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。     

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SO2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...     

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。     

SO_4~（2-）/TiO_2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明：随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温（〈550℃）焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时（〉550℃）SO42-在TiO2表面是桥式配位吸附。     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。     

电化学法去除SO2/NOX的研究进展

本文对采用电化学方法去除SO2/NOx废气这一新的研究方法进行了综述.在用酞花青钴(CoPc)修饰的碳气体扩散电极上,SO2在空气中的体积百分数在20%以下时可以完全被氧化为硫酸,以连二硫酸盐(S2O2-4)作还原剂,Fe2+-EDTA作络合剂时,NO以90%以上的程度还原为NH+4与NH2(SO3H)等低价含氮化合物,产物中未见N2、N2O与NO2等气体,氧化产物SO2-3(或HSO-3)在Pb阴极上还原再生为S2O2-4.用Ce4+作氧化剂可将SO2/NO2氧化为相应的酸,还原产物Ce3+经电解氧化后循环使用.     

电化学法去除SO2/NOX的研究进展

本文对采用电化学方法去除SO2/NOx废气这一新的研究方法进行了综述.在用酞花青钴(CoPc)修饰的碳气体扩散电极上,SO2在空气中的体积百分数在20%以下时可以完全被氧化为硫酸,以连二硫酸盐(S2O2-4)作还原剂,Fe2+-EDTA作络合剂时,NO以90%以上的程度还原为NH+4与NH2(SO3H)等低价含氮化合物,产物中未见N2、N2O与NO2等气体,氧化产物SO2-3(或HSO-3)在Pb阴极上还原再生为S2O2-4.用Ce4+作氧化剂可将SO2/NO2氧化为相应的酸,还原产物Ce3+经电解氧化后循环使用.     

TiO2纳米管催化活性再生处理技术

采用H2O2、Fe2（SO4）3和Fenton溶液对失活的TiO2纳米管进行再生处理,重点考察了3种溶液的浓度和处理时间等对再生效果的影响,初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明,经H2O2溶液处理后TiO2催化活性能得到有效再生,经Fe2（SO4）3,和Fenton溶液处理后其催化活性不仅得到再生,还能显著增强,这与H2O2和Fenton的强氧化作用,及进入TiO2纳米管的Fe3＋的阻止电子．空穴对再复合作用有关。     

纳米TiO2光催化氧化去除水中痕量双氯芬酸的研究

以TiCl4为前驱体,采用水解法经不同温度煅烧制备了具有不同理化性能的纳米TiO2光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、物理吸附仪、紫外—可见光漫反射吸收光谱(UV-Vis DRS)等手段对纳米TiO2的晶相结构、粒径、孔径分布以及禁带宽度等进行了表征。以蒸馏水配制的双氯芬酸溶液为目标物,进行了纳米TiO2光催化氧化去除双氯芬酸的活性测试,研究了纳米TiO2的理化性能与光催化氧化活性之间的关系。结果表明,经400℃煅烧制得的纳米TiO2样品具有最高的光催化氧化活性,其在紫外光照射60min下对双氯芬酸的去除率为98%左右,比单独紫外光照射高出85百分点。纳米TiO2光催化氧化去除双氯芬酸的反应近似一级反应动力学模型,其中经400℃煅烧制得的纳米TiO2光催化氧化去除双氯芬酸的表观反应速率常数为0.054 54min-1,是普通商用TiO2的2倍左右,与德国Degussa P-25TiO2的光催化氧化活性最相近。     

PbO2和掺杂的Fe-PbO2电极的制备及电催化性能研究

在0.35 mol/L、pH=1～2的Pb(NO₃)₂溶液中采用阳极恒流电沉积技术制备PbO₂电极和掺杂的Fe-PbO₂电极。用X射线衍射、扫描电镜方法研究了电极的结构及形貌。通过循环伏安测试考察了其在0.1 mol/L Na₂SO₄溶液和0.01 mol/L苯酚+0.1 mol/L Na₂SO₄溶液中的电化学性能。用PbO₂电极和掺杂的Fe-PbO₂两种电极,在50 mA/cm²电流密度下降解0.01 mol/L模拟酚类废水,120 min后测得苯酚的去除率分别为51.30%和60.23%,邻苯二酚去除率分别可达76.71%和84.26%。     

Estimated washout coefficients for sulphur dioxide,nitric oxide,nitrogen dioxide and ozone

The washout coefficient of a gas in air is the fraction of it removed in unit time by rain below cloud base. The ‘apparent’ coefficients were estimated by statistically comparing hourly ground-level concentrations just before and at the onset of heavy, non-frontal rain. The concentrations were obtained from 5 y of continuous monitoring at a rural site.The coefficient (s⁻¹) estimated for SO₂ was (2.61 ± 0.14) × 10⁻⁵ times the rate of rainfall (mm h ⁻¹). This is completely consistent with a previously published value derived from the data from 10 rural sites for one year, and both estimates are consistent with published values of dissolved SO₂ in rainwater at another rural site, giving some confidence in the technique.The values of the coefficients estimated for NO and NO₂ were about 40 and 80%, respectively of that for SO₂. Some nitrite is found in rainwater, but not enough to explain the washout found. However, the analysers used would measure HNO₃ aerosols as NO₂, and these are very soluble. In addition, fast reactions are known which can convert oxides of nitrogen into soluble nitrates, present in sufficient concentration in rainwater.The statistical process leads to the coefficient estimated for O₃ being negative, implying that O₃ is produced at the time of rain. This is most probably due to the strong winds and turbulence which accompany heavy rain, giving replenishment of low-level O₃ from upper air levels where O₃ is normally produced. No systematic changes in the other gas concentrations accompany the changes in O₃ values.     

Photochemical ozone and nitric oxide formation in air-nitrogen dioxide mixtures containing sulfur dioxide or chlorine

Experiments were performed to investigate the effects of sulfur dioxide (0–10 ppm) and chlorine (0–15 ppm) on ozone and nitric oxide concentrations in irradiated mixtures of nitrogen dioxide (1–5 ppm) and air. The mixtures were irradiated by ultraviolet fluorescent lamps while flowing at a steady speed through a 9m long, 15.2cm i.d. Pyrex tube. The presence of sulfur dioxide produced no measurable change in the ozone and nitric oxide concentrations. The addition of small quantities of chlorine increased the ozone concentration in much the same manner as the addition of a hydrocarbon. A reaction model was developed for the chlorine-nitrogen dioxide-air mixtures. The observed increase in ozone concentration could only be predicted if the following two reactions were included : ClOO + NO → NO₂ + ClO and ClOO + NO → ClNO + O₂. Significant quantities of unexpected condensation nuclei were also observed in the chlorine-nitrogen dioxide-air mixtures.     

Adsorption and oxidation of sulfur dioxide on particles

The role of atmospheric participated matter in affecting atmospheric SO₂ and its reactions has been investigated. A variety of dusts of various sources (urban particulated matters and stack emissions of industrial plants) have been characterized in terms of their physical and chemical properties and submitted to a SO₂ adsorption process at room temperature and desorption at 175°C.The interaction between particles and SO₂ can occur through two processes: adsorption and conversion to sulphate. The extent of these processes depends upon the particles, chemical composition and their nature, which can be defined in terms of pH, titratable acidity, surface area, humidity and degree of surface coverage by adsorbed components.SO₂ adsorption by particles is the primary process which occurs in two steps, only the first one being apparently of environmental significance. Humidity has an important role in the adsorption, the higher its value the higher results the amount of adsorbed SO₂. The behaviour of atmospheric dusts collected in different areas and seasons is very similar, the reaction constant of the first order process being 4–5 × 10⁻²min⁻¹.Both ‘fresh’ particles coming from stacks, which do not carry SO₂, as well as ‘aged’ atmospheric particles adsorb SO₂ the relative extent of the process being mainly determined by the dust reaction. The former in most cases do not release SO₂ by heating, this behaviour being taken as an example of chemisorption, whereas the latter lose SO₂ by heating, SO₂ being retained by only a physical bond.Conversion to sulphate occurs with a very high rate on particles coming from industrial emissions, the alkaline reaction being the determining factor, whereas it does not take place on urban atmospheric dusts to an appreciable extent.This mechanism is supported by measurements by differential thermal analysis and by X-ray photoelectron spectroscopy.Though, in the atmosphere, it is impossible to discriminate various effects due to homogeneous and heterogeneous reactions, the main interaction between SO₂ and particulated matter is adsorption, most catalytic reactions occurring at high temperature and most probably at the chimney outlet.     

Atmospheric transport and transformation rate of sulfur dioxide

Pollutants immission episodes are monitored in a semi-rural area of Belgium. The responsibility for the episodes is attributed to more or less distant industrial zones. Sulfur dioxide to sulfate conversion is studied as a function of transfer duration between the industrial sources and the immission site. Ambient temperatures, mixing heights and deposition velocities seem to be the main parameters likely to influence the conversion rates which have been estimated at 0.020 h⁻¹ at 0°C up to 0.040 h⁻¹ at 20°C, with a global activation energy of 5.7 kcal. mole⁻¹.     

Measurements of nitrogen dioxide and sulphur dioxide concentrations in urban and rural areas of Poland using a passive sampling method

Measurements of 1-month concentrations of NO(2) and SO(2) were carried out in the period from May 1993 to April 1994 in 147 points in 30 major cities of Poland and in 31 points in rural areas. The measurement points were divided into five classes representing: centres of cities, residential areas, industrial areas, traffic locations and rural areas. Passive samplers were prepared in one laboratory, mailed to local laboratories for sampling and then returned for analysis. The same samplers were used for collecting both NO(2) and SO(2). Analyses for NO(2) absorbed as nitrite were made spectrophotometrically after reaction with Saltzman reagent. Sulphur dioxide was determined as sulphate with ion chromatography. The consistency of data allowed comparison of levels of air pollution in different cities and the production of maps of spatial distribution of NO(2) and SO(2) in rural areas of Poland.     

Spectrophotometric determination of sulphur dioxide

Sulphur dioxide, an important industrial gas and air pollutant, is usually estimated using mercury salts. The authors have developed a method in which hazardous mercury salts are avoided. Sulphur dioxide is trapped in aqueous morpholine and mixed with the excess of dichromate solution in acidic medium. The hexavalent chromium in dichromate is reduced to trivalent chromium by sulphur dioxide and the excess of hexavalent chromium is determined with diphenylcarbazide which yields a soluble red-violet complex with an absorption maximum at 540 nm. The decrease in the absorbance values of the red-violet complex formed after reduction, when compared to that of a reagent control, is proportional to the concentration of sulphur dioxide used for reduction. Beer's law operates between 0.4 and 4 microg ml(-1) concentration of sulphur dioxide in solution.     

二氧化钛固定化负载及其光催化性能

利用溶胶-凝胶法及浸提技术,进行二氧化钛的固定化负载.通过XRD和SEM对其物相和微观形貌进行分析;利用甲基橙为目标污染物,探究制备以及催化工艺对二氧化钛催化降解性能的影响及其重复使用效果.结果表明,随着浸涂次数的增加,不锈钢丝网表面二氧化钛薄膜的微观形貌有所变化,对甲基橙的光催化降解效率呈现先增大后减少的趋势.浸提7次所制备的二氧化钛光催化降解效率最高,搅拌条件下的4h紫外光降解率可达77.6％.