氮掺杂二氧化钛光催化氧化降解污水中四环素

以氮掺杂二氧化钛(N-TiO_2)作为催化剂,四环素作为目标污染物,以可见光作为光源,研究N-TiO_2在可见光源条件下,光催化氧化降解四环素的效果。当四环素初始浓度为50 mg/L时,在pH=8,催化剂投加量为1. 0 g/L较优的反应条件下,N-TiO_2光催化氧化降解四环素的效率可达到97%以上。研究表明:阴离子对降解过程有抑制作用,但对最终降解效果无显著影响。反应过程中起主要作用的活性基团为光生空穴。     

NO催化氧化的初步研究

利用一套小型动态试验装置进行配气实验，分析了一系列金属氧化物对气体中低浓度ＮＯ转化率的催化活性顺序为Ｃｒ＞Ｆｅ＞Ｃｏ＞Ｍｎ＞Ｃｕ，并对其综合影响进行了分析。通过实验总结出适宜的反应条件及催化剂配方，为以后研究提供了重要的数据资料。     

选择性催化氧化NO的催化剂研究进展

工业生产过程产生的NO对大气环境造成严重污染.选择性催化氧化吸收法(SCO)脱硝是目前较有价值的脱硝技术.选择性催化氧化的关键在于催化剂的选择.目前,用于NO催化氧化的催化剂主要有活性炭类、分子筛类、贵金属类、过渡金属氧化物类催化剂.其中,过渡金属氧化物类催化剂具有良好的催化活性,价格低廉,制作简单等,是目前较有研究前...     

选择性催化氧化H2S的富氮碳催化剂研究进展

近年来,能高效净化H2S并回收硫资源的选择性催化氧化技术(H2S-SCO)受到了广泛关注.开发高性能、高选择性及低成本的催化剂是H2S-SCO技术的研究重点,其中富氮碳基催化剂(RNCC)具有高活性、无金属、易制备、低成本且易再生等优点,被认为是一类极具潜力的H2S-SCO催化剂.本文介绍了金属基催化剂的发展,总结和归纳RNCC的制备方法、催化活性和物化性质,系统地讨论RNCC的构-效关系及影响RNCC性能的关键因素,并总结了RNCC的H2S-SCO反应机理.最后指出RNCC目前存在机遇和挑战,并展望了未来的发展方向.     

铁/钴氮氟掺杂二氧化钛膜的制备研究

通过溶胶-凝胶法制备Fe,N,F-TiO2膜和Co,N,F-TiO2膜的光催化剂,以亚甲基蓝为模型污染物,探讨了制备两种膜的最佳煅烧温度、镀膜层数和铁/钴掺杂量。结果表明,当煅烧温度400℃,镀膜层数4层,Fe/Ti=0.05%,Co/Ti=0.02%时,得到的Fe,N,F-TiO2膜和Co,N,F-TiO2膜的可见光催化活性最高。其中Fe,N,F-TiO2膜的光催化活性要略优于Co,N,F-TiO2膜。     

金属掺杂二氧化钛光催化还原硝酸氮

采用光沉积法制备了负载金属Fe或Cu的P25二氧化钛光催化剂,用TEM、ICP、XRD及UV-Vis等对其进行了表征,并测定其在20 W紫外灯照射下光催化还原硝酸氮、去除总氮的效果;考察了pH值、搅拌气体、金属的负载量、空穴清除剂甲酸的用量以及金属Ag-Cu复合沉积等条件的影响.反应2 h的结果表明,二氧化钛上载铜量增加,硝酸氮转化率随之增加,但最大总氮去除率和氮气选择性均出现在0.5%Cu负载量下;氮气搅拌和酸性条件下反应,形成氮气的选择性略低(62%),但最高的硝酸氮转化率和总氮去除率分别达到36.9%和23.2%;CO2作为搅拌气体.Cu的负载量为0.5%、甲酸用量为0.06 mol/L时.形成氮气选择性最好(88.4%).硝酸氮转化率和总氮去除率分别为29.5%和25.1%.同样条件下,采用二氧化钛上共沉积金属总质量分数为1%、Ag:Cu=1:1的催化剂,硝酸氮的转化率可达48.1%,总氮去除率为34.2%,氮气选择性为72.2%.     

铈掺杂Ru/Al2O3催化臭氧氧化降解邻苯二甲酸二甲酯

考察了铈(Ce)的掺杂对Ru/Al2O3催化臭氧氧化邻苯二甲酸二甲酯(DMP)溶液过程的影响.结果表明,Ce的掺杂可以显著提高臭氧氧化的效果,反应100min后,TOC的去除率可以由原催化剂的61.3%提高到75.1%,而单独臭氧氧化仅有14.0%.在实验范围内,Ru和Ce同时浸渍催化效果较好,且活性组分的溶出最少,Ce的最佳掺杂量为1.0%.通过催化剂吸附试验、单独臭氧氧化试验、Ce的均相催化试验及Ru-Se/Al2O3催化剂的非均相催化实验,证明Ru-Ce/Al2O3催化剂对DMP溶液臭氧氧化体系TOC的去除率达到50%,这是基于Ru-Ce/A12O3催化剂的非均相催化作用.     

活性炭纤维负载氧化镧催化净化NO的实验研究

以ACF作为载体制备了负载不同质量分数La₂O₃的负载型催化剂,研究了它们催化净化NO的活性和活性的稳定性,同时对比研究了ACF、HNO₃/ACF净化NO的能力.正交实验结果表明,实验中最佳的氧气体积分数为5%,最佳空速为5 000 m³·(m³·h)^-1;催化实验结果表明,ACF的低温活性很差,HNO₃/ACF净化NO的低温活性很好,但是其活性的稳定性很差;负载了La₂O₃的ACF能大幅提升ACF净化NO的能力,其活性中心为La₂O₃,La₂O₃的最佳负载量为20%,350℃以上时,20% La₂O₃/ACF催化净化NO的效率均在95%以上,在200℃恒温条件下,其催化活性约能持续8h;催化剂的理化特征实验结果表明,ACF、HNO₃/ACF净化NO的机制与负载了La₂O₃的ACF净化NO的机制有着本质的区别.     

Mn/Co-Ba-Al-O催化氧化NO性能研究

采用共沉淀-浸溃法制备了Mn/Co-Ba-Al-O催化剂.考察了用共沉淀法制作载体Co-Ba-Al-O过程中加料顺序分别为正加法、反加法和并流法时催化剂的活性.BET测试和XBD分析表明,并流时制得的载体比表面积最大,且其中的γ-A12O3结晶度最好,不含BaCO3,对NO的催化氧化性能最好.考察了各操作条件对并流法制备的催化剂催化氧化NO效率的影响,结果显示,在NO体积分数为500 X 10-6,O2体积分数为10%,空速为4000h-1时,225°C左右,出1:3 NOX的氧化度(N02/NO2)达到50%-60%.将取得最大的吸收效率;300°C时,氧化度可达到83%左右,接近热力学平衡值.     

The kinetic study for reduction of NO by CO over cobalt tetraphenylporphyrin supported on titanium dioxide

The catalytic reduction of nitric oxide by carbon monoxide over cobalt tetraphenylporphyrin supported on titanium dioxide (Co-TPP/TiO2) has been investigated. Co-TPP/TiO2 pretreated by evacuation at 270℃ exhibited a remarkable activity. The kinetic equation for the reduction of nitric oxide by carbon monoxide in the reaction temperature ranging from 80 to 150℃ (v=kPNO 0.56Pco 0.41) suggested that the reaction can be assumed to occur via a surface reaction of the Langmuir-Hinshelwood model between nitric oxide and carbon monoxide adsorbed on the central metal ion of Co-TPP. Experimental results indicated that the reduction of nitric oxide and formation of molecular nitrogen took place simultaneously during initial stage of the reaction. The apparent activation energy was calculated to be 30.8 kJ/mol.     

新型CuMn/TiO2苯类催化燃烧催化剂的研制及活性实验

采用浸溃法制备了CuMn/TiO2新型甲苯燃烧催化剂,其活性明显优于传统CuMn/γ-Al2O3和Cu-Mn复合氧化物催化剂.研究发现,载体TiO2自身有一定催化活性,而γ-Al2O3则几乎没有活性;TiO2与Cu-Mn之间的协同作用更提高了新型催化剂的活性.XRD、LRS结果显示,CuMn/TiO2催化剂的主要活性相为铜锰尖晶石(CuMn2O4),它的存在是CuMn/TiO2催化活性优良的另一个主要原因.考察了Cu-Mn负载量、铜锰比和焙烧温度对催化剂活性的影响,CuMn/TiO2下对甲苯的去除率达95%以上时催化床层温度为215℃,比CuMn/γ-Al2O3和Cu-Mn复合氧化物对甲苯去除率达95%时分别下降了30℃、50℃左右.     

Ru/ZrO2催化剂高温焙烧对NO催化氧化反应性能的影响

采用浸渍法制备了一系列负载Ru催化剂,并将其应用于NO催化氧化反应.同时,对Ru/ZrO2样品在不同温度下进行焙烧处理,并通过X-射线衍射(XRD)、程序升温还原(TPR)和透射电子显微镜(TEM)等技术对不同温度焙烧的Ru/ZrO2进行表征,根据表征结果对导致Ru/ZrO2催化活性下降的原因进行了探讨.结果表明,Ru/ZrO2催化剂具有很好的催化活性,在空速为180000h-1条件下,275℃时即可获得93%的NO转化率.高温焙烧会导致Ru/ZrO2催化活性明显下降.     

Characterization of metal doped-titanium dioxide and behaviors on photocatalytic oxidation of nitrogen oxides

A series of nanosized ion-doped TiO_2 catalysts with different ion content(between 0.1 at.% and 1.0 at.%) have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocatalytic oxidation of nitric oxide.The catalytic activity was correlated with structural,electronic and surface examinations of the catalysts using X-ray diffraction analysis (XRD),ultraviolet-visible(UV-Vis)absorption spectroscopy,transmission electron microscopy(TEM),energy disperse spectrometer (EDS)and high resolution-transmission electron microscopy (HR-TEM) techniques.An enhancement of the photocatalytic activity was observed for Zn~(2 ) doping catalyst ranged from 0.1 at.% to 1.0 at.% which was attributed to the lengthened lifetime of electrons and holes.The improvement in photocatalytic activity could be also observed with the low doping concentration of Cr~(3 )(0.1 at.%). However,the doping of Fe~(3 ),Mo~(6 ),Mn~(2 ) and the high doping concentration of Cr~(3 ) had no contribution to photocatalytic activity of nitric oxide.     

NH3-SCR performance and the resistance to SO2 for Nb doped vanadium based catalyst at low temperatures

Niobium oxide as the promoter was doped in the V/WTi catalyst for the selective catalytic reduction(SCR)of NO.The results showed that the addition of Nb_2O_5could improve the SCR activity at low temperatures and the 6 wt.%additive was an appropriate dosage.The enhanced reaction activity of adsorbed ammonia species and the improved dispersion of vanadium oxide might be the reasons for the elevation of SCR activity at low temperatures.The resistances to SO_2of 3V6Nb/WTi catalyst at different temperatures were investigated.FTIR spectrum and TG-FTIR result indicated that the deposition of ammonium sulfate species was the main deactivation reason at low temperatures,which still exhibited the reactivity with NO above 200°C on the catalyst surface.There was a synergistic effect among NH_3,H_2O and SO_2that NH_3and H_2O both accelerated the catalyst deactivation in the presence of SO_2at 175°C.The thermal treatment at 400°C could regenerate the deactivated catalyst and get SCR activity recovered.The particle and monolith catalysts both kept stable NO_xconversion at 225°C with high concentration of H_2O and SO_2during the long time tests.     

Simultaneous removal of NO and dichloromethane（CH2Cl2） over Nb-loaded cerium nanotubes catalyst

Herein, a series of niobium oxide supported cerium nanotubes（Ce NTs） catalysts with different loading amount of Nb₂O₅（0–10 wt.%） were prepared and used for selective catalytic reduction of NOxwith NH₃（NH₃-SCR） in the presence of CH₂Cl₂. Commercial V₂O₅-WO₃-TiO₂ catalyst was also prepared for comparison. The physcial properties and chemical properties of the Nb₂O₅ lo...     

Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO

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-.     

磁性氮掺石墨烯活化过硫酸钾降解水中亚甲基蓝

活化过硫酸盐产生硫酸根自由基的高级氧化技术在水环境污染物治理中引起了广泛的关注和研究.本研究采用水热法制备磁性氮掺石墨烯(M-N-G)作为催化剂.利用SEM、BET、XRD和VSM等手段表征材料,系统研究了该材料活化过硫酸盐降解亚甲基蓝的效能.结果表明:M-N-G的比表面积为94.35 m2·g-1,磁性Fe3O4分布在材料表面,能有效的活化过硫酸钾降解亚甲基蓝.当催化剂的用量为200 mg·L~(-1),过硫酸钾浓度为0.4~0.5 mmol·L~(-1)时,在p H=3~6时对10 mg·L~(-1)亚甲基蓝的降解率达90%以上.体系温度在15~32℃时,降解速率常数在0.0227~0.0488 min-1,反应活化能为33.7 k J·mol-1.EPR分析及自由基漼灭实验证明了体系中有羟基自由基和硫酸根自由基产生.TOC分析结果表明:TOC去除率可达50%.M-N-G经过简单的稀硫酸和水洗后,可高效重复利用4次.该技术方法简单、高效、无二次污染,能为有机污染物废水处理提供一种新的方法选择.     

Selective oxidation of benzyl alcohols to benzoic acid catalyzed by eco-friendly cobalt thioporphyrazine catalyst supported on silica-coated magnetic nanospheres

A novel magnetically recoverable thioporphyrazine catalyst (CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex (CoPz(S-Bu)8) on silica-coated magnetic nanospheres (SiO2@Fe3O4). The composite CoPz(S-Bu)8/SiO2@Fe3O4 appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide (H2O2) as oxidant under Xe-lamp irradiation, with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number (TON) of 61.7 at ambient temperature. The biomimetic catalyst CoPz(S-Bu)8 was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz(S-Bu)8 can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.     

风干工艺强化催化氧化除氨氮/锰活性滤料膜负载

为强化地下水处理中催化氧化除氨氮/锰活性滤料表面膜负载强度,系统研究了风干温度对锰氧化物滤料氧化膜的活性、负载强度及负载量的影响,将不同温度风干的生产性滤料填充滤柱,检测沿滤柱深度的氨氮、锰浓度随时间的变化,分析风干温度对生产滤料活性恢复期、除氨氮锰能力和膜负载强度的影响规律.结果表明,滤料经风干处理可以明显缩短滤柱除氨氮/锰的恢复期,其中除氨氮活性最先恢复的是自然风干和60℃风干滤柱;经过风干处理的滤料氨氮/锰的处理能力明显增强,出水氨氮浓度更稳定,不同风干温度之间的差异不明显;滤料风干能显著增强膜负载强度;滤料在运行过程中,表面膜负载量呈现先减少后增长的趋势,特别是未风干处理滤料的运行初期膜量下降明显.利用XRD测定滤料样品表面锰氧化物的晶体结构,比较不同温度风干的初始滤料发现它们具有相同复杂的晶型.