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.     

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).     

Hydrothermal-treated Pt/Al2O3 as an excellent catalyst for toluene total oxidation

The preparation of highly active supported noble metal catalysts with a low noble metal loading has always been the ultimate goal of researchers working on catalysis. Hydrothermally treated Pt/Al₂O₃ (Pt/Al₂O₃-H) exhibits better catalytic activity than that (Pt/Al₂O₃-C) treated via the conventional calcination approach. At the high space velocity of 100,000 mL/(g∙hr), the temperature that correspond to 50% toluene conversion (T₅₀) of Pt/Al₂O₃-H is 115°C lower than that of Pt/Al₂O₃-C, and the turnover frequency (TOF) value can reach 0.0756 sec⁻¹. The mechanism by which the hydrothermal approach enhances Pt/Al₂O₃ activity has been investigated. The structure associated with the high catalytic activity of Pt nanoparticles (NPs) can be retained via hydrothermal treatment. Furthermore, the support is transformed to AlO(OH) with numerous surface hydroxyl groups, which in turn can facilitate the adsorption of toluene. And the synergistic effects of Pt NPs and AlO(OH) increases the contents of Pt in oxidation state and active oxygen, which are beneficial for toluene oxidation.     

Removal of elemental mercury by photocatalytic oxidation over La2O3/Bi2O3 composite

La₂O₃/Bi₂O₃ photocatalysts were prepared by impregnation of Bi₂O₃ with an aqueous solution of lanthanum precursor followed by calcination at different temperatures. The composite materials were used for the first time for the photocatalytic removal of Hg⁰ from a simulated flue gas under UV light irradiation. The results showed that the sample containing 6 wt.% La₂O₃ and calcined at 500°C has the highest dispersion of the active sites, which was promoted by the strong interaction with the support (i.e., the formation of Bi-O-La species). Since they are fully accessible on the surface, the material also exhibits excellent optical properties while the heterojunction formed in La₂O₃/Bi₂O₃ promotes the separation and migration of photoelectron-hole pairs and thus Hg⁰ oxidation efficiency is enhanced. The effects of the various factors (e.g., the reaction temperature and composition of the simulated flue gas (i.e., O₂, NO, H₂O, and SO₂)) on the efficiency of the Hg⁰ photocatalytic oxidation were investigated. The results demonstrated that O₂ and SO₂ enhanced the efficiency of the reaction while the reaction temperature, NO, and H₂O had an inhibitory effect.     

Catalytic oxidation of gas-phase elemental mercury by nano-Fe2O3

Heterogeneous oxidation of gas-phase Hg0 by nano-Fe2O3 was investigated on a fixed bed reactor, and the e ects of oxygen concentration, bed temperature, water vapour concentration and particle size have been discussed. The results showed that Hg0 could be oxidized by active oxygen atom on the surface of nano-Fe2O3 as well as lattice oxygen in nano-Fe2O3. Among the factors that a ect Hg0 oxidation by nano-Fe2O3, bed temperature plays an important role. More than 40% of total mercury was oxidized at 300°C, however, the test temperature at 400°C could cause sintering of nano-catalyst, which led to a lower e ciency of Hg0 oxidation. The increase of oxygen concentration could promote mercury oxidation and led to higher Hg0 oxidation e ciency. No obvious mercury oxidation was detected in the pure N2 atmosphere, which indicates that oxygen is required in the gas stream for mercury oxidation. The presence of water vapour showed di erent e ects on mercury oxidation depending on its concentration. The lower content of water vapour could promote mercury oxidation, while the higher content of water vapour inhibits mercury oxidation.     

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.     

MnOx/a-Al2O3催化氧化燃煤烟气中Hg0的试验研究

在模拟烟气中研究了MnOx/a-Al2O3催化剂对烟气零价汞(Hg0)的催化氧化效果,以及反应条件对Hg0氧化率的影响.结果表明,300℃时催化剂的活性最大,模拟烟气含有20mL/m3 HCl时Hg0的氧化率达到91%.在8000~32000h-1空速范围内,Hg0氧化率保持在90%以上;空速提高到96000h-1时,氧化率开始下降,并与空速成反比.烟气中的SO2与HCl竞争催化剂上的活性位,对催化氧化反应有一定抑制,500mL/m3 SO2使零价汞的氧化率下降约20%.此外,还对MnOx催化氧化零价汞的反应机制进行了探讨.     

Effect of oxidation treatment on the adsorption and the stability of mercury on activated carbon

Oxidation treatment on the adsorption and the stability of Hg on activated carbon （AC） was inrestigated. Both MnO2-AC and FeCl3-AC were produced during oxidation treatment. The measurement of modified AC＇s mercury adsorption capacity was conducted in a simulated coal-fired flue gas by adsorbing test apparatus. TCLP and column leaching methods were used to test the stability of mercury adsorbed on ACs. The results indicate that the oxidation treatment changed the pore structure of the AC and modified the carbon surface by creating chemical components such as MnO4^-, Mn^4＋, O, NO^3-, Fe^3＋, Cl^-, etc. The Hg sorption capacity on MnO2-AC or FeCl3-AC was about three times higher than that of untreated carbon. In addition, the mercury control cost of each of the formers was about the half cost of the untreated carbon. The stability of Hg absorption was studied, it found that mercury adsorbed on the oxidation treated AC was not better than that of untreated carbon. It could concluded that the insoluble form of Hg is very important to the stability of mercury adsorbed on AC. This study suggests that the FeCl3-AC is the best absorbent for Hg with high adsorption capacity, better Hg adsorption stability in leaching environment, and lower cost among the three ACs tested.     

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).     

光Fenton反应的Ce-Fe/Al2O3催化剂制备及性能表征

采用等量浸渍法制备具有相同铁负载量的Fe/Al2O3和Ce-Fe/Al2O3催化剂,以解决光Fenton反应过程中催化剂溶出的问题并提高反应过程的pH值.通过X射线衍射(XRD)、扫描电镜(SEM)、氢程序升温还原(H2-TPR)及紫外-可见漫反射(UV-Vis DRS)等手段分别表征催化剂的物相结构、表面形貌、还原性能及光吸收特性,利用媒介黄的光Fenton脱色反应来考察催化剂的活性和稳定性.结果表明,铈掺杂使活性组分Fe2O3分散均匀,有效防止Fe2O3颗粒的长大,增加催化剂对光的吸收,增强催化剂的储氧能力,提高了催化剂的催化活性,降低铁的溶出.该催化剂在pH3.0～6.0条件下,60min内可将100mg/L媒介黄完全脱色,在pH6.0连续使用10次,其催化能力保持稳定.     

Fe2+-H2O2催化氧化加混凝处理苯酚磺酸废水

采用H2O2－Fe^2 催化氧化－混凝联合工艺对苯酚磺酸（PSA）废水进行了试验研究，对H2O2和Fe^2 的投加量、pH值、温度（T）、时间（t）等工艺参数进行了优选。结果表明，在H2O2／COD0(g/g）＝1.5，H2O2／Fe^2 (moL/moL)=10:1、pH=3.0-4.0、T＝30℃、t=30min的条件下，COD为1198mg/L的PSA废水经该工艺处理，COD去除率达94％。试运行结果表明，其出水水质达到国家排放标准（GB8978－1996）。     

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.     

Fe/Cu体系湿式催化氧化一步高效脱除H2S新方法研究

提出了Fe/Cu体系室温湿式催化氧化一步高效脱除H2S废气的新方法,阐述了反应机理、实验装置和工艺流程;考察了Fe3+、Cu2+浓度和H2S入口浓度对H2S脱除效率的影响及Fe3+、H+与添加剂NaCl浓度对CuS氧化浸出的影响,分析了Fe3+、Cu2+、H+浓度和废气中O2含量对fe3+、Cu2+再生的影响;并进行了综合实验.结果表明,当废气中O2体积分数为5%时,新方法中含40g·L-1Cu2+及80g·L-1Fe3+的吸收体系即能对体积分数为1000×10-6的H2S废气100%稳定脱硫,体系除消耗O外,过程不消耗任何原料,不产生二次污染,体系无降解问题.     

Preparation of MnO2 decorated Co3Fe1Ox powder/monolithic catalyst with improved catalytic activity for toluene oxidation

In this paper, KMnO₄ was used to pre-treat Co₃ Fe-layered double hydroxides(LDH) precursor to prepare MnO₂ decorated Co₃Fe₁O_x catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1 Mn CF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion( T₅₀ and T₉₀) were 218 and 243 ℃, respectively. The apparen...     

老化对钴铈基催化剂催化氧化丙烷的影响

采用柠檬酸络合法合成Co-CeOx多活性中心催化剂,在不同温度进行加速老化处理,测试新鲜和老化后催化剂对丙烷的催化氧化性能,同时对其结构和性质进行表征.结果表明,当加速老化温度低于650℃时,丙烷转化率达50％的温度变化幅度小于10℃;加速老化温度高于750℃时,催化剂氧化丙烷的性能快速下降.表征结果显示,Co-CeO...     

An investigation on catalytic performance and reaction mechanisms of Fe/OMS-2 for the oxidation of carbon monoxide, ethyl acetate, and toluene

The octahedral molecular sieve（OMS-2）-supported Fe（ xFe/OMS-2: x = 1, 3, 5, and 10） catalysts were prepared using the pre-incorporation method. Physicochemical properties of the as-synthesized materials were characterized by means of various techniques, and their catalytic activities for CO, ethyl acetate, and toluene oxidation were evaluated. Among all of the samples, performed the best, with the reaction temperature required to achieve 90% conversion（ T 90%） being 160 °C for CO oxidation, 210 ...     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.     

Al2O3/Ni-P-SiC复合涂层组织与性能的研究

目的 采用化学复合镀技术对微弧氧化进行封孔,进而得到抗烧蚀性能优良的Al2O3/Ni-P-SiC复合涂层。方法 通过采用扫描电镜(SEM)、光学金相显微镜(OM)、显微硬度仪(Microhardness Tester)、X射线衍射仪(XRD)、氧–乙炔烧蚀试验(Oxy-Acetylene Ablation Test)等方法,对复合涂层的表面形貌、截面形貌、厚度、显微硬度、物相和抗烧蚀性能等进行分析。结果 陶瓷层原始表面完全被化学镀层覆盖,所制得的复合涂层厚度均匀,化学镀层与陶瓷层紧密嵌合。镀液中的SiC浓度对镀覆的速度、镀层中SiC粒子的共沉积量有着较大的影响。当粒子质量浓度为16~20 g/L时,颗粒的共沉积量较大。化学复合镀60 min可以得到厚度20 μm左右的Ni-P-SiC镀层,SiC颗粒分布均匀。当镀液中SiC质量浓度为16 g/L时,镀层具有最高的硬度。对比未处理、仅微弧氧化和Al2O3/Ni-P-SiC复合涂层试样,Al2O3/Ni-P-SiC复合涂层试样具有最佳的抗烧蚀性能。结论 Al2O3/Ni-P-SiC复合涂层均匀、致密,具有良好的抗烧蚀。