Ultrasound-assistant preparation of Cu-SAPO-34 nanocatalyst for selective catalytic reduction of NO by NH3

The influence of the various preparation methods of Cu-SAPO-34 nanocatalysts on the selective catalytic reduction of NO with NH₃ under excess oxygen was studied. Cu-SAPO-34 nanocatalysts were prepared by using four techniques: conventional impregnation (IM), ultrasound-enhanced impregnation (UIM), conventional deposition precipitation (DP) using NaOH and homogeneous deposition precipitation (HDP) using urea. These catalysts were characterized in detail by various techniques such as N₂-sorption, XRD, TEM, H₂-TPR, NH₃-TPD and XPS to understand the catalyst structure, the nature and the dispersed state of the copper species, and the acid sites for NH₃ adsorption. All of the nanocatalysts showed high activities for NO removal. However, the activities were different and followed the sequence of Cu-SAPO-34 (UIM) > Cu-SAPO-34 (HDP) > Cu-SAPO-34 (IM) > Cu-SAPO-34 (DP). Based on the obtained results, it was concluded that the NO conversion on Cu-SAPO-34 nanocatalysts was mainly related to the high reducibility of the isolated Cu^2 + ions and CuO species, the number of the acid sites and the dispersion of CuO species on SAPO-34.     

循环流廊道湿地中氮归趋过程模拟研究

针对新型高效脱氮循环流廊道(CFC)湿地,构建了涵盖6种氮形态、3类介质、10种代谢途径的N循环模型,探索了湿地内N迁移转化模式.结果表明,沸石吸附(53.3%)、植物吸收NH+4-N(27.6%)、NO-3-N反硝化(10.2%)、植物吸收NO-3-N(2.9%)和NO-2-N短程反硝化(1.5%)对TN去除贡献依次降低.NH+4-N去除机制存在季节差异,其中1月NH+4-N主要通过沸石吸附去除(84.5%);4~6月通过植物吸收去除(76.4%~85.3%);7月通过沸石吸附(36.1%)、亚硝化(45.8%)及植物吸收(21.4%)共同去除.此外,定期收获植物、按期再生沸石及种植水生植物可分别提升TN去除率1.7%~7.7%、43.1%~72.2%和19.8%~36.2%.综之,CFC湿地去除途径多样性保障了TN的长期高效去除.     

生物沸石对吡啶、喹啉的降解与吸附作用

探讨了通过生物沸石的降解及吸附作用,解决吡啶、喹啉及转化产物NH 4+-N的污染问题.结果表明,生物沸石中的吡啶降解菌Shinella zoogloeoides BC026及喹啉降解菌Pseudomonas sp.BW003能有效去除吡啶、喹啉,同时转化后的NH 4+-N也能被天然沸石或改性沸石所吸附.尽管改性沸石吸附能力不如天然沸石,但其表面能更有效附着微生物,在实际工程应用上更具前景.     

Zn系LDHs覆膜改性人工湿地沸石基质除磷机制

选择Zn系层状双金属氢氧化物(LDHs),采用水热-共沉淀法合成3种不同类型的Zn-LDHs(Fe Zn-LDHs、Co Zn-LDHs和Al Zn-LDHs)并覆膜于常用人工湿地沸石基质表面;利用模拟垂直流人工湿地小试系统,对原始沸石及3种Zn-LDHs覆膜改性沸石基质进行除磷净化实验、等温吸附-解吸实验以及动力学吸附实验,通过上述实验对以Zn-LDHs覆膜改性沸石基质为代表的改性基质除磷机制进行研究.结果表明,Zn-LDHs覆膜改性沸石基质对磷素净化效果具有明显的提升功能,其中以Fe Zn-LDHs覆膜改性基质尤为突出;改性使基质的饱和吸附容量得以提高,增强了基质对磷酸盐的解吸性能,并使沸石基质对磷酸盐的主要吸附类型由物理吸附向化学吸附转换;通过对沸石基质类型及其改性方式的合理选择,可达到利用沸石人工湿地强化除磷以高效净化富营养化水体的目的.     

Metal loaded zeolite adsorbents for hydrogen cyanide removal

Metal(Cu,Co,or Zn) loaded ZSM-5 and Y zeolite adsorbents were prepared for the adsorption of hydrogen cyanide(HCN) toxic gas.The results showed that the HCN breakthrough capacity was enhanced significantly when zeolites were loaded with Cu.The physical and chemical properties of the adsorbents that influence the HCN adsorption capacity were analyzed.The maximal HCN breakthrough capacities were about the same for both zeolites at 2.2 mol of HCN/mol of Cu.The Cu2p XPS spectra showed that the possible species present were Cu2O and CuO.The N1s XPS data and FT-IR spectra indicated that CNwould be formed in the presence of Cu+/Cu2+ and oxygen gas,and the reaction product could be adsorbed onto Cu/ZSM-5 zeolite more easily than HCN.     

Use of zeolitized coal fly ash in the simultaneous removal of ammonium and phosphate from aqueous solution

Discharge of wastewater containing nitrogen and phosphate can cause eutrophication. Therefore, the development of an efficient material for the immobilization of the nutrients is important. In this study, a low calcium fly ash and high calcium fly ash were converted into zeolite using the hydrothermal method. The removal of ammonium and phosphate that coexist in aqueous solution by the synthesized zeolites were studied. The results showed that zeolitized fly ash could efficiently eliminate ammonium and phosphate at the same time. Saturation of zeolite with Ca²⁺ rather than Na⁺ favored the removal of both ammonium and phosphate because the cation exchange reaction by the NH₄ ⁺ resulted in the release of Ca²⁺ into the solution and precipitation of Ca²⁺ with PO₄ ³⁻ followed. An increase in the temperature elevated the immobilization of phosphate whereas it abated the removal of ammonium. Nearly 60% removal efficiency for ammonium was achieved in the neutral pH range from 5.5 to 10.5, while the increase or decrease in pH out of the neutral range lowered the adsorption. In contrast, the removal of phosphate approached 100% at a pH lower than 5.0 or higher than 9.0, and less phosphate was immobilized at neutral pH. However, there was still a narrow pH range from 9.0 to 10.5 favoring the removal of both ammonium and phosphate. It was concluded that the removal of ammonium was caused by cation exchange; the contribution of NH₃ volatilization to immobilization at alkaline conditions (up to pH level of 11.4) was limited. With respect to phosphate immobilization, the mechanism was mainly the formation of precipitate as Ca₃(PO₄)₂ within the basic pH range or as FePO₄ and AlPO₄ within acidic pH range.     

信号分子强化改性挂膜沸石持续抑制沉积物中氨氮释放

为寻找一种长期有效的底泥修复方式,对沸石进行了改性并挂膜的实验.考察了 4种铝盐[AlCl3、Al(NO3)3、Al2(SO4)3和KAl(SO4)2]改性挂膜沸石对上覆水中氨氮的去除情况.结果表明,AlCl3改性挂膜沸石效果最佳,且最佳改性浓度为0.8 mol·L-1.进一步分析添加信号分子OHHL后,AlCl3改性...     

不同SAPO分子筛负载MnOx催化剂的低温NH3-SCR性能研究

以磷酸硅铝分子筛SAPO-5、SAPO~(-1)1和SAPO-34为载体,采用乙醇分散法制备了用于低温氨选择性还原(NH_3-SCR)NO_x的分子筛负载MnO_x催化剂.活性测试结果显示,3种分子筛催化剂均展现出优良的NH_3-SCR活性,但三者在低温区间的SCR活性存在较明显差异,其SCR活性顺序如下:MnO_x/SAPO-34MnO_x/SAPO-5MnO_x/SAPO~(-1)1.借助XRD、N2吸附-脱附、XPS、H2-TPR、NH_3-TPD、NH_3FT-IR等技术对催化剂的表面活性物种及表面酸性等进行表征分析,结果表明,MnO_x主要以无定型状态分散于载体上,负载后载体的比表面积和孔体积均有所下降.XPS和H2-TPR分析证实,不同分子筛载体上MnO_x的表面浓度与氧化态明显不同.NH_3-TPD和NH_3FT-IR分析揭示了催化剂表面均存在Bronsted酸位和Lewis酸位,其中,Lewis酸性位对低温SCR反应起着关键作用.研究表明,催化剂的催化性能会因载体不同而存在差异,高Mn4+表面浓度和丰富的Lewis酸性位对催化剂在低温区间实现优良的催化活性尤为重要.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

纳米碳及其复合材料对油菜生长和土壤氮素保持效应的影响

采用盆栽种植实验及淋溶试验方法,研究了纳米碳及其与沸石、保水剂等材料复合对油菜生长和土壤氮素淋溶情况的影响.结果表明,在各处理中,纳米碳与沸石和保水剂复合材料处理(N4)对油菜的株高和干重影响最明显,较空白对照组(CK)分别增加21.12%和16.51%;在土壤淋溶试验中,各处理的土壤总氮淋出量较CK减少25.00%~39.21%,其中,累积淋溶中NH+4-N量占总氮量的4.44%~6.73%,各处理间无显著差异,NO-3-N量占总氮量的49.33%~60.05%,但各处理间差异显著;纳米碳和沸石复合处理能有效延缓NO-3-N峰值出现时间,减少NO-3-N流失.因此,N4处理在促进作物生长和氮素保持增效利用方面效果最佳.     

Effect of Cu loading content on the catalytic performance of Cu-USY catalysts for selective catalytic reduction of NO with NH3

Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method. The obtained catalysts were subjected to selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) performance evaluation, structural/chemical characterizations such as X-ray diffraction (XRD), N₂ adsorption/desorption, H₂ temperature-programmed reduction (H₂-TPR), NH₃ temperature-programmed desorption (NH₃-TPD) as well as detailed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments including CO adsorption, NH₃ adsorption and NO+O₂ in situ reactions. Results show that Cu-USY with proper Cu loading (in this work 5Cu-USY with 5 wt.% Cu) could be promising candidates with highly efficient NH₃-SCR catalytic performance, relatively low byproduct formation and excellent hydrothermal stability, although its SO₂ poisoning tolerability needs alleviation. Further characterizations reveal that such catalytic advantages can be attributed to both active cu species and surface acid centers evolution modulated by Cu loading. On one hand, Cu species in the super cages of zeolites increases with higher Cu content and being more conducive for NH₃-SCR reactivity. On the other hand, higher Cu loading leads to depletion of Brønsted acid centers and simultaneous formation of abundant Lewis acid centers, which facilitates NH₄NO₃ reduction via NH₃ adsorbed on Lewis acid centers, thus improving SCR reactivity. However, Cu over-introduction leads to formation of surface highly dispersed CuO_x, causing unfavorable NH₃ oxidation and inferior N₂ selectivity.     

铝污泥酸化提取液改性沸石的除磷特性及机制

为了提高沸石的除磷能力并降低改性成本,以给水厂铝污泥为铝源,采用酸化提取液合成层状双氢氧化物(LDHs)覆膜于沸石表面制备改性沸石,分别测定原沸石、Al-Zn改性沸石及铝污泥改性沸石的表面特性和化学组分,分析等温吸附及吸附动力学特性,探讨铝污泥改性沸石的除磷性能及除磷机制.结果表明,最佳酸化提取条件为60 min、150 r·min~(-1)和p H1. 0,该条件下1 g铝污泥(干重)可提取77 mg的铝;改性沸石的饱和吸附容量和解吸性能较原沸石显著提高,尤其是铝污泥改性沸石,其理论最大吸附量从30. 24 mg·kg~(-1)提升至170. 40 mg·kg~(-1);改性使得沸石对磷酸盐的主要吸附类型由物理吸附向化学吸附转变.以铝污泥为铝源改性沸石能有效地提高其对磷酸盐的吸附能力及再生能力,在降低磷浓度过高引发的水体富营养化风险的同时,实现以废治废的目的.     

粉煤灰合成沸石对Cr~(3+)的去除能力及影响因素研究

研究了粉煤灰合成沸石对废水中Cr~(3+)的去除能力,分析了接触时间、pH、沸石投加量、Cr~(3+)初始浓度、温度等因素对Cr~(3+)过程吸附的影响.试验结果表明,合成沸石的主要成分为一种无名沸石.合成沸石对Cr~(3+)具有较快的吸附速度,吸附过程符合二级反应动力学.在pH 2.0~12.0范围内,合成沸石对Cr~(3+)都具有较高的去除效率.Cr~(3+)去除率随着沸石投加量的增加而增加,随着Cr~(3+)初始浓度的升高而降低.Langmuir等温线模型对吸附数据具有更好的非线性拟合效果,所得最大吸附量为111.7 mg·g-1.热力学研究表明吸附过程为吸热反应.与原沸石相比,利用Na Cl再生后的沸石的Cr~(3+)去除率下降11.42%~14.10%,但仍可循环利用.上述实验结果表明本文合成的沸石具有较好的除Cr~(3+)的应用潜力.     

填料对潮汐流人工湿地中CANON作用强化的影响

为了缩短潮汐流人工湿地（TFCW）中基于亚硝化的全程自养脱氮（CANON）作用的启动进程并进一步提高该作用的强度,探究了不同种类填料下CANON型TFCW的启动性能及其微生物特征.结果表明,填料的理化特性可显著影响脱氮功能菌（尤其是ANAMMOX菌）的富集效果及其活性,进而可影响CANON型TFCW系统的启动进程及其脱氮性能.相较于公分石,陶粒、沸石、废砖块和龙虾壳均可不同程度地提高ANAMMOX菌在TFCW中的丰度与活性,进而可缩短CANON型TFCW的启动时间并提高其脱氮性能.当系统水力负荷为0.96 m³·（m²·d）^-1且以龙虾壳为湿地填料时,CANON型TFCW仅需300个运行周期即可完成启动,好氧氨氧化菌（AOB）和ANAMMOX菌为其中的两种优势脱氮菌群,且系统在稳定运行阶段对TN和NH₄⁺-N的去除率分别可达（88.37±1.19）%和（91.03±0.66）%,其次为废砖块、沸石、陶粒和公分石.     

Spatial and temporal patterns in summertime sulfate aerosol acidity and neutralization within a metropolitan area

A study of sulfate aerosol acidity in Metropolitan Toronto was conducted during the summer of 1986. Fine-fraction aerosol (<2.5-μm) were collected using Teflon membrane filters and analyzed for major ionic species (H⁺, NH⁺₄, NO⁻₃, SO²⁻₄). Samples were collected for 6 weeks at three study sites: one in the Center City and the others 13 km (WNW) and 20 km (NE) away. There were very strong correlations among the three sites with respect to measured aerosol species (r² > 0.9 for 24-h data). However, spatial variations in the magnitude of aerosol acidity were observed during sulfate episodes. For example, the peak concentrations for all sites occurred on 25–26 July 1986. While the 24-h data for sulfate were quite uniform at the three sites (34, 34 and 35 μg m⁻³), H⁺ concentrations were 9.4, 8.3 and 6.0 μg m⁻³ (as H₂SO₄) for the NE, WNW and Center City sites, respectively. For most of the summertime episodes, the downtown area also had lower aerosol acidity compared to the two sites in suburban areas.     

One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia

Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy. The obtained catalysts were subjected to selective catalytic reduction (SCR) of NO_x with NH₃ and were characterized by various techniques. The results show that Fe_0.63/Cu_1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580°C, excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13, signifying its great potential for practical applications. Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite (CHA) structure with good crystallinity, while isolated Cu²⁺ and monomeric Fe³⁺ are revealed as the predominant copper and iron species. At low temperatures, isolated Cu²⁺ species act as primary active sites for SCR reaction, while monomeric Fe³⁺ species provide sufficient active sites for sustain the SCR activity at high temperature. Moreover, Fe over doping would lead to the damage of zeolite structure, destruction of isolated Cu²⁺ site, as well as the formation of highly oxidizing Fe₂O₃, thus causing deterioration of catalytic performances.     

Effect of preparation methods on the performance of CuFe-SSZ-13 catalysts for selective catalytic reduction of NOx with NH3

CuFe-SSZ-13 catalyst showed excellent performance in the selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) for diesel engine exhaust purification. To investigate the effect of preparation methods on NH₃-SCR performance, Fe was loaded into one-pot synthesized Cu-SSZ-13 catalysts through solid-state ion-exchange (SSIE), homogeneous deposition precipitation (HDP) and liquid ion-exchange (IE), respectively. Three CuFe-SSZ-13 catalysts showed similar SO₂ resistance, which was better than that of Cu-SSZ-13. The improvement was attributed to the protection of Fe species. Hydrothermal stability of three CuFe-SSZ-13 catalysts was significantly different, which was attributed to the state of active species caused by different preparation methods. Compared with the other two catalysts, more active species existed inside the zeolite pores of CuFe-SSZ-13_SSIE. During hydrothermal aging, the aggregation of these active species in the pores caused the collapse of catalyst structure, ultimately leading to the deactivation of CuFe-SSZ-13_SSIE. In contrast, Fe species was dispersed better on the surface over CuFe-SSZ-13_IE, enhancing the hydrothermal stability of catalysts. Consequently, Fe loading effectively improved the resistance of SO₂ and H₂O over Cu-SSZ-13. For CuFe-SSZ-13, large amounts of active species located inside the zeolite pores are not beneficial for the hydrothermal stability.     

氨氮在饮用水生物滤池内的去除机制

为探讨饮用水生物滤池对NH4+-N的去除机制,测定生物滤池进出水中NH4+-N、NO2--N、NO3--N、高锰酸盐指数、总磷、单质氮(N2)、温度和溶解氧(dissolved oxygen,DO)等指标,并采集生物滤池不同层高(0、10、20、40、60 cm)活性炭生物填料,应用分子生物学技术,对样品中的细菌种群进行研究.结果表明,根据进水NH4+-N浓度分为3个阶段,第一、二和三阶段都发生了"氮亏损"现象(出水无机氮之和小于进水无机氮之和),氮亏损的量(出水无机氮之和与进水无机氮之和的差值)分别为0.94、0.32和0.15 mg.L-1.氮亏损的量与进水中NH4+-N浓度有很好的正相关性,但与进水中高锰酸盐指数浓度没有线性关系.第一阶段水中N2的平均浓度随着生物滤池填料层高呈上升趋势,进水中N2平均浓度是14.04 mg.L-1,出水N2平均浓度为14.67 mg.L-1.测序结果显示活性炭上生物膜中氨氧化细菌(ammonia-oxidizing bacteria,AOB)全部归为3个常见属:Nitrosococcus、Nitrosomonas和Nitrosospira.当生物滤池进水NH4+-N浓度较高时,生物滤池中发生的"氮亏损"现象是由AOB的作用.     

Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia

A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH_3-SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns(XRD), Scanning electron microscopy(SEM), Transmission electron microscopy(TEM), N_2 sorption-desorption, nuclear magnetic resonance(NMR), Inductively Coupled Plasma-Atomic Emission spectrometer(ICP-AES), X-ray absorption spectroscopy(XPS),Temperature-programmed desorption of ammonia(NH_3-TPD), Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS) and Temperature programmed reduction(TPR).The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion( 90%) among the wide activity temperature window in the range of 150–425℃.     

介质筛护岸的水质净化功能与机理

以桂林桃花江介质筛护岸工程为依托,对介质筛护岸的水质净化功能进行了试验研究.结果表明,介质筛护岸两侧水位波动促进了生物地球化学反应的发生.介质筛护岸对COD、NH 4-N和TN的平均去除率分别为76.5%、95%和81%.介质层内的COD浓度逐层降低,在距离岸边2.5 m左右的沸石强化层中,其浓度接近5 mg·L-1;在介质筛的第5、6层内NH 4-N的浓度基本稳定在0.3 mg·L-1.沸石层对NH 4-N吸附的有效厚度为10 cm,能够满足水质净化的目的.