较强的催化作用，Ｎ２Ｏ和ＮＯ的分解反应过程可用一级Ａｒｒｈｅｎｉｕｓ公式来描述，研究不同程度脱去挥发份的炭焦颗粒对Ｎ２Ｏ和ＮＯ形成的影响，脱挥发份的程度越高，焦炭氮形成Ｎ２Ｏ的量越少，表明挥发份氮形成Ｎ２Ｏ量高于相应焦炭氮燃烧产生的Ｎ２Ｏ量，焦炭燃烧过程中     

The oxycoal process with cryogenic oxygen supply

Due to its large reserves, coal is expected to continue to play an important role in the future. However, specific and absolute CO₂ emissions are among the highest when burning coal for power generation. Therefore, the capture of CO₂ from power plants may contribute significantly in reducing global CO₂ emissions. This review deals with the oxyfuel process, where pure oxygen is used for burning coal, resulting in a flue gas with high CO₂ concentrations. After further conditioning, the highly concentrated CO₂ is compressed and transported in the liquid state to, for example, geological storages. The enormous oxygen demand is generated in an air-separation unit by a cryogenic process, which is the only available state-of-the-art technology. The generation of oxygen and the purification and liquefaction of the CO₂-enriched flue gas consumes significant auxiliary power. Therefore, the overall net efficiency is expected to be lowered by 8 to 12 percentage points, corresponding to a 21 to 36% increase in fuel consumption. Oxygen combustion is associated with higher temperatures compared with conventional air combustion. Both the fuel properties as well as limitations of steam and metal temperatures of the various heat exchanger sections of the steam generator require a moderation of the temperatures during combustion and in the subsequent heat-transfer sections. This is done by means of flue gas recirculation. The interdependencies among fuel properties, the amount and the temperature of the recycled flue gas, and the resulting oxygen concentration in the combustion atmosphere are investigated. Expected effects of the modified flue gas composition in comparison with the air-fired case are studied theoretically and experimentally. The different atmosphere resulting from oxygen-fired combustion gives rise to various questions related to firing, in particular, with regard to the combustion mechanism, pollutant reduction, the risk of corrosion, and the properties of the fly ash or the deposits that form. In particular, detailed nitrogen and sulphur chemistry was investigated by combustion tests in a laboratory-scale facility. Oxidant staging, in order to reduce NO formation, turned out to work with similar effectiveness as for conventional air combustion. With regard to sulphur, a considerable increase in the SO₂ concentration was found, as expected. However, the H₂S concentration in the combustion atmosphere increased as well. Further results were achieved with a pilot-scale test facility, where acid dew points were measured and deposition probes were exposed to the combustion environment. Besides CO₂ and water vapour, the flue gas contains impurities like sulphur species, nitrogen oxides, argon, nitrogen, and oxygen. The CO₂ liquefaction is strongly affected by these impurities in terms of the auxiliary power requirement and the CO₂ capture rate. Furthermore, the impurity of the liquefied CO₂ is affected as well. Since the requirements on the liquid CO₂ with regard to geological storage or enhanced oil recovery are currently undefined, the effects of possible flue gas treatment and the design of the liquefaction plant are studied over a wide range.     

纳米助燃固硫添加剂的催化作用机理

溶胶.凝胶法制备的纳米TiO2作为CaO固硫添加剂,用热分析法对纳米TiO2催化煤燃烧以及催化CaO固硫的过程进行了实验研究.对燃烧后煤灰的孔径分布进行了分析.采用未反应收缩核模型对固硫反应的动力学过程进行表征.研究结果表明,纳米TiO2与CaO共同作用条件下对煤燃烧有明显的促进作用,即燃烧反应活化能E下降,同时纳米TiO2还能增大燃烧后煤灰的孔径,提高固硫率.氧气的存在抑制氧化钙的固硫转化率,纳米TiO2可以消弱氧气的抑制作用.对固硫反应的影响表现为在反应后期(即产物层扩散控制阶段),与固硫转化率和孔径分布的实验结果非常吻合;讨论了纳米TiO2催化燃烧催化固硫的机理,纳米TiO2导致碳晶格的扭曲,增加表面活性部位,加快氧气的吸附速度,使添加剂周围燃烧速度加快,煤灰孔隙增大从而强化燃烧,促进SO2转化成SO3的本征反应,促进二氧化硫向氧化钙内部的扩散从而提高CaO的固硫效果.     

煤半焦负载钠催化还原NO的研究

在石英固定床反应器上研究了Na对NO 半焦反应在不同气氛下的催化作用。研究结果表明 ,Na对半焦还原NO的反应具有很强的催化作用 ;热处理温度升高 ,Na的催化作用减小 ;CO和O2 气氛有助于NO的催化还原 ,但随温度的升高CO和O2 的促进作用减弱 ;低温下 ,Na催化剂易于失活 ;Na对于NO 半焦反应的催化作用是通过氧化 /还原机理实现的。     

非热等离子体结合CuO催化剂或Ca(OH)2吸收剂去除氮氧化物

采用非热等离子体结合催化或现场化学吸收的2种方法来去除气流中的NO_x.结果表明,非热等离子体结合催化,反应器内的CuO催化剂能有效地促进NO的还原反应;相对于催化还原NO而言,脉冲电晕作用下能有效地降低NO催化还原的反应温度.当催化剂为CuO,脉冲电压为18kV,反应温度为200℃,还原剂为1%CO及NO进口浓度为719 mg/m³条件下,NO的去除率达到了100%.非热等离子体结合现场化学吸收方法,是一种在常温下从气流中净化氮氧化物的有效方法,NO的去除率远远高于反应器内没有吸收剂的情况.可以认为反应器内的Ca(OH)₂吸收剂通过与NO的氧化产物NO₂或NO₃的吸收反应促进了NO的去除.当反应器内有Ca(OH)₂吸收剂存在时,在脉冲电压为18kV,O₂浓度为2%及NO进口浓度为1 050 mg/m³条件下,NO的去除率达到了100%.     

基于碳捕集的富氧燃煤烟气联合脱硫脱硝试验研究

富氧燃煤烟气压缩液化CO2的高压低温工况为NO氧化为易溶于水的NO2提供了十分有利的条件.基于小型高压吸收试验装置,采用配制的富氧燃煤模拟烟气,在高压常温下进行了NO、SO2、O2与H2O的吸收反应试验.根据反应前后的气液产物分析,测定了不同组分比例与不同压力下混合气体中NO与SO2的转化率.NO氧化与吸收试验表明,NO转化为HNO3的比率随压力升高而增加,在0.5 ～2 MPa之间增加很快,在2 ～3 MPa之间增速趋丁平缓,压力达3 MPa以上时,90％以上的NO均转化为稀硝酸,且初始NO浓度越高,NO的转化率越大.混合气体中同时存在5O2与NO的联合吸收试验发现,只有少量的NO转化成了NO3-,SO2向H2SO4的转化率随压力升高而增加,初始SO2浓度越大,转化率越高.分析表明,SO2与NO同时存在时SO2先行转化为SO3,NO充当了催化剂,但SO2转化为SO3的一次转化率小于35％,反应酸液产物的多次循环能使SO2的转化率达到90％以上.建议的工艺流程中需采用两座吸收反应塔顺序脱除SO2与NO并回收稀酸溶液,有望在富氧燃煤发电捕集CO2系统中降低脱硫脱硝成本,部分地弥补富氧燃烧机组发电成本的增加.     

Fe2O3 particles as superior catalysts for low temperature selective catalytic reduction of NO with NH3

Fe203 particle catalysts were experimentally studied in the low temperature selective catalytic reduction （SCR） of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe203 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270℃, and more than 95% NO conversion was obtained at 180℃ when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and 02 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180℃. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.     

废气再循环系统参数对柴油机燃烧特征的影响

为进一步优化柴油机燃烧过程,减少燃烧污染物排放.围绕EGR（exhaust gas recirculation,废气再循环技术）废气组分和废气温度等系统参数对柴油机燃烧特征的影响机制,采用试验与模拟相结合方法,分别研究了通入废气、N₂、CO₂时以及不同EGR废气温度时对柴油机燃烧过程的影响,阐明了燃烧关键中间产物的生成规律.结果表明,①通入CO₂时,柴油机的缸内最大爆发压力和放热率峰值最低,滞燃期最长,燃烧持续期最短,·OH、H₂O₂、CH₂O·和CO等关键中间组分的生成规律与通入N₂时相反.②通入N₂时,柴油机的缸内最大爆发压力和放热率峰值最高,滞燃期最短,燃烧持续期最长并;并且通入N₂时,·OH的峰值最高,形成时刻最早,H₂O₂、CH₂O·以及CO的峰值均有所降低且形成时刻提前.③随着废气温度增加,缸内最大爆发压力降低,放热率曲线由单峰向双峰分布发展,放热率峰值有较大幅度的降低,滞燃期缩短,燃烧持续延长,缸内·OH、H₂O₂、CH₂O·以及CO的峰值均有所降低,并且生成的区域范围变窄.④废气成分中,CO₂对燃烧过程和关键中间产物的影响最大,是阻滞燃烧反应的主要气体成分,通过控制EGR废气成分和温度可以有效改善柴油机燃烧过程,拓宽EGR技术的工况使用范围.研究显示,EGR废气成分对燃烧中间产物的自由基衍化历程影响较大,有必要进一步开展EGR废气成分预处理研究,精确控制EGR废气温度,有助于改善燃烧过程,控制排放污染物中间产物的生成历程和排放量.      

Role of NO in Hg oxidation over a commercial selective catalytic reduction catalyst V2O5–WO3/TiO2

Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst, V₂O₅–WO₃/TiO₂, to investigate mercury oxidation in the presence of NO and O₂. Mercury oxidation was improved by NO, and the efficiency was increased by simultaneously adding NO and O₂. With NO and O₂ pretreatment at 350°C, the catalyst exhibited higher catalytic activity for Hg⁰ oxidation, whereas NO pretreatment did not exert a noticeable effect. Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O₂. Although NO promoted Hg⁰ oxidation at the very beginning, excessive NO counteracted this effect. The results show that NO plays different roles in Hg⁰ oxidation; NO in the gaseous phase may directly react with the adsorbed Hg⁰, but excessive NO hinders Hg⁰ adsorption. The adsorbed NO was converted into active nitrogen species (e.g., NO₂) with oxygen, which facilitated the adsorption and oxidation of Hg⁰. Hg⁰ was oxidized by NO mainly by the Eley–Rideal mechanism. The Hg⁰ temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O₂.     

Effect of dry deposition of NOx and SO2 gaseous pollutants on the degradation of calcareous building stones

A laboratory-based atmospheric flow chamber, using realistic presentation rates of SO₂, NO and NO₂ pollutants directed to various dry and wetted surfaces, has been employed to quantify the effects of the individual pollutants and the role of ozone as an oxidant. For the individual pollutant gases reacting with stone surfaces coming to equilibrium with 84% relative humidity (r.h.), chemical reaction in the presence of a moisture film proceeds and the extent of this reaction is related to pollutant gas solubility in the moisture film, i.e. SO₂ > NO₂ > NO. After dissolution in the moisture film, the pollutant gases are oxidized in the presence of catalysts associated with the stones. The additional presence of ozone promotes oxidation of the pollutant gases and thus their reaction with the stones. For SO₂ pollutant, oxidation in the gas phase is not significant compared with that in the moisture film, with enhanced oxidation in the presence of catalysts. Ozone increases oxidation of NO and NO₂ pollutant gases in the gas phase and moisture film; however, the oxidation of SO₂ in the moisture film is more significant than that of NO or NO₂. Wetting of the stone surfaces, in the absence of ozone, reveals the consistently greatest chemical reaction with SO₂ compared with NO and NO₂, which is related to SO₂ solubility, oxidation in the presence of catalysts and production of sulphuric acid. Generally similar behaviour is evident of NO and NO₂, but NO shows a reduced extent of chemical reaction, implying that its oxidation in surface water, in the presence of catalytic species, is slow and hence the reactants are lost in the form of run-off. In the additional presence of ozone, the SO₂ pollutant gas gives rise to enhanced chemical reaction, whereas both NO and NO₂ show lower extents of chemical reaction than for the dry stones. This arises from the relatively slow conversion of N₂O₅ in the liquid phase to nitric acid, allowing loss of reactants in run-off.     

SO2对Ag/Al2O3催化剂上CH3OH还原NO性能的影响

用溶胶-凝胶混合法制备了Ag负载量为5%的Ag/A1₂O₃催化剂.研究了富氧条件下,SO₂对CH₃OH在催化剂上还原NO性能的影响.结果表明,反应气不含SO₂和H₂O时,NO还原活性温度较低,有显著量N₂O生成,这被归因为反应过程中,部分氧化态Ag被还原为金属Ag.添加SO₂或同时添加SO₂和H_{2相似文献}   

NO conversion by positive streamer discharge-effects of gas compositions and reaction conditions

The effects of gas compositions and reaction conditions on NO conversion by positive streamer discharge were experimentally investigated by using a link tooth wheel-cylinder reactor. The results showed that NO conversion increased with increasing O₂ concentration and NH₃ concentration, but decreased with increasing inlet NO concentration and gas flow rate. The addition of CO₂ or H₂O to the feed gas promoted NO conversion by increasing the maximum discharge voltage, and NH₄NO₃ was formed in the presence of NH₃. There was a most suitable range interval between discharge tooth wheels if both NO conversion and energy consumption were considered. Increasing applied voltage resulted in the increase in the amount of O₃ generated by streamer discharge.     

液相氧化-吸收脱除模拟烟气中NOx的研究

分别采用Na Cl O2和Na2SO3溶液作为氧化液和吸收液,在自行设计的鼓泡塔反应系统进行了液相氧化-吸收脱除模拟烟气NOx的研究,考察了气相SO2浓度、Na Cl O2和Na2SO3投加量以及p H值等因素对NO氧化和NOx脱除的影响.结果表明,SO2会优先于NO与氧化剂反应,从而增大氧化剂消耗量.偏酸性条件有利于NO氧化,但酸性太强会导致Na Cl O2分解为Cl O2逸出.碱性吸收液对NO几乎不具吸收脱除效果,但共存NO2能促进NO的吸收脱除.SO2对NO2吸收脱除具有促进作用.     

Avoiding CO2 capture effort and cost for negative CO2 emissions using industrial waste in chemical-looping combustion/gasification of biomass

Chemical-looping combustion (CLC) is a combustion process with inherent separation of carbon dioxide (CO₂), which is achieved by oxidizing the fuel with a solid oxygen carrier rather than with air. As fuel and combustion air are never mixed, no gas separation is necessary and, consequently, there is no direct cost or energy penalty for the separation of gases. The most common form of design of chemical-looping combustion systems uses circulating fluidized beds, which is an established and widely spread technology. Experiments were conducted in two different laboratory-scale CLC reactors with continuous fuel feeding and nominal fuel inputs of 300 W_th and 10 kW_th, respectively. As an oxygen carrier material, ground steel converter slag from the Linz–Donawitz process was used. This material is the second largest flow in an integrated steel mill and it is available in huge quantities, for which there is currently limited demand. Steel converter slag consists mainly of oxides of calcium (Ca), magnesium (Mg), iron (Fe), silicon (Si), and manganese (Mn). In the 300 W unit, chemical-looping combustion experiments were conducted with model fuels syngas (50 vol% hydrogen (H₂) in carbon monoxide (CO)) and methane (CH₄) at varied reactor temperature, fuel input, and oxygen-carrier circulation. Further, the ability of the oxygen-carrier material to release oxygen to the gas phase was investigated. In the 10 kW unit, the fuels used for combustion tests were steam-exploded pellets and wood char. The purpose of these experiments was to study more realistic biomass fuels and to assess the lifetime of the slag when employed as oxygen carrier. In addition, chemical-looping gasification was investigated in the 10 kW unit using both steam-exploded pellets and regular wood pellets as fuels. In the 300 W unit, up to 99.9% of syngas conversion was achieved at 280 kg/MW_th and 900 °C, while the highest conversion achieved with methane was 60% at 280 kg/MW_th and 950 °C. The material’s ability to release oxygen to the gas phase, i.e., CLOU property, was developed during the initial hours with fuel operation and the activated material released 1–2 vol% of O₂ into a flow of argon between 850 and 950 °C. The material’s initial low density decreased somewhat during CLC operation. In the 10 kW, CO₂ yields of 75–82% were achieved with all three fuels tested in CLC conditions, while carbon leakage was very low in most cases, i.e., below 1%. With wood char as fuel, at a fuel input of 1.8 kW_th, a CO₂ yield of 92% could be achieved. The carbon fraction of C₂-species was usually below 2.5% and no C₃-species were detected. During chemical-looping gasification investigation a raw gas was produced that contained mostly H₂. The oxygen carrier lifetime was estimated to be about 110–170 h. However, due to its high availability and potentially low cost, this type of slag could be suitable for large-scale operation. The study also includes a discussion on the potential advantages of this technology over other technologies available for Bio-Energy Carbon Capture and Storage, BECCS. Furthermore, the paper calls for the use of adequate policy instruments to foster the development of this kind of technologies, with great potential for cost reduction but presently without commercial application because of lack of incentives.

     

调理剂FeCl_3/CaO对深度脱水市政污泥燃烧特性的影响

利用热重分析仪(TG-DTG)研究了Fe Cl3/Ca O添加量和升温速率对深度脱水市政污泥燃烧特性的影响,并得出污泥燃烧的动力学参数.试验结果表明,Fe Cl3/Ca O深度脱水后的泥样燃烧过程中有4个失重阶段:水分的析出、挥发分1的燃烧、挥发分2和固定碳的燃烧、以碳酸钙的分解为主的无机物分解.随着调理剂添加量的增加,可燃性指数和挥发分特征指数得到提高,有利于污泥初期的燃烧;而燃尽指数和综合燃烧特性指数先略微上升后降低,适量的添加量有助于污泥燃烧.燃烧动力学计算表明,反应峰前的反应级数一般取0.5,峰后取2,表观活化能随Fe Cl3/Ca O添加量的增加而升高.