生物油及其衍生物催化重整制氢研究进展

氢气作为最理想的清洁能源之一，在石油、化工、冶金、石化、食品和化肥工业等行业中发挥着重要作用。生物油水蒸气催化重整制氢作为一种具有发展前景且经济可行的绿色制氢技术，近些年来受到了研究者的广泛关注。本工作对近年来该领域的研究进展进行综述，重点分析了生物油(生物原油、水相生物油以及重质生物油/焦油)、生物油模型化合物(羧酸类、醇类、酚类等)和其他生物油衍生物的催化重整产氢过程，包括其在重整反应机理、重整工艺以及催化剂等方面的研究进展。对多种混合模化物以及真实生物油催化重整反应机理的深入探究是目前研究的主要难点，研制节能、高效的催化重整反应器以及开发稳定、高活性的重整催化剂是目前乃至今后生物油催化重整制氢领域研究和推广的重点。     

CO2与CH4催化反应合成气研究

CO_2与液化天然气(98%为C_3-C_4烃)催化重整制合成气,八十年代初期在当时的西德已建立了工业生装置.近年来,由于石油资源日趋短缺,促进世界各国重视探讨和研究天然气资源利用的新途径.除甲烷氧化偶联制乙烯,甲烷氧化制甲醇和甲醛等直接转化过程已引起广泛的重视外,研究和开发由甲烷制取合成气的新过程也正日益受到人们的关注,其中利用CO_2与甲烷催化重整制合成气,可将造成温室效应,破坏人类生存环境的CO_2气体转化为宝贵的化工原料,所制得的合成气中CO/H_2=1,特别适合做羰基合成和合成有机含氧化合物的原料,近年来对该反应的研究已引起人们的重视.其反应表示如下:     

镍基催化剂催化木醋液重整制氢实验研究

为了实现木醋液的高值化利用,在固定床反应器中,进行木醋液催化重整制氢实验,采用浸渍法制备一系列不同Co添加量的Ni基催化剂,以产氢率、碳转化率、H2选择性和积炭量为主要评价指标,探究液时空速、反应温度、镍钴比等工况对木醋液催化重整制氢的影响,同时采用XRF、H2-TPR、SEM及元素分析等方法对催化剂进行了表征.结果表...     

甲烷与二氧化碳催化重整制取合成气催化剂

甲烷自然资源丰富,并且也可利用生物质通过发酵制备,而将甲烷与二氧化碳催化重整制取合成气是同时利用两种温室气体的一条有效途径,对清洁能源和环保具有重大意义。近年来,由于该方法与其他技术相比具有较大优势,催化剂、反应机理及一些非常规手段的研究引起了科学界广泛关注。本文概述了近几年来甲烷与二氧化碳催化重整催化剂的活性组分、载体、助催化剂、催化剂积炭行为及制备方法等研究新进展,归纳了影响催化剂抗积炭能力的因素,重点介绍了负载型双金属催化剂、复合氧化物催化剂、介孔型催化剂、金属氧化物载体的活性及稳定性,催化剂制备方法对催化活性和抗积炭能力的影响,催化剂抗积炭方法及等离子体技术的应用等研究,包括普遍认为反应主要受到表面氧原子、表面氢原子与催化剂表面活性位三者影响的反应机理,并展望了双金属催化剂、钙钛矿型催化剂、介孔型催化剂及等离子体协同催化技术的应用及催化机理的研究等发展前景。     

从催化导向性基础研究到工业应用的若干创新思路与实践——庆祝闵恩泽先生九十华诞

闵恩泽先生曾经指出:开展导向性基础研究对研发新技术及其实现工业应用至关重要.将高性能催化材料和化学工程技术的结合是石油化工技术创新的重要途径之一.在传统的石油化工领域引入和集成新材料、新工艺与新过程,可有力地推动石油化工技术的发展.本文对近年来在多孔催化新材料及若干石油化工关键催化技术的创新实践进行总结,包括多孔复合催化新材料与工业催化反应的结合、绿色反应工艺与催化剂、过程耦合与强化等几个方面,凝练了材料科学与化学工程结合与应用的创新思路.     

利用乙醇重整制氢进行硝基苯原位液相加氢合成苯胺

 利用乙醇液相催化重整制得的氢直接进行硝基苯原位液相加氢合成苯胺. 考察了不同催化剂、反应温度及反应时间等因素的影响. 在以Pt/Al2O3为催化剂,反应温度220 ℃和反应时间3 h的条件下,硝基苯的转化率可达99.3%, 苯胺的选择性为99.8%, 催化剂表现出较高的加氢活性和选择性.     

丙烷直接合成烃类氧化物的进步与发展

结合丙烷氧化反应的热力学和动力学特点,从催化剂选择氧化反应技术应用方面,评述了近年来丙烷选择氧化直接合成烃类氧化物技术的进步和发展趋势.提出了利用二氧化碳作氧化剂、n-p复合型半导体材料作催化剂,并借助光表面催化反应技术来直接合成烃类氧化物的新思路,以期进一步扩大丙烷和二氧化碳利用的范围和途径.     

石油的加工

575.单体烃和其天然混合物(汽油和轻质煤油)在氢压下的催化转化(1957,26,№2,176—211)——总结了近年来催化重整方法的主要研究结果及其工业应用的发展情况.列举了以氧化物     

用Xα方法对CH4在Ni(Ⅲ)表面吸附解离反应的理论研究

用Ｘ_α方法对ＣＨ_４在Ｎｉ（Ⅲ）表面吸附解离反应的理论研究马晨生,马理,杨忠志（吉林大学理论化学研究所,长春,１３００２３）关键词ＣＨ_４／Ｎｉ（Ⅲ）吸附体系,原子簇模型,ＣＨ_４／Ｍｉ_７,ＭＳ－Ｘ_α－ＳＣＦ方法甲烷在Ｎｉ表面的催化重整反应在工业和国...     

Ni/Al2O3和Fe/Al2O3催化剂催化乙醇水蒸气重整制氢的对比研究

甲醇、乙醇等低碳醇催化重整制氢是燃料电池氢源的重要技术之一.乙醇和甲醇相比,更容易存储,低毒且可以从生物质经发酵获得[1,2].乙醇可以通过裂解、部分氧化、水蒸气重整和氧化重整等途径制氢[3~6].已有的文献表明,Pt、Ru、Rh、Pd等贵金属可有效地催化乙醇重整反应,载体多选用     

芳烃酰基化后还原制备芳香醇的工艺进展

芳烃制备高附加值精细化学品芳香醇(9-芴甲醇),一直以来存在产物选择性低以及合成成本高等问题。基于此,本文主要综述了芳烃酰基化后还原合成芳香醇的工艺,包括第一步采用Friedel-Crafts酰基化反应、Vilsmeier-Haack反应、Reimer-Tiemann反应、Duff反应等过程将芳烃酰基化合成芳香醛/酮;第二步通过金属氢化物还原、催化加氢还原、活泼金属还原、Cannizarro反应、Meerwein-Ponndorf-Verley还原反应等过程将芳香醛/酮还原合成芳香醇。在总结和归纳各种工艺过程优缺点的基础上,提出了合理的芳香醇制备工艺,为9-芴甲醇产业化制备技术的开发提供帮助。     

Kinetics of the catalytic reforming of gasoline

The main routes of catalytic gasoline reforming are considered. A kinetic model is chosen, substantiated, and modified to adequately describe the most important chemical reactions occurring in the process. The kinetic model is used to construct a mathematical model taking into account the nonisothermal character of the process. To reconcile calculated data with the corresponding industrial data, kinetic parameters (activation energies of reactions and preexponential factors of the Arrhenius equation) have been corrected for basic reactions of the process and have been redetermined for some ones. Process stages and concentration profiles of groups of reactants have been analyzed. Foundations have been laid for modeling of the entire chemical technological system of the catalytic reforming process.     

煤炭间接液化:从基础到工业化

中国需要自主发展煤炭间接液化工业化技术,以缓解油品供应的紧张局面,保障经济的可持续发展.近年来中国成功地进行了煤炭间接液化示范厂的运行,掌握了成熟可靠的费托合成催化剂技术和大型合成反应器技术,正在设计和建设百万吨级合成油商业厂.本文简要介绍了国内外煤炭间接液化技术发展状态,评述了我国煤炭间接液化技术在费托合成反应机理、催化剂研制、反应动力学、反应器设计、系统工艺集成、油品加工等方面从基础到工程技术的研究进展,分析了我国建设百万吨级煤炭间接液化商业厂需要解决的关键基础和工程技术问题,并对我国未来煤制油产业化发展的前景以及所面临的挑战与对策进行了展望.     

Challenges and Development Opportunities for Catalytic Technologies in Petrochemical Industry in the 21st Century

The propellent drive and development opportunities for future catalytic technologies in petrochemical industry in the 21st century are reviewed in this paper. It focuses on the following five aspects:(1) The environmentally-friendly catalytic technologies, such as new technologies for the production of organic chemicals changing the raw material and synthetic process, the chemicals production replacing phosgene and hydrogen cyanide toxicant, and the conversion and utilization of organic wastes etc.(2) Utilization and development of cheaper light alkanes, for example, the chemical use of natural gas and the development technologies of methane chain, the production of acetic acid, ethylene and vinyl chloride from selective oxidation of ethane, as well as the manufacture of acrolein and acrylonitrile from the oxidation and ammoxidation of propane.(3) The new propylene-plus technologies of the low value higher olefins, such as catalytic cracking of C4,C5 olefins and metathesis of C4 olefin.(4) The technologies of high selective oxidation, e.g. production of propylene oxide with TS-1 molecular sieve, oxidation process by lattice oxygen and direct oxidation of benzene to phenol etc.(5) Development and application of novel catalytic materials, especially, mesopore molecular sieve materials for a larger molecule reaction, zeolite catalyst with MWW structure for alkylation of benzene and propylene, ionic liquid, and membrane reactor catalyst etc.Meanwhile,the challenging research subjects for future industrial catalysis and the several viewpoints for development strategy of new catalytic technologies are proposed. These viewpoints are as follows:(1) Catalysis discipline must be integrated with many other disciplines and should be multidisciplinary and transdisciplinary.(2) New preparation methods of catalytic materials must be originally developed.(3) The instrumentation having better time resolution and spatial resolution and applying under reaction conditions must be improved further.(4) Fundamental research for catalysis and catalytic theory must be enhanced.(5) Catalysis science must be closely integrated with catalytic reaction engineering.(6) Knowledge innovation and technical progress must be accelerated.(7) Scientific and technological co-operation between academic, industrial circles and public organization having a common interest in catalysis must be intensified.     

Sorption-enhanced steam reforming of hydrocarbons with autothermal sorbent regeneration in a moving heat wave of a catalytic combustion reaction

A novel technological concept of sorption-enhanced steam reforming of hydrocarbons is suggested. The peculiarity of the concept is the autothermal regeneration of the carbon dioxide scavenger in the moving super-adiabatic heat wave of an exothermic catalytic combustion reaction performed directly inside the adsorption-catalytic bed. The capability and high efficiency of the proposed technological approach are confirmed by process simulation. The approach proposed is shown to open a way for the creation of an inexpensive, reliable and energy-saving adiabatic packed bed methane processors of unlimited processing capacity.     

低碳烷烃与二氧化碳催化转化研究进展

页岩气革命为低碳经济发展提供了重要契机.在低碳烷烃(甲烷和乙烷)催化转化过程中,以二氧化碳作为氧化剂参与反应,通过C-H键的选择性活化可将页岩气转化为优质化工原料——合成气和乙烯,是一种低碳烷烃转化与二氧化碳资源化利用的工艺路线.本文总结了近年来甲烷干重整与乙烷和二氧化碳反应中与C-H键活化相关的研究进展,分析了甲烷干...     

催化动力学分光光度法测定痕量铜的研究与应用

评述近年来催化动力学分光光度法测定痕量铜的研究进展,包括催化褪色动力学分光光度法、催化显色动力学分光光度法和阻抑动力学分光光度法,主要探讨各反应体系及其条件、方法的检出限、测定范围、应用等.研究新的高灵敏度指示反应、寻找新的活化剂、提高监测技术的灵敏度、对反应的机理进行研究、将催化动力学分析与其它分析技术相结合将是催化...     

A Heterogeneous Multiscale Dynamic Model for Simulation of Catalytic Reforming Reactors

The present work aims to establish a generic reforming reaction scheme to evaluate the performance of catalytic reforming systems with the aid of a one‐dimensional heterogeneous dynamic model. The novelty of the numerical model stems from the direct inclusion of interphase (fluid‐to‐particle surface), intraparticle (within particle), and intrareactor heat and mass transport resistances under transient conditions. The developed model accounts for the multicomponent gas mixture physicochemical properties and correlations for calculating mass and heat transfer coefficients. Effective macroscopic properties within the particle are calculated by incorporating diffusivities and conductivities of the porous network characteristics accounting for Knudsen and molecular transport as well as tortuosity and porosity of the overall porous path. The industrial case of a steam‐methane reforming multitubular reactor was studied as the most representative case of the generic reaction scheme, with all mass/energy resistances present under severe pressure and temperature conditions. It was shown that there are notable diffusional limitations within the particle, whereas there are also temperature and partial pressure gradients due to the heat and mass transport resistances in the particle film layer. It is further demonstrated that the proposed model can be utilized as a versatile design tool for catalytic reactor development and optimization.     

Catalytic transformations of gaseous products of plasma treatment of solid wastes and hydrocarbon raw materials

The layout of a technological process including catalytic steam and carbon dioxide reforming and Fischer-Tropsch hydrocarbon synthesis is presented. The inclusion of catalytic stages in plasma technologies provides the possibility to intensify conversion processes, enhance their depth, and obtain various gaseous and solid products.     

非均相催化烯烃交叉复分解反应

烯烃交叉复分解反应作为石油化工领域一种重要过程,为各种单烯烃间的互相转化提供了一条有效的途径。特别是在利用正丁烯生产丙烯和其它重要单烯烃方面,复分解反应受到越来越多的重视。本文对烯烃交叉复分解反应(CM)的进展进行了综述,讨论了CM各种工艺的技术特点及反应机理,重点介绍了WO₃/SiO₂、Re₂O₇/Al₂O₃、MoO₃/Al₂O₃3类催化剂的最新改进及相应的理论分析,试图理清催化剂今后发展的思路,为进一步改进催化剂的性能提供相关的依据。