Effect of Al2O3 doping on the structure and performance of an Al2O3/Fe2O3 catalyst for mercury oxidation

In this study,the thermal stability of a Fe_2 O_3 catalyst for mercury oxidation was significantly improved by doping with Al_2 O_3.After 1 hr,the catalyst doped with 10 wt.% Al_2 O_3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al_2 O_3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe_2 O_3 was 23.4 nm;however,the corresponding values for 1%Al_2 O_3/Fe_2 O_3,3%Al_2 O_3/Fe_2 O_3,and 10%Al_2 O_3/Fe_2 O_3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al_2 O_3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.     

Pretreatment of cyanided tailings by catalytic ozonation with Mn2+/O3

The increasing amount of cyanided tailings produced as a by-product has gained significant attention in recent years because of the rapid development of the gold industry and extensive exploitation of gold mineral resources. The effective use of these secondary resources is becoming an important and urgent problem for all environmental protection staff. Manganese-catalyzed ozonation for the pre-oxidation of cyanided tailings was studied and the effects of Mn2+dosage, initial sulfuric acid concentration, ozone volume flow, temperature and agitation speed on pretreatment were examined. The optimum reaction conditions were observed to be: ore pulp density 2.5%, agitation speed 700 r/min,temperature 60°C, Mn2+dosage 40 g/L, ozone volume flow 80 L/hr, initial sulfuric acid concentration 1 mol/L, and reaction time 6 hr. Under these conditions, the leaching rate of Fe and weight loss could reach 94.85% and 48.89% respectively. The leaching process of cyanided tailings by Mn2+/O3 was analyzed, and it was found that the leaching of pyrite depends on synergetic oxidation by high-valent manganese and O3, in which the former played an important part.     

Ag/Al2O3催化剂用于碳氢化合物选择性还原NO

比较了富氧条件下CH4、C3H8、C3H6和C2H5OH分别用作还原剂时,NO在Ag/Al2O3催化剂上的还原活性.结果表明, CH4和C3H8还原NO的活性很低,而C3H6和C2H5OH能有效地还原NO.在此基础上,研究了H2O和SO2对C3H6和C2H5OH在Ag/Al2O3催化剂上还原NO活性的影响.结果表明,H2O的存在会降低低温区的NO还原活性,而且这种影响是可逆的.将H2O 和SO2同时加入反应混合气,引起NO还原活性较大幅度降低,结合程序升温脱附实验结果,认为可能是由于存在SO2时,Ag/Al2O3催化剂吸附NO的能力降低.     

Promotional catalytic activity and reaction mechanism of Ag-modified Ce0.6Zr0.4O2 catalyst for catalytic oxidation of ammonia

Ce_1-xZr_xO₂ composite oxides (molar, x = 0-1.0, interval of 0.2) were prepared by a cetyltrimethylammonium bromide-assisted precipitation method. The enhancement of silver-species modification and catalytic mechanism of adsorption-transformation-desorption process were investigated over the Ag-impregnated catalysts for low-temperature selective catalytic oxidation of ammonia (NH₃-SCO). The optimal 5 wt.% Ag/Ce_0.6Zr_0.4O₂ catalyst presented good NH₃-SCO performance with >90% NH₃ conversion at temperature (T) ≥ 250°C and 89% N₂ selectivity. Despite the irregular block shape and underdeveloped specific surface area (∼60 m²/g), the naked and Ag-modified Ce_0.6Zr_0.4O₂ solid solution still obtained highly dispersed distribution of surface elements analyzed by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) (mapping), N₂ adsorption-desorption test and X-ray diffraction (XRD). H₂ temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) results indicated that Ag-modification enhanced the mobility and activation of oxygen-species leading to a promotion on CeO₂ reducibility and synergistic Ag⁰/Ag⁺ and Ce⁴⁺/Ce³⁺ redox cycles. Besides, Ag⁺/Ag₂O clusters could facilitate the formation of surface oxygen vacancies that was beneficial to the adsorption and activation of ammonia. NH₃-temperature programmed desorption (NH₃-TPD) showed more adsorption-desorption capacity to ammonia were provided by physical, weak- and medium-strong acid sites. Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments revealed the activation of ammonia might be the control step of NH₃-SCO procedure, during which NH₃ dehydrogenation derived from NH_x-species and also internal selective catalytic reduction (i-SCR) reactions were proposed.     

Effect of reduction pretreatments on PdAg/Al2O3 for HCHO and CO oxidation

PdAg/Al₂O₃ were pretreated by CO and H₂ reduction pretreatments, respectively. The reduced catalysts were tested for HCHO and CO oxidation and characterized by Brunner Emmet Teller (BET), X-ray diffraction (XRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and oxygen temperature programmed desorption (O₂-TPD). These results indicate that the pretreatments have effect on PdAg reconstruction, PdAg particle size and active oxygen species, which are responsible for the catalytic performance. Compared with H₂ reduction method, CO reduction is more suitable for PdAg/Al₂O₃ pretreatment. PdAg/Al₂O₃-CO exhibited better catalytic performance.     

Effect of different reduction methods on Pd/Al2O3 for o-xylene oxidation at low temperature

Pd/Al₂O₃ was pretreated by CO, H₂ and NaBH₄ reduction, respectively. The reduced catalysts were tested for o-xylene oxidation and characterized by power X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed decomposition of palladium hydride (TPDH). The characterizations indicate the pretreatments lead to distinct Pd particle sizes and amount of surface activated oxygen species, which are responsible for the catalytic performance. Compared with H₂ and NaBH₄ reduction methods, CO reduction shows a strong interaction between Pd and Al₂O₃ with smaller Pd particle size and more surface activated oxygen. It exhibited excellent catalytic performance, complete oxidation of 50 ppmV o-xylene at 85°C with a WHSV of 60,000 mL/(g∙hr).     

Pd-W-Cu/γ-Al2O3催化氢还原脱硝的基本性能研究

采用浸渍法制备Pd-W-Cu/γ-Al2O3催化剂,用XRD和SEM方法对该催化剂进行了表征.以氢气作为还原剂,在间歇式反应器中对催化还原地下水中硝酸盐进行了实验研究,考察了催化剂制备方法对催化还原硝酸盐性能的影响.结果表明,W的添加改善了Pd的分散性,提高了催化剂的活性和选择性.金属Pd/W/Cu质量比、浸渍顺序和焙烧温度对催化性能有较大影响.Pd/W/Cu质量比为3∶1∶1,Pd、Cu和W3种金属组分同时浸渍,焙烧温度为400℃时,催化剂的活性和选择性最高.在NO3--N初始浓度为100mg·mL-1条件下,催化反应60min后水中NO3--N和NO2--N浓度均为0mg·mL-1,NH4+-N浓度为2.5mg·mL-1.     

Nano Fe2O3 embedded in montmorillonite with citric acid enhanced photocatalytic activity of nanoparticles towards diethyl phthalate

Nano-Fe₂O₃ embedded in montmorillonite particles (Fe-Mt) were prepared to degrade diethyl phthalate (DEP) with citric acid (CA) under xenon light irradiation. Compared to pristine montmorillonite (Na-Mt), the embedding process increased 14.5-fold of iron content and 1.8-fold of specific surface area. The synthesized Fe-Mt have more oxygen vacancies than Fe₂O₃ nanoparticles (nFe₂O₃), which could induce more reactive oxygen species (ROSs) generation in the presence of CA under xenon lamp irradiation. Fe-Mt with CA enhanced photo-assisted degradation of DEP 2.5 times as compared to nFe₂O₃ with CA. Quenching experiments, electron paramagnetic resonance (EPR) spectroscopy and identification of products confirmed that surface-bound ?OH was the main radical to degrade DEP. Common anions (i.e., NO₃^?, CO₃^2?, Cl^?) and humic acid could compete ?OH with DEP and cause slower degradation of DEP. The removal efficiency of DEP was more than 56% with Fe-Mt after three recycles, and the dissolved Fe concentration from Fe-Mt was below 75 μmol/L, indicating Fe-Mt had a good stability as a catalyst. Fe-Mt together with CA appeared to be a promising strategy to remove organic pollutants in surface water, or topsoil under solar irradiation.     

Pd/CZ/Al2O3催化剂的制备、表征与三效催化性能

以共浸渍法制得的氧化铝负载铈锆固溶体为载体,并浸渍贵金属Pd得到了Pd/CZ/Al2O3催化剂.实验结果表明,该催化剂在老化前后都表现出良好的三效催化活性,新鲜样品Pd/CZ/Al2O3活性与Pd/CZ相当,老化后样品前者优于后者.结合XRD,BET,TPR等表征手段,讨论了Pd/CZ/Al2O3的催化活性特别是高温老化后活性与其组成结构之间的内在关系,揭示了其老化后仍具有较高活性的主要原因在于保持了Pd与CZ/Al2O3复合载体之间的强相互作用(SMSI).     

Effect of manufacturing methods of AgCl/Al2O3 catalyst on selective catalytic reduction of NOx

The AgCl/Al2O3 catalyst has potential for use in the selective catalytic reduction (SCR) of NOx. A compound hydrocarbon, following oxygenation is used as a type of reducing agent. In this experiment, the AgCl/Al2O3 catalyst was produced by four different methods, and the differences among their reduction catalysis of NOx were compared. Ethanol was used as a type of reducing agent. X-ray diffraction analysis was performed to study the crystalline structure and scanning electron microscope and transmission electron microscope (TEM) were applied to determine the microindentation. The results indicated that, in the range of 350–400°C, there was no significant difference on the NOx reduction rate; however, there was dispersion at high and low temperature ranges. The size of the AgCl particles was about 20–100 nm.     

Preparation and characterization of Fe2O3-CeO2-TiO2/γ-Al2O3 catalyst for degradation dye wastewater

In order to develop a catalyst with high activity for catalytic wet oxidation （CWO） process at room temperature and atmospheric pressure, Fe2O3-CeO2-TiO2/γ-Al2O3 catalyst was prepared by consecutive impregnation method and the prepared parameters were optimized. The structure of the catalyst was characterized by BET, XRF, SEM and XPS technologies, and the actual wastewater was used to investigate the catalytic activity of Fe2O3-CeO2-TiO2/γ-Al2O3 in CWO process. The experimental results showed that the prepared catalyst exhibited good catalytic activity when the doping amount of Ti was 1.0 wt% （the weight ratio of Ti to carriers）, and the middle product, Fe2O3-CeO2-TiO2/γ-Al2O3, was calcined in 450℃ for 2 h. The CWO experiment for treating actual dye wastewater indicated that the COD, color and TOC of actual wastewater were decreased by 62.23%, 50.12% and 41.26% in 3 h, respectively, and the ratio of BOD5/COD was increased from 0.19 to 0.30.     

Selective catalytic reduction of NOx from exhaust of lean-burn engine over Ag-Al2O3/cordierite catalyst

A highly effective Ag-Al₂O₃ catalyst was prepared using the in-situ sol-gel method, and characterized by surface area using nitrogen adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. The catalyst performance was tested on a real lean-burn gasoline engine. Only unburned hydrocarbons and carbon monoxide in the exhaust were directly used as reductant (without any external reductant), the maximum NO _x conversion could only reach 40% at 450°C. When an external reductant, ethanol was added, the average NO _x conversion was greater than 60%. At exhaust gas temperature range of 350–500°C, the maximum NO _x conversion reached about 90%. CO and HC could be efficiently oxidized with Pt-Al₂O₃ oxidation catalyst placed at the end of SCR converter. However, NO _x conversion drastically decreased because of the oxidation of some intermediates to NO _x again. The possible reaction mechanism was proposed as two typical processes, nitration, and reduction in HC-SCR over Ag-Al₂O₃.     

PrO/γAl2O3等稀土氧化物催化还原SO2的研究

进行了负载于氧化铝上的镨，钕，锌，镧，钐等稀土氧化物上，ＣＯ，ＣＨ３及Ｈ２催化还原ＳＯ２反应的研究。实验着重考察了Ｐｒ－Ｏ／γ－Ａｌ２Ｏ３上ＣＯ２催化还在ＳＯ２的反应，测定了不同反应温度，不同反应物配比及不同空速下的活性，同时对Ｐｒ－ｏ／γ－Ａｌ２Ｏ３催化剂进行了ＴＰＤ，ＴＧ，ＸＲＤ，ＸＰＳ表征。结果表明，稀土氧化物具有非常高的ＣＯ催化还原ＳＯ２反应的活性，在５００℃，ＣＯ：ＳＯ２＝２：１，空速比     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

Gas-phase catalytic hydration of I2O5 in the polluted coastal regions: Reaction mechanisms and atmospheric implications

Marine aerosols play an important role in the global aerosol system. In polluted coastal regions, ultra-fine particles have been recognized to be related to iodine-containing species and is more serious due to the impact of atmospheric pollutants. Many previous studies have identified iodine pentoxide (I₂O₅, IP) to be the key species in new particles formation (NPF) in marine regions, but the role of IP in the polluted coastal atmosphere is far to be fully understood. Considering the high humidity and concentrations of pollutants in the polluted coastal regions, the gas-phase hydration of IP catalyzed by sulfuric acid (SA), nitric acid (NA), dimethylamine (DMA), and ammonia (A) have been investigated at DLPNO-CCSD(T)//ωB97X-D/aug-cc-pVTZ + aug-cc-pVTZ-PP with ECP28MDF (for iodine) level of theory. The results show that the hydration of IP involves a significant energy barrier of 22.33 kcal/mol, while the pollutants SA, NA, DMA, and A all could catalyze the hydration of IP. Especially, with SA and DMA as catalysts, the hydration reactions of IP present extremely low barriers and high rate constants. It is suggested that IP is unstable under the catalysis of SA and DMA to generate iodic acid, which is the key component in NPF in marine regions. Thus, the catalytic hydration of IP is very likely to trigger the formation of iodine-containing particles. Our research provides a clear picture of the catalytic hydration of IP as well as theoretical guidance for NPF in the polluted coastal atmosphere.     

SO2对Ag/Al2O3催化剂上CH3OH还原NO性能的影响

用溶胶-凝胶混合法制备了Ag负载量为5%的Ag/A12O3催化剂.研究了富氧条件下,SO2对CH3OH在催化剂上还原NO性能的影响.结果表明,反应气不含SO2和H2O时,NO还原活性温度较低,有显著量N2O生成,这被归因为反应过程中,部分氧化态Ag被还原为金属Ag.添加SO2或同时添加SO2和H2O使催化剂活性显著增加,N2O形成受到抑制,而且活性峰值温度提高.XPS分析表明SO2作用后的催化剂表面形成了硫酸盐化合物.     

TiO2/PPY/Fe3O4的水热法制备及其光催化与磁回收性能

以化学氧化法制备的聚吡咯(PPY)包覆Fe3O4复合材料为磁核,用水热反应法(170℃, pH=7±0.2)在其表面负载了纳米Ti02,制成壳/壳/核结构的磁载二氧化钛光催化剂.并用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶红外分光光度计(FT-IR)、振动样品磁强计(VSM)、Zeta电位仪对催化剂的物相组成、形貌、表面性质、磁学性质以及磁核的表面电位进行了表征分析.以初始浓度为25mg/L的苯酚溶液为模拟污染物, 对其进行光催化降解以考察其催化活性;并以自制的磁回收装置考察其磁回收率.结果表明,所制备的Ti02粒径在4~7nm,具有混晶结构,其中锐钛矿占95.2%,金红石占4.8%;PPY对Ti02在磁核表面的负载具有促进作用,TiO2在PPY/Fe3O4表面负载牢固;催化剂TPF(nTiO2:n PPY:nFe3O4 =30:2.1:1)具有良好的壳/壳/核结构,其磁感应强度为40emu/g,具有超顺磁性;所制备的催化剂光催化降解苯酚符合假一级反应动力学方程,其中纯TiO2、P25、TPF反应速率常数K值分别为0.0279、0.0264、0.0252,TPF循环使用5次后K值为0.020,催化活性略有降低,循环使用平均回收率可达到90.35%. 该法制备的磁载Ti02光催化剂具有优良的催化活性和磁回收性能,具有良好的应用前景.     

Role of NO and SO2 in mercury oxidation over a La2O3/Fe2O3 catalyst with high thermal stability

In this study, the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La₂O₃. The catalysts doped with La₂O₃ maintained a higher surface area when subjected to high-temperature calcination, with lower average pore size and a narrower pore size distribution. X-ray diffraction (XRD) results revealed that La₂O₃ doping hinders the growth of catalyst particles and crystallization of the material at high temperatures. Both NO and SO₂ inhibited Hg⁰ oxidation over the La₂O₃/Fe₂O₃ catalyst. Fourier transform infrared (FTIR) spectra revealed that SO₂ reacts with O₂ over the catalysts to form several species that are inert for mercury oxidation, such as SO₄^2?, HSO₄^?, or other related species; these inert species cover the catalyst surface and consequently decrease Hg⁰ oxidation capacity. In addition, NO or SO₂ competed with Hg⁰ for active sites on the La₂O₃/Fe₂O₃ catalyst and hindered the adsorption of mercury, thereby inhibiting subsequent Hg⁰ oxidation. Hg⁰ oxidation on the La₂O₃/Fe₂O₃ catalyst mainly followed the Eley–Rideal mechanism. Moreover, the inhibition effects of NO and SO₂ were at least partially reversible, and the catalytic activity was temporarily restored after eliminating NO or SO₂.     

不同政策调控下的水泥行业CO2排放模拟与分析

 从水泥行业CO₂排放的响应行为入手,采用系统动力学方法,构建水泥行业CO₂排放的系统动力学仿真模型,并进行验证;识别和分析水泥行业CO₂排放的主要驱动力,并设置了基准情景、产业政策调控情景、环境政策强化调控情景进行预测与分析.结果表明,3种情景下水泥消费将在2008年达到饱和点后,转入缓慢增长时期.基准情景下CO₂的直接排放量与水泥消费具有相同的规律,而产业政策情景及环境政策强化调控情景下水泥行业CO₂的直接排放量将在2008年达到最高点后,出现缓慢下降并逐渐平稳的趋势.水泥消费达到饱和点之前,3种情景下CO₂的直接排放都呈现快速增长的态势.政策变量中水泥熟料比重对CO₂的直接排放影响最大.在产业结构调整的同时,应尽快降低新型干法水泥的电耗水平,避免CO₂的直接排放由热能消耗转移到电能消耗上.     

CuO-CeO2/γ-Al2O3粒子电极对垃圾渗滤液降解特性

研制了负载型CuO-CeO2/γ-Al2O3粒子电极,并与活性炭颗粒混合填充于主阴阳极之间,实现三维电催化氧化反应,采用XRD、SEM对粒子电极进行表征.结果表明, CuO-CeO2/γ-Al2O3粒子电极对垃圾渗滤液显示了良好的电催化活性和稳定性,在pH为7.0、槽电压10V、空气流速0.04m3·h-1反应条件下,150min后, COD、氨氮去除率达到87.8%、45.4%,去除效果较传统二维平板、三维复极性电解槽更高,经20次反复使用后仍具有一定催化活性.研究了电-多相催化氧化体系对垃圾渗滤液降解的动力学规律,表明渗滤液降解符合准一级反应动力学规律;并在此条件下,体系以直接氧化占优.