低温选择性催化还原脱除NOx的催化剂的研究进展

选择性催化还原(SCR)法是目前世界上应用较为成熟的烟气脱硝技术之一,由于传统的适用催化剂的起活温度偏高,因此开发低温高效、性能稳定的催化剂已成为该技术成功运用的关键.分析了SCR法的脱硝原理,对目前广泛研究的低温SCR催化剂的分类及其运用进行了综述,提出了研究中尚需解决的问题,最后展望了未来的研究方向.     

Mn/USY分子筛催化剂低温SCR脱硝性能

以USY分子筛为载体,采用等体积浸渍法制备了不同Mn负载量的Mn/USY催化剂。借助BET、XRD、SEM和FT-IR等手段,考察了催化剂的物相结构及脱硝活性。在90~210 ℃温度范围内,随着反应温度的升高,NO转化率逐渐提高,脱硝效率在210 ℃达到50%以上,其中10 Mn/USY的NO转化率高于其他几组催化剂。通过SEM和BET结果可以看出,Mn/USY分子筛催化剂的比表面积随着Mn负载量的增加而减少。新鲜的催化剂颗粒分散均匀,呈松散的堆叠状态,H2O和SO2实验后催化剂分散程度降低,比表面积、孔径和孔体积都有所下降。XRD结果表明,10 Mn/USY催化剂中MnO2的晶体特征峰最为明显,除此之外没有发现其他Mn或MnOx衍射峰。FT-IR分析结果表明金属Mn的负载并未对USY分子筛的内部结构造成破坏。     

燃煤烟气低温SCR脱硝中试研究

低温选择性催化还原(SCR)脱硝是国内外脱硝技术研发的热点,但目前主要集中在实验室小试范围,无法完全反映催化剂在实际烟气中的运行状况。在30 t/h循环流化床燃煤锅炉脱硫除尘装置后建设了2 000~5 000 m3/h的SCR脱硝中试装置,经系统研究发现,中试使用的蜂窝式催化剂对SO2和NO具有很强的吸附能力,且反应温度、喷氨速率和气体空速均会影响催化脱硝效率。为期5 d的连续运行实验结果表明,催化剂的脱硝效率一直稳定在30%~50%,并未发现明显的失活,这证明设计除雾除尘器、较大的混合器、混合器与反应器间较长的管路均有利于缓解催化剂因SO2、H2O和飞灰中的碱性金属导致的失活。     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

CeO_x/AC催化剂NH_3选择性催化还原NO

以用不同浓度的HNO3预处理后的椰壳活性炭为载体,负载铈制备SCR催化剂。利用比表面积分析仪（BET）、X射线衍射（XRD）、扫描电镜（SEM）和催化剂活性实验,探讨了不同变量如金属离子的分布、焙烧温度和载体属性对催化活性的影响。结果表明,HNO3处理后,经500℃焙烧金属铈负载量为7%的催化剂表现出优良的催化性能。在90℃时,NO转化率在90%以上,随温度升高,达到接近100%的NO转化率。     

Recent advances in selective catalytic oxidation of nitric oxide (NO-SCO) in emissions with excess oxygen: a review on catalysts and mechanisms

Environmental Science and Pollution Research - Nitric oxides (NOx, which mainly include more than 90% NO) are one of the major air pollutants leading to a series of environmental problems, such as...     

A study on the reaction characteristics of vanadium-impregnated natural manganese oxide in ammonia selective catalytic reduction

This study investigated the effect of adding vanadium (V) to natural manganese oxide (NMO) in ammonia (NH3) selective catalytic reduction (SCR). The addition of V to NMO decreased the catalytic activity at low temperatures by blocking the active site. However, the enhancement of catalytic activity was achieved by controlling NH3 oxidation at high temperatures. From the NH3 temperature programmed desorption and oxygen on/off test, it was confirmed that the amount of Lewis acid site and active lattice oxygen of the catalyst affects the catalytic performance at low temperature.     

Cobalt-based alumina pillared zirconium phosphate catalysts for the selective catalytic reduction of NO by propane

A series of cobalt containing alumina pillared zirconium phosphate materials have been prepared by ion exchange or by impregnation, and fully characterised. The catalytic behaviour of these materials in the selective catalytic reduction of NO by propane, in excess of oxygen, at temperatures ranging between 350 and 550 degrees C, has been also evaluated. A maximum NO conversion close to 14% is obtained on Co-impregnated catalysts heated at 600 degrees C. The NO reduction seems to be related to the presence of Co3+, thus the calcination temperature of samples influences the resulting activity much more than the cobalt content.     

Performance of the supported copper oxide catalysts for the catalytic incineration of aromatic hydrocarbons

A fixed bed reactor was used to assess the catalytic incineration of toluene by various transition-metal oxide species supported on gamma-Al(2)O(3). CuO/gamma-Al(2)O(3) was found to be the most active of seven catalysts investigated. The CuO species, with a Cu content of 5% (wt), was hence used with four different supports (CeO(2), gamma-Al(2)O(3), TiO(2) and V(2)O(5)) in order to define the optimal combination. Results of the catalytic incineration of toluene, X-ray diffraction (XRD) analysis, oxygen-temperature programmed desorption (O(2)-TPD), toluene-temperature programmed desorption (toluene-TPD) and hydrogen-temperature programmed reduction (H(2)-TPR) showed that CuO/CeO(2) was the most active catalyst, followed by CuO/gamma-Al(2)O(3). The activity of CuO/CeO(2) with respect to the VOC molecule was observed to follow this sequence: toluen>p-xylene>benzene. The addition of water vapor or CO(2) significantly inhibited the activity of the CuO/CeO(2) and CuO/gamma-Al(2)O(3) catalysts. The inhibiting effect of both was reversible for CuO/gamma-Al(2)O(3). For CuO/CeO(2), the inhibiting effect of CO(2) was reversible and even insignificant at a higher temperature (220 degrees C), but the effect of H(2)O vapor was somewhat irreversible at lower incineration temperatures (220 degrees C). For complete oxidation of toluene, the required reaction temperature increased with gas hourly space velocity (GHSV) and toluene inlet concentration.     

CeOx/AC催化剂NH3选择性催化还原NO

以用不同浓度的HNO3预处理后的椰壳活性炭为载体,负载铈制备SCR催化剂。利用比表面积分析仪(BET)、X射线衍射(XRD)、扫描电镜(SEM)和催化剂活性实验,探讨了不同变量如金属离子的分布、焙烧温度和载体属性对催化活性的影响。结果表明,HNO3处理后,经500℃焙烧金属铈负载量为7%的催化剂表现出优良的催化性能。在90℃时,NO转化率在90%以上,随温度升高,达到接近100%的NO转化率。     

Recent increases in nitrogen oxide (NOx) emissions from coal-fired electric generating units equipped with selective catalytic reduction

The most effective control technology available for the reduction of oxides of nitrogen (NO_x) from coal-fired boilers is selective catalytic reduction (SCR). Installation of SCR on coal-fired electric generating units (EGUs) has grown substantially since the onset of the U.S. Environmental Protection Agency’s (EPA) first cap and trade program for oxides of nitrogen in 1999, the Ozone Transport Commission (OTC) NO_x Budget Program. Installations have increased from 6 units present in 1998 in the states that encompass the current Cross-State Air Pollution Rule (CSAPR) ozone season program to 250 in 2014. In recent years, however, the degree of usage of installed SCR technology has been dropping significantly at individual plants. Average seasonal NO_x emission rates increased substantially during the Clean Air Interstate Rule (CAIR) program. These increases coincided with a collapse in the cost of CAIR allowances, which declined to less than the cost of the reagent required to operate installed SCR equipment, and was accompanied by a 77% decline in delivered natural gas prices from their peak in June of 2008 to April 2012, which in turn coincided with a 390% increase in shale gas production between 2008 and 2012. These years also witnessed a decline in national electric generation which, after peaking in 2007, declined through 2013 at an annualized rate of ?0.3%. Scaling back the use of installed SCR on coal-fired plants has resulted in the release of over 290,000 tons of avoidable NO_x during the past five ozone seasons in the states that participated in the CAIR program.

Implications: To function as designed, a cap and trade program must maintain allowance costs that function as a disincentive for the release of the air pollutants that the program seeks to control. If the principle incentive for reducing NO_x emissions is the avoidance of allowance costs, emissions may be expected to increase if costs fall below a critical value, in the absence of additional state or federal limitations. As such, external factors as the cost of competing fuels and a low or negative growth of electric sales may also disincentivize the use of control technologies, the continuation of desirable emission rates will be best maintained by the implementation of performance standards that supplement and complement the emissions trading program.     

ACF负载复合金属氧化物催化还原NO的研究

为了研究活性碳纤维（ACF）负载复合金属氧化物催化还原NO的效果,采用浸渍法制备了系列负载氧化铈和氧化铜的ACF,在微型反应器中进行程序升温反应,通过正交试验,确定催化反应的最佳条件,考察了反应温度和复合金属氧化物的不同含量对催化活性的影响,并与ACF负载单金属氧化物作了比较,同时对催化剂进行了扫描电镜和傅里叶红外光谱分析实验。实验结果表明,在氨氮比是1.1∶1,氧气体积比为5%,体积流速为4 000 h^-1的条件下,负载复合金属氧化物的ACF低温活性相差很大,随着温度的升高,催化效率持续提高。当氧化铈与氧化铜的含量分别为10%和30%,在120～300℃区域内去除率维持80%以上,是低温催化中理想的催化剂。     

Superior pillared clay catalysts for selective catalytic reduction of nitrogen oxides for power plant emission control

Fe(3+)-, Cr(3+)-, Cu(2+)-, Mn(2+)-, Co(2+)-, and Ni(2+)-exchanged Al2O3-pillared interlayer clay (PILC) or TiO2-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe(3+)-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO2-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H2O and SO2 increase both the activity and the product selectivity to N2. The maximum activity on the Ce-Fe-TiO2-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V2O5-WO3/TiO2 catalyst, the Fe-TiO2-PILC catalysts show higher N2/N2O product selectivities and substantially lower activities (by approximately 85%) for SO2 oxidation to SO3 under the same reaction conditions. A 100-hr run in the presence of H2O and SO2 for the CeO2/Fe-TiO2-PILC catalyst showed no decrease in activity.     

Fe-Mn基分子筛催化剂NH3低温选择性催化还原NO性能

采用柠檬酸法制备了不同Fe和Mn含量的Fe-Mn/HBeta催化剂,采用BET、XRD、SEM和XPS等方法对不同催化剂的特征参数进行表征,以氨气为还原剂,在空速为5 000 h-1的条件下,考察了活性成分负载量和焙烧温度对其活性的影响;探讨了催化剂的抗水抗硫性能.研究结果表明,焙烧温度为550℃、6%Fe-6%Mn/HBeta催化剂具有相对较优的催化活性,反应温度为90~230℃时,NO转化率为63.9%~96.99%,比表面积、孔体积和平均孔径分别为356.19 m2/g、0.61 cm3/g和16.83 nm,活性成分在催化剂表面高度分散,催化剂表面Mn主要以Mn3+和Mn4+存在,且以Mn4+居多;反应温度为180℃条件下,6%Fe-6%Mn/HBeta催化剂具有较好的抗水能力和同时抗水抗SO2能力,但单独抗SO2能力较差.     

CeOx对低温选择性催化还原脱硝催化剂FeOx-MnOx/TiO2的改性研究

制备了不同CeO_x负载量的(CeO_x)_n-(FeO_x)_(0.1)-(MnO_x)_(0.4)/TiO_2催化剂(n、0.1、0.4分别为CeO_x、FeO_x、MnO_x与载体TiO_2的摩尔比),用于低温选择性催化还原(SCR)脱硝,并对其进行结构和性能的表征。结果表明,适量负载CeO_x能够显著提高催化剂的低温SCR脱硝催化活性。当n=0.07时,催化剂在160～180℃时的催化活性最高,脱硝效率可以达到99%以上。同时,水蒸气、SO_2体积分数分别小于等于10%、0.02%时,该催化剂有较好的抗水性和抗硫性。表征结果显示,(CeO_x)_(0.07)-(FeO_x)_(0.1)-(MnO_x)_(0.4)/TiO_2催化剂锐钛矿TiO_2的相对结晶度低,耗氢还原峰温度低,并且面积大,表面Lewis酸位上的NH_3稳定。因此,(CeO_x)_(0.07)-(FeO_x)_(0.1)-(MnO_x)_(0.4)/TiO_2催化剂具有良好的低温SCR脱硝活性,并且稳定。     

高炉碱矿渣负载纳米零价铁对生活污水中氮磷的去除效果

鉴于高炉碱矿渣具有高吸附性能,而污水处理中应用到的纳米零价铁(nZVI)在单独使用时具有局限性,因此,利用高炉碱矿渣作为载体,制备了6种不同质量比的高炉碱矿渣负载型纳米零价铁材料(碱矿渣-nZVI),探究了5种不同用量的材料在不同反应时间和反应温度下对水中氮磷的吸附去除效果.结果 表明:碱矿渣与nZVI的最佳反应质量比...     

预处理对CNTs低温催化氧化NH3性能的影响

用浓酸混合液(浓H2SO4,H2O2)和非热等离子体(NTP)对碳纳米管(CNTs)进行预处理,对比2种方法预处理的CNTs在负载不同活性组分时NH3的催化氧化性能,实验结果表明,浓酸混合液预处理后的CNTs,负载不同单活性组份时,NH3转化率均低于50%,产物中没有NO和NO2。负载不同双活性组分时,5%Co-5%Zr/CNTs在200~225℃间,NH3的转化效率达到55%。NTP预处理的CNTs催化剂NH3的氧化性能高于浓酸混合液预处理的CNTs催化剂,在250℃时5%Cu/CNTs催化剂NH3的转化率基本接近90%。而250℃时,5%Cu-5%Zr/CNTs催化剂NH3转化率约为80%,NO的生成率约为75%,NO2生成率约3%。     

CuCoO_x/TiO_2催化氧化NO性能研究

采用浸渍法制备了CuCoOx/TiO2催化剂,考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响,并考察了催化剂的抗硫抗水性能.XRD、TPR和BET分析表明,350℃焙烧的催化剂具有Cu-Co2O4尖晶石结构,比表面积大,对N0的氧化效果好.在空速为5 000 h-1,NO进口浓度500 mg/m3,含氧量10%的条件下,反应温度300cc时N0转化率可达79.5%,250℃时N0转化率接近50%.该催化剂具有良好的单独抗SO2、抗H2O毒化性能,H2O和SO2同时存在时很快失活.该催化剂可用于不同时含H2O和SO2的含NO气体催化氧化后再吸收处理.     

Promotional effect of rare earth-doped manganese oxides supported on activated semi-coke for selective catalytic reduction of NO with NH3

Environmental Science and Pollution Research - A composite catalyst for the selective catalytic reduction (SCR) of NOx with NH3 is investigated, in which the rare earth (RE, including La, Ce, Pr,...     

Al2O3-supported transition-metal oxide catalysts for catalytic incineration of toluene

The catalytic incineration of toluene over gamma-Al2O3-supported transition-metal oxide catalysts in the temperature range of 200-380 degrees C was investigated employing a fixed bed flow reactor. CuO/gamma-Al2O3 was found to be the most active of seven catalysts tested. Using this catalyst with different wt% Cu in the incineration of toluene, we found that the optimal Cu content was 5 wt%. X-ray diffraction, BET surface area and hydrogen-temperature-programmed reduction showed that it was mainly the formation of large CuO crystals that caused declines in catalyst activity at Cu content above 5 wt%. Addition of water vapor or CO2 inhibited catalyst activity, but this effect was reversible. Although coexistence of toluene and n-hexane resulted in a reduction in n-hexane conversion, the impact on toluene oxidation was only negligible. Temperature-programmed desorption revealed that this differential effect was due to more competitive adsorption of toluene onto active sites of the catalyst.