Progress on Porous Ceramic Membrane Reactors for Heterogeneous Catalysis over Ultrafine and Nano-sized Catalysts

Heterogeneous catalysts with ultrafine or nano particle size have currently attracted considerable attentions in the chemical and petrochemical production processes, but their large-scale applications remain challenging because of difficulties associated with their efficient separation from the reaction slurry. A porous ceramic membrane reactor has emerged as a promising method to solve the problem concerning catalysts separation in situ from the reaction mixture and make the production process continuous in heterogeneous catalysis. This article presents a review of the present progress on porous ceramic membrane reactors for heterogeneous catalysis, which covers classification of configurations of porous ceramic membrane reactor, major considerations and some important industrial applications. A special emphasis is paid to major considerations in term of application-oriented ceramic membrane design, optimization of ceramic membrane reactor performance and membrane fouling mechanism. Finally, brief concluding remarks on porous ceramic membrane reactors are given and possible future research interests are also outlined.

Charge transfer in plasma assisted dry reforming of methane using a nanosecond pulsed packed-bed reactor discharge

This paper is aimed to investigate the effect of packing material on plasma characteristic from the viewpoint of charge transfer process.Both the charge accumulation and release processes in the dielectric barrier discharge reactor and packed-bed reactor were investigated by measuring voltage and current waveforms and taking ICCD images.The packing material was ZrO2 pellets and the reactors were driven by a parameterized nanosecond pulse source.The quantity of transferred charges in the dielectric barrier discharge reactor was enhanced when decreasing pulse rise time or increasing pulse width(within 150 ns),but reduced when the gas gap was packed with pellets.The quantity of accumulated charges in the primary discharge was larger than the quantity of released charges in the secondary discharges in the dielectric barrier discharge reactor,but they were almost equal in the packed-bed reactor.It indicates that the discharge behavior has been changed from the view of charge transfer process once the gas gap was packed with pellets,and the ICCD images confirmed it.

Design and Fabrication of Ceramic Catalytic Membrane Reactors for Green Chemical Engineering Applications

Catalytic membrane reactors(CMRs),which synergistically carry out separations and reactions,are expected to become a green and sustainable technology in chemical engineering.The use of ceramic membranes in CMRs is being widely considered because it permits reactions and separations to be carried out under harsh conditions in terms of both temperature and the chemical environment.This article presents the two most important types of CMRs:those based on dense mixed-conducting membranes for gas separation,and those based on porous ceramic membranes for heterogeneous catalytic processes.New developments in and innovative uses of both types of CMRs over the last decade are presented,along with an overview of our recent work in this field.Membrane reactor design,fabrication,and applications related to energy and environmental areas are highlighted.First,the configuration of membranes and membrane reactors are introduced for each of type of membrane reactor.Next,taking typical catalytic reactions as model systems,the design and optimization of CMRs are illustrated.Finally,challenges and difficulties in the process of industrializing the two types of CMRs are addressed,and a view of the future is outlined.

Integrated Photothermal Nanoreactors for Effi cient Hydrogenation of CO_(2)

To alleviate the energy crisis and global warming,photothermal catalysis is an attractive way to effi ciently convert CO_(2)and renewable H_(2) into value-added fuels and chemicals.However,the catalytic performance is usually restricted by the trade-off between the dispersity and light absorption property of metal catalysts.Here we demonstrate a simple SiO 2-protected metal-organic framework pyrolysis strategy to fabricate a new type of integrated photothermal nanoreactor with a comparatively high metal loading,dispersity,and stability.The core-satellite structured Co@SiO_(2)exhibits strong sunlight-absorptive abil-ity and excellent catalytic activity in CO_(2)hydrogenation,which is ascribed to the functional separation of diff erent sizes of Co nanoparticles.Large-sized plasmonic Co nanoparticles are mainly responsible for the light absorption and conversion to heat(nanoheaters),whereas small-sized Co nanoparticles with high intrinsic activities are responsible for the catalysis(nanoreactors).This study provides a new concept for designing effi cient photothermal catalytic materials.

Two-dimensional Simulation for Hydrogen/Air Combustion in a Monolith Reactor

Recent studies on hydrogen combustion were reviewed briefly. The laminar flow and combustion of premixed hydrogen/air mixture in a cylindrical channel of a monolith reactor with and without catalytic wall was numerically modeled by solving two-dimensional (2-D) Navier-Stokes (N-S) equations, energy equation, and species equations. Eight gas species and twenty reversible gas reactions were considered. The control volume technique and the SIMPLE algorithm were used to solve the partial differential equations. The streamlines of the flow field, temperature contours, the entrance length, and the concentration fields were computed. It is found that the entrance zone plays an important role on flow and temperature as well as species distribution. Therefore, the flow cannot be assumed either as fully developed or as plug flow. There is a small but strong thermal expansion zone between the wall and the entrance. Both diffusion and convection affect the heat and mass transfer processes in the expansion zone. Thus the equations of momentum, energy and species conservations should be used to describe hydrogen/air combustion in the monolith reactor. The hot-spot location and concentration field of the homogeneous combustion is strongly influenced by the inlet velocity and temperature, and the equivalence ratio. The catalytic combustion of premixed hydrogen/air mixture over platinum catalyst-coated wall in a cylindrical channel was also simulated.

Ozone generation enhanced by silica catalyst in packed-bed DBD reactor

In this paper,three dielectric barrier discharge(DBD)configurations,which were plain DBD with no packing,DBD with packed pure quartz fibers and DBD with packed loaded quartz fibers,were employed to investigate the effect and catalytic mechanism of catalyst materials in a packed-bed ozone generator.From the experimental results,it was clear that the DBD configuration with packed pure fibers and packed loaded fibers promotes ozone generation.For the packed-bed reactor,ozone concentration and ozone yield were enhanced by an increase of electric field in the discharge gap with the packed-bed effect.Meanwhile,the enhancement of ozone concentration and yield for the DBD reactor packed by loaded fibers with silica nanoparticles was due to the catalysis of silica nanoparticles on the fiber surface.The adsorption of silica nanoparticles on the fiber surface can prolong the retention time of active species and enhance surface reactions.

不同低温等离子体反应器降解VOCs的研究进展

挥发性有机物(VOCs)可对人体及自然环境造成严重危害,低温等离子体技术适用范围广且能在常温常压下分解VOCs.对不同类型的低温等离子体反应器进行分类,并关注其对降解效果的影响,结果表明:在配电参数和配气参数不变的情况下,线-筒式电晕放电反应器和电极的直径、线-板式电晕放电反应器的线线间距和线板间距对降解效率影响较大;圆筒式介质阻挡放电反应器在性能上优于平板式介电阻挡放电反应器;等离子体内催化反应器降解VOCs的能力优于等离子体后催化反应器,但在副产物控制方面不如等离子体后催化反应器;催化剂的选择在VOCs的降解中有重要影响.最后,对等离子体反应器的发展进行了展望.

微通道反应器中炔烃的选择性催化半加氢反应研究进展

炔烃选择性催化半加氢反应与石油化工和精细化工生产密切相关,传统上多采用间歇工艺进行,存在自动化程度不高、反应效率低下以及安全隐患等问题。微通道反应器技术的进步使得以连续工艺进行炔烃选择性催化半加氢反应成为可能,有望从根本上解决间歇工艺所存在的问题。鉴于此,总结微通道反应器的类型以及相同反应器类型下催化剂的类别,对近年来微通道反应器中炔烃选择性催化半加氢反应的研究进展进行综述。微通道反应器包括催化毛细管反应器、填充床反应器、蜂窝反应器、独体反应器等,在炔烃选择性催化半加氢反应中的应用促进了石化领域生产技术与工艺的进步。总之,设备的微型化、过程的集成化是顺应可持续发展与高技术发展的需要,微通道反应器技术作为化工过程强化的一种新技术,在化学、化工、能源、环境等领域将会得到广泛的应用。

Rational design of MXene-based vacancy-confined single-atom catalyst for efficient oxygen evolution reaction

Two-dimensional transition metal carbides(MXenes) have been demonstrated to be promising supports for single-atom catalysts(SACs) to enable efficient oxygen evolution reaction(OER).However,the rational design of MXene-based SACs depends on an experimental trial-and-error approach.A theoretical guidance principle is highly expected for the efficient evaluation of MXene-based SACs.Herein,highthroughput screening was performed through first-principles calculations and machine learning techniques.Ti_(3)C_(2)(OH)_(x),V_(3)C_(2)(OH)_(x),Zr_(3)C_(2)(OH)_(x),Nb_(3)C_(2)(OH)_(x),Hf_(3)C_(2)(OH)_(x),Ta_(3)C_(2)(OH)_(x),and W_(3)C_(2)(OH)_(x) were screened out based on their excellent stability.Zn,Pd,Ag,Cd,Au,and Hg were proposed to be promising single atoms anchored in MXenes based on cohesive energy analysis.Hf_(3)C_(2)(OH)_(x) with a Pd single atom delivers a theoretical overpotential of 81 mV.Both moderate electron-deficient state and high covalency of metal-carbon bonds were critical features for the high OER reactivity.This principle is expected to be a promising approach to the rational design of OER catalysts for metal-air batteries,fuel cells,and other OER-based energy storage devices.

Toward Next-Generation Heterogeneous Catalysts:Empowering Surface Reactivity Prediction with Machine Learning

Heterogeneous catalysis remains at the core of various bulk chemical manufacturing and energy conversion processes,and its revolution necessitates the hunt for new materials with ideal catalytic activities and economic feasibility.Computational high-throughput screening presents a viable solution to this challenge,as machine learning(ML)has demonstrated its great potential in accelerating such processes by providing satisfactory estimations of surface reactivity with relatively low-cost information.This review focuses on recent progress in applying ML in adsorption energy prediction,which predominantly quantifies the catalytic potential of a solid catalyst.ML models that leverage inputs from different categories and exhibit various levels of complexity are classified and discussed.At the end of the review,an outlook on the current challenges and future opportunities of ML-assisted catalyst screening is supplied.We believe that this review summarizes major achievements in accelerating catalyst discovery through ML and can inspire researchers to further devise novel strategies to accelerate materials design and,ultimately,reshape the chemical industry and energy landscape.

含油废水处理方法研究进展

概述了含油废水的特征,对比分析了气浮法、絮凝法、膜分离法、生物法等处理含油废水的方法及其相应的优势和不足。重点评述了几种处理含油废水的新方法(如电化学法等)及几种联合工艺的特性,对电催化技术用于处理含油废水的研究进展及应用前景作出预测。最后分析了电催化法等高级氧化技术处理含油废水的潜力,指出电催化法处理含油废水的工业应用尚需要解决的关键问题。

规整结构催化剂及反应器研究进展

介绍了一种新颖的规整结构催化剂。它在废气排放处理等气相催化反应中已表现出优于常规催化剂的优良催化性能 ,在气液固多相催化反应领域的研究也表明它能够应用于更多的催化反应。将这种催化剂和反应器结构特性与常规催化反应中应用的固体催化剂和反应器进行了比较 ,结果表明它有可能替代浆态床和固定床反应器 。

用于甲醇制烯烃的非均相催化反应器评述

甲醇制低碳烯烃(MTO、MTP)是煤化工的关键环节,近年来相关技术已经在我国成功工业化,包括中国科学院大连化学物理研究所的DMTO技术、中石化的s-MTO技术、UOP的MTO+OCP技术以及Lurgi的MTP技术。从非均相催化反应角度分析甲醇制烯烃的过程特点,剖析了各类典型的非均相催化反应器用于该过程的优劣,对比了国内外各主流技术的关键指标,评述了甲醇制烯烃和催化裂化的异同。分子筛催化的甲醇制烯烃过程遵循烃池机理,呈现自催化和积炭失活特性,控制催化剂的工作状态和限制返混对提高催化活性及烯烃产物选择性尤为重要。具有多级结构的分子筛催化剂及低返混流化床反应器或反应器串联组合是未来的发展方向。

催化氨氧化法制备2-氰基吡嗪的研究

开发了一种由VMoOP四元素组成的氨氧化催化剂(V-II型),用该催化剂在固定床反应器内由2-甲基吡嗪为原料进行气固相接触氨氧化反应制备了2-氰基吡嗪。V-II型催化剂组分中矾、磷的比例是影响催化剂反应活性及选择性的主要因素,矾磷比为1.9时,催化活性最好。探讨了氨氧化反应机理,认为2-甲基吡嗪经过氧化、脱水分别生成了吡嗪羧酸和吡嗪酰胺中间体后最终生成2-氰基吡嗪。正交实验确定了反应的影响因素和最佳条件,结果表明:反应温度是影响产品收率的最主要因素, 当2-甲基吡嗪、氨气、空气的投料量分别为0.05mLmin-1, 200mLmin-1, 1000mLmin-1, 反应温度430C时,2-氰基吡嗪选择性大于90%, 单程收率大于87%, 产品纯度大于99%。按小试工艺条件放大100倍中试,结果与小试吻合。

n-TiO_2光催化机理及其在环境保护中的应用研究进展

本文对半导体二氧化钛的光催化机理、载体形式、反应器等方面的研究进展作了详细概述。并就其在废水处理。

浆态床合成气制二甲醚的宏观动力学研究

在甲醇合成与甲醇脱水催化剂比例为 5、催化剂浓度为 1 0 g/30 0ml液体石蜡、温度 2 50～ 2 80℃、压力 3～5MPa、气体空速 40 0 0～ 70 0 0ml/( g·h)条件下 ,建立了浆态床合成气制二甲醚宏观动力学模型 ;甲醇合成反应和甲醇脱水反应的活化能分别为 1 4 1kJ/mol和 2 3 5kJ/mol,甲醇摩生成速率的计算值与实验值的相对误差在 1 3 6%和2 2 %以内 ;动力学方程为r2D +M=k1 pCO1 954pH20 91 74/[( 1 +KCOpCO1 50 1 +KCO2 pCO20 1 795) 2 2 60 ]、rD=k2 pM0 940 2 /[( 1+KMpM1 739+KH2 OpH2 O2 2 4 3) 0 441 5]。

催化型低温等离子体反应器净化废气研究进展

催化型低温等离子体反应器可有效地提高废气治理的能量效率和净化效果。现有数据表明,在一定能量密度下,催化型低温等离子体反应器比传统低温等离子体反应器能量效率有1.1～12倍的提高,这和污染物种类,反应器构型及催化剂参数有关。本文介绍了反应机理、反应器构型及催化剂参数选择等对反应器性能的影响,并指出今后研究的发展方向。

有毒有害气体低温等离子体催化处理反应器

等离子体催化技术是目前国内外公认的治理低浓度有害气体的有效方法之一。本文概述了填充床式反应器、点对板式反应器、平板式反应器和复合式反应器中利用低温等离子体结合催化剂处理有害废气的研究结果,并对反应器的结构、脱除效率及应用情况作了介绍。

实验室中的声化学研究

综述了超声的空化效应及实验室中常用的声化学反应器 ,重点讨论了声化学最新的应用研究进展 ,其中包括声化学在纳米材料制备、污水处理和催化反应等方面的应用 .

膜反应器在乙苯脱氢反应中的应用

用上海石油化工研究院研制的ＧＳ－０５工业催化剂与γ－Ａｌ２Ｏ３微孔陶瓷膜构成膜反应器（ＣＭＲ），研究乙苯脱氢生产苯乙烯膜反应规律。相同条件下与工业上固定床（ＰＦＲ）过程比较，膜反应器收率可提高５％，最佳可达１０％。并通过反应过程的数学模型的研究进行比较和参数优化，以寻求催化反应活性和膜渗透性的匹配。