铁修饰铝柱撑黏土催化剂(Fe/Al-PILC)的制备及其对C_3H_6-SCR活性的影响

制备了铝离子柱撑蒙脱土负载铁离子的催化剂,采用XRD、H_2-TPR、Py-IR、UV-vis光谱、ICP、N_2吸附-脱附等多种分析方法,对催化剂的基础物理化学性质进行了系统地表征。在固定床微反应器内,对丙烯在该催化剂表面选择性还原NO的特性进行了研究,考察了柱撑Al~(3+)与黏土比例以及焙烧温度对催化剂的物化性质以及脱硝效果的影响。结果表明:9Fe/Al-PILC样品具有较高的C_3H_6-SCR脱硝性能,Al~(3+)/蒙脱土的比值对脱硝性能的影响较大,而载体的焙烧温度的影响相对较小;按照Al~(3+)/蒙脱土比值的大小,催化剂活性高低排序为9Fe/Al-PILC-109Fe/Al-PILC-209Fe/Al-PILC-59Fe/蒙脱土9Fe/Al-PILC-40;柱撑离子Al~(3+)使蒙脱土的比表面积急剧增大,催化剂具有微孔和介孔结构,Al~(3+)/蒙脱土比为10 mmol·g~(-1)时载体柱撑效果最佳;在负载铁离子后的Fe/Al-PILC催化剂中,铁氧化物高度分散在载体表面。H_2-TPR表明催化剂的氧化还原性能可影响催化剂的SCR活性。UV-vis结果表明,低聚态Fe_xO_y物种的形成有助于提升催化剂的反应性能。Py-IR实验结果表明,Lewis酸和Br(?)nsted酸均有利于选择性催化还原NO,9Fe/Al-PILC-10催化剂活性最好,与其Bronsted酸含量较多有关。以上结果对于进一步优化柱撑黏土催化剂的合成工艺具有参考价值。     

铟掺杂促进铜铝催化剂低温C3H6-SCR反应的机理

CuO/Al2O3催化剂为低温SCR催化剂,在其表面添加In组分,并用于丙烯选择性催化还原(C₃H₆-SCR)氮氧化物(NOx)的研究。结果表明,负载CuIn的催化剂表现出最好的反应活性,在350°C时NOx转化率可达到62%。XPS表征结果显示,同时负载In改变了Cu的化合价态和表面氧的分布,提高了催化剂表面Cu2+和化学吸附氧的比例。H2-TPR和NO+O2-TPD结果表明,同时负载CuIn能提高催化剂氧化还原性,也促进了NOx的吸附,催化剂表面生成大量的亚硝酸盐/硝酸盐。反应机理研究表明,C₃H₆-SCR过程沿着L-H反应路径进行,同时负载CuIn能促进C₃H₆的快速氧化,并有助于催化剂表面甲酸盐和乙酸盐的形成。因此,Cu²⁺和化学吸附氧比例的提高,会增强催化剂的氧化还原性能,从而加速甲/乙酸盐的形成,这可能是促进C₃H₆-SCR低温活性得以提高的主要原因。本研究可为应用于柴油车尾气控...     

制备方法对Mn-Ce/TiO2催化剂低温选择性催化还原活性的影响

采用溶胶凝胶法、浸渍法以及两者相结合的方法制备了Mn-Ce/TiO2催化剂。运用XRD、BET和SEM等技术对催化剂进行了表征,发现溶胶凝胶法制备的Mn-Ce/TiO2催化剂为锐钛矿结构,具有较大的比表面积,中孔结构丰富,Mn、Ce活性组分在载体表面高度分散或形成了无定形结构。实验研究了催化剂对氨选择性催化还原NO反应的催化性能,结果表明,用溶胶凝胶法制备的Mn-Ce/TiO2催化剂脱硝活性最好,当Mn、Ce负载量为20%,NH3/NO摩尔比为1.1,空速为9 436 h-1,烟气温度为240℃时,NO转化率大于90%。     

在Ru/Al2O3催化剂上用H2对SO2选择性催化还原的研究

本文对用H2来使SO2选择性催化还原为单质硫在Ru/Al2O3催化剂上的行为进行研究.当物料比经过优化确定为SO2/H2=12.8时,在500℃下,SO2的转化率为90%以上,单质硫的产率为70%左右.比较于其他的催化还原SO2的催化剂,本催化剂采用金属而不是金属硫化物,这样既省去了催化剂预硫化的过程,同时也使在有氧条件下的选择性催化还原成为可能.实验考察了O2及水蒸气存在对过程的影响.在实验过程中发现,H2S作为中间产物生成,可推论该过程在催化剂上分两步进行SO2首先在催化剂金属上被H2深度还原为H2S,然后在Al2O3载体的酸性中心上SO2与H2S发生Claus反应产生单质硫.     

Nb掺杂对CeO2-SnO2催化剂NH3-SCR活性的促进作用

NH₃选择性催化还原 (NH₃-SCR) 是柴油车尾气NO_x净化的主流技术。将Nb引入CeO₂-SnO₂得到了一种新型的CeSnNbO_x金属氧化物催化剂,考察了Nb掺杂对催化剂结构、元素价态、活性位点、氧化还原性能、表面酸性和吸附性能的影响,并结合BET、XRD、XPS、H₂-TPR、NH₃-TPD和in situ DRIFTS等多种表征手段明确了Nb对该催化剂活性的促进作用。结果表明,Ce₁Sn₂Nb₁O_x催化剂表现出最佳活性,在温度为250~500 ℃时,达到接近100%的NO_x转化率。Nb掺杂改善了催化剂的比表面积和总孔体积,合理调控了催化剂表面酸性和氧化还原性能。此外,催化剂表面高度分散的Nb物种可能与Ce物种耦合形成新的Ce-O-Nb活性位点,有助于催化剂NH₃-SCR性能的提升。本研究可为开发高效Ce基氧化物催化剂提供参考。     

F掺杂改性及其制备方法优化对V2O5-WO3/TiO2催化剂低温SCR脱硝性能的影响

为提高SCR脱硝催化剂的低温脱硝性能,采用正交实验的方法制备了一系列氟（F）掺杂V2O5-WO3/TiO2催化剂,并对其进行活性分析,考察了不同氟元素来源（氟钛酸铵、氟化铵）、不同钒元素（V）前驱体（乙酰丙酮氧钒、偏钒酸铵）、钨元素（W）的不同添加方式（W做助剂、W既做载体又充当助剂）、不同载体制备方式（溶胶凝胶法、浸渍法）对催化剂脱硝性能的影响。结果表明,F掺杂改性显著增强了催化剂在200~350 ℃温度范围内的脱硝性能,其中以乙酰丙酮氧钒为V前驱体,以氟化铵为F源,W既充当载体又做助剂的方式制备出的F掺杂V2O5-WO3/TiO2催化剂具有最优的脱硝效果,其在空速为10 000 h-1的情况下,在200~350 ℃的温度反应区间,活性能稳定维持在98%以上。同时采用XPS、BET、TGA、SEM、XRD、Raman一系列表征手段对催化剂的理化性质进行了分析,表征结果表明F元素掺杂提高了活性组分在载体表面的分散度,同时促使了催化剂表面的电荷发生转移,增强了催化剂表面的氧化还原能力,促进了催化剂表面化学吸附氧的生成,增加了还原态V物种与还原态W物种的数量。     

Ce-HPW-TiO2催化剂利用C3H6选择性催化还原NO反应的机理

为提高C_3H_6-SCR脱硝催化剂的低温脱硝性能,采用浸渍法合成了几种由铈和Keggin型磷钨酸改性的TiO_2催化剂。在模拟烟气的实验条件下,考察了不同催化剂在150～350℃的脱硝活性,通过XRD、FT-IR和SEM对催化剂的理化性质进行了分析,并且通过原位FT-IR探究并对比了不同催化剂在吸附NO和C_3H_6时产生的吸附物种。结果表明:铈和磷钨酸的共掺杂大大提高了TiO_2催化剂在中低温区的脱硝效率;Ce和H_3PW_(12)O_(40)(HPW)成功负载于TiO_2上,负载的HPW也保留了其Keggin结构,而且负载后的催化剂表面更加光滑,形态更加规则,分散性更好;原位FT-IR结果显示:Ce和HPW的掺杂可以促进催化剂表面硝酸盐物质和丙烯吸附物种的形成;同时发现无论是在预吸附NO还是在预吸附C_3H_6的情况下,Ce-HPW-TiO_2(CM)催化剂表面发生的反应活性最高。由此提出了Ce-HPW-TiO_2(CM)催化剂的反应机理,发现其反应中间体主要为无机硝酸盐、甲酸盐、乙酸盐和有机氮化合物。     

F和S共掺V2O5/TiO2催化剂对NH3-SCR活性的影响

在V2O5/TiO2催化剂基础上进行非金属改性载体的研究。采用溶胶凝胶法、浸渍法制备了一种新的氟、硫共掺杂氧化钒/氧化钛催化剂,探讨了新型催化剂对低温SCR活性的影响。并通过比表面积测试（BET）、X射线衍射实验（XRD）、H2和NH3的化学吸附特性测试（H2-TPR、NH3-TPD）等技术对催化剂的理化性能进行表征。研究结果表明,氟、硫掺杂催化剂提高了低温SCR活性,拓宽了活性温度范围,在F与S摩尔比为x3时,获得了最佳的脱硝性能。     

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MnOx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MnOx催化剂的低温活性依次为:MnOx(Na2CO3) > MnOx((NH4)2CO3) > MnOx(NaOH) > MnOx(NH4OH)。表征结果表明,MnOx(Na2CO3)和MnOx((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MnOx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MnOx催化剂的催化还原NO活性影响不明显。     

黄钠铁矾渣制备透明氧化铁黄的研究

研究了以黄钠铁矾渣为原料,采用滴加法制备透明铁黄的工艺条件,讨论了亚铁浓度、温度、通气量、搅拌速度及添加剂用量等因素对铁黄制备的影响.用XRD和TEM对产品进行表征.结果表明,铁黄粒子呈针状;长轴为95～125 nm,短轴为18～25 nm;无团聚现象,单分散性好.     

Influence of various reaction parameters on 2,4-D removal in photo/ferrioxalate/H(2)O(2) process

The influence of various reaction parameters on herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) removal were examined in the photo/ferrioxalate/H(2)O(2) system, with regard to: (1) sulfate, phosphate, and z.rad;OH scavenger, as solution constituent; and (2) light intensity, ferrioxalate, H(2)O(2), and oxalate concentration, as operating parameter. In terms of 2,4-D removal, the photo/ferrioxalate/H(2)O(2) system has always been superior to the photo/Ferric ion/H(2)O(2) system, despite the high presence of anions (sulfate 100 mM, phosphate 1 mM) or z.rad;OH scavenger. Not only the rate of 2,4-D removal, but also the decomposition rate of H(2)O(2) and oxalate proportionally increase with light intensity. The ferrioxalate concentration determines the light absorption fraction, and thus, controls the rates of 2,4-D removal, and the decomposition of H(2)O(2) and oxalate, are predicted from kinetic formulations. The optimal concentration of H(2)O(2) and oxalate, according to the extent of the z.rad;OH scavenging reaction with these reagents, has been demonstrated for 2,4-D removal. It was found that an increasing oxalate concentration, which bears the burden of increased dissolved organic carbon (DOC), does not occur. This is because its decomposition, as a result of the photochemical reduction of the ferric oxalate complex, results in a decrease of the equivalent DOC. The importance of the key reaction factors to be considered, when applying this system to real wastewater treatment, is also discussed.     

GeO_2改性TiO_2催化超声降解活性红（M-3BE）染料废水的应用研究

制备了经GeO2改性的纳米TiO2,并用之作为超声降解活性红M-3BE反应的催化剂,研究了各种因素对制备的GeO2改性的纳米TiO2催化超声降解活性红染料废水的影响,并用XRD,SEM等手段对催化剂进行了表征。结果表明：GeO2改性的纳米TiO2作为催化剂,其对超声降解活性红染料废水的催化剂作用明显优于单纯以锐钛矿型T...     

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).     

钙钛矿型La0.8Sr0.2MnO3催化剂的硫中毒机制及中毒催化剂的再生研究

采用共沉淀法制备钙钛矿型La0.8 Sr0.2 MnO3催化剂,以甲苯的催化燃烧为模型反应,考察了SO2对La0.8 Sr0.2 MnO3催化剂的毒性效应.通过X射线衍射(XRD)光谱、比表面积(BET)和X射线电子能谱(XPS)表征硫中毒前后催化剂的结构和理化性质.结果表明,SO2在La0.8 Sr0.2 MnO3表...     

Synthesis and antifungal activity of 2H-1,4-benzoxazin-3(4H)-one derivatives

A series of 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l) was easily synthesized by two-step process involving O-alkylation of 2-nitrophenols with methyl 2-bromoalkanoates and next “green” catalytic reductive cyclization of the obtained 2-nitro ester intermediates (3a-l). Further, 6,7-dibromo (5a-c) and N-acetyl (6) derivatives were prepared by bromination and acetylation of unsubstituted 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-c). The novel compounds (3a-l, 4d-l, 5a-c and 6) were fully characterized by spectroscopic methods (MS, ¹H and ¹³C NMR). 2-Alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l, 5a-c and 6) were screened for antifungal activity. Preliminary assays were performed using two methods: in vitro against seven phytopathogenic fungi—Botrytis cinerea, Phythophtora cactorum, Rhizoctonia solani, Phoma betae, Fusarium culmorum, Fusarium oxysporum and Alternaria alternata—and in vivo against barley powdery mildew Blumeria graminis. The tested compounds displayed moderate to good antifungal activity at high concentration (200 mg L^?1). The most potent compounds were 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a), 2-ethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)-one (4g) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6), which completely inhibited the mycelial growth of seven agricultural fungi at the concentration of 200 mg L^?1 in the in vitro tests. Moreover, 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6) were also screened for antifungal activity at concentrations of 100 mg L^?1 and 20 mg L^?1. In the concentration of 100 mg L^?1, the N-acetyl derivative (6) completely inhibited the growth of three strains of fungi (F. culmorum, P. cactorum and R. solani), while 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) completely inhibited only R. solani strain. At the concentration of 20 mg L^?1, compound 6 showed good activity only against P. cactorum strain (72%).     

Influence of chlorination pH and chlorine dose on the formation of mutagenic activity and the strong bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-5(2H)-furanone (MX) in water

Samples from two Dutch raw water sources were chlorinated in the laboratory at different pH:s and chlorine doses, and were analysed for mutagenic activity and the mutagenic compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX). Chlorination produced mutagenic activity as well as MX in both waters. The formation of MX was favoured by acidic reaction conditions and high chlorine doses, but in waters treated with excess chlorine at pH 9, no MX was detected. The mutagenicity was approximately on the same level after chlorination of both water types but the MX concentration was significantly higher in the water containing mainly humic material.

MX was found to be quantitatively extracted from acidified waters by the XAD resin adsorption technique.