Mini-Review： Green sustainable processes using supercritical fluid carbon dioxide

Environmentally benign carbon dioxide offers significant potential in its supercritical fluid phase to replace current reliance on a range of hazardous,relatively expensive and environmentally damaging organic solvents that are used on an extensive global basis.The unique combination of the physical properties of supercritical fluids are being exploited and further researched to continue the development and establishment of high efficiency,compact plant to provide energy and water efficient manufacturing processes.This mini-review is focused on the use and potential applications of supercritical fluid carbon dioxide for a selected range of key and emerging industrial processes as a sustainable alternative to totally eliminate or greatly reduce the requirement of numerous conventional organic solvents.Examples of the industries include:chemical extraction and purification,synthetic chemical reactions including polymerization and inorganic catalytic processes.Biochemical reactions involving enzymes,particle size engineering,textile dyeing and advanced material manufacture provide further illustrations of vital industrial activities where supercritical fluid technology processes are being implemented or developed.Some aspects relating to the economics of sustainable supercritical fluid carbon dioxide processes are also considered.     

Dielectric barrier discharge plasma-assisted modification of g-C3N4/Ag2O/TiO2-NRs composite enhanced photoelectrocatalytic activity

Dielectric barrier discharge (DBD) plasma applied as surface treatment technology was employed for the modification of Ag₂O and graphitic carbon nitride (g-C₃N₄) powders. Subsequently, the pretreated powders were sequentially loaded onto TiO₂ nanorods (TiO₂-NRs) via electro-deposition, followed by calcination at N₂ atmosphere. The results indicated that at the optimal plasma discharge time of 5 min for modification of g-C₃N₄ and Ag₂O, photocurrent density of ternary composite was 6 times to bare TiO₂-NRs under UV-visible light irradiation. Phenol was degraded by using DBD plasma-modified g-C₃N₄/Ag₂O/TiO₂-NRs electrode to analyze the photoelectrocatalytic performance. The removal rate of phenol for g-C₃N₄-5/Ag₂O-5/TiO₂-NRs electrode was about 3.07 times to that for TiO₂-NRs electrode. During active species scavengers’ analysis, superoxide radicals and hydroxyl radicals were the main oxidation active species for pollutants degradation. A possible electron-hole separation and transfer mechanism of ternary composite with high photoelectrocatalytic performance was proposed.     

非均相催化臭氧氧化深度处理炼油废水

采用非均相催化剂催化臭氧氧化处理炼油废水,考察了催化剂负载率、pH、催化剂投加量和臭氧投加量及反应时间对处理效果的影响。结果表明,组合工艺最佳工艺条件为:催化剂负载率2.1%、pH 9、催化剂投量80 g/L、臭氧投量8.1 mg/L、反应时间60 min,COD、石油类、NH3-N、硫化物和SS去除率分别为91.3%、92.7%、80.5%、34.5%和59%。处理炼油废水过程中组合工艺存在明显协同效应,协同因子为1.47。中间臭氧氧化和催化臭氧氧化在最优工艺条件下对炼油废水COD的降解均符合准一级动力学规律。基于叔丁醇的实验结果,结合降解动力学可以推测,降解炼油废水过程中非均相催化剂催化臭氧产生高活性羟基自由基是降解效率提高的主导因素。     

生物膜催化氧化烟气脱硫工艺条件研究

分别研究了SO2入口质量浓度、喷淋液Fe^2 浓度、喷淋率、空塔气速以及喷淋液循环使用对脱硫效率的影响。实验结果表明,在最佳操作条件下(SO2入口质量浓度小于2g/m^3,喷淋液中Fe^2 浓度≥0．06mol／L,液气比约为11 L／m^3,空塔气速约为0．15m／s),脱硫效率可达96％以上。     

炭基催化法降解烟气中二噁英研究进展

综述了炭基催化法烟气处理工艺中二噁英的降解机理,以及催化剂特性、降解气氛、温度和时间等对二噁英降解影响的研究进展,指出由于缺乏足够多的二噁英降解机理研究数据,一方面可能使得工业应用中催化剂被过量使用,另一方面可能会导致催化剂在多污染物协同处理时引发处理效率或装置运行问题。最后从超低排放背景下该技术的推广和应用角度对今后的研究方向提出了建议。     

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.     

Review on research and application of mesoporous transitional metal oxides in water treatment

This paper reviews the application of meso- porous transitional metal oxides in water treatment on basis of the catalysis and adsorption. Mesoporous transitional metal oxides are characterized by their intrinsic features, such as a high surface area, a highly ordered array of unidimensional pores with a very narrow pore size distribution, and highly dispersed active sites. Finally, the suggestions of further study on application are proposed.     

Improved dark ambient degradation of organic pollutants by cerium strontium cobalt perovskite

This work investigates the effect of cerium substation into strontium cobalt perovskites(CeSrCoO) for the oxidative degradation of Orange Ⅱ(OII) in dark ambient conditions without the aid of any external stimulants such as light,heating or chemical additives.The OII degradation rate by CeSrCoO reached 65% in the first hour,whilst for the blank sample without cerium(SrCoO) took over 2 hr to reach the same level of OII degradation.Hence,the cerium substitution improved the catalytic activity of the perovskite material,mainly associated with the Ce_(0.1)Sr_(0.9)CoO_3 perovskite phase.Upon contacting CeSrCoO,the-N=Nazo bonds of the OII molecules broke down resulting in electron donation and the formation of by-products.The electrons are injected into the CeSrCoO and resulted in a redox pair of Co~(3+)/Co~(2+),establishing a bridge for the electron transfer between OII and the catalysts.Concomitantly,the electrons also formed reactive species(·OH) responsible for OII degradation as evidenced by radical trapping experiment.Reactive species were formed via the reaction between 02 and donated electrons from OII with the aid of cobalt redox pair.As the prepared materials dispensed with the need for light irradiation and additional oxidants,it opens a window of environmental applications for treating contaminated wastewaters.     

介质阻挡放电-催化降解苯的研究

采用双介质阻挡放电管 ,当含苯气体的流量为 1 5L·min- 1 ,放电电压在 60 0 0V—1 2 0 0 0V范围内 ,放电管温度在 2 1 0℃左右 ,研究介质阻挡放电 催化降解苯的协同效应 .结果表明 ,在余辉区中放入催化剂 ,60 0 0V的电压下 ,苯的降解率可达 70 % ,产物中CO/CO2为 0 0 5 ;而在同样电压下 ,不放入催化剂 ,苯的降解率仅为 5 5 %左右 ,CO/CO2 约为 0 5 .由此可见 ,催化剂在余辉区时能与等离子体协同作用 ,促进苯的降解     

CO2+MEA反应在CaCO3催化下Eley-Rideal模型及混合胺溶液体系协同效应的机理研究

研究混合胺溶液吸收二氧化碳(CO₂)的反应机理对低碳环保具有重要意义.本文以碳酸钙(CaCO₃)为催化剂,在Eley-Rideal模型下通过Gaussian09软件模拟计算乙醇胺(MEA)+CO₂反应机理,,同时计算混合胺溶液体系乙醇胺(MEA)+二乙醇胺(DEA)/2-氨基-2-甲基-1-丙醇(AMP)/N-甲基二乙醇胺(MDEA)吸收CO₂中经实验证明的协同效应.本文在CCSD(T)/6-311++G(d,p)水平上计算在两性离子机理下中间步骤的自由能和几何振动频率.模拟结果表明,在固体催化剂CaCO₃作用下,反应活化能降低了14.9%,但是自由能没有降低.混合胺盐能量(MEA-DEA-CO₂,MEA-AMP-CO₂)低于MEA-CO₂-MEA能量,差距分别为-18.25%和-14.5%,而MEA-MDEA-CO₂体系能量与单一溶液体系差距仅为-5.88%.这表明二级胺,空间位阻胺的协同效应大于三级胺.