改性碳纳米管负载Pd基催化剂对二氯乙酸的催化加氢脱氯

以壳聚糖(chitosan,CS)为单体,采用表面沉积交联法对多壁碳纳米管(CNT)改性得到壳聚糖修饰的碳纳米管(CS-CNT).分别以CS-CNT和CNT为载体,用硼氢化钠还原法制备Pd/CNT和Pd/CS-CNT负载型催化剂.采用元素分析仪、电感耦合等离子体发射光谱仪(ICP)、透射电镜(TEM)、比表面积与孔径分布测定仪(BET)、X射线光电子能谱(XPS)等对材料进行表征,并对二氯乙酸的液相催化加氢脱氯反应进行了研究.结果表明,与Pd/CNT相比,Pd/CS-CNT对二氯乙酸有更高的催化活性.此外,该催化加氢脱氯反应受溶液pH及催化剂表面Pd颗粒的影响.二氯乙酸的催化加氢脱氯反应符合Langmuir-Hinshelwood模型,表明该反应过程由二氯乙酸在催化剂表面的吸附所控制.     

水介质中催化剂Raney Ni催化2-氯酚加氢脱氯

选择水作为反应介质,以氢气为氢源,研究了Raney Ni催化下、水溶液中2-氯酚的加氢脱氯,调查了溶剂、碱助剂和碱金属或碱土金属氯化物对加氢脱氯反应的影响.发现在水体系中,2-氯酚更容易被加氢脱氯,水作为反应介质时显著改善了加氢脱氯的反应环境,消除了无机氯化物在催化剂表面的吸附和累积,使催化剂保持了高活性.     

Al2O3负载Pd催化剂对溴氯代乙酸的催化加氢脱卤研究

分别以氧化铝、氧化硅和多壁碳纳米管为载体,采用沉淀-沉积法制备负载型Pd催化剂.采用透射电镜(TEM)、X射线衍射(XRD)、电感耦合等离子体发射光谱(ICP-AES)、X射线光电子能谱(XPS)等手段对材料进行表征,并对溴氯代乙酸(BCAA)的液相催化加氢脱卤反应进行了研究.结果表明,由于Pd/Al_2O_3催化剂具有较高的等电点,因此相对于Pd/CNT、Pd/SiO_2在BCAA的加氢脱卤反应中具有更高的活性.以Pd/Al_2O_3为目标催化剂,对BCAA的加氢脱卤展开研究,发现催化活性随Pd的负载量的增加而提高.当反应物的初始浓度为0. 1 mmol·L~(-1),pH值为5.6,Pd(1.39)/Al_2O_3用量为25 mg·L~(-1)时,BCAA在20 min时可以实现完全脱溴并在反应2 h后脱氯达60.5%.另外,pH的升高不利于脱卤反应的进行.当反应物的浓度从0. 05 mmol·L~(-1)提高到0.4 mmol·L~(-1)时,反应初活性从1.55 mmol·L~(-1) min~(-1) gCat~(-1)提高到8.37 mmol·L~(-1) min~(-1) gCat~(-1).进一步通过拟合Langumir-Hinshelwood模型,相关系数达到0.97,说明BCAA的加氢脱卤是吸附控制机制.催化过程中溴氯代乙酸的脱溴和脱氯具有协同作用,反应最终生成乙酸.     

Fe0体系降解2,4-二氯酚的影响因素及其反应机理

采用铁屑、炉渣及河砂混合介质降解2,4-二氯酚(2,4 - DCP)模拟废水,研究铁屑粒径、铁屑投加量、铁屑与炉渣配比、pH值等因素对2,4- DCP脱氯效果的影响,探讨Feo体系降解2,4- DCP的反应机理.结果表明,铁屑粒径、铁屑投加量、铁屑与炉渣配比、pH对2,4- DCP脱氯效果均有显著影响,在铁屑粒径为2～5mm、不改变废水pH、铁屑与炉渣质量比为31:9条件下,Feo体系对2,4- DCP去除率高达97％.2,4- DCP经脱氯后主要产物为2-氯酚、4-氯酚和苯酚,反应后废水的可生化性明显提高,利于后续的生物处理.     

Al_2O_3负载Pd-Cu催化剂催化1,2-二氯乙烷加氢脱氯性能

采用共浸渍法制备了一系列Al2O3负载金属Pd、Cu催化剂.通过元素分析（ICP）、氮气吸脱附（BET）、X射线粉末衍射（XRD）、透射电镜（TEM）等技术对催化剂进行了表征,并以1,2-二氯乙烷气相加氢脱氯为探针反应,考察了Pd-Cu/Al2O3催化剂的钯铜比、反应温度、反应时间等因素对催化活性以及反应产物乙烯选择性的影响.结果发现,提高Cu负载量可在催化剂中形成Pd-Cu合金,并促进催化剂对乙烯的选择性.此外,当温度为250℃,Pd、Cu负载量分别为0.78%和1.9%时的Pd-Cu/Al2O3催化剂对1,2-二氯乙烷的催化加氢脱氯效果最佳,最终产物乙烯的选择性可达到80%以上.     

Fe~0体系降解2,4二氯酚的影响因素及其反应机理

采用铁屑、炉渣及河砂混合介质降解2,4-二氯酚（2,4-DCP）模拟废水,研究铁屑粒径、铁屑投加量、铁屑与炉渣配比、pH值等因素对2,4-DCP脱氯效果的影响,探讨Fe0体系降解2,4-DCP的反应机理。结果表明,铁屑粒径、铁屑投加量、铁屑与炉渣配比、pH对2,4-DCP脱氯效果均有显著影响,在铁屑粒径为2～5 mm、不改变废水pH、铁屑与炉渣质量比为31∶9条件下,Fe0体系对2,4-DCP去除率高达97%。2,4-DCP经脱氯后主要产物为2-氯酚、4-氯酚和苯酚,反应后废水的可生化性明显提高,利于后续的生物处理。     

醇胺类物质促进飞灰中氯代芳烃加氢脱氯的研究

分别以三乙醇胺(TEA)和一乙醇胺(MEA)作为氢源,六氯苯(HCB)作为模型化合物,研究了在密闭体系下飞灰中氯代芳烃的加氢脱氯作用.考察了TEA或MEA添加量、热处理温度和时间对脱氯效率的影响,证实有明显的脱氯反应发生.当MEA或TEA添加量为8%时,经过250℃,2 h热处理,脱氯效率分别可达94.7%和78.6%...     

Pd/TiO_2催化剂对三氯生的催化加氢脱氯研究

采用沉淀-沉积法制备不同载体的Pd负载型催化剂,采用透射电镜(TEM)、X-射线衍射(XRD)和电感耦合等离子体发射光谱(ICP-AES)对材料进行表征;并以所得材料为催化剂对三氯生(TCS)的催化加氢脱氯反应进行了研究.结果表明,Pd/TiO_2型催化剂在TCS加氢脱氯反应中具有较好的效果,反应活性随着Pd负载量的提高而增强.当反应物初始浓度为0.016 mmol·L~(-1),pH值为10,催化剂0.36%Pd/TiO_2用量为20mg时,TCS在70 min可以完成脱氯过程.碱性条件下,p H的升高不利于反应的进行.当催化剂用量在15—25 mg时,催化剂质量标化的反应初活性没有明显变化,表明催化反应过程不受传质阻力的影响.当反应物初始浓度在0.009—0.02 mmol·L~(-1)时,反应初活性随浓度的提高显著增加,但进一步增加反应物的浓度时初活性没有明显提高,因此,TCS在Pd/TiO_2催化剂上的脱氯行为符合Langmuir-Hinshelwood模型,表明TCS的加氢脱氯受表面吸附所控制.催化反应的过程中生成多种脱氯中间产物,反应的最终产物为2-羟基二苯醚.     

共价三嗪有机框架材料对水中氯酚类污染物的光催化脱氯降解

利用共价三嗪有机框架材料(CTF-1)对4-氯酚(4-CP)、2,4-二氯酚(2,4-DCP)、2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)等4种不同氯原子取代数目的氯酚类污染物进行光催化降解研究,探讨了底物结构对氯酚脱氯降解效率的影响及机制.结果表明,氯酚脱氯降解过程明显受苯环氯原子取代数目的影响,氯原子数目越多,脱氯降解效率越高,氯原子数目与表观速率常数呈显著正相关,氯酚降解及脱氯速率均为：PCP>2,4,6-TCP>2,4-DCP>4-CP.对CTF-1光催化降解氯酚机制研究表明,活性物种在反应中不起作用,体系反应机制为针对氯酚上取代氯位点进行水解脱氯过程.本研究结果为深入揭示氯酚脱氯降解机制提供了理论依据,也为光催化技术处理卤代酚类废水提供了技术参考.     

杞柳对水中2,4-二氯苯酚的降解

通过在人工配制的含有2,4-二氯苯酚(2,4-DCP, 2,4-Dichlorophenol)的营养液中培养杞柳(Salix integra),研究了杞柳在不同处理条件下对水溶液中2,4-DCP的去除效率,并探讨了其对2,4-DCP降解的动力学过程.结果表明,在抑菌和不抑菌处理条件下,杞柳对水溶液中的2,4-DCP有促进降解的作用,在96h内杞柳对20 mg·L-1的2,4-DCP去除效率分别为:76.9%、81.1%,并且对2,4-DCP的去除都符合一级动力学方程;而没有杞柳生长的水体中2,4-DCP的降解率为0%.2,4-DCP的植物吸收降解、微生物降解对2,4-DCP去除的贡献率约为:92.57%、7.43%.在模拟光照下,杞柳在48 h内能去除水中约52.37%的2,4-DCP.同时,根系组织中多酚氧化酶和过氧化物酶活性受到了2,4-DCP明显的抑制.试验所采用的质量浓度对杞柳没有产生毒害作用,表明杞柳是修复水中2,4-DCP较好的材料.     

碳纳米管负载的镍及其氧化物对高毒气体PH3的催化分解性能

采用沉积-沉淀法制备了均一负载于碳纳米管(CNTs)载体的金属Ni和NiO,将其应用于PH3催化分解反应.通过XRD、TEM、XPS、BET等一系列检测手段,对样品的相结构、形貌、组分和比表面积进行了表征.研究结果表明,反应过程中,Ni和NiO很快被磷化为高活性的金属磷化物NiP2,作为反应的活性相.在420℃温度下,两样品对PH3的催化分解率均可达到99.5%以上.将反应中原位生成的NiP2进行催化反应,较钝化-还原的处理方式更有利于样品催化性能的保持.     

Fe-Mn/AC催化湿式过氧化氢氧化间甲酚

采用等体积浸渍法制备了一种新型Fe-Mn/AC催化剂,应用于催化湿式过氧化氢氧化(CWPO)间甲酚废水.通过SEM和XRF表征了其表面形态结构和元素组成,通过穆斯堡尔谱分析了催化剂中铁离子的存在形态,结果表明,新型Fe-Mn/AC催化剂中的铁以二价铁、三价铁以及四氧化三铁的形式存在.通过正交实验考察了CWPO降解间甲酚的影响因素,结果表明,各因素对间甲酚转化率影响的大小顺序依次为:底物初始p H值反应温度反应时间催化剂投加量.通过正交实验得到CWPO降解间甲酚的最佳反应条件.当间甲酚浓度为100 mg·L-1、反应温度为40℃、反应时间为40 min、催化剂投加量为0.6 g·L-1及底物初始p H值为3时,间甲酚转化率为99.8%,TOC去除率为28.3%.气相色谱/质谱联用没有检测到中间产物,气相色谱检测到CWPO降解间甲酚中间产物主要为乙酸和丙酸.     

Biofilm-electrode process with high efficiency for degradation of 2,4-dichlorophenol

2,4-Dichlorophenol (2,4-DCP) from chemical industry wastewaters has caused serious environmental pollution. Removal of 2,4-DCP using either physico-chemical or biological methods is not very efficient. In this paper, a combination of biological and electrochemical methods gave satisfactory results. By comparisons of the degradation of 2,4-DCP and the removal of chemical oxygen demand (COD) in electrochemical, biological and biofilm-electrode processes, it was found that the biofilm-electrode process possesses the highest degradation efficiency and removal rate; both the pure electrochemical and the pure biological processes were far less efficient. The removal efficiency of 2,4-DCP using the biofilm-electrode process was 100% in 48 h, while that using the pure electrochemical and the pure biological processes were 62 and 42%, respectively. The experiments show that the current of 5 mA for the cathode of 9 cm² and the initial concentration 100 mg/l of 2,4-DCP were the optimal parameters of technology for the biofilm-electrode process. The excellent effects are due to the withdrawing electron action of bacterium, electrochemically anodic oxidation and cathodic dechlorination. It is the first time that the biofilm-electrode method was applied in 2,4-DCP degradation. Here, we demonstrated that biofilm-electrode process is a promising method to remove some aromatic compounds in industrial wastewater.     

Catalytic ozonation performance and surface property of supported Fe3O4 catalysts dispersions

Fe₃O₄ was supported on mesoporous Al₂O₃ or SiO₂ (50 wt.%) using an incipient wetness impregnation method, and Fe₃O₄/Al₂O₃ exhibited higher catalytic efficiency for the degradation of 2,4-dichlorophenoxyacetic acid and para-chlorobenzoic acid aqueous solution with ozone. The effect and morphology of supported Fe₃O₄ on catalytic ozonation performance were investigated based on the characterization results of X-ray diffraction, X-ray photoelectron spectroscopy, BET analysis and Fourier transform infrared spectroscopy. The results indicated that the physical and chemical properties of the catalyst supports especially their Lewis acid sites had a significant influence on the catalytic activity. In comparison with SiO₂, more Lewis acid sites existed on the surface of Al₂O₃, resulting in higher catalytic ozonation activity. During the reaction process, no significant Fe ions release was observed. Moreover, Fe₃O₄/Al₂O₃ exhibited stable structure and activity after successive cyclic experiments. The results indicated that the catalyst is a promising ozonation catalyst with magnetic separation in drinking water treatment.     

Catalytic wet air oxidation of phenol,nitrobenzene and aniline over the multi-walled carbon nanotubes (MWCNTs) as catalysts

Wet air oxidation (WAO) is one of effective technologies to eliminate hazardous, toxic and highly concentrated organic compounds in the wastewater. In the paper, multi-walled carbon nanotubes (MWCNTs), functionalized by O₃, were used as catalysts in the absence of any metals to investigate the catalytic activity in the catalytic wet air oxidation (CWAO) of phenol, nitrobenzene (NB) and aniline at the mild operating conditions (reaction temperature of 155°C and total pressure of 2.5 MPa) in a batch reactor. The MWCNTs were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), gas adsorption measurements (BET), fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The functionalized MWCNTs showed good catalytic performance. In the CWAO of phenol over the functionalized MWCNTs, total phenol removal was obtained after 90 min run, and the reaction apparent activation energy was ca. 40 kJ·mol^-1. The NB was not removed in the CWAO of single NB, while ca. 97% NB removal was obtained and 40% NB removal was attributed to the catalytic activity after 180 min run in the presence of phenol. Ca. 49% aniline conversion was achieved after 120 min run in the CWAO of aniline.     

Catalytic decomposition of low level ozone with gold nanoparticles supported on activated carbon

Highly dispersed gold nanoparticles were supported on coal-based activated carbon (AC) by a sol immobilization method and were used to investigate their catalytic activity for low-level ozone decomposition at ambient temperature. Nitrogen adsorption-desorption, scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts before and after ozone decomposition. The results showed that the supported gold nanoparticles prepared with microwave heating were much smaller and more uniformly dispersed on the activated carbon than those prepared with traditional conduction heating, exhibiting higher catalytic activity for ozone decomposition. The pH values of gold precursor solution significantly influenced the catalytic activity of supported gold for ozone decomposition, and the best pH value was 8. In the case of space velocity of 120000h⁻¹, inlet ozone concentration of 50mg/m³, and relative humidity of 45%, the Au/AC catalyst maintained the ozone removal ratio at 90.7% after 2500min. After being used for ozone decomposition, the surface carbon of the catalyst was partly oxidized and the oxygen content increased accordingly, while its specific surface area and pore volume only decreased a little. Ozone was mainly catalytically decomposed by the gold nanoparticles supported on the activated carbon.     

Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO<Subscript>2</Subscript> microsphere catalysts at room temperature

MnO₂ microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO₂ catalysts were synthesized using the sol-gel method. We obtained three MnO₂ microspheres and Au/MnO₂ samples: coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO₂ are the main factor affecting the catalytic activities of these samples, and γ-MnO₂ shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO₂. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO₂. We also studied intermediate species. The dioxymethylene (DOM) and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO₂. A proposed mechanism of formaldehyde oxidation over Au/MnO₂ catalysts was also obtained.