Comparison between the performance of an immobilized impinging jet stream reactor and a slurry impinging jet stream reactor for photocatalytic phenol degradation

A new immobilized photocatalytic impinging jet stream reactor was designed, and the influences of the effective parameters like jet flow rate, TiO₂ coating disc diameter, nozzle-to-disc distance, and initial concentration on phenol removal were investigated. The reactor was also used as a slurry reactor, and degradation efficiencies in both reactors were compared based on their catalyst loading. The results indicated that the slurry reactor has a higher degradation efficiency than the immobilized reactor at the same TiO₂ loading and other operational conditions. The slurry reactor needs to separate and recover the TiO₂ nanoparticles from the reaction medium which increases the overall process complexity and cost, while the immobilized reactor could be reused at least 4times without any significant decrease in removal efficiency. RTD result indicates that the tank in series model (N?=?5) could properly predict the reactors hydrodynamic behavior.     

Self-regeneration of activated carbon modified with palladium catalyst for electrochemical dechlorination

Catalyst regeneration and the retention of high catalytic activity are still the critical issues in environmental application.A novel fluidized gas-liquid-solid electrochemical reactor was developed to simultaneously remove chlorinated pollutants and in situ regenerate the spent catalyst.Activated carbon modified with palladium catalyst (AC-Pd) was prepared for electrochemical dechlorination.For the 4-chloropbenol wastewater of initial concentration 200 mg L~(-1),the removal efficiency could nearly reach 100% in less than 30 min.Catalytic activity of AC-Pd catalyst was preserved effectively even in consecutive cycling run without special regeneration.OH radicals,generated by electrochemical reaction,played a critical role in self-regeneration of AC-Pd.High catalytic activity of spent AC-Pd catalyst provided an attractive alternative in wastewater treatment.     

Chlorine dioxide catalytic oxidation and online FTIR spectroscopic analysis of simulated o-chlorophenol wastewater

An activated carbon-MnO₂ catalyst was prepared and used for chlorine dioxide catalytic oxidation of simulated o-chlorophenol wastewater. The COD removal efficiencies of chemical oxidation and catalytic oxidation are 28.6 and 93.5%, respectively. The COD removal efficiency of catalytic oxidation is greater than that of chemical oxidation at the same treatment condition. By using UV?CVis and online FTIR analysis technique, the intermediates during the degradation process were obtained. The benzene ring in o-chlorophenol was degraded into quinone and carboxylic acid, and finally changed into carbon dioxide and water during the catalytic oxidation. The degradation reaction mechanism of o-chlorophenol by chlorine dioxide catalytic oxidation was proposed based upon the experiment evidence.     

Copper supported on porous activated carbon obtained by wetness impregnation: Effect of preparation conditions on the ozonation catalyst's characteristics

An activated carbon-supported copper heterogeneous catalyst based on (Cu/AC) was developed using a wetness impregnation process. The effect of preparation conditions on the catalyst's characteristics was examined. This work focuses on two key parameters: impregnation rate and calcination conditions (temperature and time). Catalysts were characterized by means of nitrogen sorptiometry at 77 K, Boehm analysis and pH_pzc analysis. It was found that the catalyst properties and the functional surface groups were affected by the operating conditions. The highest measured surface area, i.e. 1040 m²/g, was obtained for activated carbon (AC) impregnated with 12% of Cu loading after calcination at 550 °C for 2 h. The effect of adding copper on the surface of activated carbon on its adsorption capacity was also examined. The obtained results showed that after impregnation, the adsorption capacity of activated carbon was improved. Additionally, the performance of the Cu/AC catalyst on nitrobenzene ozonation was investigated. Our results show that the use of Cu/AC for heterogeneous catalytic ozonation enhanced significantly the degradation efficiency of nitrobenzene (NB) compared with simple ozonation and with ozonation catalyzed by AC without metal addition.     

金属有机骨架材料负载镍纳米颗粒催化硝基苯加氢

以MIL-53(Al)、MIL-96(Al)和MIL-120(Al) (MIL: Material Institute of Lavorisier)三种金属有机骨架材料为载体, 采用浸渍法制备了负载廉价金属镍纳米颗粒的催化剂. 将其用于催化硝基苯加氢合成苯胺反应, 发现以MIL-53(Al)为载体制得的催化剂表现出优异的催化性能. 采用不同的镍前驱体, 如硝酸镍、醋酸镍、乙二胺合镍, 制备了一系列Ni/MIL-53(Al)催化剂. 通过X射线衍射、傅里叶变换红外光谱、电感耦合等离子体、N₂物理吸附、H₂程序升温还原、透射电镜等技术对其进行了表征, 研究了镍前驱体对金属-载体相互作用、镍颗粒尺寸以及分散程度的影响.结果表明:以乙二胺合镍为镍前驱体制得的催化剂具有金属-载体相互作用适中、镍纳米颗粒更小(4-5 nm)和分布更均匀的特点, 在硝基苯加氢反应中表现出优异的催化性能, 硝基苯转化率达到100%.回收重复使用5次后, 此催化剂仍保持催化活性,硝基苯转化率达92%.     

Microfabricated reactors for on-chip heterogeneous catalysis

Microfabricated devices constructed from glass and polydimethylsiloxane with integral heaters are described, which can be used for heterogeneous catalysis reactions. Sulfated zirconia is used as the catalyst in an open channel reactor, with either a syringe pump or electroosmotic flow being used to deliver the reactants. The results clearly demonstrate that very high conversion efficiencies are possible, however, the thermodynamics of the reactions are the same as in bulk systems. Ethanol and hexanol are dehydrated to ethene and hexene, respectively, with conversion efficiencies approaching 100%, and the esterification of ethanol is investigated. Yields of approximately 30% ethyl acetate are obtained by gas chromatographic analysis. This is the first time such a method for fabricating a catalyst micro reactor has been reported, yet it demonstrates sufficient robustness and resistance to leakage. The use of electroosmotic flow in a heated catalyst reactor is a significant advancement in reactor design.     

一种新型光电催化反应器的研制及甲酸的光电催化深度氧化

 研制出一种新型的悬浮态光电催化反应器，并以甲酸为研究对象，对该光电反应器进行了光电流增强和COD脱除的表征．研究了光催化、电催化氧化及光电协同催化体系降解甲酸的电压－电流曲线．数据表明，在相同的电压下，光电协同催化体系的电流远高于电化学氧化体系的电流与光催化体系中光电流之和．同时，还研究了一系列物理化学因素如外加电压、光催化剂浓度和空气流量等对光电催化反应的影响．实验结果表明，自行研制的新型悬浮态光电催化反应器具有良好的协同效应，且所需光催化剂的最佳浓度远低于其他同类光电催化反应器的最佳浓度．在该光电催化反应器中，压缩空气可有效地增强传质效应和悬浮态中光激发的TiO2颗粒在电极表面的碰撞几率，从而使得外电场可有效地捕获光生电子．     

Elimination of Carbon Monoxide in the Gas Streams by Dielectric Barrier Discharge Systems with Mn Catalyst

Elimination of CO in air stream using the plasma catalytic reactors was investigated. Two plasma catalytic systems were evaluated in this study, one consisting of a catalyst-bed packed in plasma zone of a dielectric barrier discharge (DBD) reactor directly (CID reactor), and the other (CAD reactor) consisting of a catalyst-bed after a DBD reactor. The examined operating parameters in this study included applied voltage, discharge power, the lengths of plasma zone and catalyst-bed, and inlet CO concentration. It was found that the glass packed DBD reactor without catalyst cannot eliminate CO in air stream effectively. When MnO_x catalyst applied to DBD reactors, the removal of 1000 ppm CO can achieve to 97% by both type reactors. Under constant energy input condition, the CO removal of a CID reactor increased with the decrease of the initial CO concentration and the increase of the length of catalyst beds. In addition, the operating energy consumption of CID system was lower than that of CAD system.     

纳米氧化锡在锌-硝基苯电池反应中的电催化

以氯化锡为原料,四丙基溴化铵为表面活性剂水热法制备纳米二氧化锡（SnO₂）催化剂,并以钛网为基材,制备催化电极. 应用SEM,XRD等手段对催化剂进行表征. 考察了反应物浓度、反应温度和反应时间对催化剂形貌的影响. 研究了纳米SnO₂催化剂对锌还原硝基苯原电池反应的电催化性能. 结果表明,当 NaOH浓度为0. 5 mol•L^-1、水热反应温度160 ℃、水热反应时间15 h时,得到的SnO₂催化剂是由纳米片构成的刺球状颗粒,粒径最小,约17 nm. 与平板铂电极相比,制备的催化电极对硝基苯电还原具有更高的催化活性,硝基苯转化率为74%,最大放电功率为21.9 mW•cm^-2,远大于平板铂电极. 硝基苯的主要还原产物为苯胺、对乙氧基苯胺和对氯苯胺.     

Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO2 Reduction

Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110‐fold enhancement compared to the oleylamine‐coated AuNP in current density for electrochemical reduction of CO₂ to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches.     

Ru0.7Si0.3O2/Ti电极电催化氧化处理硝基苯废水

制备了Ru0.7Si0.3O2/Ti电极,并以该电极作为氧化阳极,不锈钢为阴极,电催化氧化降解废水中硝基苯。 实验结果表明,当硝基苯初始质量浓度为220 mg/L时,最佳条件为：电流密度25×10-3 A/cm2;Na2SO4作为电解质时加入量为8 g/L;溶液初始pH=2。 在此最佳条件下,硝基苯去除率大于85%,TOC去除率大于50%,表明Ru0.7Si0.3O2/Ti阳极能有效去除废水中有机污染物;对中间产物的检测结果表明,硝基苯的降解是阴阳两极协同作用的结果。     

三维电极电化学反应器对有机废水的降解研究

本文提出一种基于三维电极电化学反应器处理有机废水的新技术 ,结果表明 :该反应器能有效地去除苯胺 ,但其去除率受外加电压、溶液中Fe2 +的浓度、pH值及处理时间 (t)的影响较大 .该项技术处理有机废水效果明显 ,主要是基于电致过氧化氢 ,在Fe2 +存在情况下迅速生成对有机物有很强氧化作用的羟基自由基 .通过ESR法测出了在该电化学反应器处理废水过程中产生的羟基自由基     

Thermal and catalytic degradation of pyrolytic oil from pyrolysis of municipal plastic wastes

Thermal and catalytic degradation of pyrolytic oil obtained from the commercial rotary kiln pyrolysis plant for municipal plastic waste was studied by using fluid catalytic cracking (FCC) catalyst in a bench scale reactor. The characteristics of raw pyrolytic oil and also thermal and catalytic degradation of pyrolytic oil using FCC catalyst (fresh and spent FCC catalyst) under rising temperature programming was examined. The experiments were conducted by temperature programming with 10 °C/min of heating rate up to 420 °C and then holding time of 5 h. During this programming, the sampling of product oil was conducted at a different degradation temperature and also different holding time. The raw pyrolytic oil showed a wide retention time distribution in GC analysis, from 5 of carbon number to about 25, and also different product characteristics with a comparison of those of commercial oils (gasoline, kerosene and diesel). In thermal degradation, the characteristics of product oils obtained were influenced by reaction temperature under temperature programming and holding time in the reactor at 420 °C. The addition of FCC catalyst in degradation process showed the improvement of liquid and gas yield, and also high fraction of heavy hydrocarbons in oil product due to more cracking of residue. Moreover, the characteristic of oil product in catalytic degradation using both spent and fresh FCC catalysts were similar, but a relatively good effect of spent FCC catalyst was observed.     

Dynamic modeling of a H2O-permselective membrane reactor to enhance methanol synthesis from syngas considering catalyst deactivation

In this paper,the effect of water vapor removal on methanol synthesis capacity from syngas in a fixed-bed membrane reactor is studied considering long-term catalyst deactivation.A dynamic heterogeneous one-dimensional mathematical model that is composed of two sides is developed to predict the performance of this configuration.In this configuration,conventional methanol reactor is supported by an aluminasilica composite membrane layer for water vapor removal from reaction zone.To verify the accuracy of the considered model and assumptions,simulation results of the conventional methanol reactor is compared with the industrial plant data under the same process condition.The membrane reactor improves catalyst life time and enhances CO2 conversion to methanol by overcoming the limitation imposed by thermodynamic equilibrium.This configuration has enhanced the methanol production capacity about 4.06% compared with the industrial methanol reactor during the production time.     

Peroxotungstate immobilized on ionic liquid-modified silica as a heterogeneous epoxidation catalyst with hydrogen peroxide

Peroxotungstate immobilized on ionic liquid-modified SiO2 is capable of heterogeneously epoxidizing a wide range of olefins with the maintenance of the catalytic activity of homogeneous analogue. The epoxidation was immediately stopped by the removal of the catalyst, and no tungsten species could be found in the filtrate after the removal of the catalyst. These results can rule out any contribution to the observed catalysis from the tungsten species that leached into the reaction solution, and the observed catalysis is truly heterogeneous in nature. Furthermore, the catalyst was reusable without the loss of the catalytic performance.     

Comparison of the decomposition characteristics of aromatic VOCs using an electron beam hybrid system

We applied a hybrid technique to assess the decomposition characteristics of ethylbenzene and toluene that annexed the catalyst technique with existing electron beam (EB) technology. The removal efficiency of ethylbenzene in the EB–catalyst hybrid turned out to be 30% greater than that of EB-only treatment. We concluded that ethylbenzene was decomposed more easily than toluene by EB irradiation. We compared the independent effects of the EB–catalyst hybrid and catalyst-only methods, and observed that the efficiency of the EB–catalyst hybrid demonstrated approximately 6% improvement for decomposing toluene and 20% improvement for decomposing ethylbenzene. The G-values for ethylbenzene increased with initial concentration and reactor type: for example, the G-values by reactor type at 2800 ppmC were 7.5–10.9 (EB-only) and 12.9–25.7 (EB–catalyst hybrid). We also observed a significant decrease in by-products as well as in the removal efficiencies associated with the EB–catalyst hybrid technique.     

常温常压湿式催化氧化染料废水的Mo-Cu-Fe-O新型复合催化材料

染料广泛应用于纺织厂、皮革厂以及染发等各个领域.染料废水具有成分复杂、浓度高、色度大和生物难降解等特性,因此传统的处理方法难以将其完全降解.高级氧化技术已成为国内外广泛应用的染料废水处理技术之一,特别是湿式催化氧化(CWAO)技术.然而,CWAO工艺中反应往往需要高温(通常为200-280℃)和高压(通常为2-9 MPa),制约了其广泛应用.因此,人们致力于研发具有高催化活性的催化剂,通过改变反应历程和降低反应的活化能,使反应在常温常压条件下进行.本课题组曾采用钼酸盐浸渍于Zn/Al LDHs溶液中成功制备了Mo/Zn-Al LDHs催化剂,该催化剂能在常温常压下湿式催化氧化降解阳离子红GTL有机废水.Mo/Zn-Al LDHs催化剂中Mo作为主催化成分,Zn-Al LDHs作为载体.Cu-Fe LDHs本身作为一种催化剂,与Mo相结合能有效提高催化剂的活性及稳定性,因此本文采用浸渍法制备了Mo-Cu-Fe-O新型复合催化材料,采用X射线衍射、氢气程序升温还原、循环伏安法和氧气程序升温脱附等表征手段研究了Mo-Cu-Fe-O材料的结构及氧化还原特性.以阳离子红GTL、结晶紫和酸性红为染料废水代表,研究了常温常压下Mo-Cu-Fe-O催化降解染料废水的催化活性.结果表明,在中性条件下Mo-Cu-Fe-O对阳离子型染料废水具有良好的催化活性.循环使用七次后该样品对阳离子红GTL和酸性红的脱色率分别达到91.5%和92.8%,然而对酸性红阴离子型染料废水基本无催化活性.在常温常压CWAO过程中产生的羟基自由基能有效降解阳离子GTL废水,其废水毒性随着反应的进行逐渐减小.     

沸石和活性炭为载体的Fe3+和Cu2+型催化剂催化氧化苯酚的比较

以沸石和活性炭为载体，制备了Fe3 和Cu2 型沸石和活性炭催化荆，研究了非均相Fe和Cu催化剂催化氧化高浓度含酚废水．在Fenton反应机理的基础上，探讨了Cu2 的均相和非均相催化氧化机理，以人造沸石和活性炭为栽体制备了相应的4种非均相催化剂，进行了均相、非均相Fe和Cu催化剂催化氧化高浓度含酚废水的对比试验，分析了这两种载体的比表面积、孔径分布和中孔孔容，比较了4种非均相催化剂对苯酚降解率的影响．结果发现Cu2 不仅能大大提高反应速率，而且其均相、非均相反应体系的苯酚降解率均可达到约97％．     

MOF-Mediated Synthesis of Supported Fe-Doped Pd Nanoparticles under Mild Conditions for Magnetically Recoverable Catalysis**

Metal–organic framework (MOF)-driven synthesis is considered as a promising alternative for the development of new catalytic materials with well-designed active sites. This synthetic approach is used here to gradually transform a new bimetallic MOF, with Pd and Fe as the metal components, by the in situ generation of aniline under mild conditions. This methodology results in a compositionally homogeneous nanocomposite formed by Fe-doped Pd nanoparticles that, in turn, are supported on iron oxide-doped carbon. The nanocomposite has been fully characterized by several techniques such as IR and Raman spectroscopy, TEM, XPS, and XAS. The performance of this nanocomposite as an heterogeneous catalyst for hydrogenation of nitroarenes and nitrobenzene coupling with benzaldehyde has been evaluated, proving it to be an efficient and reusable catalyst.     

催化等离子体反应器中低浓度硝基苯的消除

Oxidative decomposition of dilute nitrobenzene in air was carried out in a catalytic plasma reactor with an inner electrode made of sintered metal fibres(SMF)that also acted as catalyst.The parameters of the concentration,specific input energy,and gas residence time were optimized.The modification of the SMF inner electrode with transition metal oxides like MnOx and CoOx oxides promoted complete oxidation,especially at low input energy.CoOx/SMF showed higher activity than MnOx/SMF and SMF,and could oxidise completely 100 ppm of nitrobenzene at 300 J/L.