催化还原脱除地下水中的硝酸盐

本文介绍了催化还原脱除地下水中硝酸盐的原理、催化剂的选择、催化剂的制备等问题。与传统的硝酸盐脱除技术相比，催化还原法具有运行时间短以及管理方便等优势，但是目前催化剂的活性和选择性还不够理想，而且反应过程中还会受到传质等因素的限制。     

催化还原脱除地下水中的硝酸盐

本文介绍了催化还原脱除地下水中硝酸盐的原理、催化剂的选择、催化剂的制备等问题。与传统的硝酸盐脱除技术相比 ,催化还原法具有运行时间短以及管理方便等优势 ,但是目前催化剂的活性和选择性还不够理想 ,而且反应过程中还会受到传质等因素的限制     

脱除地下水中硝酸盐氮的研究进展

地下水中硝酸盐氮的脱除可以采用传统脱除法和催化反硝化脱除法。介绍了地下水脱氮技术的发展历史,着重介绍了最新发展提出的催化反硝化脱氮法。具体阐述了催化反硝化脱氮的原理、处理效果、主要影响因素、优势和局限性,对目前存在的问题和今后的发展方向,指明催化活性和催化选择性的提高,是催化反硝化法实用化过程中需要解决的关键问题。     

改性贵金属催化剂催化还原脱除NO

含有NO的工业废气直接排放会严重污染空气,须对含有NO的工业废气进行净化处理.采用NH3为还原剂贵金属铂催化剂进行了低温还原NO脱除烟气中氮氧化物性能的研究.结果表明:实验室制备的贵金属铂催化剂具有高的低温活性和选择性催化还原脱除NO的性能,但该催化剂易被原料气中少量的硫化物(SO₂)中毒而影响其稳定性;用稀土元素La和Ce对贵金属铂催化剂进行改性,改性后贵金属铂催化剂的稳定性得到了大幅度提高,出口气体中氮氧化物浓度大幅度降低.本实验Pt∶La∶Ce最佳摩尔比为1∶3.78∶3.56.     

Pd-W-Cu/γ-Al_2O_3催化氢还原脱硝的基本性能研究

采用浸渍法制备Pd-W-Cu/γ-Al2O3催化剂,用XRD和SEM方法对该催化剂进行了表征.以氢气作为还原剂,在间歇式反应器中对催化还原地下水中硝酸盐进行了实验研究,考察了催化剂制备方法对催化还原硝酸盐性能的影响.结果表明,W的添加改善了Pd的分散性,提高了催化剂的活性和选择性.金属Pd/W/Cu质量比、浸渍顺序和焙烧温度对催化性能有较大影响.Pd/W/Cu质量比为3∶1∶1,Pd、Cu和W3种金属组分同时浸渍,焙烧温度为400℃时,催化剂的活性和选择性最高.在NO3--N初始浓度为100mg·mL-1条件下,催化反应60min后水中NO3--N和NO2--N浓度均为0mg·mL-1,NH4+-N浓度为2.5mg·mL-1.     

钛基修饰电极催化电解去除水中硝酸盐氮的研究

利用热分解法制备CuO修饰Ti基阴极和SnO2-Sb2O5修饰Ti基阳极,组成无隔膜电解体系,以模拟废水(NO3--N 50mg/L)为对象,进行了水中NO3--N去除实验研究.结果数据表明,CuO修饰Ti基阴极对水中NO3--N的去除率随电流密度、极板间距、搅拌强度和电解时间增加而增加,在电流密度10mA/cm2、极板间距9mm、中等搅拌强度下电解150min,NO3--N催化还原去除率可达93.8%.Cl-支持电解可使NO3--N催化还原产物NH4+-N氧化为N2-N去除.在电流密度10mA/cm2、极板间距9mm、NaCl添加量600mg/L、中等搅拌强度下电解120min后,NO3--N和TN的去除率达到89.3%和86.9%,NO2--N和NH4+-N未检出.分析认为NO3--N还原机制为NOx中O被阴极表面Cu吸附固定,N—O键受氢攻击破坏,逐步还原.阳极电解Cl-生成HOCl,HOCl氧化NH4+-N成N2-N.     

N掺杂TiO_2光催化还原地下水中硝酸盐

以硫酸钛为前驱体,采用水热沉淀法制备TiO2光催化剂,采用扫描电子显微镜(SEM)、X-射线能谱(EDS)、X-射线衍射(XRD)、傅立叶红外光谱仪(FTIR)和光电子能谱仪(XPS)进行表征和分析,考察了硫酸钛浓度、焙烧温度对光催化还原水中硝酸盐活性的影响.结果表明,制备的催化剂为掺杂N的锐钛矿型TiO2.硫酸钛浓度为0.5mol.L-1、焙烧温度为400℃时制备的催化剂活性最佳,反应120min后,硝酸盐转化率为95.8%,中间产物NO--N浓度为0.17mg·mL-1,副产物NH+-N浓度为1.52mg·mL-1.     

催化裂化烟气脱除NOx的选择性催化还原技术

催化裂化 ( FCC)是炼油厂中排放的最大污染源 ,排放的 NOx占炼厂的一半。选择性催化还原( SCR)是脱除 FCC装置烟气中 NOx的高效技术。通过由均一材料挤压制成的流通式蜂窝状催化剂除去 NOx,只需在 SCR上游喷入 NH3,无需外加动力 ,无污水产生 ,适用于宽范围的烟气温度。控制 FCC再生器烟气的 NOx排放的选择性催化还原 ( SCR)技术 :在氧化催化剂作用下 ,NH3与NOx反应生成氮气与水蒸汽。常用的催化剂是五氧化二钒 /二氧化钛 ,也可用分散在载体上的铂或钯贵金属催化剂或分子筛催化剂。 NH3可由无水氨、氨水或尿素提供 ,典型的 NH…     

Pd-Cu@UiO-66催化还原水中硝酸盐

为解决地下水中硝酸盐含量过高的问题,首次制备了双金属Pd-Cu@UiO-66催化剂用于催化还原水中硝酸盐的研究,重点考察了不同调节剂制备的载体和工艺条件对脱硝性能的影响。结果表明:采用盐酸制备的UiO-66载体,Pd、Cu金属负载量分别为1%,氢气流量为70 mL/min时,硝酸盐脱除率为97.4%,N₂的选择性可达到95.2%。pKa值越低的调节剂所制备的载体粒径越小,越有利于活性金属的分散,且形成的金属粒径较小。活性金属的高度分散有利于活化氢的生成及Cu的电子迁移,能够提高脱硝反应中N₂的选择性。在反应过程中,双金属的协同效应是影响催化性能的关键因素。     

Pd/TiO2-SnO2催化还原硝酸盐效能及反应调控

采用共沉淀法制备了掺杂TiO2的复合载体TiO2-SnO2;浸渍法制备了单金属负载型催化剂Pd/TiO2-SnO2.用X射线衍射（XRD）、X射线光电子能谱（XPS）、比表面仪（BET）和透射电镜（TEM）表征表明Pd和TiO2在SnO2上成单层或亚单层分散,增加了反应活性位.催化剂分散性良好,比表面积为100.8m....     

Studies on catalytic reduction of nitrate in groundwater

Catalytic reduction of nitrate in groundwater by sodium formate over the catalyst was investigated. Pd-Cu/γ-Al₂O₃ catalyst was prepared by impregnation and characterized by brunauer-emmett-teller (BET), inductive coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray (EDX). It was found that total nitrogen was effectively removed from the nitrate solution (100 mg/L) and the removal efficiency was 87%. The catalytic activity was affected by pH, catalyst amount used, concentration of sodium formate, and initial concentration of nitrate. As sodium formate was used as reductant, precise control in the initial pH was needed. Excessively high or low initial pH (7.0 or 3.0) reduced catalytic activity. At initial pH of 4.5, catalytic activity was enhanced by reducing the amount of catalyst, while concentrations of sodium formate increased with a considerable decrease in N₂ selectivity. In which case, catalytic reduction followed the first order kinetics. Translated from Acta Scientiae Circumstantiae, 2006, 26(4): 567–571 [译自: 环境科学学报]     

催化还原法深度处理污水中硝态氮的研究

为有效降低城市污水处理厂出水硝态氮的含量,减轻氮素污染,依次进行了基础性试验和验证性试验.基础性试验以Fe0为还原剂,以配置的KNO3溶液为试验用水对分别添加H+、Fe2+、Cu2+、Pd/Al2O3等后的脱氮效果进行了对比研究.试验结果表明,系统pH值为2.1,Fe2+、Cu2+投加量分别为1000mg/L时,系统均可获得较好的脱氮效果,分别为92%、41%、61%,产物均以氨氮为主;当投加10g/L催化剂Pd/Al2O3,调节系统pH值为3.02时,系统脱氮率可达48%,且其产物以氮气为主,副产物较少.在此基础上,验证性试验以北京市某污水处理厂出水为试验用水,对上述各方法的脱氮效果进行了试验验证,并对其可行性进行了分析.结果表明,在一定条件下,各方法均可达到理想的脱氮效果,其去除率分别可达到87%、36%、50%、46%.但综合脱氮效果、产物分析、出水水质等考虑,相比较而言,添加催化剂的化学催化还原法在去除污水中的硝态氮时具有更好的可行性.     

傀儡湖沉积物-水界面硝酸盐异养还原过程研究

反硝化（DNF）和硝酸盐异养还原为氨（DNRA）是水域生态系统中硝酸盐异养还原的2个主要过程.DNF和DNRA之间的竞争控制着硝酸盐在水域生态系统中的异养还原方式和最终归趋.选取太湖流域的傀儡湖为研究对象,采用室内培养实验和稳定氮同位素示踪技术,考察傀儡湖沉积物-水界面的DNF和DNRA速率及其对硝酸盐异养还原过程的贡献.结果显示,沉积物表现为NH₄⁺-N的源和NO₃^--N的汇,潜在DNF速率为18.89~54.00μmol/（kg·h）[均值（36.39±3.86）μmol/（kg·h）],DNRA反应速率为1.02~5.89μmol/（kg·h）[均值（3.21±1.15）μmol/（kg·h）].DNF与沉积物有机质含量和含水率存在显著的正相关关系,DNRA与沉积物需氧量（SOD）之间存在相关性.反硝化是傀儡湖中硝酸盐异养还原的主导过程,贡献率为84.23%~96.90%,而DNRA过程只占3.10%~15.77%.与海洋河口区域相比,淡水湖泊生态系统中DNRA速率和DNRA在硝酸盐异养还原中所占的比重均较小.     

Marine aquaculture regulates dissimilatory nitrate reduction processes in a typical semi-enclosed bay of southeastern China

Marine aquaculture in semi-enclosed bays can significantly influence nutrient cycling in coastal ecosystems. However, the impact of marine aquaculture on the dynamics of dissimilatory nitrate reduction processes (DNRPs) and the fate of reactive nitrogen remain poorly understood. In this study, the rates of DNRPs and the abundances of related functional genes were investigated in aquaculture and non-aquaculture areas. The results showed that marine aquaculture significantly increased the denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) rates and decreased the rate of anaerobic ammonium oxidation (ANA), as compared with non-aquaculture sites. DNF was the dominant pathway contributing to the total nitrate reduction, and its contribution to the total nitrate reduction significantly increased from 66.72% at non-aquaculture sites to 78.50% at aquaculture sites. Marine aquaculture can significantly affect the physicochemical characteristics of sediment and the abundances of related functional genes, leading to variations in the nitrate reduction rates. Although nitrate removal rates increased in the marine aquaculture area, ammonification rates and the nitrogen retention index in the aquaculture areas were 2.19 and 1.24 times, respectively, higher than those at non-aquaculture sites. Net reactive nitrogen retention exceeded nitrogen removal in the aquaculture area, and the retained reactive nitrogen could diffuse with the tidal current to the entire bay, thereby aggravating N pollution in the entire study area. These results show that marine aquaculture is the dominant source of nitrogen pollution in semi-enclosed bays. This study can provide insights into nitrogen pollution control in semi-enclosed bays with well-developed marine aquaculture.     

人工湿地沟壕系统中硝酸盐异化还原成铵细菌群落特征研究

硝酸盐异化还原成铵（Dissimilatory nitrate reduction to ammonium，DNRA）过程，是将易损失的NO₃^--N转化为NH₄⁺-N，而被植物或微生物重新吸收利用，从而有助于湿地沉积物的氮保留.本研究选取石臼漾人工湿地冬、夏两季沟壕中心、边缘表层沉积物，采用高通量测序等分析方法，研究了DNRA细菌群落结构特征.研究结果表明：在空间尺度上，沟壕中心DNRA细菌丰度高于沟壕边缘，分别为（2.26±1.19）×10⁹和（1.22±1.46）×10⁹ copies·g^-1.在时间尺度上，冬夏两季样品中DNRA细菌丰度具有显著性差异（p<0.05）.多样性分析表明，沟壕中心沉积物的DNRA群落丰富度高于沟壕边缘.所有样品中占比最高的DNRA属为Caldilinea（69.75%±3.64%）、Anaeromyxobacter（66.41%±1.19%）.Caldilinea属在夏季样品的占比（39.78%±5.15%）高于冬季样品（29.98%±0.57%），而Anaeromyxobacter属在沟壕中心的占比（35.14%±0.83%）高于沟壕边缘（31.28%±0.76%），且小沟（34.33%±1.40%）高于大沟（32.08%±1.33%）.主坐标分析（PcoA）结果表明，DNRA细菌群落结构具有明显的时间异质性.DNRA细菌丰度与有机质（TOM）、碳氮比（C/N）和含水率（MC）显著相关.本研究揭示了人工湿地沉积物中DNRA细菌的丰度、群落组成、多样性及其与环境因子的关系.     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

崇明东滩湿地土壤硝酸盐异化还原成铵过程及其影响因素

以崇明东滩湿地为研究对象,采用同位素示踪结合泥浆实验,研究了从低潮滩向高潮滩变化的土壤硝酸盐异化还原成铵过程(DNRA)及其影响因素.结果表明,土壤硝酸盐异化还原成铵的潜在速率为0.17～0.71 nmol·g~(-1)·h~(-1),表现为低潮滩位较高、高潮滩位较低的空间变化特征.相关性分析表明,酸盐异化还原成铵潜在速率与氧化还原电位、可溶性有机碳、硝酸盐和硫化物呈显著相关性.此外,nrfA基因丰度与硝酸盐异化还原成铵潜在速率呈显著相关性.逐步回归分析发现,可溶有机碳和总有机碳是影响硝酸盐异化还原成铵潜在速率和nrfA基因丰度的关键性环境因子,分别贡献了总变异的78.8%和50.3%.通过估算得出,东滩湿地硝酸盐异化还原成铵过程将硝酸盐转化成铵盐的潜力为2.5～10.4 t·km~(-2)·a~(-1),贡献了长江口每年无机氮输入量的0.68%～2.85%,因此,硝酸盐异化还原成铵过程在控制河口湿地氮赋存方面具有着重要的作用.河口潮汐作用导致的湿地环境特征与有机质和硝酸盐含量的变化影响着硝酸盐异化还原成铵过程,进而对河口湿地生态系统中氮动态产生较大的影响.     

Reduction of nitrate from groundwater: powder catalysts and catalytic membrane

The reduction of nitrate contaminant in groundwater has gained renewed and intensive attention due to the environmental problems and health risks. Catalytic denetrification presents one of the most promising approaches for the removal of nitrate from water. Catalytic nitrate reduction from water by powder catalysts and catalytic membrane in a batch reactor was studied. And the effects of the initial concentration, the amounts of catalyst, and the flux H2 on the nitrate reduction were also discussed. The results demonstrated that nitrate reduction activity and the selectivity to nitrogen gas were mainly controlled by diffusion limitations and the mass transfer of the reactants. The selectivity can improved while retaining a high catalytic activity under controlled diffusion condition or the intensification of the mass transfer, and a good reaction condition. The total nitrogen removal efficiency reached above 80%. Moreover, catalytic membrane can create a high effective gas/liquid/solid interface, and show a good selectivity to nitrogen in comparative with the powder catalyst, the selectivity to nitrogen was improved from 73.4 % to 89.4%.