Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

FBC-DPF在柴油机颗粒物控制中的应用研究

目前针对加装FBC-DPF(燃油添加剂-柴油机颗粒捕集器)后的柴油机放特性研究较少,并且缺乏FBC-DPF对颗粒物中PAHs排放量的影响效果研究.为全面评估加装FBC-DPF后柴油机颗粒物排放特性和FBC-DPF对柴油机尾气中的颗粒物排放污染控制效果,在发动机台架上对装有FBC-DPF的重型柴油机进行了颗粒物排放特性试验.利用电子低压撞击仪(ELPI)测量加装FBC-DPF前、后柴油机颗粒物的数浓度与粒径分布,用玻璃纤维滤膜采集加装FBC-DPF前、后尾气中的固相PAHs,利用色谱质谱联用仪对加装FBC-DPF前、后尾气中的固相PAHs进行定量分析.结果表明:①加装FBC-DPF后柴油机排放的颗粒物数浓度大幅降低,FBC-DPF对尾气中颗粒物的捕集效率平均值在95%左右;②加装FBC-DPF后柴油机固相PAHs总比排放量有所降低,在大负荷区域降幅在25.0%～88.0%之间;③加装FBC-DPF前的颗粒物中位直径为30～89 nm,而加装FBC-DPF后的颗粒物中位直径为41～98 nm,平均增幅为38.2%.对于国Ⅳ及未来国Ⅴ柴油机排放法规,FBC-DPF是解决柴油机颗粒物排放的有效手段;此外,FBC-DPF可以大幅降低柴油机尾气中的有毒成分,并且能够适应高含硫量的燃油环境.     

湿式静电除尘技术研究及应用

燃煤烟气细颗粒物排放的高效控制是控制雾霾天气的重要手段之一,为此国家颁布了世界上最严格的标准之一:《火电厂大气污染物排放标准》(GB13223-2011),要求火电厂粉尘排放浓度低于30 mg/m3,重点地区低于20 mg/m3。干式静电除尘器由于反电晕和二次扬尘等问题,对亚微米级颗粒物脱除效率较低,难以完全满足新标准的要求。湿式静电除尘技术(WESP)通过水膜清灰方式代替振打清灰,可有效控制湿法脱硫塔后细颗粒物的排放,实现燃煤烟气细颗粒物的深度脱除。该文详细阐述了湿式静电除尘器在粉尘脱除效率、材料润湿、抗腐蚀特性及多种污染物协同脱除等方面的最新研究进展,重点介绍了湿式静电除尘技术在燃煤电厂中的应用现状,并在此基础上对我国湿式静电除尘技术的发展做了总结和展望。     

超声波处理含油污水的物性实验探究

利用超声波处理含工业废机油的污水,阐述了超声波对裂解含油污水中油分子的作用主要是超声波的空化作用。在空化作用产生空化泡后,在局部形成瞬间的高温高压并进而产生强烈冲击波使得泡体周围的油分子键断裂,形成自由基,而后随着超声波的机械效应在污水表面形成一层大分子薄油膜,达到裂解复杂油分子除油的作用。文章通过实验得到了超声波的作用时间、超声功率和频率(40 kHz和28 kHz)对污水作用后对污水粘度和裂解效果的影响。实验表明:在频率相同的情况下,随着功率的增加,污水的粘度下降不断加快,裂解效果先增加后降低,约在70 W左右出现最大值;而在相同功率时间下频率为40 kHz的超声波比28 kHz的超声波作用含油污水后对粘度和裂解效果的影响更大;随着超声时间的增加,污水的粘度和裂解效果将持续下降,但是存在临界值。     

CFB-FGD一体化除尘器内气固流动特性的数值研究

采用k-ε双方程湍流模型和离散相模型对循环流化床烟气脱硫(CFB-FGD)一体化除尘器内气固两相流动进行了数值模拟,分析了气流均布板、气室结构形式和锅炉负荷等对改进前后一体化除尘器的流场分布、处理风量、阻力特性及颗粒相流动状况的影响规律。模拟结果表明,渐扩型滤袋室和一定开孔率的气流均布板可很好地改善除尘器内流场分布的均匀性,与一体化除尘器原型相比,改进型除尘器内的颗粒流动更加均匀,同时灰斗积灰对颗粒相均匀分散有一定的改善作用。不考虑粉尘堆积情况下,改进型一体化除尘器总阻力损失与锅炉负荷满足二次函数关系。     

SCR催化剂对汞的催化氧化研究进展

文章综述了目前国内外选择性催化还原(SCR)催化剂催化氧化燃煤烟气中汞的研究现状。介绍了钒基、铜基、铁基、锰基、铈基以及贵金属SCR催化剂对汞的催化氧化性能;分别分析了烟气温度、烟气组分(Cl2、HCl、SO2、NH3等)、空速等因素对各催化剂汞氧化性能的影响;最后运用文献对比方法综合概括了燃煤烟气条件对汞氧化的影响,并结合我国燃煤电厂现状,对SCR催化脱汞技术的发展方向提出建议:利用SCR催化剂实现燃煤烟气中汞的氧化,结合现有污染物控制设备实现汞的脱除,是一种经济、高效的燃煤烟气脱汞技术;当前应深入研究SCR催化剂对汞的催化氧化机理,开发能够实现NOx与汞协同控制的,稳定、高效、普适性强的低温SCR催化剂。     

催化臭氧氧化降解水溶液中亚甲基蓝的动力学研究

以废啤酒酵母为原材料、采用吸附-活化法制备得到负载过渡金属铁的活性炭(Fe/AC),对Fe/AC吸附亚甲基蓝(MB)性能和催化臭氧氧化MB效果进行了评价。Fe/AC对MB的吸附符合Langmuir等温吸附模型;20℃,pH=7的条件下,Fe/AC对MB的最大吸附量达到107.43 mg/g。吸附MB达到平衡的Fe/AC催化臭氧氧化降解水中MB,30 min内MB的转化率达到99%以上,5 h后总有机碳(TOC)的降解率达到70%。结合Fe/AC吸附MB特性和催化臭氧氧化MB行为,将Langmuir等温吸附模型分别与近似一级和二级反应动力学模型进行耦合,构建了Langmuir-Kinetic近似一级和近似二级耦合模型,均能较好地拟合MB转化率的动力学数据,但对体系的TOC去除率动力学数据的拟合度较低。     

MIL-101(Cr~(3+))可见光催化氧化降解甲基橙的研究

以金属有机多孔材料MIL-101(Cr3+)为非均相催化剂,过硫酸钠(Na2S2O8)为类Fenton体系的氧化剂,在可见光(300 W)下对甲基橙进行催化氧化降解研究。结果表明,MIL-101(Cr3+)在反应时间为120 min时对甲基橙降解率高达91.0%,且回收利用3次后仍表现出优异的降解性能(降解率达到81.0%)。同样条件下,把MIL-101(Cr3+)替换为TiO2或者不添加任何催化剂,甲基橙的降解率分别为25.6%和8.8%。采用紫外-可见漫反射光谱考察了常温下MIL-101(Cr3+)的禁带宽度大小,进一步证明其优异的光催化降解性能;同时还探讨了MIL-101(Cr3+)催化降解甲基橙的可能机理。     

燃煤电厂烟气汞连续自动在线监测系统实测比对分析

介绍了云南省某燃煤电厂烟气汞连续在线自动监测系统(Hg-CEMS)的组成和原理,利用目前主要的烟气汞采样监测方法对Hg-CEMS数据进行实测比对,并对采样方法和比对结果进行分析评价。