湿式氧化用于染料废水脱色:过去20年回顾（英文）简

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℃) 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.     

Effect of Additives on the Selectivity and Reactivity of Enzymes

Enzymes have been widely used as efficient, eco‐friendly, and biodegradable catalysts in organic chemistry due to their mild reaction conditions and high selectivity and efficiency. In recent years, the catalytic promiscuity of many enzymes in unnatural reactions has been revealed and studied by chemists and biochemists, which has expanded the application potential of enzymes. To enhance the selectivity and activity of enzymes in their natural or promiscuous reactions, many methods have been recommended, such as protein engineering, process engineering, and media engineering. Among them, the additive approach is very attractive because of its simplicity to use and high efficiency. In this paper, we will review the recent developments about the applications of additives to improve the catalytic performances of enzymes in their natural and promiscuous reactions. These additives include water, organic bases, water mimics, cosolvents, crown ethers, salts, surfactants, and some particular molecular additives.     

Critical review of perovskites-based advanced oxidation processes for wastewater treatment: Operational parameters,reaction mechanisms,and prospects

In the field of advanced oxidation processes(AOPs) of wastewater, many materials can be used as heterogeneous catalysts. The role of these catalysts is to activate oxidants and generate reactive oxygen species(ROS) to decompose refractory pollutants. Perovskite oxide, an emerging catalyst in the field of AOPs, has been extensively studied in wastewater treatment. Nevertheless, the application of perovskite in AOP systems still faces some problems, such as leaching of metal ions, a small surface ...     

Electrochemical Treatment of Heavy Metal‐containing Wastewater with the Removal of COD and Heavy Metal Ions

The use of electricity to treat water was employed for the first time in the UK a century ago, and since then has been considered a highly reliable method for wastewater treatment. In recent years, the demand for hydrogen gas as a valuable, clean energy source has increased considerably; from this point of view, the electrolysis of wastewater can meet the demand for energy during the process of treating wastewater. In this work, wastewater containing heavy metal ions has been treated by an electrochemical method which not only decreased the chemical oxygen demand value and lowered the number of heavy metals ions but also generated hydrogen throughout the process. A series of experiments were performed under optimum conditions of selected electrode materials, pH values, supply power, and working time. The results obtained indicate that by controlling the key factors of the process, a practical method can be achieved for wastewater treatment which also produces a noticeable amount of green energy. Differential pulse voltammetry measurements were used to determine the properties of an industrial wastewater source before and after treatment, while scanning electron microscopy and energy dispersive X‐ray spectroscopy were applied to investigate the proficiency of the electrode material.     

Preparation for Magnetic Nanoparticles Fe3O4 and Fe3O4@SiO2 and Heterogeneous Fenton Catalytic Degradation of Methylene Blue

Dyestuff textile wastewater treatment has become a research hotspot due to its high chroma, poor biodegradability, and low toxicity characteristics. In this paper, we have synthesized magnetic Fe₃O₄ and core‐shell Fe₃O₄@SiO₂ materials by hydrothermal methods. These materials were characterized by XRD, TEM, N₂ adsorption‐desorption and so on. These materials’ heterogeneous Fenton has been applied to dye wastewater treatment. Methylene blue was used as a typical target of dye wastewater. Decolorization ratios of methylene blue were determined by different nanostructure composites catalysts. A serious of results of study showed that decolorization ratios of magnetic nanoparticles and core‐shell composites arrived at above 90 % under the weakly acidic or neutral conditions and room temperature. When these catalysts were reused, the results show that Fe₃O₄@SiO₂ materials were possessed with good cycle performance.     

非晶非贵金属催化剂的研究进展及展望

近年来电解水产氢作为一种具有前景的制备及储存可再生能源的方法受到了各界的广泛关注.在此过程中,电解水催化剂是提高能源转换效率的关键.优秀的催化剂应具备高催化活性、高稳定性、低成本以及可大规模生产等性质.科研工作者对电解水的两部分反应,即析氢反应以及析氧反应均进行了广泛及深入的研究.目前,贵金属催化剂,如铂基、钌基催化剂的催化活性要高于其他元素催化剂,但由于其价格昂贵,储量较少使得贵金属催化剂无法得到大规模应用,因此发展非贵金属催化剂对绿色能源的发展具有重要意义.一般而言,催化剂的结晶度越高,其催化活性越好,而近年来非晶催化剂以其更高的催化活性位密度也越来越受到人们的重视.同时,非晶催化剂的成分更加灵活,相比晶体催化剂来说非晶催化剂可以在更大范围内对成分进行调节.此外,非晶催化剂的制备通常都在较为温和的反应条件下进行,这也能够降低生成成本,促进其工业化发展.在这篇综述里我们介绍了电解水反应的基本原理,总结了近期非晶析氢、析氧以及双功能催化剂的研究进展.并随后探讨了电解水反应目前的难点并对非晶催化剂的制备进行了展望.     

微生物电化学污水处理技术的优势与挑战

微生物电化学技术（Microbial Electrochemical Technology, MET）最为一种新型水处理工艺,因其具有污染物同步去除和能源化的特点受到广泛重视. 近年来微生物电化学系统（Microbial Electrochemical System, MES）的研究者在其电子传递机理、功能菌群分析、系统功能拓展、低成本材料开发和大型系统构建等方面取得大量进展. 然而该技术作为污水处理工艺的可行性却始终存在争议. 本文从应用角度将MET工艺与现有厌氧、好氧工艺进行对比,分析各工艺在有机物降解和能量回收方面的特点,有助于找到MET工艺在水处理领域中的适宜定位. 相对厌氧与好氧工艺,MET工艺具有低污泥产率,运行过程能量自给以及电流加速污染物去除等优势特征,但在推进MET工艺的实用化进程中仍需进一步简化其系统结构、降低构筑成本、提高运行稳定性,并应基于MET的运行特征确定其适宜的应用范围以发挥MET工艺的技术优势.     

Preparation of superhydrophobic materials for oil/water separation and oil absorption using PMHS–TEOS-derived xerogel and polystyrene

Fabrication of suerhydrophobic materials towards oil/water separation and oil absorption has been receiving great attention nowadays, due to the significant increase of industrial oily wastewater and frequent accident of oil spill. In most previous studies, the usage of expensive precursors restricted the wide applications of prepared superhydrophobic materials. In this work, superhydrophobic filter paper, fabric and polyester sponges were fabricated by dip-coating the mixed solution of polystyrene and xerogels, which were prepared with tetraethoxysilane and polymethylhydrosiloxane, based on previous work. The as-fabricated fabric can effectively separate oil and water mixtures and possesses excellent reusability; more significantly, the materials maintained its good hydrophobic and excellent oil/water separation capacity even after ten cycles. Interestingly enough, the stability was provided, as a result, the fabric still exhibited superhydrophobic after 100 abrasion times and showed high repellency towards many liquids with different pH values. Additionally, the coated polyester sponges can quickly absorb various oil and organic liquid, which will offer a practical application for the treatment of seawater or oily wastewater. By contrast, this experiment process is simple and avoided using costly fluoro-chemicals or complicated fabrication process.     

碳酸氢盐活化的过氧化氢：一种有机废水处理的新技术

水污染问题已成为影响我国可持续发展的关键问题之一,为有效提高现有污水处理的效率及其回收利用,各种催化氧化技术受到了广泛的关注。目前发展的各类高级氧化技术在实际的应用过程中明显受到了氧化剂的利用率、催化剂的浸出、寿命及成本等问题的严重限制。因此基于新的理念、发展新的催化氧化技术仍然受到广泛的关注。
　　最近几年,利用碳酸氢盐活化过氧化氢,应用于有机废水的降解逐渐受到环境催化领域的关注。碳酸氢盐本身是一种低毒性、广泛存在于环境及生物体系的化学物质,通过它活化过氧化氢产生过碳酸氢盐氧化剂,该氧化剂能够直接氧化有机物。同时,在各种过渡金属催化剂的存在下,通过该过碳酸氢盐可以形成氧化能力更强的各种自由基(如羟基自由基等) 及高价态的过渡金属离子参与有机废水的降解。虽然传统认为碳酸盐及碳酸氢盐对高级氧化法降解有机废水不利,原因是认为它们能捕捉羟基自由基,形成氧化能力更低的碳酸根自由基。现有的研究已充分表明,较低浓度的碳酸氢盐能够加快有机废水的氧化降解,而且通常比单独使用过氧化氢效率更高,这些新的发现已明显突破了传统意义上对碳酸氢盐作用的理解。更为重要的是,在微量碳酸氢盐的存在下,其产生的微碱性环境极大地消除了负载型氧化物催化剂在废水降解过程中的金属离子流失、从而极大地延长了催化剂的寿命。该缺点是各种基于过渡金属氧化物催化剂的高级氧化技术难以广泛推广的关键性挑战,原因是随着氧化降解的进行,废水体系由于有机酸的生成而逐渐酸化,进而引发氧化物催化剂的酸溶而流失。在这点上,碳酸氢盐活化过氧化氢系统由于其天然的微碱性环境体现出了其明显的优势。
　　本文即是在本课题组工作基础上,对该领域内国内外研究进展加以总结,以期获得国内外同行的进一步关注。综述的主要内容包括：(1)碳酸氢氧活化过氧化氢的相关知识介绍,(2)均相碳酸氢氧活化过氧化氢降解有机废水的研究进展,(3)基于金属氧化物催化剂的碳酸氢氧活化过氧化氢降解有机废水的研究进展,和(4)碳酸氢盐在其他高级氧化技术中的应用。虽然基于碳酸氢氧活化过氧化氢降解有机废水的研究还处于早期探索阶段,还有很多基础科学问题如降解机理等值得进一步探索,期望通过该综述的介绍能够让同行对碳酸氢氧活化过氧化氢降解有机废水有一个比较全面的了解,进而推动该研究方向的发展,为有机废水的催化处理提供新的机会。     

Titania Nanomaterials Produced from Ti-Salt Flocculated Sludge in Water Treatment

Titania is the most widely used metal oxide for the applications of pigments, paper, solar cells and environmental purification. In order to meet the demand of a large amount of titania, our group has developed a novel process which could significantly lower the cost of waste disposal in water treatment, protect the environment and public health and yield economically valuable titania. Titanium tetrachloride (TiCl₄) or titanium sulfate (Ti(SO₄)₂) as an alternative coagulant in water treatment has been explored for the removal of various pollutants from contaminated water or wastewater. Flocculation efficiencies of the Ti-salts were superior to those of Al- and Fe- salts with additional benefits in that a large amount of titania can be produced by calcinating the flocculated floc. The produced titania showed high photocatalytic activity for the removal of volatile organic compounds. The large amount of titania can be applied to pigments, environment and construction materials which require a lot of titania usages. This review paper presents an historical progress from fundamental to application in terms of the detailed production process, characterization, photoactivity of titania produced from Ti-salt flocculated sludge, and its various applications.     

水滑石及其衍生物处理水中污染物的研究进展

水滑石(LDH)由于具有记忆效应、内部结构可调性、层间阴离子可交换性等优良性质,而在水处理领域具有广阔应用前景。综述了水滑石及其衍生物处理水中污染物的最新研究进展。介绍了LDH处理重金属废水和有机废水,利用催化氧化性能或通过与不同材料复合处理废水。此外,还简述了LDH的规模化生产现状及存在问题,对LDH材料在水处理领域的未来发展方向进行了展望。     

Optimization of environmental friendly process for removal of cadmium from wastewater

Simple, efficient and eco-friendly electrochemical method for removal and recovery of Cd(II) from wastewater has been studied. Experiments were carried out in a batch electrochemical reactor with iron electrodes. The removal was examined at different pH values and electrical potentials. It was observed that the experiments carried out at 20 V and at pH 9 were sufficient for the maximum removal of Cd(II). This method is highly efficient in removal of Cd(II) from wastewater containing up to 1000 mg L^?1. The removal is faster in comparison with the adsorption on activated carbon, which is one of the most important requirements for practical application of this treatment method. In this process, the use of different electrical potentials can provide a wide range of pH values for performing this process. The removal data were used to determine the adsorption kinetics by using the first-order adsorption kinetics model. The data can be analyzed in terms of various adsorption models. The results of Cd(II) removal from real samples indicate that the method used in this study can provide an efficient and cost-effective technology for the treatment of Cd(II)-containing wastewater. The parameters can be used for designing a plant for an economical treatment of Cd(II)-rich water and wastewater.     

Modular Functionalization of Metal-Organic Frameworks for Nitrogen Recovery from Fresh Urine**

Nitrogen recovery from wastewater represents a sustainable route to recycle reactive nitrogen (Nr). It can reduce the demand of producing Nr from the energy-extensive Haber-Bosch process and lower the risk of causing eutrophication simultaneously. In this aspect, source-separated fresh urine is an ideal source for nitrogen recovery given its ubiquity and high nitrogen contents. However, current techniques for nitrogen recovery from fresh urine require high energy input and are of low efficiencies because the recovery target, urea, is a challenge to separate. In this work, we developed a novel fresh urine nitrogen recovery treatment process based on modular functionalized metal–organic frameworks (MOFs). Specifically, we employed three distinct modification methods to MOF-808 and developed robust functional materials for urea hydrolysis, ammonium adsorption, and ammonia monitoring. By integrating these functional materials into our newly developed nitrogen recovery treatment process, we achieved an average of 75 % total nitrogen reduction and 45 % nitrogen recovery with a 30-minute treatment of synthetic fresh urine. The nitrogen recovery process developed in this work can serve as a sustainable and efficient nutrient management that is suitable for decentralized wastewater treatment. This work also provides a new perspective of implementing versatile advanced materials for water and wastewater treatment.     

The Utilization of Algae and Seaweed Biomass for Bioremediation of Heavy Metal-Contaminated Wastewater

The presence of heavy metals in water bodies is linked to the increasing number of industries and populations. This has serious consequences for the quality of human health and the environment. In accordance with this issue, water and wastewater treatment technologies including ion exchange, chemical extraction, and hydrolysis should be conducted as a first water purification stage. However, the sequestration of these toxic substances tends to be expensive, especially for large scale treatment methods that require tedious control and have limited efficiency. Therefore, adsorption methods using adsorbents derived from biomass represent a promising alternative due to their great efficiency and abundance. Algal and seaweed biomass has appeared as a sustainable solution for environmentally friendly adsorbent production. This review further discusses recent developments in the use of algal and seaweed biomass as potential sorbent for heavy metal bioremediation. In addition, relevant aspects like metal toxicity, adsorption mechanism, and parameters affecting the completion of adsorption process are also highlighted. Overall, the critical conclusion drawn is that algae and seaweed biomass can be used to sustainably eliminate heavy metals from wastewater.     

Recent advances on hydrogels based on chitosan and alginate for the adsorption of dyes and metal ions from water

In contemporary times, water resources have become increasingly scarce and suffer from anthropogenic pollution sources with an organic and inorganic origin that are products of industrial, agricultural, and everyday waste. Contamination with heavy metals and dyes in wastewater is considered a risk for water sources that can leak into underground and surface sources, leading to increased biological and chemical contamination. The pollutant removal process is performed by adsorption treatment methods, which is the most common method, and it is considered an effective method with a high and economical removal rate.In this review, we discuss the use of biobased hydrogel adsorbents in the removal of organic dyes and metal ions from water. The literature indicates that hydrogels exhibit rapid absorption kinetics and a dye removal absorption capacity that can reach more than 100 mg/g and sometimes more than 2000 mg/g, with a metal adsorption capacity ranging from 38 mg/g to more than 440 mg/g. These results are discussed and compared by taking into account hydrogel materials that contain biopolymers such as alginate, chitosan or both. In general, absorption depends mainly on biobased materials, which have a natural origin and can be utilized to synthesize hydrogels to remove pollutants, dyes and heavy metals. Chitosan and alginate are prominent materials for this use and they can be incorporated with other components to obtain hydrogels or nanocomposite materials with different efficacies to remove dyes and metal ions.     

Study on the Catalyst for Catalytic Air Wet Oxidation on Highly Organic Wastewater

The industrial effluents are as varied as the industries themselves, in terms of nature of contaminants, their concentration treatment, and disposal methods required. For the highly organic wastewater, the technique of wet air oxidation (WAO) is more available. Currently more than 200 full scale WAO plants are in operation for the treatment of a wide variety of effluent streams. In the recent years, the use of homogeneous and heterogeneous catalysts has received a great attention. The homogeneous catalysts are in general more effective oxidation catalysts for increasing the rates of oxidation. But it is necessary to make precipitation step to recover/remove the toxic catalyst from the final effluent In view of this, heterogeneous catalyst systems are preferable. So we investigated on the way of preparation of copper oxide on a spinel support of Al₂O₃) and its effects on the catalytic wet air oxidation (CWAO) on highly organic wastewater.     

化纤单体生产的绿色化进程回顾与量化

纵观以往化纤单体生产的革新化措施和绿色化进程,大致可分成3个层面:(1)优化工艺,减少跑冒滴漏;(2)改变反应方式或引入新催化剂;(3)彻底改变原料路线.前两个层面的革新多数能达到节能、降耗、降低生产成本的效果,已取得了较多工业化成果.丁二烯或生物质等原料路线试图从第3个层面解决问题,绿色化虽彻底,但或因引入新的有害物质,或因副产物多,目的产物收率太低,物耗和能耗尚难与传统的芳烃原料路线媲美,工业化道路更艰难.为了推进化纤单体生产的绿色化进程,尽早发现新的切入点,找准绿色化方向,本文综述了前人的绿色化成果,试图从原料路线、制备工艺和"三废"处理3个方面追寻"领跑者"的足迹.针对已有工艺的物耗、能耗和生产成本分析比较以及取舍绿色化革新措施时,常因比较边界(范围)不一致,得出偏颇的观点,误导读者,建议先导入原子经济性(质量效率)评价和全生命周期清单分析等过渡指标,再建立更完善的评价体系,逐步达到严格的全生命周期评价、多维评价的水平.     

Chitosan-based membranes preparation and applications: Challenges and opportunities

Chitosan is an abundant natural biopolymer which finds a variety of applications due to its functionalization extending to pharmacology, controlled drug delivery, healing materials, biomedical engineering, food industry, agriculture, catalysis, biosorbents, wastewater treatment, etc. Chitosan can be transformed to distinct derivatives and composites and be modified and grafted for specific use. Many products like flakes, fine powders, beads, membranes, sponges, fibers, and gels can be formed from chitosan. Degradable membranes made of chitosan in conjunction with other materials have increased their scope and include adsorptive membranes for heavy metal and dyes, biomedical applications of chitosan electrospun nanofibers, metal complexation, polymer and modified chitosan-based nanocomposites, cellulose and chitosan composites in wastewater treatment, fuel cells and catalysis. The review has focused on a number of issues related to the said areas. Application of these composite membranes with real industrial effluents should be done with reference to the commercial adsorbents and then their application for removal of aromatics, oils, surfactants, etc. will become practical. The review covers existing gaps and gives future scope for research and innovation.     

An overview of heterogeneous photocatalysis for the degradation of organic compounds: A special emphasis on photocorrosion and reusability

Heterogeneous photocatalysis has been extensively investigated for the degradation of organic pollutants from wastewater. The remarkable advantages of the heterogeneous photocatalysis process depend upon its ability to produce reactive oxygen species under visible/UV/solar light irradiation. However, the long-term stability and reuse potential of these catalysts are of great concern these days, yet understudied. This review aims to systematically present a state of the art understanding of such catalysts' reuse potential. Various important surface characteristics of the photocatalysts for improving the photostability and activity of the catalyst are discussed. Besides, the synergistic effect of different surface modified materials, composite materials and their surface characteristics for their enhanced activity are also covered. Finally, a discussion on various regeneration processes used for such catalysts is also presented, identifying some vital research needs in this field.