Tributyl phosphate additive enhancing catalytic absorption of NO2 for simultaneous removal of SO2/NOx in wet desulfurization system

Removal of SO₂ and NO emissions from coal-fired power plants have always been the focus in coal's utilization industries for which traditional wet desulfurization system hold the potential to achieve simultaneous removal of SO₂/NO_x. In this work, a novel liquid catalyst (tributyl phosphate, TBP) was investigated for the simultaneous removal of SO₂ and NO_x in a NO pre-oxidation (ozone oxidation) assisted process. The absorption process and reaction mechanism of SO₂ and NO₂ were studied in a small-scale experimental system, and the removal efficiency of pollutant and the key parameters were examined in a pilot-scale system. The results show that the removal efficiency of NO₂ in traditional wet desulfurization system is only 20–40%; however greatly increases to >90% when TBP is added. Moreover, TBP can enhance the NO₂ removal performance in the presence of SO₂ due to the formation of TBP–NO₂–SO₃²⁻ complex. Considering the oily nature of TBP that can be easily separated, such addition strategy hold great potential for industrial SO₂/NO_x simultaneously removal.     

电催化氮气还原合成氨催化材料研究进展

氨是纺织、制药、化肥等领域重要的化工原料，也是一种清洁的能源载体，需求量大。目前氨的工业生产主要为Haber-Bosch法，反应条件严苛，能源消耗大且碳排放较高。电催化氮气还原(NRR)合成氨是一种在常温常压下进行的反应，工作电位低，且电能可通过清洁能源提供，是一种很有潜力的合成氨新工艺。但目前电催化NRR材料的产氨速率和法拉第效率低、工作稳定性不够高、溶液中痕量氨的定量检测困难及检测标准不统一等都为其发展带来了巨大挑战。本文首先介绍了电催化NRR的反应机理和常用研究方法，然后重点梳理了2019年以来NRR催化材料的最新研究进展，最后对该领域研究面临的挑战和机遇进行了展望。     

Evaluation of Transport Phenomena for Removing Vanadium from Petrochemical Industry Solid Waste

Transport phenomena are investigated which are involved in the electrokinetic remediation process used for removing vanadium from deactivated catalysts from oil catalytic cracking that are currently allotted to cement plants and class-I landfills. Variables such as the concentration of electrolyte, electric potential, and applied electric current were evaluated in order to determine the effects produced by electroosmosis, diffusion, hydraulic gradient, and electromigration on the removal of vanadium from the catalyst. It was observed that migration is the most relevant phenomenon in the remediation tests, and for the best remediation condition, the migratory flow accounted for about 87 % of the vanadium removal.     

异丙醇铝控制水解制备高纯拟薄水铝石和多孔氧化铝

主要进行异丙醇铝水解制备高纯拟薄水铝石和高纯多孔γ-Al_2O_3的研究。合成路线以异丙醇铝为原料,改变反应过程中水化液组成、水化温度和水化时间,制备一系列拟薄水铝石及其焙烧产物多孔γ-Al_2O_3。结果表明,水化液中异丙醇的存在会抑制无定型氢氧化铝的晶化,但也有助于形成大孔径、高比表面和大孔容的氧化铝;纯水体系下,60℃以下水化会出现三水铝石,60℃以上水化的产物则为拟薄水铝石;γ-Al_2O_3孔结构与前驱体拟薄水铝石的结晶度有关,晶粒越大的拟薄水铝石,焙烧所得氧化铝的孔径和孔容也增大。因此,水化条件的改变可以实现拟薄水铝石结构的控制,进而获得不同结构的多孔氧化铝。为由异丙醇铝水解制备高纯拟薄水铝石和多孔氧化铝的工业化提供相应的研究基础。     

催化裂化管式待生剂分配器颗粒分配特性及内部流动特性的CPFD模拟

基于CPFD(Computational particle fluid dynamics)方法，对实验室前期研究的催化裂化管式分配器内的颗粒分配特性及内部流动特性进行了数值模拟，系统研究了输送风、松动风及分配器倾斜角度对颗粒分配不均匀指数的影响，并进一步考察了输送风和松动风对分配器各出口气体流量分布及内部气 固流动特性的影响。结果表明，增大输送风量、松动风量以及分配器的倾斜角度均可以降低颗粒分配不均匀指数，但改变松动风量的效果不如改变输送风量和倾斜角度显著。分配器倾斜角存在一个最优值时，颗粒分配均匀性最佳。输送风的增大会使得颗粒出料量最高的排料口的位置逐渐向分配器的末端移动，中间排料口所流出的气体流量占比增大，末端排料口排风量占比减小。引入松动风后，各出口的颗粒排料量更加接近，同时靠近末端排料口的气体流量占比明显增大。     

甲烷干重整及金属-载体相互作用

CO2和CH4均是温室气体的重要成员并且数量可观，其资源化利用对于应对气候变化和能源危机具有重要意义。甲烷干重整是经典转化方式之一，将CO2 “供氧”还原反应和CH4 “需氧”氧化反应结合起来并相互转化，其产物合成气(H2和CO)可用于费 托合成碳氢化合物液态燃料。近年来，干重整已经成为能源环境领域热点之一，在重整新工艺和催化剂设计策略方面取得了重要进展，推动了高活性和高稳定性催化剂和新工艺研发。详细综述了甲烷干重整工艺和催化剂的研究成果，重点介绍了干重整工艺新发展和催化剂功能设计，结合Ni载体相互作用、双金属协同效应、界面效应、单原子催化等新策略对干重整工艺中的基础科学问题进行了探讨，并对干重整技术现有难点和未来发展方向进行了展望。     

高温固定流化床费托合成技术及其产物加工路线

与采用低温费托合成主产油品技术相比，产品更为多元化和高值化的高温费托合成技术在目前市场环境下显示出非常明显的优势。本文综述了高温费托合成技术的发展历程及其最新进展，重点介绍了高温费托合成过程中的核心问题，主要包括高温费托合成工艺、固定流化床反应器、费托合成催化剂；介绍了高温费托合成产物分布与特性，讨论了高温费托合成产物的加工路线，并对高温费托合成煤间接液化的工业应用前景和产业化方向进行了展望。结果表明：高温费托合成技术具有产物附加值高、兼顾油品和化学品、技术发展成熟等优势，产物中轻组分含量高、碳数分布较窄、高附加值的α-烯烃含量高；精细化、高端化、差异化加工是实现高温费托合成产物高值化利用的关键。     

水热晶化法制备RhCeZrLaNdOx催化剂及其性能研究

采用水热晶化法一步制备了RhCeZrLaNdOx系列催化剂，测定其比表面积、储氧量和还原温度等性能参数，并进行结构和形貌表征，研究了制备过程中水热晶化温度和时间、表面活性剂等条件对催化剂性能、结构和形貌的影响。结果表明，以月桂酸作为表面活性剂，在160℃水热晶化4 h制备的催化剂具有较大的比表面积、较高的储氧量和较低的还原温度，微观结构为四方相的固溶体纳米颗粒。与传统浸渍法制备的Rh/CeZrLaNdOx催化剂比较，水热晶化法制备的催化剂对CO还原NO具有更好的低温催化活性。     

Deactivation of hydrodesulfurization catalysts during reactor startup

Metal sulfide catalysts for ultra-deep hydrodesulfurization of diesel generally lose a fraction of their catalytically active sites during reactor startup. The underlying mechanisms are discussed. A laboratory diagnostic tool consisting of three probe molecules is developed for testing metal sulfide catalysts' start-of-run (SOR) activity maintenance. It is found that a significant fraction of the active sites on a commercial supported catalyst are deactivated permanently, but this is not the case with a bulk metal sulfide catalyst. The SOR deactivation of the bulk catalyst is completely reversible, while that of the supported catalyst is partially reversible. The diagnostic tool may provide a basis for developing a high-throughput approach for evaluating and enhancing catalyst SOR stability, thereby increasing plant productivity.     

Effect of Fe/Zn ratio in composite catalyst for synthesizing polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers (PODE_n) are extremely effective diesel additives to reduce soot formation during combustion. We introduce a series of Fe-Zn composite solid acid catalysts (SO₄²⁻/xFe₂O₃-yZnO), for the condensation reaction of methanol and paraformaldehyde (PF) with a cheap and feasible route to efficiently synthesize PODE_n. These catalysts were characterized by different characterization techniques, namely BET, XRD, SEM, EDS, FTIR, and NH₃-TPD and the results showed that Fe/Zn molar ratios strongly influenced the physicochemical characteristics of catalysts, thus affecting the methanol conversion and PODE_1-6 and PODE_3-6 selectivity. Accordingly, the methanol conversion was decreased and the selectivity of PODE_3-6 was increased after increasing the Zn molar content. Comparatively, SO₄²⁻/Fe₂O₃-2ZnO exhibited superior catalytic activity among the various investigated catalysts due to the high acid density of strong acid sites. The optimal reaction conditions were observed to be at a 3.0 wt% catalyst loading (catalyst/reactant mass ratio), 2.5 hours ours of reaction time, a reaction temperature of 403 K, and a molar ratio of 3:1 of CH₂O to methanol, achieving a high selectivity of 99.09% PODE_1-6 and 28.23% PODE_3-6 with 55.16% methanol conversion during the reaction.