MgO低温催化臭氧降解氨氮的机制研究

研究了低温条件下单独臭氧及MgO催化臭氧化降解水中氨氮的效率和特征,并对其反应机制分别进行了探讨.结果表明,pH是影响臭氧和催化臭氧化除氨的重要因素,不仅影响溶液中NH_3与NH~+_4的比例和臭氧氧化氨氮的速率,还影响氧化产物种类,从而影响脱氮效果.10℃时,单独臭氧对水中氨氮的氧化降解效率随pH的升高而增大,pH≤9时整体降解效率不高,pH=9时仅为16.39%,而pH=10时达到41.77%.臭氧和·OH共同参与降解氨氮的过程.单独臭氧氧化氨氮生成氮气的选择性具有pH依赖性,并与Cl~-密切相关.pH低(≤9)时,氨氮多以NH~+_4形态存在,O_3与Cl~-反应生成ClO~-_x(x=1、3),再氧化NH~+_4,从而生成气态产物N_2或N_2O.MgO在低温条件下具有很强的催化臭氧化降解氨氮的能力且温度升高有利于反应的进行,0、10、20℃时,MgO催化臭氧化氨氮的效率分别为77.53%、80.17%、91.26%.此过程中,·OH参与反应的程度低,一部分氨氮降解依靠ClO~-_x氧化NH~+_4,而氨氮降解的主要途径为O_3对NH_3的直接氧化.     

Photocatalytic remediation of γ-hexachlorocyclohexane contaminated soils using TiO2 and montmorillonite composite photocatalyst

TiO2 and montmorillonite composite photocatalysts were prepared and applied in degrading γ-hexachlorocyclohexane(γ-HCH)in soils.After being spiked with γ-HCH,soil samples loaded with the composite photocatalysts were exposed to UV-light irradiation.The results indicated that the photocatalytic activities of the composite photocatalysts varied with the content of TiO2 in the order of 10%＜70%＜50%＜30%.Moreover,the photocatalytic activity of the composite photocatalysts with TiO2 content 30% was higher than that of the pure P25 with the same mass of TiO2.The strong adsorption capacity of the composite photocatalysts and quantum size effect may contribute to its increased photocatalytic activities.In addition,effect of dosage of composite photocatalysts and soil pH on γ-HCH photodegradation was investigated. Pentachlorocyclohexene,trichlorocyclohexene,and dichlorobenzene were detected as photodegradation intermediates,which were gradually degraded with tlle phOtOdegradation evolution.     

Cu／A1-Ce-PILC在丙烯选择性催化还原NO反应中的失活研究

采用聚合羟基复合阳离子合成交联黏土A1-Ce-PILC，经SO4^2-改性后，以浸渍法制备了铜基交联黏土催化剂Cu／A1-Ce-PILC，并将其应用于C3H6选择性催化还原NO的反应，350℃时NO转化率达到最大值56％，700℃时下降至22％．为探究催化剂高温失活的原因，采用XPS、TPR、TGA、Py-IR和DSC对反应前后催化剂的物化性能进行了表征．结果表明，经过H2预处理活化后活性组分Cu物种以Cu^＋形式存在，而高温反应后Cu物种除以Cu^＋和Cu^2＋ 2种形式存在外，还出现了少量CuO物种；高温反应过程中A1-Ce-PILC上结构羟基和SO4^2-流失导致催化剂表面酸性减弱；此外，还存在表面积炭覆盖了部分活性中心并堵塞了催化剂孔道的现象．这三者的共同影响促进了C3H6深度氧化，抑制了NO还原，从而导致催化剂的失活．     

氧化铝载体下二氧化氯催化氧化处理印染废水

研究了二氧化氯化学氧化体系和二氧化氯催化氧化体系。实验结果表明:单用二氧化氯化学氧化处理COD为2700mg/L的活性艳红染料配制废水时,最佳反应pH值为10,氧化剂经济用量为800mgClO2/L废水,反应时间为30min,COD去除率可达63%左右,氧化指数(COD削减量∶ClO2投加量)=2.18。当二氧化氯与自制催化剂所组成的催化氧化体系用于对活性艳红染料配制废水的处理时,最佳反应pH值为10左右,氧化剂经济用量为1000mgClO2/L废水,反应时间为90min,COD去除率可达83.4%,氧化指数=2.25。结果表明,二氧化氯催化氧化法是一种新型高效的处理难降解废水的技术,有着广阔的应用前景。     

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.     

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℃.     

硫酸/硫酸钠复合淋洗剂对铬渣的淋洗效果研究

以湖南长沙某铬盐厂铬渣为研究对象,通过室内模拟实验,采用振荡淋洗方法研究了硫酸-硫酸钠复合淋洗剂对铬渣污染场地Cr的淋洗效果,探讨了淋洗剂浓度、液固比和淋洗时间等对淋洗效果的影响,以及淋洗前后重金属形态的变化,并通过对比试验研究了硫酸钠、柠檬酸、草酸、Na2-EDTA、硫酸、柠檬酸-柠檬酸三钠以及盐酸-氯化钠作为淋洗剂对总铬和六价铬的淋洗效果。结果表明:硫酸/硫酸钠复合淋洗剂在浓度为0.4 mol/L,液固比为20∶1,反应时间为6 h,常温条件下可以达到最佳淋洗效果,总铬和六价铬的浸出效率分别为70.35%和71.56%;另外,重金属形态分析表明,该复合淋洗剂有效减少了铬渣中弱酸可提取态和有机物结合态Cr的百分比,使得残渣态Cr的百分比增加,从而降低了Cr的活性,达到修复目的。淋洗剂对比试验结果表明,与其他淋洗剂相比,硫酸-硫酸钠淋洗效果最好,其中的氢离子能与Cr~(3+)进行离子交换,而硫酸根能够有效地将钙与六价铬分离,对此高钙铬渣的处理更具针对性和有效性。     

CuSnZr三元催化剂应用于NTP强化催化脱硫过程的特性

为高效地在低温下处理大量低浓度电解铝烟气, 采用浸渍法制备了Sn Zr型金属氧化物并添加Cu作为助剂的催化剂, 并首次测试了它在低温等离子体(NTP)技术上的脱硫效果, 结果表明负载了20wt% Cu老化温度为40℃的催化剂表现出最佳的脱硫性能.并对强化之后的催化剂进行了表征, 与新鲜的催化剂对比, X射线衍射分析(XRD)结果表明放电对催化剂晶型基本不产生影响; 扫描电子显微镜(SEM), 氮吸附和脱吸(BET)表明放电会使催化剂的吸附脱附能力与孔道结构有较大提升; X射线光电子光谱(XPS)也表明放电会使催化剂表面元素价态变化, 从而使其氧化还原性能改变, 反应路径发生偏向; 催化剂性能理论计算表明铜含量的上升会导致催化剂能带结构改变, 更好利用于激发气体.     

碳包覆Pd/Al2O3催化剂催化4-溴苯酚加氢脱溴的活性和稳定性调控研究

在污染物液相催化加氢脱卤过程中,提高催化剂的稳定性至关重要.以水热合成法制备了不同碳包覆量的Pd/Al₂O₃@C催化剂,对催化剂进行了系列表征,并将催化剂应用于4-溴苯酚(4-BP)污染物的催化加氢脱溴反应.表征结果显示碳层提高了Pd/Al₂O₃的表面疏水性,有利于4-BP在催化剂上的吸附.并且在Pd/Al₂O₃@C催化剂的碳化过程中,碳还原部分Pd颗粒,并保留部分正价态Pd活性位,增强了4-BP中C-Br键的活化.与Pd/Al₂O₃相比,碳涂层提高了催化剂的催化活性.但当碳包覆量超过最佳包覆量后,暴露的Pd粒子随碳包覆量的增加而减少,导致活性下降.此外,碳层修饰后,催化剂的稳定性显著提高,从而大大抑制了Pd粒子的团聚和损耗.Pd/Al₂O₃@C表面的碳涂层对卤素具有较高的耐受性,从而减轻了液相催化加氢脱卤反应中活性中心的中毒.     

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.