过渡金属氧化物催化氧化NO实验研究

采用沉淀法制备出一系列过渡金属氧化物催化剂,在内径为10 mm的固定床反应器中考察其对低浓度NO的催化氧化活性,催化反应活性顺序为:MnCrCoCuFeZn,并考察了以锰为活性组分采用低温固相法、流变相法和浸渍法制备的催化剂催化氧化NO的活性。实验结果表明,采用流变相法和低温固相法制备的锰氧化物催化剂,在反应温度150℃,NO浓度为5×10-4,O2为3%,N2为平衡气,空速51 000 h-1条件下,NO转化率分别为65%和57%;采用浸渍法制备的Mn/TiO2-10%催化剂,在反应温度200℃,空速相同的条件下,NO转化率为47%。     

Ozone-enhanced catalytic oxidation of monochlorobenzene over iron oxide catalysts

In this study, we examined the experimental catalytic oxidation of gaseous monochlorobenzene (MCBz) with O₃ over Fe₂O₃ in a packed bed reactor to investigate the feasibility of economical low temperature decomposition at a high space velocity (SV). We investigated the effects of several reaction parameters (temperature, O₃ concentration, and SV) on the MCBz oxidation. At 150 °C, the conversion of MCBz over Fe₂O₃ in the absence of O₃ was only 3%; it increased to 91% over Fe₂O₃ in the presence of 1200 ppm of O₃ at a high SV of 83 s⁻¹. A long-term operation study revealed that the conversion of MCBz was stable for more than 96 h. In the steady state, the carbon and chlorine balances were 88% and 86%, respectively. Applying a Langmuir-Hinshelwood kinetic model, we estimated an activation energy of 16.7 kJ mol⁻¹ for MCBz oxidation over Fe₂O₃ in the presence of O₃.     

Mn-Ce复合金属氧化物催化氧化甲苯性能

通过等体积浸渍法制备了一系列Mn-Ce/γ-Al₂O₃催化剂, 并考察不同CeO₂负载量对MnO₂/γ-Al₂O₃催化剂催化氧化甲苯性能的影响。利用XRD、N₂吸脱附曲线、TEM、H₂-TPR、XPS和O₂-TPD等方法表征催化剂比表面积、表面形貌及氧化还原性能。结果表明,CeO₂的负载一定程度上降低了MnO₂/γ-Al₂O₃催化剂的比表面积, 且催化剂仍保持介孔结构。CeO₂的存在增加了催化剂表面的化学吸附氧含量,其良好的储放氧能力促进了Mn³⁺向Mn⁴⁺的转化;Mn和Ce之间存在较强的协同作用, 与MnO_x相邻的CeO₂更容易打开Ce—O键释放活性氧, 加速氧化还原进程,Mn_0.6Ce_0.4/γ-Al₂O₃催化剂T₁₀和T₉₀与MnO₂/γ-Al₂O₃催化剂相比分别降低20和40 ℃。本研究可为VOCs催化氧化技术中低成本金属催化剂的开发提供参考。     

Mn/GO复合催化剂催化氧化NO

针对尾气中NO浓度高且传统方法脱除NO代价高的问题,研究了锰固载氧化石墨诱导单过硫酸氢钾(PMS)催化氧化并吸收NO方法。通过浸渍法在氧化石墨上负载了Mn3O4制得Mn/GO催化剂,以此为催化剂催化PMS氧化NO。研究了pH、PMS投加量、催化剂投加量以及温度等因素对NO氧化率的影响。结果表明,该系列Mn/GO催化剂可以有效地诱导PMS氧化NO,热处理时间为7 h时催化效果最佳。同时,对Mn/GO(7 h)的FT-IR、XRD、SEM、EDS以及XPS表征可知,Mn3O4是主要的锰氧化物,并成功负载在GO表面。     

Activities of different metal oxide catalysts on NO reduction and CO oxidation

A series of transition metal oxide catalysts (Zn, Ti, Cu, Ni, Fe and V) supported on Al₂O₃ and SiO2 were prepared using the incipient wetness impregnation method. Their performances on NO reduction and CO oxidation followed the sequence of TiO₂ > CuO/ZnO > CuO > ZnO. TiO₂ supported on SiO₂ was more active than that on Al₂O₃, while ZnO had the opposite performances. The activities of CuO/Al₂O₃ and ZnO/SiO₂ were both decreased with the calcination temperature increasing because the sintering and agglomerations of catalysts were occurred at high temperature.     

催化湿式氧化农药废水及催化剂的研究

通过浸渍法制备了4种氧化物为主活性组分的负载固定型催化剂,用于过氧化氢催化湿式氧化(CWHPO)处理有机农药废水。用实验确定了催化湿式氧化的条件,不同催化剂处理效果的比较表明,四元组合MnO2CuOCeO2CoO催化剂性能较好,当反应在常温常压下,维持pH=7～9,反应时间为40min时,COD的去除率大于80%,色度去除率大于90%。     

低温CO催化氧化催化剂研究进展

对低(常)温下一氧化碳(CO)催化氧化进行了综述与讨论,介绍了各种催化体系催化反应的机理,着重分析了制备方法(共沉淀法、沉积沉淀法和溶剂化金属原子浸渍法等)、制备条件(前驱物、pH值、焙烧温度和焙烧时间等)、载体种类(金属氧化物、复合氧化物和沸石等)及助剂(Ce、Sm和La等)对催化剂在CO低(常)温催化氧化反应中的活性及稳定性的影响,并指出了今后的研究方向.     

Aqueous suspensions of carbon nanotubes: Surface oxidation, colloidal stability and uranium sorption

The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid.     

废水催化湿式氧化稀土金属氧化物催化剂的研制

采用共沉淀法制得锰铈复合氧化物催化剂,催化湿式氧化处理高浓度苯酚废水。通过正交实验筛选催化剂制备条件,单因素实验优化制得催化剂。研究了CWAO处理废水条件下的金属离子溶出和催化剂的表征。结果表明,该催化剂在低温低压条件下具有优良的湿式氧化催化活性,且金属离子溶出量低,是一种CWAO处理高浓度有机废水中极具应用前景的新型高效催化剂。     

臭氧催化氧化处理活性蓝染料废水及催化剂的研究

进行了臭氧化学氧化体系和臭氧催化氧化体系对活性蓝处理效果的比较。提出了常温常压下臭氧催化氧化预处理活性蓝染料废水的新方法。实验结果表明,臭氧催化氧化处理COD为13 800 mg/L的活性蓝染料废水时,最佳反应pH值为5～6,臭氧用量为80 mg/L时,反应时间约40 min,COD去除率大于80%,色度去除率大于90%,达到了预处理要求。     

稀土系列催化剂对焦化废水的催化湿式氧化

以稀土元素Ce制得催化剂系列 ,在高温、高压条件下对焦化废水进行催化湿式氧化研究 ,考察载体、焙烧温度、活性组分的配比对催化剂的催化活性的影响 ,以及反应温度、氧气分压、反应时间和催化剂用量对氧化过程的影响 ,设计正交实验确定最佳的工艺参数 :反应温度为 2 40℃、氧气分压 3 .0MPa ,催化剂用量 30g/L ,此时废水的COD去除率达到90 %以上     

Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.     

抗氧化性活性炭的制造及表征

活性炭是一种应用广泛的吸附催化剂,具有发达的空隙结构和巨大的比表面积,在环境污染治理方面具有广泛的应用。但是,活性炭较低的抗氧化性能限制了其在工业上的广泛应用。针对提高活性炭抗氧化性能的问题进行了初步的研究,提供了一种新型的增强活性炭抗氧化性的实验方法,经过实验验证,在温度为200℃时,与原始活性炭相比,改性活性炭的重量损失降低了28.9％。且通过氮气和亚甲基蓝吸附实验证明其孔大小和吸附量并没有显著改变,是一种较为可行的新方法,在工业生产中具有极大的经济意义。     

Single walled carbon nanotube reactivity and cytotoxicity following extended aqueous exposure

Globally carbon nanoparticles are increasingly utilized, yet it is not known if these nanoparticles pose a threat to the environment or human health. This investigation examined ‘as-prepared’, and acid cleaned carbon nanoparticle physicochemical characteristics (by FTIR, TEM, FESEM, UV-VIS and X-ray microanalysis), and whether these characteristics changed following 2.5-7 yr exposure to pH neutral saline or fresh water. To determine if these aqueous aged nanotubes were cytotoxic, these nanotubes were incubated with human epithelial monolayers and analyzed for cell viability (vital staining) and ultrastructural nanoparticle binding/localization (TEM, FESEM). The presence of Ni and Y catalyst, was less damaging to cells than CNT lattice surface oxidation. Extended fresh water storage of oxidized CNTs did not reduce surface reactive groups, nor lessen cell membrane destruction or cell death. However storing oxidized CNTs in saline or NOM significantly reduced CNT-induced cell membrane damage and increased cell survival to control levels.     

Mn-Ce复合氧化物微球的制备及其催化氧化甲苯性能

为了开发高效稳定、具有低温活性的降解VOCs催化材料,采用传统水热法制备了一系列不同锰铈比的催化剂(MnO₂、Mn_0.95Ce_0.05O_x、Mn_0.90Ce_0.10O_x、Mn_0.80Ce_0.20O_x及Mn_0.60Ce_0.40O_x),利用SEM、BET、XRD、H₂-TPR、O₂-TPD、拉曼光谱等技术对催化剂的物理化学性质进行了表征分析,同时考察了其对甲苯的催化氧化活性。结果表明：通过简单的水热合成法合成出的Mn-Ce复合氧化物均为微球,但Ce的加入使得微球催化剂表面的纳米针消失,变为光滑的微球体;而不同的催化剂在氧化甲苯时呈现不同的催化氧化性能,其中Mn_0.80Ce_0.20O_x具有最佳的甲苯氧化性能,这是由于其具有较强的氧化还原性能、较高的化学吸附氧含量及存在Mn-Ce固溶体。因此,通过控制催化剂中Ce含量,可调控催化剂的形貌和物理化学特性,从而使Mn-Ce复合氧化物在甲苯催化氧化中展现出优异的催化性能。研究结果为新型高效降解VOCs催化材料的设计和开发提供了新思路。     

TiO2薄膜气相光催化氧化低浓度三氯甲烷和三氯乙烯的研究

自行设计了气固相光催化实验系统,以铝材为担载体,TCM和TCE为模拟污染物,在常温、常压下,对辐射光源、气体相对湿度、污染物反应浓度等因素对TCM和TCE的光催化降解反应的影响进行了研究.结果表明,在研究所采用的实验条件下,辐射光源采用254 nm时的降解效率要比采用365 nm时高10%左右;气体相对湿度为40%时光催化降解效率最高;随着污染物反应浓度的增加,TCM的降解效率降低,而TCE的降解效率增加.初步的反应动力学研究结果表明,TCM和TCE在二氧化钛表面的光催化降解反应可采用Langmuir-Hinshelwood动力学方程来表征.     

基于碳烟颗粒催化氧化的三维有序大孔催化剂制备及性能

三维有序大孔钴锰尖晶石催化剂（3DOM CoMn2O4）以及三维有序大孔镧、铈掺杂的钴锰尖晶石催化剂（3DOM RxCo1-xMn2O4（R=Ce, La））由胶晶模板法成功合成。通过对所得的催化剂在NOx协助下的碳烟催化氧化活性评价,优化了Ce/Co和La/Co的配比。此外,还对目标催化剂进行了XRD、N2吸脱附、Raman、H2-TPR、SEM、XPS等表征。结果表明：3DOM结构增强了催化剂与碳烟颗粒之间的接触,对碳烟氧化等“固-固-气”非均相催化反应具有明显的提升作用。此外,铈和镧的掺杂增大了活性氧物种的浓度,从而增强了钴锰尖晶石催化剂的催化氧化能力。在松散接触工况下,3DOM Ce0.9Co0.1Mn2O4的Tig（起燃温度）和Tm（CO2出口浓度最大时的温度）分别为285 oC和377 oC,3DOM La0.3Co0.7Mn2O4的Tig和Tm分别为287 oC和376 oC。     

Fenton氧化剩余污泥过程重金属迁移及其形态变化

采用Fenton氧化处理含重金属剩余污泥,通过BCR法测定并分析了污泥处理过程各重金属形态的变化,重点考察了pH、H2O2投加量、H2O2/Fe2+比、温度（T）和反应时间（t）5个因素对重金属迁移及形态变化的影响。结果表明,利用Fenton氧化处理剩余污泥,污泥重金属形态变化显著,且受到初始pH、H2O2投加量、H2O2/Fe2+比和温度的影响,但反应时间的影响较小。正交实验结果显示,Fenton氧化处理污泥的最佳条件为：初始pH1、H2O2投加量12 g·L-1、H2O2/Fe2+比10和温度50℃,此时污泥Cu、Mn和Zn 3种重金属的弱酸溶解态含量达到最高值,分别为72.66%、90.12%和87.51%。在最佳条件时,污泥上清液中Cu、Mn和Zn含量可分别从0.08、0.263和0.01 mg·L-1增加到15.08、17.49、32.74 mg·L-1。研究表明,Fenton氧化污泥过程提高了污泥中弱酸溶解态重金属含量,利于重金属从固相向液相转移,从而有效降低污泥饼中重金属含量,有利于污泥脱水后的进一步处理及其资源化。     

Quantification of potassium permanganate consumption and PCE oxidation in subsurface materials

A series of laboratory scale batch slurry experiments were conducted in order to establish a data set for oxidant demand by sandy and clayey subsurface materials as well as to identify the reaction kinetic rates of permanganate (MnO(4)(-)) consumption and PCE oxidation as a function of the MnO(4)(-) concentration. The laboratory experiments were carried out with 31 sandy and clayey subsurface sediments from 12 Danish sites. The results show that the consumption of MnO(4)(-) by reaction with the sediment, termed the natural oxidant demand (NOD), is the primary reaction with regards to quantification of MnO(4)(-) consumption. Dissolved PCE in concentrations up to 100 mg/l in the sediments investigated is not a significant factor in the total MnO(4)(-) consumption. Consumption of MnO(4)(-) increases with an increasing initial MnO(4)(-) concentration. The sediment type is also important as NOD is (generally) higher in clayey than in sandy sediments for a given MnO(4)(-) concentration. For the different sediment types the typical NOD values are 0.5-2 g MnO(4)(-)/kg dry weight (dw) for glacial meltwater sand, 1-8 g MnO(4)(-)/kg dw for sandy till and 5-20 g MnO(4)(-)/kg dw for clayey till. The long term consumption of MnO(4)(-) and oxidation of PCE can not be described with a single rate constant, as the total MnO(4)(-) reduction is comprised of several different reactions with individual rates. During the initial hours of reaction, first order kinetics can be applied, where the short term first order rate constants for consumption of MnO(4)(-) and oxidation of PCE are 0.05-0.5 h(-1) and 0.5-4.5 h(-1), respectively. The sediment does not act as an instantaneous sink for MnO(4)(-). The consumption of MnO(4)(-) by reaction with the reactive species in the sediment is the result of several parallel reactions, during which the reaction between the contaminant and MnO(4)(-) also takes place. Hence, application of low MnO(4)(-) concentrations can cause partly oxidation of PCE, as the oxidant demand of the sediment does not need to be met fully before PCE is oxidised.     

锌、铁等离子对氧化锌烟气脱硫工艺中亚硫酸锌氧化的影响

在氧化锌法脱除烟气SO2工艺中,脱硫产物亚硫酸锌的氧化是实现锌、硫资源回收的关键环节。在pH为4～5,25℃等条件下,考察了锌、铁、镉离子对亚硫酸锌氧化过程的影响。结果发现,铁离子对亚硫酸锌氧化过程有较强的催化作用,锌离子有一定的催化作用,而低浓度的镉离子几乎不影响氧化过程。进一步的研究表明,锌、铁离子的独自催化氧化速率对各自的浓度均为0．5级响应,但在混合状态下,锌离子对铁离子的催化过程有抑制作用。