High performance of catalytic sheet filters of V2O5-WO3/TiO2 for NOx reduction

Environmental Science and Pollution Research - Nitrogen oxide (NOx) emissions in fuel from the stationary as well as from mobile sources primarily from power stations, industrial heaters,...     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Evaluation of PCDD/F oxidation catalysts: confronting studies on model molecules with tests on PCDD/F-containing gas stream

Titania supported vanadium oxide is a renowned catalyst for the abatement of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from gas effluents. To develop more active formulations, researchers mainly rely on lab-scale experiments on “PCDD/Fs-mimicking substances”, like (chloro)-benzene. Using such model compounds is convenient whereas handling PCDD/Fs in the laboratory is potentially hazardous and complicated. Recent studies, however, challenged some foremost conclusions of model compound based studies, starting from the observation that different model compounds gave contrasted results. Thus the present work aims at confronting some of these dubious conclusions with direct experimental tests on PCDD/Fs. One reference V₂O₅/TiO₂ catalyst and three modified formulations (V₂O₅/TiO₂-SO₄, V₂O₅-MoO₃/TiO₂, and V₂O₅-WO₃/TiO₂) have been evaluated. A dedicated apparatus was used which allows safe and reliable tests on a mixture of PCDD/Fs congeners. Some of the previously proposed catalyst improvement strategies actually prove to be disadvantageous in the removal of PCDD/Fs. In particular, MoO₃- and WO₃-modified catalysts were significantly less active than the reference catalyst. These observations show that conclusions from model compound based studies must be drawn with care and should ideally be confronted with tests on the actual target pollutants.     

多孔TiO2为载体的V2O5-WO3脱硝催化剂制备和表征

以硫酸氧钛为钛源,氨水为沉淀剂,制备得到大比表面积(60m2/g)的锐钛矿TiO2载体.TiO2载体具有多孔结构,孔径集中在5～12nm,孔体积达到0.24cm3/g.以多孔TiO2为载体,采用浸渍法制备不同V2O5负载量的V2O5-WO3催化剂,利用拉曼(Raman)光谱、X射线衍射(XRD)对催化剂进行表征,并研究了不同V2O5负载量催化剂的脱硝活性,以及NO浓度和NH3/NO摩尔比对催化剂活性的影响.结果表明,V2O5在TiO2表面高度分散,当V2O5负载量在3%(质量分数)以下时,载体表面钒物种为单体钒,表现出最好的脱硝活性,在280～450℃内NO转化率均能达到90%以上.该催化剂对不同进口NO浓度有较强的适应能力.采用该催化剂的脱硝工艺,NH3/NO摩尔比宜保持在0.8～1.0.     

Catalytic destruction of 1,2-dichlorobenzene on V2O5-WO3/Al2O3-TiO2 catalyst

Studies on the catalytic destruction of 1,2-dichlorobenzene were carried out on a specially constructed semi-technical equipment whose most important element was a catalytic reactor with a monolithic catalyst in the form of 150 x 150 x 100 mm cubes. A catalyst made from cordierite with an active layer composed of Al2O3 - 64 wt%, TiO2 - 26 wt%, V2O5 - 6.6 wt% and WO3 - 3.4 wt% was used. The reactor made it possible to carry out the process in the temperature range 150-350 degrees C, at variable catalyst loading and different velocities of gas flow through the reactor. The content of 1,2-dichlorobenzene in the air was analysed by a chromatographic method. A significant effect of catalyst loading and temperature on 1,2-dichlorobenzene destruction efficiency was observed and no effect of the linear flow velocity through the catalyst on o-dichlorobenzene destruction efficiency was reported. The applied vanadium-tungsten catalyst on a monolithic carrier made from TiO2/gamma-Al2O3 revealed very good activity that resulted in an over 80% efficiency of 1,2-dichlorobenzene destruction at the temperature around 250 degrees C at a very high catalyst loading reaching ca. 8200 h(-1). Additionally, in this study the kinetics of 1,2-dichlorobenzene decomposition was determined, specifying the order of reaction and dependence of the decomposition rate constant on temperature, using a simple power-rate law model.     

负载V2O5-WO3／TiO2掺炭纤维脱除烟气中Hg^0

通过固定床实验系统研究烟气脱除零价汞的实验,首先研究了滤袋常用的聚苯硫醚（polyphenylene sulfide,PPS）以及活性炭纤维（activated carbon fiber,ACF）在不同温度、不同气体组分下负载V2O5-WO3／TiO2催化剂,对模拟燃煤烟气中零价汞（Hg^0）的脱除效果。然后对比研究了活性炭纤维协同滤袋常用纤维负载催化剂后,对模拟燃煤烟气中Hg^0的脱除性能。结果表明,在汞蒸气人口浓度为50μg／m^3,纯N2气氛下,当温度为25℃时,两者脱除率均能达到99％,当温度为200℃,负载催化剂的活性炭纤维脱除率在30％左右,PPS纤维仅为10％左右。在200℃情况下,模拟烟气的组分为N2＋O2时,2种纤维的Hg^0脱除率提高了10％～20％,当在混合气体中添加0．01％。后,负载催化剂的PPS纤维Hg^0脱除率能达到80％,活性炭纤维Hg^0脱除率能达到98％。当温度为200℃,模拟烟气的组分为N2＋O2＋HCl时,不同性能掺炭纤维负载催化剂后Hg^0脱除率在69％～95％范围之间变化,其中PPS掺炭纤维对Hg^0脱除效率最高达到95％,因此,负载V2O5-WO3／TiO2催化剂的PPS掺炭纤维能在高温烟气中保持较高的Hg^0脱除率。     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

Catalytic reduction of N2O over Ag-Pd/Al2O3 bimetallic catalysts

A study of the catalytic conversion of N2O to N2 over a bimetallic Ag-Pd catalyst is described in this article. Several Ag-Pd catalytic systems were prepared supported on Al2O3 with different ratios and their catalytic activity for the direct decomposition of N2O and their reduction with CO was measured. Based on the experimental results, it was observed that Ag-Pd bimetallic catalyst (5-0.5%) was the most active for both nitrous oxide reduction and direct decomposition. This high activity seems to be connected with a synergistic effect between Ag and Pd.     

The catalytic incineration of styrene over an Mn2O3/Fe2O3 catalyst

In this study, styrene monomer (SM) was treated by a commercial catalyst, Mn2O3/Fe2O3, in a fixed-bed reactor. The study can be classified into two major parts. First, the effects of operating factors, such as temperature, SM concentration, space velocity, and O2 concentration, on the performance of the catalyst were investigated. Second, two catalyst life tests were carried out to characterize the deactivation effect of SM. The results show that the catalyst results in higher conversion of SM at a higher inlet temperature and higher O2 concentrations. The conversion of SM decreases with increasing SM concentration and space velocity. From the statistical analysis of the data, we find that temperature is the most important factor on the catalytic incineration. Oxygen concentration, SM concentration, and space velocity are significant parameters as well. This paper also provides information on the deactivation effect of SM. The catalysts were characterized by surface and pore-size analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron spectroscopy for chemical analysis (ESCA) before and after the tests. The results show that the catalytic deactivation may be caused by carbon coating, and the pore size and surface area of the catalyst are smaller after deactivation.     

The kinetic of the catalytic decomposition of methyl isobutyl ketone over a Pt/gamma-Al2O3 catalyst

Environmental catalysis also can refer to catalytic technologies for reducing emission of environmentally unacceptable compounds. Catalytic decomposition also is one of the cost-effective technologies to solve the troublesome volatile organic compounds. This study treated methyl isobutyl ketone (MIBK) by a commercial catalyst, Pt/gamma-Al(2)O(3), in an isothermal fixed bed differential reactor. The effects of O(2) and MIBK content in carrier gas on the catalysis's reaction rate are also observed. Three kinetic models, i.e. the Mars and van Krevelen model, Langmuir-Hinshelwood model and power-rate law were applied to best fit the experimental results. The results indicate that the kinetic behavior of MIBK oxidation with catalysis can be accounted for by using the rate expression of the Mars and van Krevelen model and Langmuir-Hinshelwood model. Kinetic parameters are also determined on the basis of the differential reactor data. The experimental results are compared with those of the model predicted.     

Formation of PCDD/Fs from oxidation of 2-monochlorophenol over an Fe2O3/silica surface

The role of iron in surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from 2-chlorophenol (2-MCP) was investigated over the temperature range of 200-550 °C under oxidative conditions. In order to compare and contrast with previous work on copper and ferric oxide-mediated pyrolysis of 2-MCP, identical reaction conditions were maintained (50 ppm 2-MCP, model fly-ash particles containing 5% Fe₂O₃ on silica). Observed products included dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), dibenzofuran (DF), 4,6-dichlorodibenzofuran (4,6-DCDF), 2,4- and 2,6-dichlorophenol, 2,4,6-trichlorophenol, quinone, catechol, chloro-o-quinone, chlorocatechol and polychlorinated benzenes. Yields of DD and 1-MCDD were 2 and 5 times higher than under pyolysis conditions, respectively. Although 4,6-DCDF was the major PCDD/F product formed with a yield that was 2.5× greater than under pyrolysis, the yield of non-chlorinated DF, which was the dominant PCDD/F product under pyrolysis, decreased by a factor of 3. Furthermore, the ∼2× higher yield of PCDDs under oxidative conditions resulted in a PCDD to PCDF ratio of 0.75 compared to a relatively low ratio of 0.39 previously observed under pyrolytic conditions.     

Hydrodechlorination of dichlorobiphenyls over Ni-Mo/Al2O3 catalysts prepared by spray-drying method

The hydrodechlorination (HDCl) process of 2,3-, 2,4- and 2,5-dichlorobiphenyls was studied over a sulphided Ni-Mo/Al(2)O(3) catalyst in a stirred autoclave at a hydrogen pressure of 3 MPa. The catalysts were prepared by spray-drying. They were characterized by N(2) adsorption, thermogravimetry and scanning electron microscopy with X-ray microanalysis. The reaction temperature of the catalytic HDCl process was varied in the range of 230-290 degrees C. Polychlorinated biphenyls (PCBs) free transformer oil was used as reaction medium. The HDCl degree of dichlorobiphenyl isomers was in the range of 82-93%. The efficiency in the chlorine removal was found to be related to the position of the substituted chlorine atom and decreased as follows 2,4-dichlorobiphenyl approximately 2,5-dichlorobiphenyl>2,3-dichlorobiphenyl. For comparison, the HDCl process of 2,3-dichlorobiphenyl (2,3-PCB) without catalyst was also studied. The chlorine removal was 85% for the catalytic HDCl of 2,3-PCB whereas non-catalytic process led only to 16% of dechlorination in the same operating conditions, i.e. at 290 degrees C after 120 min. Monodichlorobiphenyls were not detected in the reaction products. The data for both catalytic and non-catalytic conversion of 2,3-PCB fit to a first-order model. Kinetic constants and the activation energy of the overall HDCl reaction of 2,3-PCB to biphenyl were evaluated. Compared to non-catalytic process, a nearly threefold decrease in the activation energy was observed in the presence of Ni-Mo/Al(2)O(3) catalyst prepared by spray-drying (48 kJ mol(-1) vs. 124 kJ mol(-1)).     

The effects of manganese precursors on Mn-based/TiO2 catalysts for catalytic reduction of NO with NH3

Manganese acetate (MnAc) and manganese nitrate (MnN) were employed as precursors for the preparation of MnAc)/TiO2, Mn (N)/TiO2, Mn(Ac)-Ce/TiO2, and Mn(N)-Ce/TiO2 by impregnation. These complexes were used as catalysts in the low-temperature selective catalytic reduction of NO with NH3. The influence of manganese precursors on catalyst characteristics, the reduction activity, and the stability of the catalysts to poisoning by H2O and SO2 were studied. Experiments showed that Mn(N) produced MnO2 with large grain sizes in Mn(N)/TiO2 catalyst. On the contrary, Mn(Ac) led to highly dispersed and amorphous Mn2O3 in Mn (Ac)/TiO2 catalyst, which had better catalytic activity and stability to SO2 at low temperatures. The doping of cerium reduced the differences in catalytic performance between the catalysts derived from different Mn precursors.     

钾对催化剂选择性催化还原氮氧化物的性能影响特性研究

试验就碱金属钾对两种催化剂V2O5/TiO2(VT)和V2O5/TiO2-SiO2(VTS)选择性催化还原(SCR)氮氧化物的性能影响作了相关研究.运用BET比表面积、X射线衍射(XRD)谱图、傅立叶变换透射红外光谱(FT-IR)谱图对催化剂进行表征.结果表明,试验制备的TiO2-SiO2比表面积达360 m2/g,催化剂表面活性组分高度分散;NH3吸附红外谱图显示催化剂VTS具有丰富的表面酸;催化剂抗钾毒害试验发现,钾易与B酸位结合从而降低对NH3的吸附量和吸附活性,催化刺VTS具有明显优于VT的抗钾毒害性能.归因于部分钾优先与VTS表面酸结合,从而降低对钒活性物种的毒害.此外,失活程度跟钾/钒(K/V)的摩尔比密切相关.催化活性随反应进行不断降低,且24 h内难以恢复到原有水平.     

臭氧光催化降解地下水中天然有机物的研究

在现场开展了中试规模的臭氧光催化降解天然有机物的研究。研究表明，对大分子天然有机物占很大比例且重碳酸盐含量较高的地下水，臭氧投加量10mg／L和反应时间10min条件下，TOC的去除率不到20％，但uV254和三卤甲烷生成潜力（THMFP）去除率分别达到近60％和33．5％。臭氧光催化与活性炭吸附相连，能显著提高UV254的THMFP的去除率，但TOC去除率并不明显高于单独活性炭吸附。臭氧光催化使大分子有机物转化为小分子有机物，后者在活性炭上的吸附性提高且生化性改善，可望在生物活性炭上更有效地去除。     

The kinetics of catalytic incineration of dimethyl sulfide and dimethyl disulfide over an MnO/Fe2O3 catalyst

The catalytic incineration of dimethyl sulfide and dimethyl disulfide [(CH3)2S and (CH3)2S2] over an MnO/Fe2O3 catalyst was carried out in a bench-scale catalytic incinerator. Three kinetic models (i.e., the power-rate law, the Mars and Van Krevelen model, and the Langmuir-Hinshelwood model) were used to analyze the results. A differential reactor design was used for best fit of kinetic models in this study. The results show that the Langmuir-Hinshelwood model may be feasible to describe the catalytic incineration of (CH3)2S and (CH3)2S2. This suggests that the chemical adsorption of O2 molecules is important in this incineration.     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体,考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况,其中,铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性,证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制,以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明,与单独臭氧化相比,该催化剂既能有效去除水中的溶解性有机物,又能明显抑制溴酸盐的生成,反应50h,其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降,可以通过负载铁氧化物来实现催化剂的再生。     

The characteristics of wet air oxidation of phenol over CuOx/Al2O3 catalysts: effect of copper loading

The nature of active copper species is well-known to vary with copper loading, i.e., isolated Cu(2+) to bulk CuO. In this work, however, the effect of copper loading on the activity and the selectivity was investigated for the wet oxidation of phenol over CuO(x)/Al(2)O(3) catalysts. The activity and the mineralization selectivity of the catalysts increased with copper loading up to 7wt% and remained almost the same at a higher loading. The optimum copper loading was about 7wt% for the wet oxidation of phenol over CuO(x)/Al(2)O(3) catalysts in this work. The nature of copper species with different loading was characterized with TPR, XRD, and XANES. The chemical states of copper in the CuO(x)/Al(2)O(3) catalysts were confirmed as varying with copper loading: isolated Cu(2+) ions for 1wt%; highly dispersed Cu(2+) cluster for 5wt% and 7wt%, and bulk CuO for 10-25wt%. The stability of the CuO(x)/Al(2)O(3) catalysts with different copper loading was also studied with respect to carbonaceous deposits and copper leaching.     

Mn的氧化价态对Mn／γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法,以Al2O3为载体制备Mn／γ-Al2O3和Mn—Ce／Mn／γ-Al2O3催化剂,并分别在N2气氛和O2气氛下焙烧。采用固定床连续流动反应器,研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明,Mn／Mn／γ-Al2O3催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能,共沉淀法制备催化剂的最佳Mn负载量为20％。O2气氛焙烧和Ce的加入,可以有效提高催化剂的活性和寿命。原因是O2气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积,失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。