还原剂对Ag／Al2O3催化剂上NO还原的影响

在富氧条件下，研究了CH4、C3H8、C3H6、C8H18CH3OH、C2H5OH，以及C3H6与CH30H、C3H6与C2H50H组合作还原剂时，在Ag／Al2O3催化剂上NO的还原活性。结果表明，不同碳氢化合物还原NO的活性温度存在较大的差异。SO2的存在会导致CH，OH还原NO的活性提高，而其他碳氢化合物还原NO的活性降低。随着还原剂浓度提高，NOx转化率增大，不过，过高的还原剂浓度对NO还原不利。组合使用CH，OH与C3H。或C2H，OH与C3H。作为还原剂，能显著拓宽活性温度范围。     

钒硅催化脱硫脱硝的研究

考察了经10% H2-90% Ar(体积分数)还原的钒硅催化剂在固定床石英玻璃反应器中的脱硫脱硝活性,研究了反应温度、SO2/NO摩尔比及O2浓度对SO2和NO脱除率的影响.结果表明,还原后的钒硅催化剂的平均NO脱除率提高了15%左右;反应温度对脱硫脱硝影响较大,当温度为400℃以上时SO2和NO脱除率基本保持稳定;SO2/NO摩尔比为2和5时,钒硅催化剂的NO脱除率较高;模拟烟气中有O2条件下的脱硫脱硝活性明显高于无O2条件,O2体积分数为6.00%时SO2和NO脱除率达到最大.     

高效钙钛矿型H2-SCR催化剂的制备与研究

用溶胶凝胶法合成了3种不同B位的钙钛矿催化剂,同时用X射线衍射(XRD)、比表面积分析(BET)、扫描电镜(SEM)、程序升温化学吸附(TPR)4种手段对催化剂进行了物理化学表征.从经济性和实际性考虑,本研究使用了清洁无二次污染的H2作为SCR的还原剂,同时控制了H2的加入比例,在小NO/H2比(1∶1、1∶5、1∶10)情况下,考察了3种催化剂的催化效率.由于实际燃煤烟气中含有大量的O2,因此,同时考察了高O2(O2/NO=100∶1)的加入对氧化还原反应的影响.从考察结果我们得知,在NO/H2为1∶1时,LaCoO3和LaNiO3的催化活性优于LaMnO3,达到80％.而在高H2/NO比时,则是LaMnO3的催化活性最高,达95％以上.O2的加入对氧化还原反应影响较大,温度高于250℃时,O2出现竞争性反应,消耗了大部分的还原剂,使得NO脱除率降低,而在250℃以下,O2的影响较小.     

负载氧化镧的活性炭还原NO的研究

稀土金属具有一些特殊的性能,这使得其对碳质材料还原NO的反应可能表现出特殊的催化效果,而此方面的研究没有报道.为了研究稀土金属对活性炭还原NO反应的催化效果,采用浸渍法制备了负载氧化镧的活性炭颗粒(La/C),并在无氧的固定床反应器中进行了程序升温反应和等温反应,考察了气体流量、NO的入口浓度、反应温度和氧化镧负载量对反应活性的影响,同时对反应机理和动力学进行了初步探讨.研究结果表明负载氧化镧的活性炭还原NO的反应是一级反应.由于炭表面3%(质量分数)的氧化镧的存在,C-NO反应的起始反应温度从500 ℃降低到300 ℃,反应活性大大提高,反应活化能从88.95 kJ/mol降低到51.05 kJ/mol.氧化镧的负载量对反应活性有重要影响,但负载量的大量增加对反应活性的提高效果甚微,最佳负载量为1.5%.La/C体系在反应中较稳定,而反应温度的升高对其稳定性不利.     

溶胶-凝胶法制备颗粒状催化剂低温SCR脱硝性能

采用溶胶凝胶法制备了Mn-Ce/Ti O2催化剂,并将其用于低温NH3选择催化还原NO的反应(NH3-SCR),考察了反应温度、空速、氧气浓度、氮氧化物浓度和氨氮比等反应条件对催化剂性能的影响。结果表明,NO入口浓度为800~1 600 mg/m3时,催化剂活性受NO初始浓度的影响较小。反应温度和氨氮比对NO转化率影响显著,100~150℃温度范围内,NO转化率随温度升高快速上升;当[NH3]/[NO]1.1时,随着[NH3]/[NO]的增加,NO转化率很快上升。反应体系中适当的O2浓度可促进NO还原为N2。空速大于10 000 h-1时,NO转化率随着空速的增大而降低。     

过渡金属离子复合掺杂的六铝酸盐催化剂的脱硝性能

采用CO为还原气催化还原NO,考察了Mn与Fe复合掺杂六铝酸盐对催化剂结构和NO+CO反应活性的影响,采用X射线衍射(XRD)、比表面积、H2-程序升温还原(H2-TPR)等对形成的SrMnFex Al11-x O19-δ系列催化剂(x为铁的掺杂量,x为1、2、4、6、8;δ为校正系数,在多数情况下小于0.5)进行表征...     

利用旋转炉热解城市污泥的产物特性

采用旋转管式加热炉实验台在惰性条件下对城市污泥进行了热解实验,系统研究了不同热解温度对气态产物和固态产物成分的影响。结果表明:污泥经热解后的产物在600℃时,比表面积最大值为158.02 m2/g,孔容最高为109.58 mm3/g。随着热解温度的升高,气态产物和液态产物的产率增加,而固态产物则减少。在热解温度450~750℃,热解产物中的固态产物产率由53.65%降至31.69%;气体产率从11.23%升至24.74%,其中H_2、CO、CO_2、CH_4、C_2H_4、C_2H_6和C_2H_2占总气体的75%以上,H_2含量随着热解温度的升高而升高。热解气中小分子碳氢化合物含量较高,600℃时热解气体中含氢气体主要包括:H_2、CH_4、C_2H_4、C_3H_8、正丁烷(C_4H_(10))及C_2H_6等,其中H_2和CH_4含量分别为27.98%和23.63%。CH4、C3H8、C_4H_(10)等气体的含量随着热解温度的升高呈现先增后减趋势,且在600℃达到最大值,C_2H_2、C_2H_6在450℃时其浓度最高。随着热解温度的升高,N、C和H3种元素在热解固态产物中的质量分数呈明显下降的趋势。     

制备条件对锰氧化物SCR脱硝性能的影响

分别考察不同沉淀剂、溶液pH、煅烧温度和煅烧时间对制备Mn Ox催化剂及其低温SCR脱除NO性能的影响,并借助XRD和BET等表征手段分析各催化剂的物相和孔隙特性。结果表明,不同沉淀剂制备的Mn Ox催化剂的低温活性依次为:Mn Ox(Na2CO3)Mn Ox((NH4)2CO3)Mn Ox(Na OH)Mn Ox(NH4OH)。表征结果表明,Mn Ox(Na2CO3)和Mn Ox((NH4)2CO3)催化剂之所以表现出突出的低温SCR活性,归因于混合氧化态的无定型结构和较大的比表面积。优选Na2CO3沉淀剂制备Mn Ox催化剂,最佳的煅烧温度和时间分别为350℃和6 h,而溶液pH对制备的Mn Ox催化剂的催化还原NO活性影响不明显。     

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。     

Fe/Ga2O3-Al2O3催化甲烷还原NO的性能

以甲烷为还原剂的选择性催化脱硝技术(SCR-CH_4)是一种很有潜力的新的脱硝方法,但催化剂的催化活性比较低。为了提高催化剂的活性以及抗水能力,可使用Fe对Al_2O_3负载的Ga_2O_3催化剂进行改性。采用共沉淀法,制备了xFe/Ga_2O_3-Al_2O_3催化剂,在固定床反应器中测试其选择性催化CH_4还原NO的性能。使用XRD、N_2吸附脱附、XPS、H_2-TPR、Py-IR等方法进行表征。结果表明:经过Fe改性后的催化剂提高了中高温的催化活性,提高了催化剂的N_2选择性,并改善了催化剂的抗水特性;5Fe/Ga_2O_3-Al_2O_3催化剂在500℃、富氧条件下,达到76%的NO转化率和100%的N_2选择性;在5%水蒸气条件下,5Fe/Ga_2O_3-Al_2O_3在500℃仍保持60%以上的NO转化率。N_2吸附脱附结果显示,引入Fe后,催化剂保持了原有比表面积,并且大大增加了催化剂孔径,可提高催化剂抗水能力。XPS与UV-vis显示,5Fe/Ga_2O_3-Al_2O_3具有高含量的游离态Fe~(3+),可提高催化剂的中高温活性。H2-TPR结果显示,Fe的引入提高了催化剂氧化还原能力,增强了原有Ga_2O_3-Al_2O_3中高温的还原活性。Py-FT-IR结果显示,催化剂表面同时存在Lewis酸和Br?nsted酸,铁的引入增加了催化剂表面的Lewis酸量。因此,Fe修饰Ga_2O_3-Al_2O_3是提高Ga_2O_3-Al_2O_3催化剂的SCR-CH_4脱硝性能的有效方法。     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.     

Regeneration of a compost biofilter degrading high loads of ammonia by addition of gaseous methanol

The long-term stability of a biofilter loaded with waste gases containing NH3 concentrations larger than 100 ppmv was studied in a laboratory-scale compost reactor. At an empty bed residence time (tau) of 21 sec, elimination capacities of more than 300 g NH3/m3/day were obtained at elimination efficiencies up to 87%. Because of absorption and nitrification, almost 80% of the NH3-N eliminated from the waste gas could be recovered in the compost as NH4(+)-N or NO2-/NO3(-)-N. The high elimination capacities could be maintained as long as the NH4+/ NOX- concentration in the carrier material was less than 4 g NH4+/NOx(-)-N/kg wet compost. Above this critical value, osmotic effects inhibited the nitrifying activity, and the elimination capacity for NH3 decreased. To restore the biofilter performance, a carbon source (methanol) was added to reduce NH4+/NOx- accumulated in the compost. Results indicate that methylotrophic microorganisms did convert NH4+/NOx- into biomass, as long as the NO3- content in the compost was larger than 0.1 g NO3(-)-N/kg compost. Removal efficiencies of CH3OH of more than 90% were obtained at volumetric loads up to 11,000 g CH3OH/ m3/day. It is shown that addition of CH3OH is a suitable technique for regenerating the compost material from osmotic inhibition as a result of high NH3 loading. The biofilter was operated for 4 months with alternating load ing of NH3 and CH3OH.     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

Photo-induced degradation of diuron in aqueous solution by nitrites and nitrates: kinetics and pathways

The photo-induced degradation of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) in aqueous solution under simulated solar irradiation has been investigated in the presence of NO3-/NO2- ions. The degradation rates were compared by varying environmental parameters including substrate and inducer concentrations, oxygen content and pH. The photoproducts were identified by extensive LC-ESI-MS and LC-ESI-MS-MS studies after SPE preconcentration on prepacked cartridges. In both NO3- and NO2- conditions, oxidation of the N-(CH3)2 terminus group is the main process leading to the N-monodemethylated (NHCH3), N-formyl (N(CH3)CHO) and the uncommon and unstable carbinolamine (N(CH3)CH2OH) by-products. Cl/OH substituted and nitrated phenylureas are formed minorily. Degradation pathways involving OH* and NO2* (or dimer) radicals as reactive species are proposed.     

Study of inhibition mechanism of NO3- on photoreduction of Hg(II) in artificial water

Photoreduction is of immense importance to mercury transfer from water to atmosphere. In this investigation, the reduction of HgCl(2) and Hg(NO(3))(2) under dark, natural light and ultraviolet radiation (UV) was estimated using series of laboratory experiments. The result showed that the role of light irradiation in HgCl(2) reduction was entirely different from that in Hg(NO(3))(2). The rate of HgCl(2) reduction was in the order of UV>natural light>dark, compared with dark>natural light>UV of Hg(NO(3))(2). The experiments of mercury reduction treated by KNO(3) and CH(3)OH, which was used as a NO(3)(-) provider and a ?OH scavenger respectively, indicated that ?OH which was produced via direct photolysis of NO(3)(-) in water should be responsible for the unexpected inhibition of UV to Hg(NO(3))(2) reduction. The reduction of Hg(NO(3))(2) under different radiation intensity each of UVA, UVB and UVC was investigated. The result showed that UVB induced the highest mercury reduction while mercury reduction increased with light intensity. In addition, the kinetic study of mercury reduction under natural light was conducted through both concentration gradient method and trial method. The pseudo first rate constant was estimated to be 7×10(-4) min(-1).     

A new model of tropospheric hydroxyl radical concentrations

A chemistry model of the global troposphere is presented which focuses on the hydroxyl radical, OH. Global distributions of OH are calculated based on known chemical reaction pathways, experimentally measured values of precursor species O3, H2O, NOx (defined as NO+NO2), CO, CH4, and actinic flux (which includes the effects of cloud cover and O3 column absorption). Model grid resolution is 1 km in altitude by 10 degrees latitude, and zonally divided into land or ocean. Species are calculated as seasonal averages. Global annual mean OH in the troposphere (up to 14 km altitude) is calculated to be 9.2 x 10(5) molcm(-3) with averages of 9.8 x 10(5) in the northern hemisphere, and 8.5 x 10(5) in the southern hemisphere. Global CO and CH(4) oxidation rates by OH are calculated to be 1840 Tgyear(-1) and 580 Tgyear(-1), respectively. OH is found to be most sensitive to O3 and H2O concentrations, as well as to the photolysis rate of O3 to O1D. Sensitivity of CO and CH4 oxidation rates to cloud presence shows an inverse relationship to cloud amount and optical depth. Model results are shown to be consistent with results from two other published models.     

Atmospheric peroxides over the North Pacific during IOC 2002 shipboard experiment

Atmospheric hydrogen peroxide and methyl hydroperoxide were determined onboard the Melville over the North Pacific from Osaka to Honolulu during May-June 2002. The concentrations of H(2)O(2) and CH(3)OOH increased from 0.64+/-0.57 ppbv and 0.27+/-0.59 ppbv in subpolar region (30-50 degrees N) to 1.96+/-0.95 ppbv and 1.56+/-1.3 ppbv in subtropical region (24-30 degrees N). The increase in concentrations towards the Equator was more pronounced for CH(3)OOH than H(2)O(2). In contrast, the levels of O(3) and CO were decreased at lower latitudes as air mass was more aged, denoted by the ratios of C(2)H(2)/CO and C(3)H(8)/C(2)H(6). CH(3)OOH concentrations showed a clear diurnal variation with a maximum around noon and minimum before sunrise. Frequently, the concentrations of peroxides remained over 1 ppbv in the dark and even gradually increased after sunset. In addition, the ratios of C(2)H(4)/C(2)H(6) and C(3)H(6)/C(3)H(8) were increased in aged subtropical air, which implies that these alkenes were emitted from the ocean surface. As a result, the reaction of these biogenic alkenes with O(3) was suggested to be a potential source for peroxides in aged marine air at lower latitudes.     

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Assessment of the photochemistry of OH and NO3 on Jeju Island during the Asian-dust-storm period in the spring of 2001

In this study, we examined the influence of the long-range transport of dust particles and air pollutants on the photochemistry of OH and NO3 on Jeju Island, Korea (33.17 degrees N, 126.10 degrees E) during the Asian-dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26. Average concentration levels of daytime OH and nighttime NO3 on Jeju Island during the ADS period were estimated to be about 1x10(6) and 2x10(8) moleculescm(-3) ( approximately 9 pptv), respectively. OH levels during the ADS period were lower than those during the non-Asian-dust-storm (NADS) period by a factor of 1.5. This was likely to result from higher CO levels and the significant loading of dust particles, reducing the photolysis frequencies of ozone. Decreases in NO3 levels during the ADS period was likely to be determined mainly by the enhancement of the N2O5 heterogeneous reaction on dust aerosol surfaces. Averaged over 24 h, the reaction between HO2 and NO was the most important source of OH during the study period, followed by ozone photolysis, which contributed more than 95% of the total source. The reactions with CO, NO2, and non-methane hydrocarbons (NMHCs) during the study period were major sinks for OH. The reaction of N2O5 on aerosol surfaces was a more important sink for nighttime NO3 during the ADS due to the significant loading of dust particles. The reaction of NO3 with NMHCs and the gas-phase reaction of N2O5 with water vapor were both significant loss mechanisms during the study period, especially during the NADS. However, dry deposition of these oxidized nitrogen species and a heterogeneous reaction of NO3 were of no importance.     

A comprehensive review on the carcinogenic potential of bisphenol A: clues and evidence

Environmental Science and Pollution Research - Bisphenol A [BPA; (CH3)2C(C6H4OH)2] is a synthetic chemical used as a precursor material for the manufacturing of plastics and resins. It gained...