H2O和SO2对V2O5-WO3/TiO2催化剂催化氧化NO的影响

研究了在120℃的反应温度下,H2O和SO2对V2O5-WO3/TiO2催化剂选择性催化氧化（SCO）NO的影响。结果表明,在H2O和SO2存在的情况下催化剂失活很快,停止通入H2O和SO2后活性不能恢复,但在加热到250℃后催化活性基本恢复。FT-IR分析表明,催化剂表面形成了金属硝酸盐和Ti的硫酸盐,对催化活性有一定影响,但不影响催化剂在250℃下催化活性的恢复。SO2、H2O和NO的竞争吸附与SO2和NO2的铅室反应是影响催化剂活性的主要原因。     

双氧水催化氧化中Cu/γ-Al_2O_3催化剂的稳定性研究

针对废水湿式双氧水催化氧化,采用浸渍法制备Cu催化剂,研究非均相Cu催化剂在常温常压湿式双氧水催化氧化中的稳定性与失活问题。研究表明,催化剂制备条件及催化氧化反应条件对催化剂中Cu2＋溶出均有影响。研究同时表明,催化剂失活与活性组分流失和活性组分被有机中间产物覆盖有关,高温焙烧可对催化剂再生。     

双氧水催化氧化中Cu/γ-Al_2O_3催化剂的稳定性研究

针对废水湿式双氧水催化氧化,采用浸渍法制备Cu催化剂,研究非均相Cu催化剂在常温常压湿式双氧水催化氧化中的稳定性与失活问题。研究表明,催化剂制备条件及催化氧化反应条件对催化剂中Cu2＋溶出均有影响。研究同时表明,催化剂失活与活性组分流失和活性组分被有机中间产物覆盖有关,高温焙烧可对催化剂再生。     

CuCoOx/TiO2催化氧化NO性能研究

采用浸渍法制备了CuCoOx/TiO₂催化剂,考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响,并考察了催化剂的抗硫抗水性能。XRD、TPR和BET分析表明,350℃焙烧的催化剂具有CuCo₂O₄尖晶石结构,比表面积大,对NO的氧化效果好。在空速为5 000 h^-1,NO进口浓度500 mg/m³,含氧量10%的条件下,反应温度300℃时NO转化率可达79.5%,250℃时NO转化率接近50%。该催化剂具有良好的单独抗SO₂、抗H₂O毒化性能,H₂O和SO₂同时存在时很快失活。该催化剂可用于不同时含H₂O和SO₂的含NO气体催化氧化后再吸收处理。     

SO2的气相光催化氧化及催化剂的失活和再生研究

在模拟大气环境中,紫外光照射以及纳米TiO2光催化剂的作用下,气相无机污染物SO2被完全氧化为SO3或H2SO4.本文提出了SO2的非均相光催化氧化机理,并得出光催化反应速率符合一级动力学过程;经过连续使用之后,TiO2的光催化活性降低,最后活性消失;经过水洗之后,失活的TiO2可以得到再生.失活的TiO2和新鲜的TiO2的IR和XPS光谱差异表明,失活的TiO2表面存在H2SO4,其被认为是使催化剂失活的成分.     

H2O和SO2对V2O5-WO3/TiO2催化剂催化氧化NO的影响

研究了在120℃的反应温度下,H2O和SO2对V2O5-WO3TiO2催化剂选择性催化氧化(SCO)NO的影响.结果表明,在H2O和SO2存在的情况下催化剂失活很快,停止通入H2O和SO2后活性不能恢复,但在加热到250℃后催化活性基本恢复.FT-IR分析表明,催化剂表面形成了金属硝酸盐和Ti的硫酸盐,对催化活性有一定...     

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。     

用H2O2/Fe3+处理高浓度含甲醛废水的研究

研究采用H₂O₂/Fe³⁺催化氧化处理高浓度含甲醛废水,探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响,并通过酸溶解回用失活催化剂。结果表明,较优的操作条件为：H₂O₂/COD（质量比）=2.2～2.6,Fe³⁺/H₂O₂（摩尔比）=0.048～0.058,反应pH 1.80～2.68,反应温度50℃,反应时间40 min;在上述操作条件下,甲醛去除率达到99%以上,COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用,其效果与三价铁盐作催化剂的基本相同。采用H₂O₂/Fe³⁺处理含甲醛废水具有比采用H₂O₂/Fe³⁺较优的效果。     

SO2对La0.65X0.35FeO3钙钛矿催化剂协同催化氧化NO和甲苯的影响

采用KIT-6硬模板辅助溶胶凝胶法制备了不同过渡金属元素A位掺杂改性的La_0.65X_0.35FeO₃(X=Cu、Ce、Mn、Co)钙钛矿催化剂,并利用XRD、BET、SEM、H₂-TPR、热重(TGA)、SO₂-TPD及XPS表征了SO₂对La_0.65X_0.35FeO₃钙钛矿催化剂协同催化氧化NO和甲苯的活性影响机制。结果表明,过渡金属的引入可提高催化剂催化性能,La_0.65X_0.35FeO₃钙钛矿催化剂在温度为100~400 ℃时表现出比LaFeO₃催化剂更高的活性。其中,La_0.65Co_0.35FeO₃催化剂活性最佳,在300 ℃时其NO转化率为60%,甲苯的T₉₀为330 ℃。另外,SO₂对La_0.65X_0.35FeO₃钙钛矿催化剂协同催化氧化NO和甲苯的活性均表现为抑制作用。这是由于SO₂容易和催化剂的金属位点发生反应生成表面硫酸盐沉积物,导致活性位点失效并堵塞孔道结构,从而会抑制NO和甲苯的氧化反应。然而,过渡金属的A位掺杂可增大表面积、增强氧化还原性,以引起结构畸变而产生更多的氧空位,提供更多活性位点,从而减弱SO₂的抑制作用。本研究可为开发高效协同催化氧化氮氧化物(NO_x)和挥发性有机化合物(VOCs)的抗硫催化剂提供参考。     

Ce-TiO2催化剂在含SO2气氛下的NH3-SCR中毒机理及其Co3O4改性性能

通过对Ce-TiO₂催化剂在含硫气氛下、不同温度的NH₃-SCR活性演变,结合含硫组分的定量分析、原位红外分析,研究了Ce-TiO₂催化剂在不同温度的SO₂中毒机理。结果表明,在180 ℃下,Ce-TiO₂脱硝活性对硫酸铈的生成极为敏感,0.1 mmol·g⁻¹的硫酸铈生成导致脱硝活性从50.7%降至18.5%,随后硫酸铈持续沉积,低温脱硝活性缓慢下降;在240 ℃下,Ce-TiO₂脱硝活性对硫酸铈的生成敏感性较低,脱硝活性随时间缓慢下降,0.18 mmol·g⁻¹的硫酸铈生成导致脱硝活性从100%降至53.8%,随后硫酸铈持续生成。Co改性活性结果表明：在180 ℃时,脱硝活性从50.7%提升至94.2%,且180 ℃和240 ℃抗硫性能均有所提升。进一步的表征测试表明：Co的掺杂能提升Ce-TiO₂催化剂的氧化还原性能,并抑制SO₂在催化剂表面的吸附,提升催化剂的抗硫性能。原位红外测试结果表明：硫酸化后的Ce-Co-TiO₂催化剂仍能维持了E-R、L-H脱硝反应路径的进行,保证了一定的低温脱硝活性。本研究探索了SCR催化剂的中毒机制,可为其改性与活性提升提供参考。     

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 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.     

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.     

O_3、H_2O_2/O_3及UV/O_3在焦化废水深度处理中的应用

采用O3、H2O2/O3和UV/O3等高级氧化技术(AOPs)对某焦化公司的生化出水进行深度处理,考察了O3与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响,确定出O3氧化反应的最佳工艺参数为:接触时间40 min,溶液pH 8.5,反应温度25℃,此条件下废水COD及UV254的去除率最高可达47.14%和73.47%;H2O2/O3及UV/O3两种组合工艺对焦化废水COD及UV254的去除率均有一定程度的提高,但H2O2/O3系统的运行效果取决于H2O2的投加量.研究结论表明,单纯采用COD作为评价指标,并不能准确反映出O3系列AOPs对焦化废水中有机污染物的降解作用.     

O3、H2O2／O3及UV／O3在焦化废水深度处理中的应用

采用O3、H2O2／O3及UV／O3等高级氧化技术（AOPs）对某焦化公司的生化出水进行深度处理,考察了O3与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响,确定出O3氧化反应的最佳工艺参数为：接触时间40min,溶液pH8．5,反应温度25℃,此条件下废水COD及UV254的去除率最高可达47．14％和73．47％;H2O2／O3及UV／O3两种组合工艺对焦化废水COD及UV254的去除率均有一定程度的提高,但H2O2／O3系统的运行效果取决于H2O2的投加量。研究结论表明,单纯采用COD作为评价指标,并不能准确反映出O3系列AOPs对焦化废水中有机污染物的降解作用。     

Temperature dependence of hydroxyl radical formation in the hv/Fe3+/H2O2 and Fe3+/H2O2 systems

The thermal enhancement of the formation of *OH by the hv/Fe(III)/H2O2 system (including the Fe(III)/H2O2 system) was quantitatively investigated with reaction temperatures ranging from 25 to 50 degrees C. A temperature dependent kinetic model for the hv/Fe(III)/H2O2 system, incorporating 12 major reactions with no fitted rate constants or activation energies, was developed, and successfully explained the experimental measurements. Particularly, the thermal enhancement of Fe(OH)2+ photolysis which is the most significant step in the hv/Fe(III)/H2O2 system was effectively explained by two factors; (1) the variation of the Fe(OH)2+ concentration with temperature, and (2) the temperature dependence of the quantum yield for Fe(OH)2+ photolysis (measured activation energy=11.4 kJ mol(-1)). Although in both the hv/Fe(III)/H2O2 and Fe(III)/H2O2 systems, elevated temperatures enhanced the formation of *OH, the thermal enhancement was much higher in the dark Fe(III)/H2O2 system than the hv/Fe(III)/H2O2 system. Furthermore, it was found that the relative thermal enhancement of the formation of *OH in the presence of *OH scavengers (tert-butyl alcohol) was magnified in the Fe(III)/H2O2 system but was not in the hv/Fe(III)/H2O2 system.     

Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes

Ozonation of three different synthetic pharmaceutical formulation wastewater containing two human antibiotics and a veterinary antibiotic has been studied to enhance the their biodegradability. The effects of pH and initial chemical oxygen demand (COD) value as well as addition of hydrogen peroxide on ozonation process were investigated. Total organic carbon (TOC), COD, biochemical oxygen demand (BOD), and aromatic content (UV254) were the parameters followed to evaluate the performance of ozonation process. Comparison of the biodegradability of selected wastewaters containing different antibiotics confirmed that the variation of biodegradability was associated with the target compound. While BOD5/COD ratio of veterinary antibiotic formulation wastewater was increased from 0.077 to 0.38 with an applied ozone dosage of 2.96 g/l, this ratio for human antibiotic I and human antibiotic II was increased from 0 to 0.1 and 0.27 respectively. Moreover the results of this investigation showed that the ozonation process is capable of achieving high levels of COD and aromaticity removals at about their natural pH values.     

活性炭辅助微波活化煤矸石的“枣糕”模型

采用活性炭辅助微波活化煤矸石,将煤矸石的活化时间由传统高温焙烧方法的2 h缩短到了24 min以内。将70目活性炭与200目煤矸粉以2.0∶1的质量配比充分混合后在800 W微波功率下活化24 min,铝铁浸出率可达750℃焙烧2 h的1.71倍。将微波看做实体物质,将活化过程看做是由活性炭向煤矸粉的单向微波能量传递,引入化学反应工程学方法,"枣糕"模型计算表明,在680 W功率下,活性炭的微波附着速率常数ka=0.334 min-1,微波脱附速率常数k’a=0.050 min-1,煤矸粉的微波附着速率常数kb=0.262 min-1,相关系数R=0.99997。在528、680、800 W 3个功率水平下,"枣糕"模型的计算值均与实验值拟合良好,相关系数均高于0.999,在以上3功率下,发现极限铝铁相对浸出率a与极限温升ΔTmax近似成正比。     

The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere

Background, aim, and scope  

Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate.     

The promoter effect and a rate expression of the catalytic incineration of (CH3)2S2 over an improved CuO-MoO3/gamma-Al2O3 catalyst

The CuO-MoO3/gamma-Al2O3 catalyst, confirmed previously as having good activity in the catalytic incineration of (CH3)2S2, was employed as the principal catalyst in this study. With the aim of improving catalyst activity and resistance to deactivation by sulfur compounds, a promoter was added either before adding the precursors of Cu and Mo or together with Cu and Mo onto the gamma-Al2O3. Promoters included transition metals and elements from groups IA-VIIA in the chemical periodic table. Experimental results reveal Cr2O3 as the most effective promoter, with an optimal composition of 5 wt.% Cu, 6 wt.% Mo and 4 wt.% Cr (designated as Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3). Knowing that higher acidity can improve activity, we further investigated the effect of acid treatment on the performance of the Cu(5)-Mo(6)-Cr(4)/gamma-Al2O3 catalyst. Experimental results indicate the H2SO4-treated catalyst (Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3) has a better activity and durability. A study for finding an appropriate rate expression for the catalytic incineration of (CH3)2S2 by Cu(5)-Mo(6)-Cr(4)/sulfated-gamma-Al2O3 was carried out in a differential reactor. The results show that the Mars-Van Krevelen model is applicable to this destructive oxidation reaction. Results additionally reveal that competitive adsorption of CH4 reduces conversion of (CH3)2S2.