含镍WP/MCM-41催化剂二苯并噻吩加氢脱硫性能

以MCM-41为载体,以镍（Ni）为助剂,制备了Ni含量不同的WP/MCM-41催化剂。采用XRD、BET、SEM和XPS对催化剂进行了表征;以二苯并噻吩（DBT）为模型化合物,通过高压微反装置考察催化剂的加氢脱硫（HDS）活性。结果表明,Ni的加入促进了活性组分WP的生长并使其晶相尺寸略有增加,一定含量的Ni有利于提高催化剂的比表面积。Ni对WP/MCM-41催化剂二苯并噻吩HDS反应具有促进作用。少量Ni的加入有利于WP活性相的生成并增加了活性位的数量;加入过量的Ni,在催化剂中形成了具有一定活性的类似Ni-W-P结构的物种,减少了活性组分WP所占的比例,从而使催化剂DBT的 HDS活性降低。其中,Ni的质量分数为1%的催化剂（cat-Ni-1）具有相对较高活性,其DBT 脱硫率和转化率分别为76.78%和72.16%,比不加Ni的催化剂分别提高了30.04%和21.62%。二苯并噻吩在WP/MCM-41催化剂上以加氢脱硫途径为主,Ni的加入对提高加氢脱硫途径选择性起到了促进作用,且加氢脱硫选择性随Ni含量的增加而提高。     

Ni2P/SBA-15催化剂的结构及加氢脱硫性能

以硝酸镍为镍源, 磷酸氢二铵为磷源, 介孔分子筛SBA-15为载体, 用共浸渍法制备了含磷化镍前驱体的样品, 然后在氢气流中采用程序升温还原法, 制备了Ni2P质量分数为5%-40%的Ni2P/SBA-15催化剂. 用X射线衍射(XRD)、N2吸附脱附、透射电子显微镜(TEM)、傅立叶变换红外光谱(FTIR)等分析测试技术对催化剂的结构进行了表征, 以噻吩和二苯并噻吩(DBT)为模型化合物, 在微型固定床反应器上对催化剂的加氢脱硫(HDS)性能进行了评价. 结果表明, Ni2P/SBA-15催化剂中SBA-15 的介孔结构依然存在, 活性组分Ni2P具有良好的分散性, 但随Ni2P含量的增加, 催化剂的比表面积、孔容和孔径均有明显减小. 当反应温度为320 ℃时, Ni2P含量为15%-25%(w)的催化剂就具有很好的加氢脱硫催化性能; 反应温度在360 ℃以上时, 所有催化剂都具有优异的深度脱硫催化性能. Ni2P/SBA-15催化剂对二苯并噻吩的加氢脱硫(HDS)主要以直接脱硫机理(DDS)进行.     

Ni2P/SBA-15催化剂的结构及加氢脱硫性能

以硝酸镍为镍源,磷酸氢二铵为磷源,介孔分子筛SBA-15为载体,用共浸渍法制备了含磷化镍前驱体的样品,然后在氢气流中采用程序升温还原法,制备了Ni2P质量分数为5%-40%的Ni2P/SBA-15催化剂.用X射线衍射(XRD)、N2吸附脱附、透射电子显微镜(TEM)、傅立叶变换红外光谱(FTIR)等分析测试技术对催化剂的结构进行了表征,以噻吩和二苯并噻吩(DBT)为模型化合物,在微型同定床反应器上对催化剂的加氧脱硫(HDS)性能进行了评价.结果表明,Ni2P/SBA-15催化剂中SBA-15的介孔结构依然存在,活性组分Ni2P具有良好的分散性,但随Ni2P含量的增加,催化剂的比表面积、孔容和孔径均有明显减小.当反应温度为320℃时,Ni2P含量为15%-25%(w)的催化剂就具有很好的加氢脱硫催化性能;反应温度在360℃以上时,所有催化剂都具有优异的深度脱硫催化性能.Ni2P/SBA-15催化剂对二苯并噻吩的加氢脱硫(HDS)主要以直接脱硫机理(DDS)进行.     

4，6—二甲基二苯并噻吩加氢脱硫反应机理的研究I．NiW体系催化剂的催化行为

分别以γ－Al2O3、无定形硅铝和含少量稀土分子筛的γ－Al2O3为载体，制备了不同系列的NiW体系加氢脱硫催化剂，并在连续流动微反装置上评价了催化剂对4，6－二甲基二苯并噻吩（DMDBT）加氢脱硫反应的催化性能。结果表明，NiW体系催化剂对该反应具有较高的芳烃加氢和脱硫活性；先加氢后脱硫是加氢脱硫（HDS）反应的主要途径，提高加氢活性是提高HDS活性最有效的途径；增强载体的酸性，直接脱硫和裂解活性均有所提高。同时，酸性载体负载的催化剂还显示出一定的异构化性能，但其加氢活性低于氧化铝负载的催化剂。酸性载体负载的NiW催化剂的异构化性能在邻二甲苯异构化反应中得到进一步证实。根据实验结果，讨论了NiW体系催化剂上DMDBT转化反应的不同途径。     

4,6-二甲基二苯并噻吩加氢脱硫反应机理的研究 Ⅰ.NiW体系催化剂的催化行为

 分别以γ－Al2O3、无定形硅铝和含少量稀土分子筛的γ－Al2O3为载体，制备了不同系列的NiW体系加氢脱硫催化剂，并在连续流动微反装置上评价了催化剂对4，6－二甲基二苯并噻吩（DMDBT）加氢脱硫反应的催化性能．结果表明，NiW体系催化剂对该反应具有较高的芳烃加氢和脱硫活性；先加氢后脱硫是加氢脱硫（HDS）反应的主要途径，提高加氢活性是提高HDS活性最有效的途径；增强载体的酸性，直接脱硫和裂解活性均有所提高．同时，酸性载体负载的催化剂还显示出一定的异构化性能，但其加氢活性低于氧化铝负载的催化剂．酸性载体负载的NiW催化剂的异构化性能在邻二甲苯异构化反应中得到进一步证实．根据实验结果，讨论了NiW体系催化剂上DMDBT转化反应的不同途径．     

植物固体纤维丝在NiMo柴油加氢脱硫催化剂中的应用

通过在氧化铝载体加入微米级植物固体纤维丝扩孔，制备出NiMo柴油加氢脱硫催化剂。采用BET、XRD、SEM、Raman与TEM对制备的载体及催化剂进行表征研究。结果表明，植物固体纤维丝能够在催化剂中构建出部分直筒大孔，NiMo活性组分在催化剂载体上实现了高度分散，活性相MoS₂堆叠层数集中在3-5层，平均MoS₂条长度为4.49 nm。研究了催化剂载体中植物固体纤维丝含量对催化剂活性的影响，并与常规氧化铝载体催化剂进行了对比，高压微反评价结果表明，开发的含有3%（质量分数）植物固体纤维丝NiMo柴油加氢脱硫催化剂比常规NiMo催化剂活性更高，其加氢脱硫活性提高了5%-15%。     

WP/γ-Al2O3催化剂负载方式对噻吩加氢脱硫性能的影响

以γ-Al2O3为载体，分别采用机械混合法、共浸渍法、分步浸渍法和程序升温、高纯氢气还原无定型磷钨酸盐的方法，制备了活性组分为磷化钨，负载量为20%的WP/γ-Al2O3催化剂。考察了不同方法制备的催化剂对噻吩加氢脱硫（HDS）反应的催化活性。结果表明：不同负载方式对催化剂结构有一定影响，对噻吩加氢脱硫性能的影响在低温时较明显。采用机械混合方式，先混合后还原方法制备的催化剂其HDS活性比先还原后混合方法制备的催化剂高；采用共浸渍和分步浸渍方式，通过焙烧所形成的催化剂其HDS活性分别比不经焙烧所形成的催化剂高或接近；浸渍焙烧所形成的催化剂其HDS活性远远高于机械混合法制备的催化剂。     

不同磷含量对NiMoP/Al2O3加氢处理催化剂的影响

采用NiMoP浸渍液浸渍载体γ Al₂O₃制备了不同磷含量的NiMoP/Al₂O₃加氢处理催化剂。为了研究磷对该系列催化剂活性相结构的影响,用二苯并噻吩（DBT）和喹啉为模型化合物,考察了催化剂的加氢脱硫（HDS）和加氢脱氮（HDN）性能。结果表明,添加适当的磷能够提高催化剂的HDS和HDN活性,但是高含量的磷能显著的降低催化剂的催化性能。通过对催化剂进行XRD和HRTEM表征发现,添加磷能够增加MoS2的堆积层数以及Ⅱ型“Ni-Mo-S”相的相对含量,这是因为在制备过程中添加磷降低了活性组分与载体之间的相互作用。     

CO吸附原位红外光谱结合分子模拟计算研究FCC汽油加氢脱硫催化剂的选择性

以脱硫选择性不同的2组催化裂化汽油加氢脱硫催化剂为研究对象, 采用CO吸附原位红外光谱表征了2组催化剂的活性相特征, 并通过分子模拟计算方法比较了助剂Co加入前后噻吩和1-己烯在催化剂表面的电荷分布、吸附能及其加氢反应的活化能等, 探讨了助剂Co的加入对选择性加氢脱硫催化剂脱硫选择性的作用机理. 结果表明, 加氢脱硫催化剂CoMoS活性相的增加有利于提高催化剂的加氢脱硫/加氢降烯烃(HDS/HYD)选择性. 与1-己烯加氢位相比, Co的加入显著提高了噻吩分子加氢位的缺电子性, 噻吩在催化剂表面的吸附度增强, 显著降低噻吩加氢反应的能垒, 从而使噻吩加氢反应更易进行. 这也表明CoMoS为高HDS活性、高HDS/HYD选择性的活性相.     

噻吩加氢脱硫和四氢萘催化加氢反应中的载体和助剂的影响

 为了更好地认识加氢脱硫和催化加氢反应中的载体影响和助剂效应，在同样的催化剂制备方法及反应条件下，研究了噻吩加氢脱硫（HDS）和四氢萘催化加氢（HYD）反应．结果表明，对于无助剂的Mo和W催化剂，载体对催化活性的影响顺序为TiO2－Al2O3＞ZrO2＞Al2O3．助剂的添加改变了催化剂活性顺序．Ni助剂催化剂的活性明显高于Co助剂催化剂．ZrO2担载的添加Ni的Mo和W催化剂分别获得了最佳的HDS和HYD活性．然而，添加Pt的Mo和W催化剂其HDS和HYD活性仅是Pt与Mo（W）二者的加和，Pt与Mo（W）之间没有协同效应．先将担载的Mo和W预硫化再将助剂引入体系的催化剂制备方法可以避免Ni和Co过早硫化形成类硫化镍（或硫化钴）物相，与采用螯合物分子方法制备的催化剂间有一定的相似性．     

Investigation and optimization of the recovery of coal fines using oil agglomeration process: Use of waste oils from different sectors

The high cost of the bridging liquid subdues the implementation and commercialization of oil agglomeration process. To overcome this problem, waste oils from different sectors were used in this present study. The performance of the process was assessed based on the responses like ash rejection and organic matter recovery. The aim of the present study was to investigate the usage of waste oils from different sectors and to optimize and analyze the behavioral pattern showcased by different variables (pulp density, oil dosage, agglomeration time and oil type) using response surface methodology (Box-Behnken design). Experimental investigation shows that the optimum pulp density, oil dosage, agglomeration time and oil type condition obtained as 3%, 15%, 15?min and waste engine oil, respectively. At optimum condition, the % ash rejection and % organic matter recovery obtained as 63.94% and 81.8%, respectively.     

绿色化学在基层检验室有机废液处理中的应用

针对一些基层质监部门检验室有机废液的处理现状及存在的问题,提出应鼓励实验室利用现有条件自行处理部分废液。介绍了几种绿色化学方法在有机废液特别是非食用物质标准物质废液处理中的应用。     

射频等离子体热解废轮胎的研究

Disposal of the huge piles of used tires is increasingly becoming a problem all over the world. Incineration may utilize the energy content of waste tires, but it is associated with the generation of SO2, NOx and other hazardous emissions. Pyrolysis is an alternative disposal method with the possibility for recovery of valuable products from used tires. Recently, waste processing technology based on plasma processes has received much attention due to a number of advantages such as high treatment rate, small space volume, etc. In this paper, the pyrolysis of waste tire using a capacitively coupled radio-frequency （RF） plasma reactor was investigated. The lab-scale RF plasma reactor was operated with RF powers between 1 600 W and 2 000 W, pressures between 3 000 Pa and 8 000 Pa （ absolute pressure） and temperatures between 1 200 K and 1 800 K. In the tire powder pyrolysis experiments, two product streams are obtained： combustible gas and char. The physical properties （surface area, porosity, particle morphology） as well as chemical properties （elemental composition, heating value and surface functional groups） of char were examined to exploit the potential applications of the char. The results indicate that the RF plasma pyrolysis would be a useful technology for waste disposal.     

Effect of the Introduction of Reactive Fillers and Metakaolin in Waste Clay-Based Materials for Geopolymerization Processes

In this study, the role of two reactive fillers, specifically a sand from a clay washing process as an alternative to waste glass powder and a commercial metakaolin (MK), into the geopolymerization process of waste clay-based materials was assessed. Three kinds of clayey wastes from mining operations—halloysitic, kaolinitic and smectitic clays—were tested as potential precursor of geopolymeric materials in view of a potential valorisation of these by-products. A mix-design based on the addition of low percentages (20%) of these fillers or MK to improve the mechanical and chemico-physical properties of geopolymeric formulations was evaluated. All the clays were thermally treated at a temperature of 650 °C, while the geopolymeric pastes were cured at room temperature. In particular, the chemical stability in water (pH and ionic conductivity of leachate water, weight loss), the variations in the microstructure (XRD, SEM), and in the mechanical performance (compressive strength) were analysed. The most reactive additive was MK, followed by sand and waste glass at very similar levels—1:1 or 2:1—depending upon the type of the clay but not strictly related to the clay type. The increase of geopolymeric gel densification due to the presence of MK and sand was replaced by a crack deflection mechanism in the case of the WG grains. The worst performance (chemical stability and mechanical properties) was found for the halloysitic clay, while kaolinitic and smectitic clays developed strengths slightly below 30 MPa.     

Waste biomass from production process co-firing with coal in a steam boiler to reduce fossil fuel consumption: A case study

Waste biomass is always generated during the production process in industries. The ordinary way to get rid of the waste biomass is to send them to landfill or burn it in the open field. The waste may potentially be used for co-firing with coal to save fossil fuel consumption and also reduce net carbon emissions. In this case study, the bio-waste from a Nicotiana Tabacum (NT) pre-treatment plant is used as the biomass to co-fire with coal. The samples of NT wastes were analysed. It was found that the wastes were of the relatively high energy content which were suitable for co-firing with coal. To investigate the potential and benefits for adding NT wastes to a Fluidised Bed Combustion (FBC) boiler in the plant, detailed modelling and simulation are carried out using the European Coal Liquefaction Process Simulation and Evaluation (ECLIPSE) process simulation package. The feedstock blending ratios of NT waste to coal studied in this work are varied from 0% to 30%. The results show that the addition of NT wastes may decrease the emissions of CO₂ and SO_x without reducing the boiler performance.     

辐射技术在环境保护中的应用

由于高能电子束和γ射线本身具有的特性,其辐射技术在环境保护领域具有巨大的应用潜力。本文介绍了国内外利用辐射技术在废水、废气和固体废物(“三废”)处理中的研究和应用,涉及印染废水、造纸废水、硝基苯胺类物质、卤系阻燃剂类物质、环境内分泌干扰物和藻毒素的处理,燃煤尾气脱硫脱硝,以及挥发性有机物、污泥等方面的处理研究,并对辐射处理各种有机污染物的机理进行了探索和分析。表明辐射技术是处理“三废”的一种十分有效的方法。同时,讨论了辐射技术在环境处理应用中的有限性,并对该技术的研究和发展方向进行了展望。     

Reducing Environmental Plastic Pollution by Designing Polymer Materials for Managed End-of-Life

Plastics are widely used synthetic materials in various industries worldwide. The abundance of plastics, which are mainly carbon-based polymers, has led to a significant accumulation of plastic waste in landfills and the environment due to their durability and affordability. Although plastic pollution of the oceans has been known for many years, there is still limited knowledge about the composition, distribution, impact, and fate of plastic waste in the environment. In this review, the focus is on environmental pollution by plastics, highlighting the source (feedstock) and degradation behavior of these materials. The goal is to provide insights for material design strategies that address the management of plastic waste at the end of its life cycle. The authors argue that the development of materials labeled marine biodegradable or universally biodegradable is not a sufficient solution on its own to address plastic pollution. Instead, it is critical to incorporate practical plans for recovery and treatment into material and product design principles. These plans should be based on existing systems or possibly developed in parallel. In summary, this article highlights the widespread pollution of the environment by plastics and emphasizes the need for comprehensive material design strategies that include not only biodegradability but also practical recovery and treatment methods. By considering the entire lifecycle of plastics, we can work to reduce the harmful impact of plastic waste on our planet.     

环境固体废物的监测技术及其应用

介绍了固体废物的特点和分类、我国固体废物监测技术的发展历程及现有固体废物的监测及管理标准体系,在此基础上列举了具有代表性的测定固体废物中污染物的前处理及监测技术应用实例。     

Suspension Fertilizers Based on Waste Phosphates from the Production of Polyols

Phosphorus raw materials are non-renewable, and their resources are shrinking faster and faster as a result of increased fertilizer production. This is due to the increasing population and the need to produce more food. Phosphorus, on the other hand, is one of the main nutrients of plants, without which it is impossible to conduct intensive agricultural production. There are no economically significant phosphate resources in Europe, so they must be imported. That is why it is so important to reduce losses and recover this element from waste streams, which was reflected in the new EU Regulation 2019/1009. A prospective option is to use waste phosphates from the production of polyether polyols. Previous studies show that they contain about 20% phosphorus. Due to their high water content, the most advantageous form of their application is the production of fertilizers in the form of a suspension. The aim of the study is to assess the possibility of using waste phosphates from the production of polyols as raw materials for the production of suspension fertilizers.