Promotional effect of H_3PO_4 on ceria catalyst for selective catalytic reduction of NO by NH_3

A series of H3PO4-modified CeO2 samples were prepared by impregnation of CeO2 with H3PO4solution,and evaluated for the selective catalytic reduction of NOx by NH3.The samples were characterized by X-ray diffraction,N2 adsorption-desorption,infrared spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy,temperature-programmed desorption of NH3,and temperature-programmed reduction of H2.The results showed that more than 80%NO conversion was achieved in the temperature range 250-550℃ over the H3PO4-CeO2 catalyst.The enhanced catalytic performance could be ascribed to the increase in acidic strength,especially Bronsted acidity,and reduction in redox properties of the CeO2 after H3PO4 modification.

Investigation of low-temperature hydrothermal stability of Cu-SAPO-34 for selective catalytic reduction of NO_x with NH_3

The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)activities(mainly the low‐temperature activities)of all the Cu‐SAPO‐34catalysts declined after low‐temperature steam treatment(LTST).These results show that the texture and acid density of Cu‐SAPO‐34can be better preserved by increasing the Cu loading,although the hydrolysis of Si-O-Al bonds is inevitable.The stability of Cu ions and the stability of the SAPO framework were positively correlated at relatively low Cu loadings.However,a high Cu loading(e.g.,3.67wt%)resulted in a significant decrease in the number of isolated Cu ions.Aggregation of CuO particles also occurred during the LTST,which accounts for the decreasing NH3oxidation activities of the catalysts.Among the catalysts,Cu‐SAPO‐34with a high Si content and medium Cu content(1.37wt%)showed the lowest decrease in NH3‐SCR because its Cu2+content was well retained and its acid density was well preserved.

Growth of Cu/SSZ-13 on SiC for selective catalytic reduction of NO with NH_3

Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown via a hydrothermal method using the silicon and silica contained in SiC as the source of silicon,which led to the formation of a chemically bonded SSZ‐13layer on SiC.Characterization using X‐ray diffraction,scanning electron microscopy,and N2adsorption‐desorption isotherms revealed that the alkali content strongly affected the purity of zeolite and the crystallization time affected the coverage and crystallinity of the zeolite layer.Upon ion exchange,the resulting Cu/SSZ‐13@SiC catalyst exhibited enhanced activity in NH3‐SCR in the high‐temperature region compared with the unsupported Cu/SSZ‐13.Thus,the application temperature was extended with the use of SiC as the support.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Cu-SAPO-17:A novel catalyst for selective catalytic reduction of NOx

The high-temperature(HT) and low-temperature(LT) hydrothermal stabilities of molecular-sieve-based catalysts are important for the selective catalytic reduction of NOx with ammonia(NH3-SCR). In this paper, we report a catalyst, Cu2+ loading SAPO-17, synthesized using cyclohexylamine(CHA), which is commercially available and inexpensive and is utilized in NH3-SCR reduction for the first time. After systematic investigations on the optimization of Si and Cu2+ contents, it was concluded that Cu-SAPO-17-8.0%-0.22 displays favorable catalytic performance, even after being heated at 353 K for 24 h and at 973 K for 16 h. Moreover, the locations of CHAs, host–guest interaction and the Bronsted acid sites were explored by Rietveld refinement against powder X-ray diffraction data of as-made SAPO-17-8.0%. The refinement results showed that two CHAs exist within one eri cage and that the protonated CHA forms a hydrogen bond with O4, which indicates that the proton bonding with O4 will form the Bronsted acid site after the calcination.

Multi-stage ammonia production for sorption selective catalytic reduction of NO_(x)

Sorption selective catalytic reduction of nitrogen oxides(NO_(x))(sorption-SCR)has ever been proposed for replacing commercial urea selective catalytic reduction of NO_(x)(urea-SCR),while only the single-stage sorption cycle is hitherto adopted for sorption-SCR.Herein,various multi-stage ammonia production cycles is built to solve the problem of relative high starting temperature with ammonia transfer(AT)unit and help detect the remaining ammonia in ammonia storage and delivery system(ASDS)with ammonia warning(AW)unit.Except for the singlestage ammonia production cycle with MnCl2,other sorption-SCR strategies all present overwhelming advantages over urea-SCR considering the much higher NO_(x) conversion driven by the heat source lower than 100℃ and better matching characteristics with low-temperature catalysts.Furthermore,the required mass of sorbent for each type of sorption-SCR is less than half of the mass of AdBlue for urea-SCR.Therefore,the multifunctional multi-stage sorption-SCR can realize compact and renewable ammonia storage and delivery with low thermal energy consumption and high NO_(x) conversion,which brings a bright potential for efficient commercial de-NO_(x) technology.

Effects of Na+on Cu/SAPO-34 for ammonia selective catalytic reduction

Copper-exchanged chabazite（Cu/CHA） catalysts have been found to be affected by alkali metal and alkaline earth ions. However, the effects of Na＋ ions on Cu/SAPO-34 for ammonia selective catalytic reduction（NH_3-SCR） are still unclear. In order to investigate the mechanism, five samples with various Na contents were synthesized and characterized. It was observed that the introduced Na＋ ion-exchanges with H＋and Cu2＋of Cu/SAPO-34. The exchange of H＋is easier than that of isolated Cu2＋. The exchanged Cu2＋ions aggregate and form ＂CuAl_2O4-like＂ species.The NH_3-SCR activity of Cu/SAPO-34 decreases with increasing Na content, and the loss of isolated Cu2＋and acid sites is responsible for the activity loss.

Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system

Selective catalytic reduction(SCR) denitration may increase the emission of NH4+and NH3.The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization(WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system.The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH4+will generate new ammoniumcontaining particles and gaseous ammonia.The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation.Therefore,even if the concentration of NH4+in the desulfurization slurry is quite low, a high level of NH4+was still contained in the fine particles at the outlet of the scrubber.When the accumulated NH4+in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH3 to NH4+and increased the additional emission of primary NH4+aerosols.With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH4+emitted from entrainment and evaporation of the desulfurization slurry decreased.In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH4+concentration and p H values of the slurry.

Promotional roles of ZrO_2 and WO_3 in V_2O_5-WO_3/TiO_2-ZrO_2 catalysts for NO_x reduction by NH_3:Catalytic performance,morphology,and reaction mechanism

V2O5/TiO2-ZrO2 catalysts containing various amounts of WO3 were synthesized.The catalyst morphologies,catalytic performances,and reaction mechanisms in the selective catalytic reduction of NOx by NH3 were investigated using in situ diffuse-reflectance infrared Fourier-transform spectroscopy,temperature-programmed reduction（TPR）,X-ray diffraction,and the Brunauer-Emmett-Teller（BET） method.The BET surface area of the triple oxides increased with increasing ZrO2 doping but gradually decreased with increasing WO3 loading.Addition of sufficient WO3 helped to stabilize the pore structure and the combination of WO3 and ZrO2 improved dispersion of all the metal oxides.The mechanisms of reactions using V2O5-9%WO3/TiO2-ZrO2 and V2O5-9%WO3/TiO2were compared by using either a single or mixed gas feed and various pretreatments.The results suggest that both reactions followed the Eley-Ridel mechanism;however,the dominant acid sites,which depended on the addition of WO3 or ZrO2,determined the pathways for NOx reduction,and involved[NH4^＋-NO-Bronsted acid site]^＊ and[NH2-NO-Lewis acid site]^＊ intermediates,respectively.NH3-TPR and H2-TPR showed that the metal oxides in the catalysts were not reduced by NH3 and O2did not reoxidize the catalyst surfaces but participated in the formation of H2O and NO2.

Overwhelming low ammonia escape and low temperature denitration efficiency via MnOx-decorated two-dimensional MgAl layered double oxides

Low temperature catalysts are attracting increasing attention in the selective catalytic reduction(SCR)of NO with NH3.Mn Ox-decorated Mg Al layered double oxide(Mn/Mg Al-LDO)was synthesized via a facile fast pour assisted co-precipitation(FP-CP)process.Compared to the Mn/Mg Al-LDO obtained via slow drop assisted coprecipitation(SD-CP)method,the Mn/Mg Al-LDO(FP-CP)has excellent activity.The Mn/Mg Al-LDO(FP-CP)catalyst was shown to possess a high NO conversion rate of 76%-100%from 25 to 150℃,which is much better than the control Mn/Mg Al-LDO(SD-CP)(29.4%-75.8%).In addition,the Mn/Mg Al-LDO(FP-CP)offered an enhanced NO conversion rate of 97%and a N2selectivity of 97.3%at 100℃;the NO conversion rate was 100%and the N2selectivity was 90%at 150℃with a GHSV of 60,000 h^-1.The Mn/Mg Al-LDO(FP-CP)catalyst exhibited a smaller fragment nano-sheet structure(sheet thickness of 7.23 nm).An apparent lattice disorder was observed in the HRTEM image confirming the presence of many defects.The H2-TPR curves show that the Mn/Mg Al-LDO(FP-CP)catalyst has abundant reducing substances.Furthermore,the enhanced surface acidity makes the NH3concentration of the Mn/Mg Al-LDO(FP-CP)catalyst lower than 100 ml·m^-3after the reaction from 25 to 400℃.This can effectively reduce the ammonia escape rate in the SCR reaction.Thus,the Mn/Mg Al-LDO(FP-CP)catalyst has potential applications in stationary industrial installations for environmentally friendly ultra-low temperature SCR.

A Comparison of Hydrothermal Aging, SO2 and Propene Poisoning Effects on NH3-SCR over Cu-ZSM-5 and Cu-SAPO-34 Catalysts

This study was aimed to investigate the effects of hydrothermal aging, propene and SO2 poisoning on the ammonia-selective catalytic reduction (NH3-SCR) performance of both Cu-SAPO-34 and Cu-ZSM-5. The catalytic activities of fresh, aged and poisoned samples were tested in ammonia-selective catalytic reduction (NH3-SCR) of NOx conditions. The XRD, TG and N2-desorption results showed that the structures of the Cu-SAPO-34 and Cu-ZSM-5 remained intact after 750˚C hydrothermally aged, SO2 and propene poisoned. After hydrothermal aging at 750˚C for 12 h, the NO reduction performance of Cu-ZSM-5 was significantly reduced at lower temperatures, while that of Cu-SAPO-34 was less affected. Moreover, Cu-SAPO-34 catalyst showed high NO conversion with SO2 or propene compared to Cu-ZSM-5. However, Cu-ZSM-5 showed a larger drop in catalytic activity with SO2 or propene compared to Cu-SAPO-34 catalyst. The H2-TPR results showed that Cu2 ions could be reduced to Cu and Cu0 for Cu-ZSM-5, while no significant transformation of copper species was observed for Cu-SAPO-34. Meanwhile, the UV-vis DRS results showed that CuO species were formed in Cu-ZSM-5, while little changes were observed for the Cu-SAPO-34. Cu-SAPO-34 showed high sulfur and hydrocarbon poison resistance compared to Cu-ZSM-5. In summary, Cu-SAPO-34 with small-pore zeolite showed higher hydrothermal stability and better hydrocarbon and sulfur poison resistant than Cu-ZSM-5 with medium-pore.

Support effect of the supported ceria-based catalysts during NH_3-SCR reaction

To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2/γ‐Al2O3,CeO2/ZrO2,and CeO2/TiO2catalysts were prepared.The physicochemical properties were probed by means of X‐ray diffraction,Raman spectroscopy,Brunauer‐Emmett‐Teller surface area measurements,X‐ray photoelectron spectroscopy,H2‐temperature programmed reduction,and NH3‐temperature programmed desorption.Furthermore,the supported ceria‐based catalysts'catalytic performance and H2O+SO2tolerance were evaluated by the NH3‐SCR model reaction.The results indicate that out of the supported ceria‐based catalysts studied,the CeO2/γ‐Al2O3catalyst exhibits the highest catalytic activity as a result of having a high relative Ce3+/Ce4+ratio,optimum reduction behavior,and the largest total acid site concentration.Finally,the CeO2/γ‐Al2O3catalyst also presents excellent H2O+SO2tolerance during the NH3‐SCR process.

Control of an Industrial SCR Catalyst Using Ceramic NOx Sensors

Selective Catalytic Reduction (SCR) catalysts respond slowly to transient inputs, which is troublesome when designing ammonia feed controllers. An experimental SCR test apparatus installed on a slipstream of a Coo-per-Bessemer GMV-4, 2-stroke cycle natural gas engine is utilized. Ammonia (NH3) feed rate control algo-rithm development is carried out. Two control algorithms are evaluated: a feed forward control algorithm, using a pre ammonia injection ceramic NOx sensor and a feed forward plus feedback control algorithm, us-ing a pre ammonia injection ceramic NOx sensor and post catalyst ceramic NOx sensor to generate feedback signals. The feed forward algorithm controls to constant user input NH3/NOx molar ratio. The data show the lack of pressure compensation on the ceramic NOx sensors cause errors in feed forward NOx readings, re-sulting in sub optimal ammonia feed. The feedback system minimizes the post catalyst ceramic NOx sensor signal by adjusting the NH3/NOx molar ratio. The NOx sensors respond to ammonia + NOx;therefore, the feed forward plus feedback algorithm minimizes the sum of NOx emissions and ammonia slip. Successful application of the feedback control minimization technique is demonstrated with feedback periods of 15 and 5 minutes with molar ratio step sizes of 5 and 2.5%, respectively.

低SO_(2)氧化率钒钛基选择性催化还原脱硝催化剂研究进展

选择性催化还原(SCR)脱硝技术是目前烟气氮氧化物控制最主流的技术。商用SCR催化剂主要由V 2O 5-WO_(3)(MoO_(3))/TiO_(2)组成,其中V 2 O 5不仅对烟气中的氮氧化物有催化还原作用,同时也能促进SO_(2)的氧化,导致硫酸铵盐的生成,进而造成催化剂孔道堵塞,活性位点减少,使催化剂活性降低,脱硝效率下降。基于此,主要探讨了钒钛基SCR催化剂对SO_(2)的氧化机理及其研究进展,总结了国内外降低钒钛基SCR催化剂SO_(2)氧化率的一些主要措施,并对此进行了分析和讨论。

Promotional catalytic activity and reaction mechanism of Ag-modified Ce_(0.6)Zr_(0.4)O_(2) catalyst for catalytic oxidation of ammonia

Ce1-xZrxO_(2) composite oxides(molar,x=0-1.0,interval of 0.2)were prepared by a cetyltrimethylammonium bromide-assisted precipitation method.The enhancement of silver-species modification and catalytic mechanism of adsorption-transformationdesorption process were investigated over the Ag-impregnated catalysts for lowtemperature selective catalytic oxidation of ammonia(NH_(3)-SCO).The optimal 5 wt.%Ag/Ce_(0.6)Zr_(0.4)O_(2) catalyst presented good NH_(3)-SCO performancewith>90% NH_(3) conversion at temperature(T)≥250°C and 89% N_(2) selectivity.Despite the irregular block shape and underdeveloped specific surface area(∼60m2/g),the naked and Ag-modified Ce_(0.6)Zr_(0.4)O_(2) solid solution still obtained highly dispersed distribution of surface elements analyzed by scanning electron microscope-energy dispersive spectrometer(SEM-EDS)(mapping),N_(2) adsorptiondesorption test and X-ray diffraction(XRD).H2 temperature programmed reduction(H2-TPR)and X-ray photoelectron spectroscopy(XPS)results indicated that Ag-modification enhanced the mobility and activation of oxygen-species leading to a promotion on CeO_(2) reducibility and synergistic Ag0/Ag+and Ce^(4+)/Ce^(3+)redox cycles.Besides,Ag+/Ag_(2)O clusters could facilitate the formation of surface oxygen vacancies that was beneficial to the adsorption and activation of ammonia.NH3-temperature programmed desorption(NH_(3)-TPD)showed more adsorption-desorption capacity to ammoniawere provided by physical,weakandmedium-strong acid sites.Diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)experiments revealed the activation of ammonia might be the control step of NH3-SCO procedure,during which NH3 dehydrogenation derived from NHx-species and also internal selective catalytic reduction(i-SCR)reactions were proposed.

基于7状态船舶柴油机SCR脱硝系统的精细化建模与控制

传统的3状态选择性催化还原(SCR)脱硝模型只关注NO和NH3对系统的影响,忽略了NO2的作用,但研究发现,NO2的影响也不可忽视。为此,考虑NO和NO2对SCR脱硝系统的影响,设计面向双催化剂、包含NO2的7状态船舶SCR脱硝系统机理模型,分析NO2对船舶脱硝系统性能的影响,讨论精细化模型的精度。此外,从节能降耗角度出发,设计模型预测控制器,对比不同模型的控制效果,结果表明,相比于传统的3状态模型,基于7状态的精细化模型具有更优的控制效果。

喷氨调平技术在燃煤锅炉SCR法烟气脱硝中的应用

我国大部分火电机组使用选择性催化还原(selective catalytic reduction,SCR)技术对锅炉烟气进行NO_(x)脱除,以满足日趋严格的环保要求。但在锅炉装置实际运行过程中,经SCR反应器脱硝处理后,锅炉烟气出口仍普遍出现NO_(x)浓度分布不均现象,造成出口NO_(x)排放超过标准要求,同时也增加了氨逃逸风险。以某公司的燃煤锅炉脱硝装置为例,分析喷氨调平改造前后烟气中氨逃逸指标和NO_(x)浓度数据的差异,从而论证喷氨调平技术在控制氨逃逸及NO_x脱除中所起到的作用。

催化剂结构对SCR脱硝性能影响分析

为评估新能源大规模并网下,煤电机组频繁调峰引起选择性催化还原(selective catalytic reaction,SCR)脱硝装置氨逃逸率的变化问题,通过MATLAB编程方法构建SCR脱硝三维数值模型,就催化剂结构参数对脱硝性能的影响进行了研究。结果表明:催化剂孔节距对脱硝效率及氨逃逸率影响显著,反应温度为629.15K时,催化剂孔节距从6 mm增加到12 mm,SCR脱硝效率由72.63%降到51.04%,氨逃逸率由9.76%上升到25.1%;SCR脱硝性能随催化剂长度增加而增强,反应温度为639.15 K时,催化剂长度从300 mm增加到1000 mm,脱硝效率由36.23%上升至69.05%;氨逃逸率由51.15%降低至8.90%。电厂负荷下降有利氨逃逸率降低,负荷从550 MW降低至330 MW脱硝效率由67.71%上升至73.28%,氨逃逸率由1.1%降低至0.14%。煤质劣化使氨逃逸率上升,煤质热值由16747.2 J下降至15491.16 J脱硝效率由71.14%上升至71.73%,氨逃逸率由1.47%上升至1.72%。

SCR脱硝系统在危废焚烧烟气处理中的应用研究

选择性催化还原(Selective Catalytic Reduction,SCR)是危废焚烧企业广泛应用的烟气处理工艺。某危废焚烧处置项目SCR脱硝系统位于烟气处理的湿法脱酸工艺后端,SCR反应器设计温度为260℃,升温过程需要消耗大量天然气加热烟气。因此,有必要优化工艺方案设计,开展经济效益分析,明确SCR脱硝系统运行风险,提出应对措施。经设计,采用两级烟气换热系统,湿法脱酸后的烟气与袋滤房出口烟气一次换热,再与SCR反应后的烟气二次换热,两次加热升温后烟气温度达到220℃,然后烟气进入SCR反应器。与天然气直接加热方式相比,该工艺可明显减少天然气消耗量,每年可节省天然气费用约530万元,具有很好的环境效益与经济效益。

再生铅富氧侧吹熔炼SNCR干法脱硝工艺实践

再生铅富氧侧吹熔炼在再生铅领域占有突出地位。由于国家环境政策趋严,要求富氧侧吹熔炼进行脱硝处理。脱硝工艺主要有氧化法、SCR法及SNCR法。本文中,笔者介绍了再生铅富氧侧吹熔炼炉脱硝工艺,重点介绍了氧化法脱硝工艺和SNCR高温干法脱硝工艺,分析了这两种工艺的优、缺点。并且,详细讨论了SNCR高温干法脱硝工艺在生产实践中的应用。

基于储氨停喷响应特性的SCR系统氨泄漏识别

有效识别出氨(NH_(3))泄漏是柴油机NO_(x)转化(De NO_(x))系统实现精确闭环控制与自适应修正的基础.针对NO_(x)传感器对排气中的NH_(3)和NO_(x)存在交叉敏感这一情况,提出了一种基于停喷状态下选择性催化还原(SCR)系统储氨响应特性的NH_(3)泄漏识别方法.在工况条件合适时,持续将NO_(x)转化效率的传感器测量值和预测值的比值与标定限值进行对比,超过限值时则触发停喷诊断动作,并在停喷过程中通过对比催化器的储氨消耗超过限值的时间与转化效率低于限值的时间先后,实现对NH_(3)泄漏状态的准确识别.结果表明:该方法能够有效识别出SCR系统的NH_(3)泄漏,并能够在NO_(x)排放超过车载故障诊断(OBD)限值时准确识别出NO_(x)排放超标.