Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater. Translated from Techniques and Equipment for Environmental Pollution Control, 2005, 6(2): 40–44 [译自: 环境污染治理技术与设备]     

巯基改性高岭土负载CeO2-CdS光催化降解结晶紫

为获得高效催化活性的光催化材料,实现偶氮类染料的高效降解,试验以巯基乙酸钠作为硫源和高岭土改性剂合成了巯基高岭土/CeO₂-CdS催化剂,并以降解结晶紫为模板反应,优化确定了巯基高岭土/CeO₂-CdS催化剂的制备条件.采用XRD（X射线衍射）、SEM（扫描电子显微镜）、TEM（透射电子显微镜）、FTIR（傅里叶红外光谱）和UV-Vis（紫外-可见光漫反射光谱）对催化剂进行了表征.结果表明:①催化剂是由巯基高岭土、立方相结构的CdS和萤石结构的CeO₂组成;②CdS和CeO₂的负载破坏了巯基高岭土的层状结构;③最优催化剂和巯基高岭土/CeO₂的可见光的响应范围分别为550和450 nm;④当CeO₂:CdS（摩尔比,下同）为4:6,巯基高岭土:CeO₂-CdS（质量比,下同）为1:3时,催化剂具有最优的光催化活性;⑤在50 mL结晶紫浓度为10 mg/L的溶液中,添加0.1 g最优催化剂后,采用350 W氙灯对其光照150 min时,结晶紫的降解率为95.1%;⑥最优催化剂具有良好的重复使用性能,重复使用5次时,对结晶紫的降解率为90.4%.研究显示,结晶紫降解的最终产物为CO₂和H₂O,催化剂对结晶紫的降解机理是以羟基自由基氧化为主和超氧基氧化为辅的共存氧化机理.      

废水催化湿式氧化稀土金属氧化物催化剂的研制

采用共沉淀法制得锰铈复合氧化物催化剂,催化湿式氧化处理高浓度苯酚废水。通过正交实验筛选催化剂制备条件,单因素实验优化制得催化剂。研究了CWAO处理废水条件下的金属离子溶出和催化剂的表征。结果表明,该催化剂在低温低压条件下具有优良的湿式氧化催化活性,且金属离子溶出量低,是一种CWAO处理高浓度有机废水中极具应用前景的新型高效催化剂。     

纳米CeO2催化氧化甲苯的形貌效应研究

采用水热法合成CeO2纳米棒、纳米颗粒和纳米立方体,利用XRD、BET-N2、TEM/HRTEM、Raman、O2-TPD和H2-TPR等表征手段进行表征,并利用连续流固定床反应法研究各催化剂对甲苯的催化氧化性能.结果表明,CeO2纳米棒因具有高比表面积和细颗粒尺寸,且表面主要暴露高活性的{100}/{110}晶面,拥有更多的氧空位和高活性氧物种,因此,催化活性最高,CeO2纳米颗粒次之,立方体最低.原位红外甲苯催化氧化机理分析进一步表明,CeO2纳米颗粒和纳米立方体上生成的羧酸盐物质难以进一步深度氧化,而纳米棒能在贫氧和低温条件下诱导甲苯的完全氧化和产物脱附,使甲苯得以快速降解.     

Preparation methods and thermal stability of Ba-Mn-Ce oxide catalyst for NOx-assisted soot oxidation

Manganese oxide-loaded and -doped ceria as well as the corresponding barium-modified oxide catalysts were prepared for soot oxidation in the presence of NOx, and were characterized by using X-ray diffraction, Brunauer-Emmett-Teller and NO temperatureprogrammed oxidation measurements. The activity of catalyst depended strongly on the NO2 production capacity, and the importance of surface nitrates was weakened without heat transfer limitations. The formation of perovskite-type oxides after the high-temperature calcination caused the loss of NOx storage capacity for the Ba-modified catalysts, but did not seem to affect the NO oxidation activity obviously. The addition of barium did not prevent the phase separation of MnOx-CeO2 solid solutions, whereas it inhibited the sintering of oxide crystallites effectively. This, as well as the relatively high surface area, resulted in a small increase in soot oxidation temperature for the thermally aged Ba/Mn-Ce catalyst.     

二氧化铈纳米催化剂的制备及臭氧化应用

分别以Ce(NO3)3.6H2O和(NH4)2Ce(NO3)6作为铈源,通过简便的化学沉淀法,制备了二氧化铈纳米材料,考察了铈源对所得纳米结构、表面特征的影响。并将纳米材料应用于降解废水用臭氧化催化剂。结果表明,铈源的不同,导致纳米材料的表面态不同,从而引起二者的催化性能具有显著差异。其中,以Ce(NO3)3.6H2O为铈源获得的样品显示了较好的催化活性,以臭氧化反应60 min降解苯酚为例,苯酚降解效率提高了70%,开拓了纳米氧化铈作为臭氧化催化剂的新应用,为臭氧化水处理技术提供了新的选择。     

MO_x-CeO_2/HZSM-5催化剂催化氧化含氯挥发性有机物研究

采用浸渍法制备了不同过渡金属掺杂的MOx-CeO2/HZSM-5（M分别表示Cr、Mn、Fe、Co、Ni和Cu）催化剂,研究了各催化剂对1,2-二氯乙烷（DCE）的催化降解性能.结果表明,过渡金属掺杂后,MOx-12%CeO2/HZSM-5催化剂催化氧化1,2-二氯乙烷（DCE）的活性明显提高.各催化剂（记为M-CeO...     

Preparation, characterization, and photocatalytic activities of boron- and cerium-codoped TiO2

Boron- and cerium-codoped TiO2 photocatalysts were synthesized using modified sol-gel reaction process and characterized by X- ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, particle size distribution （PSD）, diffuse reflectance spectra （DRS）, and Brunauer-Emmett-Teller （BET）. The photocatalytic activities were evaluated by monitoring the degradation of dye Acid Red B （ARB）. The results showed that the prepared photocatalysts were mixed oxides mainly consisting of titania, ceria, and boron oxide. The structure of TiO2 could be transformed from amorphous to anatase and then to rutile by increasing calcination temperature; the transformation being accompanied by the growth of particle size without any obvious change in phase structure of CeO2. The XPS of B1.6Ce1.0-TiO2 prepared at 500℃ showed that a few boron atoms were incorporated into titania and ceria lattice, whereas others existed as B2O3. Cerium ions existed in two states, Ce^3＋ and Ce^4＋, and the atomic ratio of Ce^3＋/Ce^4＋ was 1.86. When boron and cerium were doped, the UV-Vis adsorption band wavelength showed an obvious shift toward the visible range （〈526 nm）. As the atomic ratio of Ce/Ti increased to 1.0, the absorbance edge wavelength increased to 481 nm. The absorbance edge wavelength decreased for higher cerium doping levels （Ce/Ti=2.0）. The particles size ranged from 122 to 255 nm with a domain at 168 nm （39.4%）. The degradation of ARB dye indicated that the photocatalytic activities of boron- and cerium-codoped TiO2 were much higher than those of P25 （a standard TiO2 powder）. The activities increased as the boron doping increased, whereas decreased when the Ce/Ti atomic ratio was greater than 0.5. The optimum atomic ratio of B/Ti and Ce/Ti was 1.6 and 0.5, respectively.     

叶面喷施铈硅复合溶胶抑制生菜砷积累效应研究

采用水热合成法,利用正硅酸乙酯和硝酸铈分别制备了二氧化硅和二氧化铈溶胶。通过土培盆栽试验,在广东省汕头市莲花山钨矿区砷污染土壤上种植意大利生菜,研究了叶面喷施不同浓度二氧化硅、二氧化铈以及不同掺杂比的铈硅复合溶胶对生菜地上部生物量、叶绿素含量、砷含量以及生菜地上部砷积累量的影响。结果表明：叶面喷施不同浓度铈、硅溶胶及不同掺杂比的铈硅复合溶胶均可以缓解生菜砷毒害,表现为生菜的地上部鲜重升高了9%～58.8%,砷含量降低了23%～48%。叶面喷施低浓度的二氧化铈掺杂5mmol·L-1二氧化硅复合溶胶可以增加生菜叶片叶绿素含量,进一步提高二氧化硅缓解生菜砷毒害效果。其中以叶面喷施5mmol·L-12%铈掺杂二氧化硅复合溶胶生菜地上部鲜重最高为对照的1.6倍;砷含量最低为对照的51.4%。叶面喷施铈、硅复合溶胶不仅可以降低生菜可食用部位砷浓度,而且可以减少生菜地上部吸收积累砷总量,从而降低了砷通过食物链对人体健康的危害。与传统土壤施用硅肥相比,叶面施用硅溶胶具有经济高效的优点,为土壤砷污染控制提供了一种新的选择。     

水合氧化铈铝柱撑锂皂石对氟的吸附性能研究

以锂皂石为层间黏土原料,通过微波插层反应,制备了水合氧化铈铝柱撑锂皂石新型层柱材料,采用FTIR、XRD、SEM等分析手段对材料的结构进行了表征,并研究了该材料对氟的吸附性能.结果表明,水合氧化铈铝进入锂皂石层间,形成具有层状微晶结构的柱撑锂皂石材料.随着铈铝柱化剂与锂皂石质量比(Xm)的增大,材料片层结构的层间距扩大、结晶度提高、表面结构更丰富.该材料对F-的吸附率随Xm、吸附剂用量的增大而提高,吸附过程符合Langmuir等温吸附方程;当Xm达到0.1、吸附剂用量为0.2g/L时,该材料在60min内对F-的吸附率可达到90%,吸附量达13.5mg/g,该吸附作用受温度、pH值的影响不大.