制备及反应条件对Pt/Al2O3蜂窝状催化剂性能的影响

采用多次涂层 浸渍法制备了蜂窝状Pt Al2 O3 催化剂 .并对焙烧温度和焙烧时间等不同制备条件和反应温度、O2 浓度和空速等不同反应条件下NOx 的选择性催化还原性能进行了研究 .实验表明 ,蜂窝状Pt Al2 O3 催化剂上NOx 转化率在反应温度为 30 0℃左右时出现最高值 .而随反应温度的升高 ,达到最高转化率所需的O2 浓度不断减小 ,分别为 8% ,6 %和 4 % .这可能是由于在高温下O2 会与NO发生竞争吸附 ,从而阻碍了NO催化还原反应的进行 ;同时随着空速的依次增加 ,催化剂的活性逐渐下降 ,催化剂活性曲线的峰值依次向高温方向移动 .实验还说明 ,在过高的焙烧温度和较长的焙烧时间的制备条件下 ,蜂窝状Pt Al2 O3 的催化性能明显下降 .这是因为高的焙烧温度和较长的焙烧时间能够导致蜂窝状Pt Al2 O3 催化剂的表面发生烧结现象 ,使得催化剂的比表面减小 ,从而导致活性降低 .     

负载型Mn-Co/TiO2催化剂的制备及其低温NH3选择催化还原NO

采用浸渍法制备了一系列以成型TiO2为载体的Mn-Co/TiO2低温SCR催化剂,研究分析了活性组分担载量、Mn含量、焙烧温度、焙烧时间等制备参数和进口NO浓度、空速、O2体积分数、NH3/N2摩尔比等操作条件对催化剂脱硝反应活性的影响.结果表明:活性组分担载量为30%,Mn/(Mn+Co)摩尔比为80%,在500℃下焙烧6 h得到的Mn-Co/TiO2催化剂具有较高的NO转化率;在进口NO浓度为600×10-6、O2体积分数6%、空速10000 h-1、150℃条件下,NO脱除率接近100%.     

混晶纳米TiO_2薄膜光催化降解亚甲基蓝

以钛酸四丁酯为原料采用浸渍提拉法在普通瓷片表面制备TiO2混晶薄膜,用XRD对薄膜进行表征,选用亚甲基蓝催化降解考察TiO2混晶薄膜的催化能力,探讨了紫外光光照强度、亚甲基蓝初始浓度和pH对光催化降解的影响。结果表明:600℃煅烧4h可制备金红石为13.2%的混晶薄膜,平均粒径为22nm;初始浓度在0.313～0.937mg/L,催化反应符合一级动力学方程,半衰期随初始浓度的增加而减小;在光照强度为40W和pH为13时降解率为45.6%,并可多次重复使用。     

负载型纳米TiO2/AC对偶氮染料的光催化降解研究

以钛酸四丁酯和粒状活性炭(AC)为主要原料,采用溶胶-凝胶-浸渍法制备出负载型纳米TiO2/AC催化剂.在流化床反应器中分别对2种典型的偶氮类染料橙黄G、活性艳红X-3B模拟废水进行了光催化降解研究,探讨了pH值、外加氧化剂对光催化降解率的影响,并对催化剂进行了回收再生利用试验.结果表明,TiO2/AC催化剂具有良好的光催化活性、吸附特性及可再生性,60 min后对2种染料反应的光催化降解率分别可达到99.71%和97 12%,反应180 min后的TOC去除率分别达到81.54%和81.99%;反应后TiO2/AC催化剂回收率大于95%,经焙烧再生后对橙黄G反应60 min的光催化降解率仍高达95.93%.     

纳米TiO2/硅藻土复合材料的制备研究

以无水乙醇和钛酸四丁酯为原料,采用溶胶-凝胶法制备了TiO2/硅藻土复合材料,利用DSC,TGA,XRD,SEM和比表面积测试仪等仪器对纳米复合粒子的结构进行了表征.结果发现,当硅藻土质量为0.6 g时,在温度400℃下可制得锐钛型TiO2.     

负载型TiO2光电催化降解孔雀石绿的动力学研究

以钛酸四丁酯(TBOT)为钛源,硝酸镧为镧源,尿素为氮源,采用溶胶-凝胶法合成了La-N共掺杂的TiO2光催化剂,并探究了其对孔雀石绿氧化降解的性能.结果表明该反应遵循一级动力学,得到动力学模型;其中外加偏电压的反应分级数(0.935 8)高于pH的反应分级数(0.611 9)以及初始浓度的反应分级数(0.335),表明外加偏电压对反应的影响最大.模型值与实验值吻合良好(R2为0.910～0.996 1),说明该反应动力学模型能较好地描述光电催化降解孔雀石绿过程.     

SO2对Pd掺杂La0.9Sr0.1MnO3催化剂去除NOx和碳烟的影响

采用柠檬酸络合法制备了掺杂贵金属Pd的La_0.9Sr_0.1Mn_0.03Pd_0.97O₃钙钛矿型催化剂,并通过X射线衍射光谱及暂态响应、扫描电子显微镜、傅立叶变换红外光谱及程序升温等技术研究了Pd对钙钛矿形貌结构和NOx转化率的影响以及SO₂对La_0.9Sr_0.1Mn_0.97Pd_0.03O₃催化剂脱除NOx的作用机制.结果显示,Pd的成功掺入增大了原催化剂的比表面积,使得催化剂中的活性组分与NOx能够反应的更加充分,有效提高了催化剂对NO的转化率.催化剂La_0.9Sr_0.1Mn_0.97Pd_0.03O₃在含SO₂气氛下反应后出现了微弱的硫酸盐相,说明硫使催化剂发生了一定程度的钝化.在较低浓度SO₂存在时催化剂对NO的转化效率维持在80%以上,碳烟的起燃温度为353℃,但随着SO₂浓度的增加NO的转化效率最高只有67%,碳烟的起燃温度升高到368℃.     

钛酸四丁酯水解制备TiO2光催化氧化五氯苯酚钠

为制备高效、实用的TiO2半导体光催化剂,通过光催化氧化五氯苯酚钠实验,结合对催化剂晶型结构、比表面积的表征分析,研究了钛酸四丁酯水解制备TiO2粉末的两大影响因素R值(R是水和钛酸四丁酯的摩尔比)和烧结温度.实验结果表明,当R=100、温度为650℃烧结1h,钛酸四丁酯水解所制备的TiO2粉末光催化活性和使用寿命均比较理想.用R100-650型催化剂做光催化实验,当反应液初始五氯苯酚钠(PCP-Na)浓度为100 mg/L、pH值为6.5,TiO2投加量为2 g/L,光照强度为30W/m2时,五氯苯酚钠2 h光催化氧化率达95.5%.     

Mn-Ce-Fe/TiO2低温催化还原NO的性能

采用浸渍法制备了Mn-Ce-Fe/TiO2.研究了其组分配比、焙烧温度等制备条件和NO进口浓度、空速、O2含量、NH3/NO摩尔比等操作条件对Mn-Ce-Fe/TiO2 NH3低温还原NO活性的影响,并探讨了H2O、SO2对Mn-Ce-Fe/Ti O2活性的影响.结果表明,Mn:Fe:Ce摩尔比为5:2:4、500℃下焙烧的Mn-Ce-Fe/TiO2在无H2O、SO2,NO体积分数为0.1%,空速为5000h～,反应温度为130℃、O2含量为6%、NH3/NO摩尔比为1.1的条件下,NO转化率接近98%,Fe的加入大大提高了催化剂的单独抗水和同时抗硫抗水性能,130℃下,体积分数10%的H2O对该催化剂的活性基本没有影响,转化率保持在96%以上;通硫、水后的400min内,活性仅下降3%.单独通人S02时,该催化剂中毒程度较深.该催化剂有望应用于基本不含SO2的燃气锅炉烟气和不含SO2的硝酸尾气等NO,工业废气的低温脱硝.     

H_3PW_(12)O_(40)/TiO_2可见光下光催化降解孔雀石绿的研究

以钛酸四丁酯为原料,采用溶胶-凝胶法制备TiO2光催化剂,然后浸渍法制备出H3PW12O40/TiO2复合型光催化剂,并运用XRD、SEM、FT-IR和DRS对催化剂进行表征和分析.研究了可见光光照下H3PW12O40/TiO2对孔雀石绿降解的光催化活性,考察了浸渍量、催化剂用量、底物浓度、pH值对光催化降解率的影响.实验表明,在pH=5条件下,H3PW12O40/TiO2催化剂用量为0.3g.L-1,浓度为10mg·mL-1的孔雀石绿溶液在2L·min-1曝气、300W可见光下光照4h后光催化降解率为78%,比TiO2光催化活性提高了24%.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. 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.     

富氧条件下SnO2/Al2O3催化剂上丙烯选择性还原NOx的研究

考察了分别用浸渍法、共沉淀法和溶胶-凝胶法制备的SnO₂/Al₂O₃催化剂上丙烯选择性还原NO_x的催化活性,发现制备方法与Sn的负载量对其活性有重要影响.溶胶-凝胶法制备的SnO₂/Al₂O₃催化剂活性最高,Sn的最佳负载量为5%.与浸渍法和共沉淀法制备的5%SnO₂/Al₂O₃催化剂相比,溶胶-凝胶法制备的5%SnO₂/Al₂O₃催化剂受水蒸汽的抑制作用较弱,并且在水和SO₂共存的条件下活性最高.此外,反应气中丙烯及氧气浓度的增加有利于NO_x转化率的提高.     

V2O5/TiO2催化剂中毒机理的试验研究

选择性催化还原(SCR)催化剂是SCR烟气脱硝技术的核心,是整个SCR系统脱硝效率和经济性的决定因素.本文工作的主要研究思路是以钒钛SCR催化剂为研究对象,研究了H2O和SO2,以及相同含量下K、Na、Ca、Pb的氧化物对钒钛催化剂NO转化率的影响.H2O的存在会抑制V2O5/TiO2催化剂脱硝活性,而SO2在一定程度上促进(V2O5/TiO2)催化剂的SCR脱硝反应,提高NO转化率;碱金属K对钒钛催化剂的钝化作用都是最强,K2O和Na2O的掺入会抑制钒钛催化剂上V2O5的还原能力,而CaO和PbO的掺入对钒钛催化剂上V2O5的还原能力影响较小.     

Effect of pretreatment on Pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature

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.     

UV/H2O2降解美罗培南的影响因素及毒性研究

利用波长为254 nm的紫外灯活化过氧化氢(H_2O_2)氧化降解美罗培南(MPN),考察了H_2O_2投加量、初始pH值、水中常见共存阴离子(Cl~-、HCO~-_3、NO~-_3)和天然有机化合物(NOM)等重要影响因素对MPN降解的影响.结果表明,紫外光功率为4 W,初始pH为7.0,n(H_2O_2)/n(MPN)=20∶1时,反应20 min后,MPN的降解率达到97.8%.H_2O_2投加量的增加会加快MPN的降解速率,Cl~-和HCO~-_3对UV/H_2O_2体系中MPN去除效果的影响较小,极少量的NO~-_3会促进MPN的降解,当NO~-_3的浓度≥10 mg·L~(-1)时,MPN的降解受到抑制,且离子浓度越高,抑制程度表现越明显.NOM的存在对MPN的降解有抑制作用.与纯水相比,MPN在实际水体中的去除受到抑制,归因于水体基质的影响.大肠杆菌的急性毒性实验研究表明,MPN的中间转化产物保留了一些抗菌性能,但光解的最终产物无抗菌性能.     

Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density （SED）, and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar 〉 Ar 〉 02/Ar. The highest energy yield of 3.31 g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals.     

NOx和/或NH3气氛下SO2在高岭土表面非均相转化的实验研究

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.     

Preparation and characterization of Pd/Fe bimetallic nanoparticles immobilized on Al2O3/PVDF membrane: Parameter optimization and dechlorination of dichloroacetic acid

Using a liquid–solid phase inversion method, a hybrid matrix poly(vinylidene fluoride)(PVDF) membrane was prepared with alumina(Al2O3) nanoparticle addition. Pd/Fe nanoparticles(NPs) were successfully immobilized on the Al2O3/PVDF membrane, which was characterized by Scanning Electron Microscopy(SEM) and Transmission Electron Microscopy(TEM). The micrographs showed that the Pd/Fe NPs were dispersed homogeneously. Several important experimental parameters were optimized, including the mechanical properties, contact angle and surface area of Al2O3/PVDF composite membranes with different Al2O3 contents. At the same time, the ferrous ion concentration and the effect of hydrophilization were studied. The results showed that the modified Al2O3/PVDF membrane functioned well as a support. The Al2O3/PVDF membrane with immobilized Pd/Fe NPs exhibited high efficiency in terms of dichloroacetic acid(DCAA) dechlorination. Additionally, a reaction pathway for DCAA dechlorination by Pd/Fe NPs immobilized on the Al2O3/PVDF membrane system was proposed.     

关中盆地NO2和SO2对颗粒物污染的协同效应

基于WRF-Chem模式模拟了关中盆地2019年1月2—14日一次颗粒物污染事件,评估了NO_x和SO₂减排及其在颗粒物污染中的协同作用对PM_2.5污染的影响。敏感性实验结果表明：NO_x减排可使PM_2.5中硝酸盐含量下降,但大气中O₃浓度上升,大气氧化能力增强,其他二次组分上升,导致PM_2.5下降不明显;SO₂人为源减排可使硫酸盐质量浓度下降,但由于硫酸盐在PM_2.5中占比较低,当SO₂减排75%时,PM_2.5仅下降1.74%;当减排比例较高时,NO_x和SO₂同时减排更有利于颗粒物污染防治。PM_2.5质量浓度在NO_x和SO₂同时减排75%时比分开减排75%时多下降0.75%,主要是硫酸盐下降所致;对气溶胶含水量进行分析,发现NO_x对气溶胶含水量影响较大,当NO_x减排75%时,气溶胶含水量可下降15.51%;此外,NO_x和SO₂同时减排比分开减排时气溶胶含水量更低,更不利于二次颗粒物生成。     

Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst

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.