添加剂对选择性非催化还原脱硝过程影响的研究进展

简介了选择性非催化还原(SNCR)脱硝的反应机理和主要影响因素,综述了各种添加剂对SNCR脱硝过程影响的研究进展。不同添加剂对SNCR脱硝过程影响的作用机理不同,但都能有效扩宽反应的温度窗口,使其往低温方向移动,提高SNCR在低温段的脱硝率。通过分析添加剂的作用机理,为研究脱硝效果更好的添加剂提供理论依据,以提高脱硝率、减少二次污染。     

Na/K添加剂对SNCR脱硝及NO还原机制的影响

基于构建的Na-K-C-H-O-N-Cl化学反应机理模型,采用Chemkin动力学模拟软件,研究Na/K添加剂(NaOH、Na_2CO_3、NaCl、KOH、K_2CO_3和KCl)对选择性非催化还原(SNCR)脱硝性能影响,通过敏感性分析和产率分析,探讨Na/K添加剂对SNCR过程中NO还原的促进机理和路径。模拟结果表明,在温度为700~800℃且无Na/K添加剂条件下,SNCR脱硝效率几乎为零;Na/K添加剂能够显著提高低温区(小于800℃)SNCR脱硝效率,而其对高温区(大于900℃)SNCR脱硝的促进作用不明显。在温度为700℃和Na/K添加剂参与条件下SNCR脱硝效率可达43.86%~60.76%。不同Na/K添加剂对NO还原促进顺序为Na OH≈Na_2CO_3KOH≈K_2CO_3KClNa Cl,但同一种Na/K添加剂的浓度变化(6.25~25.0μmol·mol~(-1))对SNCR脱硝效率影响较小。Na/K添加剂通过不同的循环路径产生OH基,进而通过NH_2基团促进NO的还原,其中碱金属氢氧化物(MOH)对SNCR脱硝的促进路径为NaOH→NaO_2→Na→NaO→NaOH,碱金属氯化物(MCl)则主要通过MCl→M→MCl削弱Na/K添加剂的促进作用。     

氨选择性非催化还原烟气脱硝研究进展

针对以氨为还原剂的选择性非催化还原(SNCR)系统进行综述,分析了SNCR工艺基本原理,总结了SNCR脱硝过程的各影响因素,指出了SNCR运行中的一些问题,最后对SNCR系统的应用给予建议.     

煤矿链条锅炉烟气SNCR脱硝工艺设计

大气中氮氧化物严重影响人体健康和生态环境,根据《锅炉大气污染物排放标准》(GB13271—2014)的要求,煤矿锅炉应采取脱硝措施。介绍了陕北某煤矿链条锅炉烟气SNCR脱硝的工艺设计。烟气经处理后氮氧化物排放浓度为140～200mg/m~3,脱硝效率23%～46%。结果表明,煤矿链条锅炉由于氮氧化物初始值不高,排放指标要求相对较低,宜采用SNCR脱硝工艺,充分发挥其设备简单、投资低、工期短的优点,未来还可作为超净排放的辅助手段,继续发挥功效。     

固体高分子脱硝剂选择性非催化还原NOx特性

在流化床反应器中研究了固体高分子脱硝剂选择性非催化还原(PNCR)脱硝效率、影响因素及反应机理。结果表明,固体脱硝剂炉内发生非催化还原反应,在850～1150℃范围内,随着温度升高,脱硝效率逐步增加,在950℃达到最佳(97%左右),之后脱硝剂主要受高温氧化反应的影响,脱硝效率下降。氧气不利于脱硝反应,随着氧气的增加,脱硝效率逐渐降低;水蒸气加入能减弱O₂的氧化作用,延迟脱硝剂的高温氧化反应。固体脱硝剂热分解过程的O元素主要以CO₂形式析出,N和C元素生成NH、CH₂和CN等自由基,CH₂和CN则通过与O₂、O和OH反应而消耗炉内强氧化性基团,抑制NO的生成,加快NH等自由基与NO还原反应而实现高效脱硝。该研究结果为高分子脱硝技术的应用提供了理论支撑和技术参考。     

氨选择性催化还原脱硝催化剂的研究进展

综述了氨选择催化还原(SCR)脱硝催化剂的研究现状、进展及其存在的问题,对未来发展趋势做了展望,指出开发低成本、高效率、长寿命的SCR催化剂,降低脱硝运行成本是我国烟气脱硝技术研究、应用的主要方向。     

烟气选择性催化还原脱硝的数值模拟研究进展

采用数值模拟方法对火电厂SCR系统的预报具有经济、快捷和实用的优点。本文在总结国内外大量文献资料的基础上,对数值模拟技术在烟气SCR脱硝中的应用进行了综述。并把SCR模拟的发展归纳为:非均相动力学模型;均相反应速率模型;催化剂单孔道反应数值模拟;系统流场的数值模拟。在此基础上,提出了三维流动和详细反应的耦合是今后SCR模拟的一个重要发展方向。     

选择性非催化还原法(SNCR)脱硝技术在玻璃工业中的应用探讨

介绍了选择性非催化还原法(SNCR)脱硝技术的原理,针对玻璃行业脱硝难的原因,从玻璃工艺和熔窑使用寿命角度分析了SNCR脱销技术的优势与局限性,提出了SNCR脱硝技术在玻璃工业中应用的可行性。     

火电厂选择性催化还原脱硝技术的可行性研究

选择性催化还原（SCR）技术是目前研究较多的治理氮氧化物的方法。本文综述了选择性催化还原法降低氮氧化物排放的机理,介绍了SCR技术反应器的设计,催化剂的使用情况和研究现状,同时展望了这一技术领域的重点研究方向。     

选择性催化还原脱硝技术专利分析

在众多的烟气脱硝技术中,选择性催化还原(SCR)技术以其高效性、选择性和经济性,而越来越受到青睐,成为最为广泛应用的烟气脱硝技术之一。文章通过在S系统中的检索,对SCR脱硝技术的国内外专利申请状况进行了统计分析,探讨了本领域的技术热点,分析SCR脱硝技术的发展趋势,并对国内企业的研究方向提出了建议。     

Effect of operating conditions on NO reduction by acetylene-ethanol mixtures

An experimental and theoretical study of the influence of different operating conditions on NO reduction by acetylene-ethanol mixtures has been carried out. The present investigation includes the evaluation of the impact of adding different amounts of ethanol for NO reduction by an acetylene-ethanol mixture, and the evaluation of the capacity of acetylene-ethanol mixtures to reduce different amounts of NO. The experiments were conducted in a quartz flow reactor at atmospheric pressure in the 775-1375 K temperature range operating under different oxygen concentrations, from fuel-rich to fuel-lean conditions, considering the influence of these operating variables. The experimental results have been simulated and interpreted in terms of a literature detailed gas-phase kinetic mechanism. The present results show that ethanol addition to acetylene shifts the onset for NO consumption to higher temperatures; however, the maximum NO reduction levels reached by pure acetylene oxidation are not significantly modified by its addition. The initial concentrations of NO and oxygen are important parameters affecting NO reduction by acetylene-ethanol mixtures oxidation, since they are closely coupled to the fate of hydrocarbon radicals responsible of NO consumption.     

Catalytic reduction of NO by CO over NiO/CeO2 catalyst in stoichiometric NO/CO and NO/CO/O2 reaction

A new catalyst composed of nickel oxide and cerium oxide was studied with respect to its activity for NO reduction by CO under stoichiometric conditions in the absence as well as the presence of oxygen. Activity measurements of the NO/CO reaction were also conducted over NiO/γ-Al₂O₃, NiO/TiO₂, and NiO/CeO₂ catalysts for comparison purposes. The results showed that the conversion of NO and CO are dependent on the nature of supports, and the catalysts decreased in activity in the order of NiO/CeO₂ > NiO/γ-Al₂O₃ > NiO/TiO₂. Three kinds of CeO₂ were prepared and used as support for NiO. They are the CeO₂ prepared by (i) homogeneous precipitation (HP), (ii) precipitation (PC), and (iii) direct decomposition (DP) method. We found that the NiO/CeO₂(HP) catalyst was the most active, and complete conversion of NO and CO occurred at 210 °C at a space velocity of 120,000 h⁻¹. Based on the results of surface analysis, a reaction model for NO/CO interaction over NiO/CeO₂ has been proposed: (i) CO reduces surface oxygen to create vacant sites; (ii) on the vacant sites, NO dissociates to produce N₂; and (iii) the oxygen originated from NO dissociation is removed by CO.     

Electrochemical promotion of Rh catalyst in gas-phase reduction of NO by propylene

The concept of non-faradaic electrochemical modification of catalytic activity (NEMCA) has been applied for the in situ control of catalytic activity of a rhodium film deposited on YSZ (yttria stabilized zirconia) solid electrolyte towards reduction of 1000 ppm NO by 1000 ppm C₃H₆ in presence of excess (5000 ppm) O₂ at 300 °C. A temporary heating at this feed composition results in a long-lasting deactivation of the catalyst under open circuit conditions due to partial oxidation of the rhodium surface. Positive current application (5 A) over both the active and the deactivated catalysts gives rise to an enhancement of N₂ and CO₂ production, the latter exceeding several hundred times the faradaic rate. While active rhodium exhibits a reversible behaviour, electrochemical promotion on the deactivated catalyst is composed of a reversible and an irreversible part. The reversible promotion results from the steady-state accumulation of current-generated active species at the gas exposed catalyst surface whereas the irreversible effect is due to the progressive reduction of the catalyst resulting in an increased recovery rate of lost catalytic activity. The results are encouraging with respect to application of rhodium for the catalytic removal of NO from auto-exhaust gases under lean-burn conditions.     

甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

为改善工业窑炉以及锅炉低负荷运行工况下的脱硝特性,本文对甲胺作还原剂的选择性非催化还原（SNCR）脱硝特性进行了实验研究,探讨了各控制因素对脱硝特性的影响以及分析了反应机理。实验结果表明：脱硝效率随反应温度呈双峰特性,拐点温度为750℃,最佳温度窗口为450～600℃;脱硝效率随氨氮比（NSR）增大而升高,反应产生的副产物NO₂和N₂O浓度随之增大;氧含量对SNCR脱硝特性具有双重特性,高浓度和低浓度氧气均对脱硝反应不利;物料浓度随NO初始浓度增加而增大,脱硝效率和副产物也提高; SO₂浓度越高,脱硝效率下降越多;水汽含量增大,脱硝效率也随之增大。本文的实验结论有助于SNCR脱硝工艺应用于工业窑炉以及优化锅炉低负荷运行时的脱硝特性。     

Detailed surface reaction mechanism for reduction of NO by CO

In order to meet the stringent regulatory norms of NO_x and CO emitted by automobiles, reduction of these pollutants has become an intense field of research. Various catalysts like Pt, Rh, Ir, Cu, and Fe have been found to possess high activity for the reduction of NO. However, the available detailed surface reaction mechanisms are not satisfactory in clarifying all the aspects of the simultaneous reduction of NO and oxidation of CO. Here we have developed a quantitative surface reaction mechanism based on elementary steps, in order to comprehend the phenomena of catalytic reduction of NO by CO. Eleven elementary steps are proposed for the NO–CO and NO–CO–O₂ systems on Pt group catalysts. The elementary reaction mechanism is coupled with the continuously stirred tank reactor/packed bed reactor models and the simulation results are validated against literature experiments for the NO–CO reaction on Pt, and the NO–CO–O₂ reaction on Ir catalyst. Despite the simplicity, the CSTR model is able to capture the observed phenomena well on Pt and Ir catalysts. The effect of O₂ on the activity of CO for NO reduction is also analysed in detail through the simulations.     

NO2 formation and its effect on the selective catalytic reduction of NO over Co/ZSM-5

Catalytic performance of Co/ZSM-5 with different metal loadings and of HZSM-5 was compared in the NO + O₂, C₃H₈ + O₂, and NO + C₃H₈ + O₂ reactions. It was found that Co/ZSM-5 catalysts containing only isolated cobalt ions in cationic positions are inactive in NO₂ formation. To achieve appreciable NO conversion in the SCR process over these catalysts higher reaction temperatures are required. These results make it possible to suggest that NO₂ formation is not a prerequisite for the SCR of NO with hydrocarbons over Co/ZSM-5. With increasing Co loading, however, Co/ZSM-5 begins to exhibit activity in NO₂ formation. This is explained by the formation of cobalt oxide particles on the zeolite carrier, which are active in the NO₂ formation. Increase in NO₂ formation strongly enhances catalytic activity in SCR of NO at lower reaction temperatures. Comparison of the C₃H₈ conversion in the C₃H₈ + O₂ and C₃H₈ + O₂ + NO reactions provides evidence that NO₂ activates hydrocarbon molecules resulting in the formation of the reaction intermediates of the SCR process.On leave from N.D. Zelinskii Institute of Organic Chemistry, Leninskii Pr. 47, Moscow, Russia.     

Hydroliquefaction of subbituminous coal Effectiveness of pretreatment by organic reduction with Na or k

Hydroliquefaction of subbituminous Taiheiyo coal, without any pretreatment and after organic reduction, was carried out in the presence of tetralin using fine iron powder as catalyst. Two pretreatment procedures were used (A) reduction of coal with Na in liquid ammonia solution and (B) treatment with K in refluxing THF. Samples of treated coal with well-dispersed iron powder were prepared by co-reduction of coal coated with FeBr₂ using both procedures. Non-catalytic liquefaction of coal treated by A showed double the yield of hexane-solubles compared with that from liquefaction of the original coal while non-catalytic liquefaction of the coal treated by B roughly tripled the hexane-solubles yield and consumed the same amount of hydrogen. The presence of iron powder increased hexane-solubles by 5 wt% while increasing benzene-solubles by 13 wt% compared with non-catalytic liquefaction of treated coal by procedure B. The coals prepared by co-reduction (A and B) showed highest conversion (73 and 77%) along with highest yield of HS (38 and 43%). This significant effect on hydroliquefaction could be correlated with a slight increase of hydrogen atoms added to coal organic materials and the loosening of clusters of aromatic sheets.     

Selective catalytic reduction of NO and NO2 at low temperatures

The fast SCR reaction using equimolar amounts of NO and NO₂ is a powerful means to enhance the NO_x conversion over a given SCR catalyst. NO₂ fractions in excess of 50% of total NO_x should be avoided because the reaction with NO₂ only is slower than the standard SCR reaction.

At temperatures below 200 °C, due to its negative temperature coefficient, the ammonium nitrate reaction gets increasingly important. Half of each NH₃ and NO₂ react to form dinitrogen and water in analogy to a typical SCR reaction. The other half of NH₃ and NO₂ form ammonium nitrate in close analogy to a NO_x storage-reduction catalyst. Ammonium nitrate tends to deposit in solid or liquid form in the pores of the catalyst and this will lead to its temporary deactivation.

The various reactions have been studied experimentally in the temperature range 150–450 °C for various NO₂/NO_x ratios. The fate of the deposited ammonium nitrate during a later reheating of the catalyst has also been investigated. In the absence of NO, the thermal decomposition yields mainly ammonia and nitric acid. If NO is present, its reaction with nitric acid on the catalyst will cause the formation of NO₂.     

Activity during reduction of NO by CO over bimetallic palladium-rhodium/silica catalysts

A study of the activity of bimetallic Pd-Rh catalysts supported on silica in the reduction of NO by CO is presented. The catalysts were prepared by three different methods: (1) Pd and Rh were coimpregnated on the support, (2) Rh was impregnated first and, after calcining, the sample was impregnated with Pd, (3) the monometallic Pd and Rh catalysts were physically mixed. The results showed that the activity of the catalysts prepared by coimpregnation was much lower than that of the other two catalysts.     

Ion-exchanged pillared clays for selective catalytic reduction of NO by ethylene in the presence of oxygen

Ion-exchanged pillared clays (PILCs) were studied as catalysts for selective catalytic reduction (SCR) of NO by ethylene. Three most important pillared clays, Al₂O₃-PILC (or Al-PILC), ZrO₂-PILC (or Zr-PILC) and TiO₂-PILC (or Ti-PILC), were synthesized. Cation exchanges were performed to prepare the following catalysts: Cu–Ti-PILC, Cu–Al-PILC, Cu–Zr-PILC, Cu–Al–Laponite, Fe–Ti-PILC, Ce–Ti-PILC, Ce–Ti-PILC, Co–Ti-PILC, Ag–Ti-PILC and Ga–Ti-PILC. Cu–Ti-PILC showed the highest activities at temperatures below 370°C, while Cu–Al-PILC was most active at above 370°C, and both catalysts were substantially more active than Cu-ZSM-5. No detectable N₂O was formed by all of these catalysts. H₂O and SO₂ only slightly deactivated the SCR activity of Cu–Ti-PILC, whereas severe deactivation was observed for Cu-ZSM-5. The catalytic activity of Cu–Ti-PILC was found to depend on the method and amount of copper loading. The catalytic activity increased with copper content until it reached 245% ion-exchange. The doping of 0.5 wt% Ce₂O₃ on Cu–Ti-PILC increased the activities from 10% to 30% while 1.0 wt% of Ce₂O₃ decreased the activity of Cu–Ti-PILC due to pore plugging. Cu–Ti-PILC was found to be an excellent catalyst for NO SCR by NH₃, but inactive when CH₄ was used as the reducing agent. Subjecting the Cu–Ti-PILC catalyst to 5% H₂0 and 50 ppm SO₂ at 700°C for 2 h only slightly decreased its activity. TPR results showed that the overexchanged (245%) PILC sample contained Cu²⁺, Cu⁺ and CuO. The TPR temperatures for the Cu–Ti-PILC were substantially lower than that for Cu-ZSM-5, indicating easier redox on the PILC catalyst and hence higher SCR activity.