湿式氧化用于染料废水脱色:过去20年回顾（英文）

Wet air oxidation(WAO), a liquid phase reaction between organic materials in water and oxygen, is one of the most economical and technologically viable advanced oxidation processes for wastewater treatment, particularly toxic and high organic content wastewater. WAO is the liquid phase oxidation of organics or oxidizable inorganic components at elevated temperatures(125–320 °C) and pressures(0.5–20 MPa) using gaseous oxygen(or air) as oxidant. In the past two decades, the WAO process was widely studied and applied in the treatment of dye wastewater. Compared to conventional WAO, catalytic WAO processes have higher efficiency and use moderate reaction conditions. The catalysts included homogenous and heterogeneous types. The key points that need to be solved are recycling of homogenous catalysts and better stability of heterogeneous catalysts. In the present review, the technological processes are first introduced, then some research history and hotspots of WAO research are presented, and finally, its application in the treatment of dye wastewater in the past two decades is summarized to reveal the impressive changes in modes, trends, and conditions used. The application includes model pollutant studies and wastewater tests.     

环己烷氧化反应:有机小分子的催化作用简

考察了酮、醛、酯、醇与胺等几类有机小分子在环己烷氧化反应中的催化作用. 结果表明,有机小分子催化剂的活性与其极性的强弱、与环己烷形成氢键的强弱、α氢的活性及清除自由基的能力有关. 因此,对于环己烷氧化反应,溶剂很可能存在催化作用. 三丙胺在环己烷氧化反应中表现出较高的催化活性,具有进一步开发应用的前景.     

Ni-Mo氮化物催化剂:合成及其丙烷氨氧化催化性能简

分别采用溶胶-凝胶法、旋转蒸发微波干燥法、共沉淀法、浸渍法和机械混合法制备Ni-Mo氧化物前驱体. 以H₂和N₂的混合气为氮化气体,采用程序升温氮化法合成了镍钼氮化物催化剂. 利用X射线衍射、总氮含量分析、X射线光电子能谱及H₂程序升温还原对Ni-Mo氧化物前体及氮化物催化剂进行了表征. 将上述Ni-Mo氮化物催化剂用于丙烷氨氧化反应中. 结果表明,Ni-Mo氧化物前驱体的制备方法影响其氮化物催化剂上丙烷氨氧化反应性能. Ni-Mo氮化物催化剂中氮物种的移动性及反应性对产物丙烯腈选择性的影响较大,共沉淀法制备的催化剂存在大量的活性氮物种,因而具有良好的催化丙烷氨氧化反应活性.     

长度可控杆状SBA-15的合成简

以三嵌段共聚物P123为结构导向剂,天然高聚物壳聚糖为添加剂,合成出分散性较好的杆状结构SBA-15. 通过调节体系中壳聚糖的含量,可以实现对产物形貌的控制,即从颗粒到短杆状,最后到长杆状. 壳聚糖的加入不仅使SBA-15的介孔结构更加长程有序,同时也提高了其比表面积和孔容,其最高值分别达到1157 m2/g和1.53 cm3/g.     

聚乙烯基胺包裹Fe3O4@SiO2磁性微球用于Knoevenagel缩合（英文）简

Polyvinyl amine coated Fe₃O₄@SiO₂ composite microspheres with a core-shell structure were prepared and employed as a magnetic catalyst for Knoevenagel condensation under mild conditions. The catalyst can be readily recovered using a magnet and reused several times without loss in activity or selectivity. The performance of the magnetic base catalyst was compared with that of polyvinyl amine functionalized mesoporous SBA-15, which showed that the magnetic nanoparticles gave improved reaction rate and yield.     

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.     

TiO2-CeO2催化剂湿式氧化苯酚的活性研究

采用共沉淀法制备了湿式氧化降解苯酚的TiO2-CeO2催化剂，测定了反应过程中不同反应时间的COD去除率，结果表明，当Ti、Ce摩尔比为3：1时，在150℃、总压5MPa（其中氧分压4．5MPa）时，所制备的催化剂活性最高，反应90分钟COD去除率可以达到71％．对催化剂进行了比表面积、XRD和XPS测试，结果表明，高效的催化剂具有较多的活性位、催化剂粉末体系Ce的变价特性以及大量的表面吸附氧．     

TiO_2-CeO_2催化剂湿式氧化苯酚的活性研究

采用共沉淀法制备了湿式氧化降解苯酚的TiO2-CeO2催化剂,测定了反应过程中不同反应时间的COD去除率,结果表明,当Ti、Ce摩尔比为3∶1时,在150℃、总压5MPa(其中氧分压4.5MPa)时,所制备的催化剂活性最高,反应90分钟COD去除率可以达到71%.对催化剂进行了比表面积、XRD和XPS测试,结果表明,高效的催化剂具有较多的活性位、催化剂粉末体系Ce的变价特性以及大量的表面吸附氧.     

Removal of organic dye pollutants from wastewater by electrochemical oxidation

The removal of chemical oxygen demand (COD) and color from simulated dye wastewater containing organic dyes, direct yellow 4, C₂₆H₂₀N₄O₈S₂Na₂ and acid yellow 17, C₁₆H₁₀O₇N₄S₂Cl₂Na₂ experimentally investigated using an electrochemical undivided cell reactor with Pt as anode and steel as cathode. Particular attention was paid to probe the effect of supporting electrolyte (NH₄Cl), cell voltage, pH, and treatment time on the electrochemical treatment efficiency. Experiments were also carried out using 0.2?M NH₄Cl as supporting electrolyte under the condition of free pH. The experimental results showed that the process could efficiently remove the color and COD from simulated dye waste water. The overall COD removal reached at 69.9% by using supporting electrolyte and increasing voltage. The process can be described by pseudo first-order kinetics for the removal of COD.     

Irradiation treatment of azo dye containing wastewater: An overview

The radiation-induced decolouration and degradation of aqueous solutions of azo dyes and their model compounds (anilines, phenols, triazines) are reviewed together with practical applications and the experimental methods (pulse radiolysis, steady-state gamma radiolysis, as well as end-product analysis) used for studying the reactions. The proposed mechanisms and the rate coefficients for the reactions of OH, e_aq⁻ and H water radiolysis intermediates with the dye molecules and with model compounds are summarized.     

Intercalation modification of Fe OCl and its application in dye wastewater treatment

The textile industry spreads globally with the challenges of its wastewater treatment,especially dyes,which are difficult to degrade.To improve coagulation-flocculation process in dye wastewater treatment,an intercalation process was employed to prepare a new efficient coagulant of lithium borohydride-iron oxychloride(LiBH_4_FeOCl) in this study.The layered crystal pristine iron oxychloride(FeOCl) material was prepared by chemical gas phase migration.LiBH4 was introduced into the layers of two dimensional(2 D) FeOCl nanosheets by a simple method of liquid phase insertion.The samples were characterized by a field emitting scanning electron microscopy(SEM),a rotating anode X-ray powder diffractometer(XRD),etc.The cationic dye was employed as the simulated pollutant.A coagulation and decolorization experimental device was built to study the coagulation performance of the new coagulant LiBH_4_FeOCl.It is found that the intercalation modified LiBH_4_FeOCl exhibits the characteristics of crystal structure,and the layered structure of FeOCl is preserved.LiBH_4_FeOCl,as an insoluble inorganic solid coagulant,performs well for dye pollutants of methyl red,basic yellow 1,methylene blue,rhodamine B,ethyl violet and Janus green B.The reaction rate is significantly 68% higher than the current commercial coagulants of Al_2(SO_4)_3.The mechanism analysis reveals that LiBH_4_FeOCl breaks and disperses rapidly in the water environment.Its negatively charged material particles can be electrostatically adsorbed with dye pollutant molecules through electrostatic action.The above collaborative actions of breaking,dispersion and electrostatic adsorption are the main coagulation mechanisms of LiBH_4_FeOCl.The solid inorganic coagulant of LiBH_4_FeOCl provides a competitive alternative for traditional inorganic salts and organic coagulants.     

湿式氧化催化剂RuO2/γ-Al2O3降解高浓度含酚配水的研究

采用浸渍法制备了RuO2／γ-Al2O3催化剂，利用XRD和SEM对催化剂进行了表征，研究了焙烧温度、反应温度、反应溶液pH值和氧分压对RuO2／γ-Al2O3催化剂活性影响．结果表明，RuO2／γ-Al2O3催化剂组分Ru在表面有较好的分散性；焙烧温度升高使RuO2晶粒长大，在低温焙烧，RuO2晶粒细小，RuO2／γ-Al2O3催化剂的活性较高；反应温度升高，使RuO2／γ-Al2O3催化剂的活性显著提高；反应溶液pH值为酸性时比在碱性条件的催化剂活性高；氧分压达到3MPa后，对于RuO2／γ-Al2O3催化剂的活性几乎没有影响．在150℃、3MPa、pH值为5．6时，反应150min后，苯酚全部被氧化．研究表明，RuO2／γ-Al2O3催化剂具有较好的催化活性．     

湿式催化氧化处理含高浓度甲醛的草甘膦废水

草甘膦结晶母液经蒸发或纳滤浓缩回收后,产生大量含有高浓度甲醛的废水,常规的废水处理方法难以达到回用或排放要求.以过量溶液浸渍法制备的Pt-Bi-CeO2/AC为催化剂,采用湿式催化氧化法处理2.5%的HCHO溶液,HCHO去除率高达99.9%以上,COD去除率达到96.6%.采用Pt-Bi-CeO2/AC催化剂对含低浓度草甘膦(PMG,50 mg/L)的生产废水直接进行湿式催化氧化处理,催化剂使用23次后,HCHO去除率稳定在85%左右,COD去除率稳定在87%左右,催化剂具有良好的稳定性.湿式催化氧化处理后的废水可直接回用于PMG生产.采用固定床湿式催化氧化装置处理HCHO溶液以及PMG生产废水,处理效果也非常理想,连续使用720 h,催化剂的稳定性能良好.通过XRD、N2吸附-脱附、HRTEM、ICP-OES和XPS等分析手段对催化剂进行了系统表征.