含硫油品储罐腐蚀产物自燃性的研究

通过模拟储油罐中硫铁化物的生成方式, 分析和研究了H2S气体在无氧条件下,与不同相对湿度的Fe2O3、Fe3O4和Fe(OH)3反应所生成的硫铁化物的自燃性.不同相对湿度的试样经6 h硫化后,其自燃性明显不同.以Fe2O3试样为例,相对湿度为0的硫化产物氧化升温最高为256 ℃,平均升温速率为10.8 ℃/min; 相对湿度为5%、10%和15%的硫化产物,氧化升温最高温度分别为474 ℃、408 ℃和388 ℃,平均升温速率分别为20.5 ℃/min、18.3 ℃/min和13.5 ℃/min.实验结果表明, 不同相对湿度、不同物质的硫化产物,其自燃性有显著差异,样品的相对湿度对硫化产物的自燃性有重要影响.对各种干燥样品的硫化产物进行电镜分析发现,由不同物质硫化所生成的硫化产物结构不同,致使其自燃性有较大差异.硫铁化物氧化反应放热是引发油罐着火的主要因素.     

ZnOOH/O3催化臭氧化体系去除水中痕量对氯硝基苯

以实验室制备的羟基化锌（ZnOOH）为催化剂,考察了其催化臭氧化去除水中痕量对氯硝基苯（ppCNB能力.本实验条件下,蒸馏水中反应20　min时,催化臭氧化比单独臭氧化对pCNB的去除率提高了51 .3个百分点;催化过程遵循自由基反应机理,催化剂表面结合的羟基基团有利于催化反应;pCNB的去除效果随催化剂投量的增加而更佳,催化剂重复使用3次后,催化效果基本没有变化,水中的重碳酸盐以及缓冲溶液中的磷酸盐可以明显降低催化活性,中性条件下,催化作用最佳.     

催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚

催化剂Ru/ZrO₂-CeO₂催化湿式氧化苯酚的过程表明,Ru/ZrO₂-CeO₂可以显著提高COD和苯酚去除效果,当反应温度为170℃,压力为3 MPa,反应120 min后,COD和苯酚的去除率分别达到了99％和100％.试验还考察了不同反应条件对苯酚溶液COD去除的影响,并获得了最优的反应条件：温度为170℃,压力为3 MPa,催化剂的投加量为5　g/Ｌ,搅拌速度为500 r/min.通过对中间产物的分析,本研究提出了催化湿式氧化苯酚的简单路径图,认为苯酚首先被氧化成小分子有机酸,接着小分子有机酸被氧化成二氧化碳和水.前一个过程是快速反应,后一个过程中的乙酸氧化是慢速过程,需要在高温下才能完成.乙酸的氧化主要是自由基攻击α碳上的C—H键,先生成甲酸,并最终生成二氧化碳和水.     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

非均相催化臭氧处理高浓度制药废水的研究

非均相催化臭氧是一种对高浓度制药废水进行预处理的有效方法.本研究采用单一活性炭吸附、单一臭氧氧化和臭氧/活性炭联用3种体系对实际制药废水进行预处理,并对处理过程中的工艺参数进行优化.结果表明,相比单一活性炭吸附和单一臭氧降解体系,臭氧/活性炭联用体系能显著提高COD、TOC的去除率及BOD5/COD值,并显示出良好的协...     

Effect of manufacturing methods of AgCl/Al2O3 catalyst on selective catalytic reduction of NOx

The AgCl/Al2O3 catalyst has potential for use in the selective catalytic reduction (SCR) of NOx. A compound hydrocarbon, following oxygenation is used as a type of reducing agent. In this experiment, the AgCl/Al2O3 catalyst was produced by four different methods, and the differences among their reduction catalysis of NOx were compared. Ethanol was used as a type of reducing agent. X-ray diffraction analysis was performed to study the crystalline structure and scanning electron microscope and transmission electron microscope (TEM) were applied to determine the microindentation. The results indicated that, in the range of 350–400°C, there was no significant difference on the NOx reduction rate; however, there was dispersion at high and low temperature ranges. The size of the AgCl particles was about 20–100 nm.     

Modification of Ce02-ZrO2 catalyst by potassium for NOx-assisted soot oxidation

Potassium-modified ceria-zirconia catalyst was synthesized by wetness impregnation method. The ageing treatment was performed in static air at 800℃ for 20 hr to evaluate the thermal stability of the catalyst. The catalysts were characterized by X-ray diffraction,BET surface area, oxygen storage capacity, NOx-temperature programmed desorption and soot-temperature programmed oxidation measurements. By introduction of potassium, the maximum soot oxidation rate temperature (Tm) of the ceria-zirconia based catalyst decreased from 525 to 428℃ in the presence of NO under a loose contact mode. The shift of Tm of the K-modified catalyst after ageing is only 15℃. The enhanced activity of the aged catalyst mainly lies in the promotional effect of potassium on the NOx/oxygen storage cacity as well as the soot-catalyst contact.     

Complete catalytic oxidation of o-xylene over Ce02 nanocubes

The activities of CeO2 nanocubes calcined at different temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210℃. The CeO2 nanomaterials were characterized by means of BET, X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all Ce02 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive {001}planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of Ce02 nanocubes calcined at 550℃ than those calcined at above 550℃ was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

小型燃煤工业锅炉NO_x形成与释放规律模拟研究

NOx是我国十二五期间重点控制的污染物,燃煤工业锅炉是其重要来源。为了研究燃煤工业锅炉NOx的形成与释放规律,在实验室模拟了不同煤种的燃烧过程。采用原煤/焦炭燃烧法分别研究挥发分氮和焦炭氮生成NOx的反应,探讨燃料型NOx的形成与释放规律,并解释试验模拟条件下燃煤NOx产污系数和现场实测值的差异。结果表明,试验中烟煤、无烟煤、煤焦的NO转化率平均值分别为25.77%,22.17%和11.98%,产污系数平均值分别为4.31,5.08和2.00kg/t,高于现场实测结果核算值。燃煤工业锅炉NOx以燃料型为主,燃料型NOx的形成和释放是一个复杂的多相反应过程,由挥发分氮的氧化还原反应和焦炭氮的氧化还原反应组成,煤种、温度、空气流量、粒径、氧含量等因素对4种反应各自影响及影响程度并不相同。     

La-Co-Fe-Cu/HZSM-5在尾气碳颗粒燃烧中的催化性能

采用柠檬酸络合低温浸渍法制备分子筛负载钙钛矿型复合氧化物催化剂。采用XRD、SEM和H2-TPR等手段对催化剂性能进行表征,并在微型固定床反应器中对催化剂进行活性评价。结果表明,在钙钛矿型复合氧化物中进行B位离子掺杂,可以改善催化活性,碳颗粒燃烧温度降低。在20%LaCoO3/HZSM-5催化剂中用铁离子部分取代钴离子可以改善碳颗粒的燃烧性能,取代量增加碳颗粒燃烧温度降低,但是生成CO2的选择性也降低,以20%LaCo0.2Fe0.8O3/HZSM-5为催化剂,Tig、Tm和Tf分别为256℃、399℃和403℃,但生成CO2的选择性只有72.5%。在20%LaCo1-xFexO3/HZSM-5中的钙钛矿型复合氧化物B位离子中加入铜离子后,在碳颗粒燃烧反应中生成CO2的选择性得到明显改善,Sco2提高10个单位以上。以20%LaCo0.2Fe0.6Cu0.2O3/HZSM-5为催化剂,在碳颗粒燃烧反应中生成CO2的选择性可以达到94.7%,Tig、Tm和Tf分别为242℃、427℃和445℃。