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1.
Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO2 and NOx in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O3 and NOx. The concentration of N2O5 was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO2 and N2O5 during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO2 was found to be negligible. To produce NO2, the optimal residence time was 1.25 sec and the molar ratio of O3/NO about 1. For the generation of N2O5, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O3/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NOx by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NOx.  相似文献   

2.
This study introduced TiO2-pillared clays (TiO2-PILC) as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350℃, the NO conversion was 61% under conditions of GHSV = 23600 hr^-l. The BET data showed that the support particles had a mesoporous structure. Hz-TPR showed that Cr(10)TiP (10 wt.% Cr doping on TiO2-PILC) clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO + O2 adsorption, the intensity of evolution of superoxide ions (O2^-) increased. The content of Cr^3+ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr^3+ increased to 50.28%. Additionally, Oα/Oβ increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4^2-.  相似文献   

3.
于2012年12月—2013年12月在广州城区(市站)和东部郊区(九龙)开展为期一年的PM2.5样品采集,并同步收集气象因子和气态污染物质量浓度等数据.结果表明,PM2.5中主要化学组分为有机质(OM)和硫酸盐(SO2-4),分别占市站和九龙PM2.5质量浓度的49.4%和15.2%及57.0%和17.3%.碳质气溶胶(OM和EC)贡献接近50%,二次无机气溶胶(SO2-4、NO-3和NH+4总和,SIA)贡献超过30%.由于以机动车尾气为代表的移动污染源在城市区域贡献较大,市站[NO-3]/[SO2-4]比值显著高于九龙.两个站点[NH+4]/[SO2-4]摩尔质量比均高于1.5,表明观测期间广州市干季大气处于富铵状态.市站和九龙站硫氧化率(SOR)和氮氧化率(NOR)的时空变化趋势与O3类似,表明大气光化学过程是影响广州市SOR和NOR的重要因素.相对湿度低于65%时,SOR和NOR均较高;温度对SOR和NOR的影响有显著的城郊差异.降雨对PM2.5及各化学组分浓度有显著去除作用.  相似文献   

4.
采用共沉淀法合成了TiO_2及TiO_2-Fe_2O_3载体,并对硫酸氢铵与上述载体之间的相互作用及硫酸氢铵的具体分解行为进行了研究.结果表明,催化剂载体表面含硫官能团主要以双齿硫酸盐的形式存在,含氮官能团以铵根离子的形式存在.当硫酸氢铵沉积于催化剂载体表面时,由于硫酸根离子具有较强的电负性,Ti原子及Fe原子处于电子缺失状态.对于TiO_2载体,硫酸根离子主要与Ti原子相连;而对于TiO_2-Fe_2O_3载体,Ti原子及Fe原子均为硫酸根离子主要的附着位点.采用热分析方法及原位红外对硫酸氢铵在TiO_2及TiO_2-Fe_2O_3载体表面的分解行为进行了研究,发现铁氧化物的添加显著促进了硫酸氢铵在低温区间内的分解行为;与铵根离子相比,硫酸根离子具有更高的热稳定性.催化剂稳定性测试结果表明,铁氧化物的添加显著提高了低温抗硫抗水性能,为实现低温SCR技术的工业应用提供了理论基础.  相似文献   

5.
The oxidation of SO2 is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO2 and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J30) showed a moderate correlation with the concentration of sulfuric acid ([H2SO4]) calculated from the measured mixing ratio of SO2 in long-term NPF events and some short-term NPF events (Category I) (R2 = 0.66). The exponent in the fitting line of J30 ~ [H2SO4]n in these events was 1.6. It was also found that SO2 mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO2-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO2 probably made a negligible contribution to the growth of >10 nm new particles.  相似文献   

6.
The oxidation of SO2 is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO2 and observed long-term (duration > 3 hr) and short-term (duration < 1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J30) showed a moderate correlation with the concentration of sulfuric acid ([H2SO4]) calculated from the measured mixing ratio of SO2 in long-term NPF events and some short-term NPF events (Category I) (R2 = 0.66). The exponent in the fitting line of J30 ~ [H2SO4]n in these events was 1.6. It was also found that SO2 mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO2-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO2 probably made a negligible contribution to the growth of > 10 nm new particles.  相似文献   

7.
利用自制气溶胶反应器研究了NO_x和/或NH_3气氛下SO_2在高岭土表面的非均相转化过程,应用扫描电镜(SEM)对高岭土颗粒物形貌进行了表征.结果表明:高岭土颗粒表面的SO_2非均相转化致使其成分和形貌产生了较大变化.相同实验条件下,SO_2转化的协同作用程度由高到低依次为NH_3、NO_x/NH_3和NO_x气氛,相对湿度40%、有光照条件下,SO_2转化量增幅最高可分别达125%、75%和50%.所有气氛下,协同作用在无光照时在高相对湿度(40%~70%)区间更为突出,有光照时其显著性则体现在低相对湿度(20%~40%)区间.SO_2、NO_x、NH_3三者共存时,在高岭土颗粒表面发生的非均相反应过程既有协同作用又存在竞争反应.  相似文献   

8.
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.  相似文献   

9.
The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.  相似文献   

10.
采用等体积浸渍法制备了锰氧化物负载凹凸棒石(MnOx/PG)低温SCR催化剂,通过SO2暂态响应、程序升温表面反应(TPSR)等实验技术研究了烟气中SO2对催化剂SCR脱硝活性的影响行为.采用程序升温脱附(TPD)、BET比表面及孔径分布测定、XPS等表征技术对催化剂硫中毒的机理及化学本质进行了深入分析.结果表明,低温下烟气中SO2对MnOx/PG催化剂的SCR脱硝活性存在显著的抑制作用,催化剂中毒主要由烟气中SO2的催化氧化引起.一方面SO2氧化为SO3后与NH3及H2O竞争反应形成复杂的硫酸铵盐堵塞催化剂孔道,另一方面与活性组分MnO2结合形成MnSO4使得部分活性组分形态发生变迁.其中硫酸铵盐的形成可通过适当的热处理得以去除,而MnSO4则不可恢复,但催化剂SCR活性却显著增加,表明MnSO4的形成不是催化剂失活的主要因素.吸附态的硫可显著增加催化剂表面酸性,因此对SCR活性有促进作用.催化剂失活主要机理为:由气相SO2的连续氧化并与NH3相结合形成硫酸铵盐,并且在低温下难以分解,以致堵塞催化剂活性中心.  相似文献   

11.
The present article studies the effect of CeO2 and Al2O3 on the activity of Pd/Co3O4/cordierite catalyst in conversion of NO, CO, CnHm. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO2 on the properties of Pd/Co3O4/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O2 and CO + NO) and total hexane oxidation (C6H14 + O2). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO2 addition promotes the SO2 resistance of Pd/Co3O4/cordierite. The second support decreases the activity of Pd/Co3O4/cordierite catalyst in the reactions of CO and C6H14 with oxygen because of CoAl2O4 formation.  相似文献   

12.
The effect of pretreatment on Pd/Al2O3 catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al2O3 catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al2O3 activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al2O3 pre-reduced at 300℃/400℃, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al2O3, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al2O3 catalyst for the catalytic oxidation of o-xylene at low temperature.  相似文献   

13.
二氧化硫(SO_2)是一种常见的大气污染物,目前关于SO_2对木本植物的毒害作用及相关机制并不清楚.本文以木本植物胡杨的愈伤细胞为材料,研究SO_2衍生物对胡杨细胞的致死效应,以及过氧化氢(H_2O_2)与一氧化氮(NO)在SO_2诱导胡杨细胞死亡中的信号调节作用.研究发现:SO_2衍生物处理(1~5 mmol·L-1)可诱发胡杨细胞死亡,且SO_2衍生物浓度越大、处理时间越长,细胞死亡率越高.2 mmol·L-1SO_2衍生物处理胡杨细胞后,胞内H_2O_2和NO水平显著升高,且H_2O_2水平的升高先于NO.一定浓度的外源H_2O_2或NO供体SNP能够提高SO_2胁迫下胡杨细胞的死亡率;而使用H_2O_2清除剂CAT和ASA、NO清除剂c PTIO、NO合成抑制剂钨酸钠后,SO_2诱导的细胞死亡率明显降低.进一步实验发现,外源H_2O_2可以提高SO_2胁迫下胡杨细胞的硝酸还原酶(NR)活性,促进胞内NO产生;而利用CAT和ASA清除H_2O_2后,细胞NR活性和NO产生均受到明显抑制.此外,SO_2胁迫下,外源SNP能够抑制抗氧化酶(CAT和APX)活性,增加胡杨细胞内的H_2O_2水平,而一定浓度的c PTIO和钨酸钠均可提高CAT和APX活性,降低胞内H_2O_2水平.结果表明:SO_2胁迫下,胡杨细胞快速产生的H_2O_2能够激活硝酸还原酶活性,促进NO生成,同时NO能够通过抑制抗氧化酶活性而提高H_2O_2水平.H_2O_2与NO互作调控SO_2诱导的胡杨细胞死亡.  相似文献   

14.
为获得高效催化活性的光催化材料,研究不同煅烧氛围对材料在可见光下催化性能的影响,以膨胀珍珠岩(EP)为载体,采用溶胶-凝胶法,在不同煅烧氛围(O2和/或NH3)下制备Fe2O3/TiO2负载EP的光催化复合材料〔Fe2O3-TEP(O2)、Fe2O3-TEP(NH3)、Fe2O3-TEP(O2,NH3)、Fe2O3-TEP(NH3,O2)〕,采用EDS(X-射线色散能谱)、BET(比表面积及孔径分析)、XRD(X射线衍射)、SEM(扫描电子显微镜)、XPS(X射线光电子能谱)等对复合材料进行表征,并研究了其在可见光下对罗丹明B的光催化降解效果.结果表明:①复合材料成功负载了Ti、Fe元素,负载的TiO2以锐钛矿型存在,Fe2O3的掺杂增强了TiO2对可见光的响应能力;②不同的煅烧氛围明显影响复合材料的晶粒尺寸、比表面积和光催化性能,其中,Fe2O3-TEP(O2,NH3)的光催化性能最好,4 h后罗丹明B降解率达到87.59%,Fe2O3-TEP(NH3,O2)、Fe2O3-TEP(O2)和Fe2O3-TEP(NH3)4 h后对罗丹明B的降解率则分别为65.02%、62.48%和47.48%;③在试验条件下,复合材料的光催化反应符合一阶反应动力学方程,Fe2O3-TEP(O2,NH3)、Fe2O3-TEP(NH3,O2)、Fe2O3-TEP(O2)和Fe2O3-TEP(NH3)相应的降解速率常数分别为0.008 3、0.004 3、0.004 3和0.002 7 min-1.研究显示,通过溶胶-凝胶法所制备的复合材料(Fe2O3-TEP)经煅烧后所得矿相均一;Fe2O3掺杂TiO2可形成Ti—O—Fe键,减小TiO2固有的禁带宽度;复合材料光催化性能也受到煅烧氛围的影响,先O2后NH3煅烧条件下所得材料的光催化性能最佳.   相似文献   

15.
李蒋  王雁  张秀芳  赵旭 《环境科学》2018,39(8):3713-3718
采用静电纺丝法制备了Co_3O_4/BiVO_4复合薄膜电极,并以之为光阳极,在过一硫酸盐(PMS)辅助作用下开展了光电催化降解双酚A研究.结果表明,PMS在可见光下可显著强化Co_3O_4/BiVO_4复合阳极光电催化降解双酚A,在0.25 V外加偏压以及可见光照射下,当加入2 mmol·L-1PMS时,双酚A在2 h内的降解效率为96%.降解动力学常数为0.471 4 min-1.系统研究了PMS初始浓度、外加偏压对双酚A降解性能的影响.结果发现,双酚A在较低的PMS投加量和较低的外加偏压(0.25 V)下即可有效降解.采用电子自旋共振波谱仪鉴定体系的主要活性自由基为SO·-4和·OH.并进一步通过淬灭实验结果证明空穴、SO·-4和·OH起主要氧化作用.光电反应后的体系中未检测到金属离子溶出,可避免二次污染.  相似文献   

16.
基于碳捕集的富氧燃煤烟气联合脱硫脱硝试验研究   总被引:1,自引:0,他引:1  
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.  相似文献   

17.
CeO2–TiO2composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5–WO3/CeO2–TiO2catalysts for the selective catalytic reduction(SCR) of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV–Vis,Raman and XPS techniques. The results showed that the catalytic activity of V2O5–WO3/TiO2 was greatly enhanced by Ce doping(molar ratio of Ce/Ti = 1/10) in the TiO2 support.The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning.  相似文献   

18.
分别采用沉积沉淀、直接混合和传统的浸渍法制备1% Pd/Ce0.5Zr0.5O2 催化剂, 研究了Pd负载方法对催化剂活性影响.运用H2-TPR和原位漫反射红外(DRIFTS)研究了Pd-铈锆载体间的相互作用及Pd/Ce0.5Zr0.5O2催化剂上的三效反应机理.结果表明沉积沉淀法制备的Pd/Ce0.5Zr0.5O2催化剂(Pd-DP)表现出最强的Pd-载体作用及最优活性,原位红外实验发现Pd-DP上存在与传统的浸渍法制备的Pd-IMP催化剂不同的NO催化还原途径,推测Pd-载体间相互作用引起NO还原机理差异,进而导致活性差异.  相似文献   

19.
Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.  相似文献   

20.
纳米Fe3 O4-H2 O2 非均相Fenton反应催化氧化邻苯二酚   总被引:4,自引:3,他引:1  
何洁  杨晓芳  张伟军  王东升 《环境科学》2013,34(5):1773-1781
由四氧化三铁(Fe3O4)-过氧化氢(H2O2)构成的非均相Fenton体系主要利用H2O2分解产生的羟基自由基氧化去除难降解有机污染物.研究了邻苯二酚在纳米Fe3O4-H2O2构成的非均相Fenton体系中的催化氧化特征,同时对实验室制备的纳米级Fe3O4和商品微米级Fe3O4两种催化剂的催化活性进行比较,并考察了H2O2初始浓度对邻苯二酚的催化氧化的影响.结果表明,自制纳米Fe3O4-H2O2体系较商品Fe3O4-H2O2体系,能更快速地去除溶液中的邻苯二酚和总有机碳(TOC),邻苯二酚的去除率接近100%,同时能迅速催化H2O2分解.邻苯二酚的催化氧化反应遵循准一级反应动力学方程,H2O2的分解反应能用三级反应动力学方程较好拟合.此外,反应过程中铁释放低于0.3 mg.L-1,不足以启动均相Fenton反应,反应机制为由界面反应控制的非均相反应机制.  相似文献   

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