Low-temperature ozone decomposition,CO and iso-propanol combustion on silver supported MCM-41 and silica

Silver modified (5 and 2 wt% loading) mesoporous molecular sieves (H-MCM-41, with Si/Al ratio 20, 40 and 50) and silica were synthesized by incipient wetness impregnation and ion-exchange methods. The obtained catalysts were characterized by different techniques (ICP, XRD, XRF, SEM, FTIR and nitrogen physisorption) and they were tested in heterogeneous catalytic decomposition of ozone and oxidation reactions involving ozone at ambient temperature. All the mesoporous catalysts have very high catalytic activities towards ozone decomposition at room temperature and they do not reveal any deactivation with the time on stream. The activities of the catalysts are enhanced upon increasing the amount of supported silver, decreasing the support acidity and modifying the catalyst with some additional metal having basic properties, such as Ce. The most active catalyst in the reaction of ozone decomposition—5Ag-H-MCM-41-50, shows also high activity at ambient temperature in the oxidation of CO and iso-propanol with ozone.     

铁矿石尾矿渣制备催化剂催化氧化甲醛

采用浸渍法将废弃尾矿渣中的金属离子负载于g-Al2O3载体,焙烧制备催化剂,对其进行了表征,并于石英玻璃管固定床反应器中研究催化剂对甲醛的转化效率. 结果表明,450℃焙烧所制载体g-Al2O3的结晶性好,Fe2O3在载体中分散程度高,比表面积为214.87 m2/g,而添加银离子改性后催化剂性能提高,比表面积增大为237.70 m2/g. 450℃焙烧所制催化剂对甲醛的转化效率最高达67%,而掺杂银离子所制催化剂对甲醛的转化率提高10%以上;随反应温度升高,催化剂对甲醛的转化率提高,表明利用废弃铁矿石尾矿渣所制催化剂去除甲醛具有可行性.     

活性炭纤维负载TiO2光催化降解甲醛研究

用浸渍-提拉法将TiO₂负载到活性炭纤维(ACF)上,在254 nm的紫外光源下,利用复合材料进行吸附光催化氧化甲醛气体动态实验研究。结果表明,甲醛的降解率随进口气量的增加有所下降;随TiO₂负载质量分数的增加,复合材料的比表面积由830 m²·g^-1降低到128.31 m²·g^-1;反应温度升高,去除率下降;当湿度小于40%时,随着湿度的增加,甲醛去除率增大;湿度继续增加时,光催化反应速率反而降低;活性炭负载TiO2光催化降解甲醛过程长时间使用会产生催化剂失活。     

活性炭纤维负载纳米TiO2在光反应器中降解空气中微量甲醛的研究

以活性炭纤维为载体,用浸涂法制备了TiO2/ACF(活性炭纤维)光催化剂,设计了栅式光反应器用于空气中微量甲醛的净化,研究了ACF/TiO2的组成和光反应器构造对甲醛净化量的影响。结果表明,TiO2/ACF对空气中微量甲醛有较高的光催化降解活性,催化剂m(TiO2)/m(ACF)=0.082 1,光反应器催化层厚度为2 mm,各催化层间隔为20 mm时,甲醛净化量较大。TiO2/ACF催化剂稳定性好,累计运行45 h,甲醛的净化速率仍保持在0.150μg/(g.m in)左右。     

活性炭负载催化剂臭氧催化氧化处理印染废水研究

以堇青石蜂窝陶瓷、硅藻土、活性氧化铝和活性炭作为载体、金属氧化物(FexOy、CuO、NiO、MnxOy、BaO)作为催化活性组分,对臭氧催化氧化印染废水进行了试验对比,并对影响载铁型活性炭催化剂臭氧催化氧化印染废水的因素进行了研究。结果表明,载铁型的催化剂活性相对较高,当焙烧温度为750℃时,催化性能最好。利用载铁型活性炭催化剂,在臭氧质量浓度为10mg/L、pH值为6、反应时间为60min的条件下,催化氧化具有最佳的效果,COD去除率达86%;催化剂的重复利用性好,连续使用12次,COD的去除率仍可达64%。     

臭氧催化氧化深度处理炼油废水催化剂的开发

以金属硝酸盐为原料,采用等体积浸渍法制备了CuMnCo/γ - Al2O3催化剂,通过臭氧催化氧化中试试验装置,对炼油厂废水的二级处理出水进行深度研究.累计1000h的反应结果表明,在保证出口COD为100 mg·L-1以下,炼油废水的CODCr平均去除率达到60.3％.通过物理吸附、热重-差热、扫描电镜、X射线衍射和...     

Synthesis of Novel Ag Modified MCM-41 Mesoporous Molecular Sieve and Beta Zeolite Catalysts for Ozone Decomposition at Ambient Temperature

Mesoporous molecular sieve Na-MCM-41 with Si/Al ratio 20 and 50 and Na-beta zeolite with Si/Al ratio 11 were synthesized and characterized using X-ray powder diffraction, scanning electron microscope and nitrogen adsorption. The Ag (5 and 2 wt%) modifications of H-MCM-41-20, H-MCM-41-50 and H-beta-11 catalysts were carried out using impregnation method. The catalysts were tested in the decomposition of ozone at ambient temperature. The 5 wt% Ag-H-MCM-41 catalyst showed a very high decomposition of ozone (~98%). The 5 wt% Ag-H-MCM-41-50 catalyst exhibited higher decomposition rate than 2 wt% Ag-H-MCM-41-50. The Ag modified H-MCM-41 catalyst with higher Si/Al ratio showed higher reaction rate than the catalyst with lower Si/Al ratio. The H-MCM-41 catalyst without Ag exhibited the lowest decomposition of ozone indicating an important role of Ag in the reaction.     

Preparation,characterization and kinetic behavior of supported copper oxide catalysts on almond shell-based activated carbon for oxidation of toluene in air

Dispersed copper oxide nano-catalysts supported on almond shell-based activated carbon were prepared for catalytic oxidation of toluene in air. The response surface methodology was used to express the catalyst removal efficiency in terms of catalyst metal loading and calcination temperature. Catalyst activity increased with both increasing calcination temperature and metal loading. Calcination temperature had a significant effect on the catalyst activity only at high metal loadings. Two different catalyst preparation methods were employed to investigate the effect of impregnation technique on the deposition–precipitation method. Well-dispersed nano catalysts with higher efficiency towards oxidation of toluene were prepared by the heterogeneous deposition–precipitation (HDP) as compared with the combined impregnation and deposition–precipitation method. The support and catalyst properties were determined by X-ray diffraction, Transmission electron microscopy, field-emission scanning electron microscope, Boehm test, Brunauer–Emmett–Teller surface area measurements, and energy-dispersive X-ray spectroscopy. Characterization analyses and reaction experiments indicated the antonym effect of impregnation method on the deposition–precipitation method for catalyst preparation. Two types of crystallite (large and small) were formed on the support as a consequence of using the combined catalyst preparation method. Kinetic models were proposed for oxidation of toluene using copper oxide catalysts prepared by the HDP method. The kinetic study indicated that an Eley–Rideal mechanism could adequately describe the kinetic behavior of toluene oxidation.     

改性凹凸棒土负载铜和稀土催化氧化印染废水

随着服装行业的迅速发展,纺织工业中印染废水的总量与日俱增,对人类的健康造成严重的威胁。本文采用浸渍法制备负载铁和镧的改性凹凸棒土当作催化剂,以臭氧为氧化剂催化氧化含亚甲基蓝的印染废水,考察了不同催化剂用量、反应温度、亚甲基蓝初始浓度以及臭氧流量对亚甲基蓝降解率的影响。结果表明：当改性凹凸棒土用量为0.3g、臭氧流量为100mL/min、搅拌转速为500r/min、反应温度为45℃、反应时间为30min时,50mg/L亚甲基蓝废水的降解率就达到了96%左右;改性凹凸棒土表征结果表明Fe³⁺、La³⁺活性组分已经负载在凹凸棒土上,且负载效果较好。     

Fe2O3/改性沸石催化剂的制备及其催化臭氧氧化对氯苯酚

为了提高非均相催化臭氧氧化体系处理难降解有机废水的效率,分别以十六烷基三甲基溴化铵（CTMAB）改性的天然沸石和Fe(NO₃)₃·9H₂O溶液作为载体和活性组分前体,采用浸渍法制备Fe₂O₃/改性天然沸石催化剂（MNZ）,利用能谱仪（EDS）、扫描电镜（SEM）、傅里叶变换红外光谱仪（FTIR）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）、N₂-吸附/脱附等方法分析催化剂的结构和组成,研究其催化臭氧氧化对氯苯酚的效果和催化机制。结果表明：Fe₂O₃/MNZ催化剂保持了天然沸石的表面结构。Fe₂O₃均匀负载在沸石表面,属于典型的分子筛结构,比表面积、孔容和孔径分别为12.776m²/g、0.042cm³/g和3.932nm。在对氯苯酚初始浓度为100mg/L、臭氧浓度为2.6mg/L、温度为25℃、pH为7.0±0.2的条件下,对氯苯酚和化学需氧量（COD）去除率分别为87.26%和48.83%。天然沸石与Fe₂O₃共同促进臭氧分解生成强氧化能力的羟基自由基（·OH）,提高了对氯苯酚的去除率,反应体系遵循羟基自由基作用机理。     

Ag-modified H-Beta, H-MCM-41 and SiO2: Influence of support, acidity and Ag content in ozone decomposition at ambient temperature

Silver-modified H-MCM-41-50, H-Beta-11 and SiO₂ catalysts were synthesized by incipient wet impregnation method using aqueous solution of silver nitrate. The catalysts were characterized using X-ray powder diffraction, scanning electron microscope, X-ray fluorescence, nitrogen physisorption and FTIR spectroscopy. The catalysts were tested in the heterogeneous catalytic decomposition of ozone at ambient temperature. The highest degree of ozone decomposition was observed over the mild acidic 5 wt.% Ag-H-MCM-41-50 (98%) mesoporous molecular sieve catalyst followed by 5 wt.% Ag-SiO₂ (90%). It was found that the most acidic catalyst 5 wt.% Ag-H-Beta-11 showed the lowest ozone decomposition. The content of Ag was also observed to influence the ozone decomposition. The 5 wt.% Ag-H-MCM-41-50 mesoporous molecular sieve catalyst exhibited higher catalytic activity than 2 wt.% Ag-H-MCM-41-50. The acidic properties, structure of catalyst supports and the metal content were found to be important for the ozone decomposition reaction.     

MCM-41分子筛负载金属酞菁在氧化脱硫反应中的催化性能

采用浸渍法将8种金属酞菁分别负载到MCM-41分子筛上制得负载型金属酞菁,通过红外光谱进行表征。以二苯并噻吩（DBT）为反应底物,空气为氧化剂,己内酰胺四丁基溴化铵离子液体为溶剂考察了这8种催化剂在氧化脱硫反应中的催化活性,筛选出较优催化剂,并对工艺条件进行优化。结果表明,合成的8种负载型金属酞菁催化剂中,MCM-41分子筛负载钴酞菁具有较好的催化性能,最优工艺条件为：剂油比1：1,催化剂用量0.004 g·（10 ml模型油）^-1,空气流速50 ml·min^-1,反应时间1 h,室温,DBT脱硫率最高可达97.56%。DBT的氧化产物为DBT砜。又考察了此催化氧化系统对不同硫化物的催化氧化效果,发现不同硫化物的脱硫率均在90%以上。该催化剂在重复利用4次后脱硫率无明显的降低。     

不同有机化合物在TiO2负载活性炭纤维上的

以环氧树脂为炭质前驱体将TiO₂粉体粘附于ACF表面，然后在N2气氛460 ℃焙烧，树脂热解、逸失使剩余残炭成为二者之间的连接体，获得TiO₂/ACF复合产品。ACF负载TiO₂后，其比表面积降低，但仍很好地维持了ACF的孔隙结构。由SEM可知，纳米级单体TiO₂颗粒以微小团簇结构分布于ACF表面。以对氨基苯酚、亚甲基兰和β-环状糊精三种不同分子尺寸的有机化合物为探针，通过TiO₂/ACF对它们的光催化降解研究发现，化合物自身分子尺寸对其降解程度有重要影响。具有适宜分子尺寸亚甲基兰的去除程度最高，TiO₂/ACF的降解速率高于悬浮态P25，在重复利用过程中未见降低。通过对比三种有机分子在有、无紫外光照下的去除程度，可确认有机分子是被降解而非吸附于TiO₂/ACF上。     

Beta分子筛加氢裂化催化剂的催化性能

以改性的Beta分子筛为酸性组元,W、Ni为活性金属组分,采用等体积浸渍法制备加氢裂化催化剂。在中压条件下对制备的加氢裂化催化剂进行活性评价,考察反应温度、反应压力及空速对催化性能的影响,结果表明,在反应温度376℃、反应压力10 MPa和空速1.0 h-1条件下,催化剂活性及选择性达到最佳。     

基于催化臭氧氧化去除煤化工废水中污染物——苯系物

苯、甲苯、乙苯和二甲苯(BTEX)是煤化工废水中典型的难降解有机污染物,通常情况下BTEX较难通过传统的化学氧化技术去除。笔者自主制备了多孔臭氧催化剂,并对催化剂进行表征分析;考察了催化臭氧化降解BTEX的最佳反应条件,并对不同反应体系中自由基的激发情况进行比对;在此基础上探究催化臭氧化对BTEX的去除机理,为BTEX在实际处理过程中的技术应用提供理论基础。XRD分析结果表明,多孔臭氧催化剂含有氧化铝、氧化硅等,且含有沸石结构的化合物。XPS分析结果表明,所合成的催化剂含Si、O、Cu、Fe、Mn、Al等元素。SEM结果表明,催化剂由许多不规则的细小块状粉末构成,且表面非常蓬松,堆叠成多级结构,使催化剂呈多孔性。比表面积分析表明,催化剂的比表面积为20.8 m^2/g,孔隙直径主要集中在3.8 nm。使用该催化剂对BTEX进行催化臭氧化试验,结果表明,反应温度为30℃、溶液pH=8、臭氧投加量为3.5 mg/L、催化剂投加量为5 g/L时,BTEX的降解效果最佳。在该反应体系中有机物去除率为99.1%,其中苯、甲苯、乙苯、二甲苯的去除率分别为95.6%、98.2%、100%、100%。ESR分析结果表明,催化臭氧化反应体系中羟基自由基和超氧自由基的激发强度明显高于臭氧氧化反应体系,这是因为本文制备的催化剂含有Al、Fe、Mn、Cu氧化物,使催化反应过程中负载的金属氧化物价态间相互变化,转移的电子可促进臭氧分子分解,从而产生更多的自由基。催化臭氧化技术是以羟基自由基为主导,超氧自由基、催化剂吸附为辅助,协同实现煤化工废水中典型有机污染物BTEX的高效去除。     

An Optimization Study of Cobalt Supported on Activated Carbon for the Catalytic Ozonation of Oxalic Acid: Effect of Operating Parameters and Synergetic Combination

In this study, new heterogeneous cobalt (Co) catalysts supported on activated carbon (Co/AC) were developed using a wetness impregnation process. The effect of preparation conditions on catalyst characteristics was examined. This work focused on two key parameters: the impregnation rate and the calcination atmosphere (temperature and time). Different catalysts were prepared by varying the Co loading on AC. Various catalysts were characterized by means of nitrogen sorptiometry at 77K, Boehm and pHpzc analysis. It was found that the catalyst properties and the functional surface groups were affected by the operating conditions. The best surface area was 997.5 m2/g obtained when the activated carbon was impregnated with 5% Co loading and calcined at 350°C for 2 h. The effects of parameters, such as cobalt loading, pH, catalyst dose, and ozone dose, were explored on oxalic acid removal (OA). Results show that the use of Co/AC for heterogeneous catalytic ozonation enhanced the degradation efficiency of oxalic acid (OA) significantly compared with simple ozonation and O3/AC. The main results indicate that the optimum catalytic activity was observed when 5% (wt/wt) of Co was supported on AC reaching a catalytic ozonation efficiency of 95%. The results of total organic carbon removal of 91% were achieved at optimum conditions.     

纳米δ-FeOOH催化臭氧氧化降解水中萘普生

以氯化亚铁和氢氧化钠为原料,采用双氧水快速氧化氢氧化亚铁的方式,成功制备了δ-FeOOH纳米材料。首次将其应用于催化臭氧氧化,并探究了催化剂投加量、臭氧浓度、萘普生(NPX)初始浓度对目标污染物降解效果的影响。采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、低温N2吸附脱附等温线对催化剂的晶体结构、形貌等进行表征。结果表明,制备的材料纯度高,是厚度约为4 nm的六角片层结构。该材料的BET比表面积达191.73 m2/g,并具有介孔特征。试验制备的材料显著提升了催化臭氧氧化萘普生的能力,反应15 min后TOC的最高去除率为64.5%,与单独臭氧相比提高了38.4%。同时,通过·OH抑制试验,初步探究了可能的纳米δ-FeOOH催化臭氧氧化机理。     

Zr改性Y分子筛中油型加氢裂化催化剂设计制备

采用等体积浸渍法对Y分子筛进行了Zr修饰改性,系统考察了不同用量Zr对改性Y分子筛的结构、催化剂的理化性质和加氢裂化反应性能的影响规律。通过XRD、NH₃-TPD、H₂-TPR和TEM等方法对改性分子筛和催化剂进行表征分析。结果表明：Zr改性降低了Y分子筛的酸量,随着改性Zr用量的增加,这种变化趋势不断增大。同时,Zr改性有效地削弱了分子筛催化剂中金属活性组分与载体间的作用,提高了W物种在催化剂表面的分散程度。加氢裂化反应结果表明：与Y分子筛催化剂相比,Zr改性Y分子筛催化剂的减压馏分油(VGO)转化率降低,中间馏分油选择性提高约20%,随着改性Zr用量的增加,VGO的转化率不断降低,中间馏分油选择性略有增加。     

Removal of NO using surface modified activated carbon fiber (ACF) by impregnation and heat-treatment of propellant waste

The surface of activated carbon fiber was modified by impregnation and heat-treatment of propellant waste to introduce nitrogen functional groups such as pyridines, pyridones and pyrrols. The pore structure and specific surface area of those modified ACFs were slightly changed; however, the NO removal capacity of the surface modified ACF by propellant waste increased about twice that of the as-received ACF due to the addition of chemical adsorption by nitrogen functional groups. Propellant waste can be used as an ACF surface modifier for the removal of NOx.     

Pb(II) ion adsorption by biomass-based carbonaceous fiber modified by the integrated oxidation and vulcanization

Biomass-based activated carbonaceous fiber (ACF) was modified by nitric-acid oxidation under microwave heating (ACF-O) and then further treated by thioglycolic acid (ACF-S) to prepare carbon materials with high capability for the removal of Pb(II) ions. The physico-chemical properties of the original and modified ACF samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Zeta potential, Boehm titration, BET, Raman spectrum and X-ray photoelectron spectroscopy (XPS). It was found that modification treatments damage the pore and graphite crystalline structure of ACF, while the micropore structure is protected and extra oxygen-containing surface functional groups are grafted on its surface. The adsorption performance of the original and the modified ACF samples affected by adsorption conditions regarding to Pb(II) ion strength (10 mg/L–105 mg/L), contact time (10 min–120 min), pH value (2.5–6.5), and solvent temperature (15 °C–45 °C) was investigated through batch experiments. Compared to the maximum Pb(II) ion adsorption capacity of 75.24 mg/g by ACF sample, the value was substantially improved by the integrated modification method (193.42 mg/g for ACF-O and 209.21 mg/g for ACF-S sample). The Biot number determined from the homogeneous surface diffusion model (HSDM) was between 1 and 100 for the original and modified ACF samples, suggesting that the adsorption process of Pb(II) ions is limited by both the surface diffusion and film mass transfer.