废塑料化学转化制燃料的催化剂研究进展

在简要介绍和比较热裂解、催化裂解、热裂解-催化改质和催化裂解-催化改质4种废塑料化学转化制燃料基本方法的基础上,综述了近年来国内外在废塑料裂解催化剂和废塑料裂解产物改质催化剂的研究进展,重点讨论了催化剂酸性、比表面积、孔径以及负载金属离子的类型等对废塑料催化裂解和催化改质反应性能的影响,并介绍了聚烯烃（包括聚乙烯和聚丙烯）废塑料和聚苯乙烯废塑料热裂解和催化裂解的反应机理。最后对废塑料化学转化制燃料技术的研究与开发提出了一些建议,指出采用催化裂解-催化改质组合技术是未来废塑料化学转化制燃料过程的发展趋势,其今后的研究重点将是开发具有较强酸性和有利于大分子扩散与传质性能孔道结构的分子筛催化剂。     

生物质微波热解制备液体燃料和化学品的研究进展

微波热解是一种高效的生物质转化利用技术,具有独特的热效应和非热效应,可将生物质转化为液体燃料和化学品,能有效缓解能源压力,减少环境污染。本文着重探讨了生物质原料特性、微波吸收剂、催化剂对生物质微波热解制备高品质液体燃料和化学品的影响。原料特性的影响主要从生物质的水分含量、灰分含量和有效氢碳比三方面展开论述,催化剂包括金属盐、金属氧化物、ZSM-5、微波驱动型催化剂以及其他一些催化剂,如HY、MCM-41和碳基催化剂等。简述了生物质的微波热解特性、液体燃料的组成以及转化机理,并对现存的热解机理复杂、产物复杂不稳定、目标产物选择性差、催化剂易结焦失活、重复性差等问题进行了分析,展望了未来的发展方向,以期为生物质的高效转化利用提供依据。     

Recent advances in the catalytic pyrolysis of biomass

Biomass is considered as a renewable and alternative resource for the production of fuels and chemicals, since it is the only carbon and hydrogen containing resource that we can find in the world except for fossil resources, capable of being converted to hydrocarbons. The pyrolytic liquefaction of biomass is a promising way to convert biomass to useful products. This paper briefly surveys the present status of the direct catalytic pyrolysis for the liquefaction of biomass. The direct use of catalysts could decrease the pyrolysis temperature, increase the conversion of biomass and the yield of bio-oil, and change the distribution of the pyrolytic liquid products then improve the quality of the bio-oil obtained. The fact that biomass is in solid state present great challenges for its conversion and for the effective use of catalysts due to the bad heat transfer characteristics and bad mass transfer properties. These barriers appeal for the development of a new catalyst and new catalytic process as well as the integration of both. Process design and process intensification are of significant importance in the catalytic conversion of biomass.     

木质素类生物质催化热解制备精细化学品研究进展

能源和环境是当今世界的两大挑战,将生物质转化为燃料和化学品是应对该挑战的低碳方案。其中,催化热解木质素获得燃料和化学品是低碳方案的重要部分。本文以能源和环境问题为出发点,阐述了木质素催化热解制备燃料和化学品的可行性和必要性,并对催化裂解行为、催化裂解过程和催化产物等方面的国内外研究现状进行了系统介绍。文章首先对木质素的结构和转化过程进行了概述;然后从催化热解行为、催化热解产物以及催化剂的研究现状等方面进行了系统阐述,并对现有的催化木质素热解过程的机理研究进行了讨论。通过对木质素催化热解制备燃料和化学品的发展前景、技术瓶颈以及逻辑方面进行评估表明,木质素转化为燃料和化学品过程中提高产品的产率和能量效率是今后的总体目标,而原料供给和生产、催化剂开发、产品分离纯化、反应机理和动力学以及计算模拟等方面将是深入研究木质素高效利用的重要研究内容。     

纤维素典型热解产物生成机理研究进展

利用生物质热解来生产液体燃料和高价值化学品受到广泛的关注,对生物质组分热解机理的研究有助于对生物质热解规律的理解和对热解过程的调控。对纤维素热解及其典型热解产物如脱水糖类、呋喃类以及小分子化合物等的生成机理进行综述,并指出后续的研究应该选用合适的模化物;为实现纤维素的高值化利用,还应对纤维素在不同类型催化剂作用下的催化热解机理进行研究。     

生物质双级催化热解制备燃料化学品的研究进展

生物质热解所得目标产物生物油因高含氧量、组分复杂等问题难以直接应用,通过使用适宜的催化剂升级热解蒸气可实现生物油的脱氧提质。本文基于前人研究,首先总结了生物质催化热解中金属氧化物和分子筛催化剂的结构特点、催化原理与催化效果。然后详细介绍了微介孔复合型、金属氧化物/ZSM-5复合型双级催化体系的构建原理、催化模式及其对于生物质催化热解产物分布规律产生的影响,并说明了双级催化体系的可行性与实用性;同时概述了影响生物质催化热解的其他因素,包括原料特性、工艺参数、操作模式等。最后针对目前双级催化热解研究与发展中存在的问题,对进行双级催化模式的比较研究、改进催化体系以降低生产成本、发掘双级催化剂的多种使用价值等方向提出了展望。     

煤与生物质的共热解液化研究进展

煤与生物质共热解液化将是燃料与化学品重要的转化技术之一。本文从共热解液化机理、共热解液化反应动力学、煤与生物质的协同作用、催化剂、共热解液化工艺、共热解液化产物等方面对煤与生物质共热解液化研究进展进行了综述,指出煤与生物质的快速共热解液化将是重要的发展方向,催化剂的应用和液化产物的精制将对提升液化油的品位和降低成本,对实现共液化油替代现行石化液体油具有更重要的意义。     

Upgrading of derived pyrolysis vapors for the production of biofuels from corncobs

A bubbling fluidized bed pyrolyzer was integrated with an in-situ honeycomb as a catalytic upgrading zone for the conversion of biomass to liquid fuels. In the upgrading zone, zeolite coated ceramic honeycomb (ZCCH) catalysts consisting of ZSM-5 (Si/Al=25) were stacked and N₂ or recycled non-condensable gas was used as a carrier gas. Ground corncob particles were fast pyrolyzed in the bubbling bed using fine sand particles as a heat carrier and the resulting pyrolysis vapors were passed on-line over the catalytic upgrading zone. The influence of carrier gas, temperature, and weight hourly space velocity (WHSV) of catalyst on the oil product properties, distribution and mass balance were studied. Using ZCCH effectively increased the hydrocarbon yield and the heating value of the dry oil, especially in the presence of the recycled noncondensable gas. Even a low usage of zeolite catalyst at WSHV of 180 h⁻¹ was effective in upgrading the pyrolysis oil and other light olefins. The highest hydrocarbon (≥C2) and liquid aromatics yields reached to 14.23 and 4.17 wt-%, respectively. The undesirable products including light oxygenates, furans dramatically decreased in the presence of the ZCCH catalyst.     

Catalysis in biomass processing

Biomass has in recent years been considered as a raw material for the production of fuels and chemicals. This work discusses the reasons for the increased interest in mainly lignocellulosic biomass. Gasification, pyrolysis, and depolymerization by hydrolysis are analyzed as key biomass technology. We also discuss which of the sugars obtained via depolymerization by hydrolysis can be processed into fuel or key intermediates of the chemical industry. Lignocellulosic biomass contains such extractants as fatty acids and terpenes, and we therefore describe the catalytic reactions of these substances for the synthesis of fuels and chemicals. Some typical reactions of biomass processing (oxidation, hydrogenation, cracking, etc.) are conceptually close to the process widely known in the refining and chemical industries. There are, however, other considerations due to, e.g., the large number of functional (hydroxyl and other) groups, and the processing of biomass components therefore requires dehydration, aldol condensation, ketonization, decarboxylation, etc. We cover the fundamentals of the approaches to selecting catalysts for these reactions.     

炭基催化剂应用于热转化过程的研究进展

生物炭具有环境友好、来源广泛、成本低廉等优点,作为催化剂及催化剂载体被广泛应用于热转化过程,但存在易结焦失活、产物定向调控机理尚不明确等问题。对生物质炭基催化剂应用于热转化过程的研究进行了综述,介绍了生物质炭基催化剂制备、改性(杂原子掺杂和金属负载)方案的研究现状。从常规催化热解、微波辅助热解、焦油脱除、酯化合成运输燃料和水热液化5个方面对炭基催化剂的应用进行讨论,并指出探索催化剂深层次的催化机理以及构建具有多级孔隙结构的炭基催化剂以定向生产高值化学品是未来的研究方向。     

木质纤维素多元醇液化及液化产物提质的研究进展

生物质作为唯一的可再生含碳资源,通过热化学液化可以实现其高附加值转化为燃料和化学品。木质纤维素多元醇液化产物富含活性羟基,具有可调变的羟值和黏度,在聚氨酯材料的生产中得到了广泛的应用。由于液化过程中同时存在缩聚、重排等副反应的发生,导致液化产物中含有醛、酮、酸、酯等羰基化合物,使用合适的催化剂对液化产物进行加氢提质是提高下游聚氨酯泡沫品质的必需步骤。为此,对木质纤维素多元醇液化工艺、液化动力学和液化机理等方面进行了总结,对液化产物的提质方法及工艺技术的选取进行了阐述,提出了“液化耦合提质”的新工艺,并对未来的研究重点及发展趋势提出了可行的建议。     

Catalytic upgrading of bio‐oils by esterification

Biomass is the term given to naturally‐produced organic matter resulting from photosynthesis, and represents the most abundant organic polymers on Earth. Consequently, there has been great interest in the potential exploitation of lignocellulosic biomass as a renewable feedstock for energy, materials and chemicals production. The energy sector has largely focused on the direct thermochemical processing of lignocellulose via pyrolysis/gasification for heat generation, and the co‐production of bio‐oils and bio‐gas which may be upgraded to produce drop‐in transportation fuels. This mini‐review describes recent advances in the design and application of solid acid catalysts for the energy efficient upgrading of pyrolysis biofuels. © 2015 Society of Chemical Industry     

Hydrothermal catalytic production of fuels and chemicals from aquatic biomass

One of the promising avenues for biomass processing is the use of water as a reaction medium for wet or aquatic biomass. This review focuses on the hydrothermal catalytic production of fuels and chemicals from aquatic biomass. Two different regimes for conversion of aquatic biomass in hydrothermal conditions are discussed in detail. The first is hydrothermal liquefaction, and the second is hydrothermal gasification. The goals of these processes are to produce liquid‐fuel‐range hydrocarbons and methane or hydrogen, respectively. The catalytic upgrading of biocrude resulting from noncatalytic liquefaction and the stability and degradation of catalysts in high temperature water are also discussed. The review concludes with a brief discussion of the outlook for and opportunities within the field of hydrothermal catalytic valorization of biomass. Copyright © 2012 Society of Chemical Industry     

生物质热解技术研究进展

生物质能源是一种可再生的能源,占世界能源的 14% 以上,可以有效地替代日渐枯竭的化石能源。生物质热解转化为高能量密度的燃料,不仅可以缓解能源的短缺,还可以减少大气污染,改善生态环境。本文介绍了生物质的分类及其结构组成,并从热解反应起始温度和终止温度以及热解产物组成和分布等方面,阐述了生物质类别、催化剂、热解温度、热解压力、升温速率以及气相滞留期等因素对热解过程的影响。     

Hydro-pyrolysis of lignocellulosic biomass over alumina supported Platinum,Mo<Subscript>2</Subscript>C and WC catalysts

In-line hydro-treatment of bio-oil vapor from fast pyrolysis of lignocellulosic biomass (hydro-pyrolysis of biomass) is studied as a method of upgrading the liquefied bio-oil for a possible precursor to green fuels. The nobel metal (Pt) and non-noble metal catalysts (Mo₂C and WC) were compared at 500 °C and atmospheric pressure which are same as the reaction conditions for fast pyrolysis of biomass. Results indicated that under the pyrolysis conditions, the major components, such as acids and carbonyls, of the fast pyrolysis bio-oil can be completely and partially hydrogenated to form hydrocarbons, an ideal fossil fuel blend, in the hydro-treated bio-oil. The carbide catalysts perform equally well as the Pt catalyst regarding to the aliphatic and aromatic hydrocarbon formation (ca. 60%), showing the feasibility of using the cheap non-noble catalysts for hydro-pyrolysis of biomass.

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Biofuel potential production from cottonseed oil: A comparison of non-catalytic and catalytic pyrolysis on fixed-fluidized bed reactor

Conversion of vegetable oils predominantly composed of triglycerides using pyrolysis type reactions represents a promising option for the production of renewable fuels and chemicals. The purpose of this article was to compare catalytic cracking with thermal cracking on production of gaseous hydrocarbon and gasoline conversion by cottonseed oil, and to discuss the difference on composition of products from catalytic cracking and thermal cracking. Reaction products are heavily dependant on the catalyst type (catalyst activation) and reaction conditions. They can range from dry gas to light distillate, such as dry gas, liquefied petroleum gas and gasoline. When the temperature of catalytic cracking is over 460 °C, the effects of thermal cracking must be considerable.     

生物质快速热解液化技术的研究进展

本文论述了生物质热解关键技术和热解制备生物油的工艺原理,同时综述了国内外快速热解反应器的现状.重点分析了传统的生物质快速热解关键技术--加料技术、气--固快速分离技术及反应温度、升温速率等因数的影响,提出了目前生物质热裂解液化技术的难点和液化燃料油的利用和开发技术的发展方向.     

生物质能源转化技术与应用(Ⅰ)

生物质能源是唯一可再生、可替代化石能源转化成液态和气态燃料以及其它化工原料或者产品的碳资源。随着化石能源的枯竭和人类对全球性环境问题的关注,生物质能替代化石能源利用的研究和开发,已成为国内外众多学者研究和关注的热点。本文综述了我国年可获得生物质资源量达到3.14亿吨煤当量,其中秸秆和薪材分别占 54% 和 36%;现有180多亿吨林木生物质资源量、8~10亿吨可获得量和3亿吨可作为能源的利用量。生物质能转化利用的主要途径是:热化学高效转化利用的热解气化发电(供热、供气)、快速热解制备液体燃料和生物质气化合成液体燃料,以及生物化学转化技术等。同时,论述了目前已经进行的生物质研究开发技术和产业化利用进展。     

生物质热解制生物油及其提质研究现状

生物质能源作为可再生能源的重要组成部分,其综合高效利用在能源替代与补充、保护生态环境等方面具有重要的战略意义。生物油是生物质通过热裂解技术获得的液体产物,具有能量密度较高、环境友好、可再生及可直接输送等优点,可替代传统化石燃料推广使用,解决日益严重的能源紧缺与环境污染等问题。生物质热解制油技术的开发与利用,已成为新世纪可持续能源研究领域的重要课题之一。总结了近年来生物质热解制油技术的主要研究进展,重点关注热解反应器、催化热解技术与生物油的提质利用方面的研究,介绍了碱金属、氧化物和分子筛3种生物质热解催化剂,以及乳化、催化加氢、催化裂解、催化酯化和重整制氢5种生物质提质方法,最后对生物质热解技术的现状及发展趋势进行了总结和概括。     

A review on ex situ catalytic fast pyrolysis of biomass

Catalytic fast pyrolysis (CFP) is deemed as the most promising way to convert biomass to transportation fuels or value added chemicals. Most works in literature so far have focused on the in situ CFP where the catalysts are packed or co-fed with the feedstock in the pyrolysis reactor. However, the ex situ CFP with catalysts separated from the pyrolyzer has attracted more and more attentions due to its unique advantages of individually optimizing the pyrolysis conditions and catalyst performances. This review compares the differences between the in situ and ex situ CFP operation, and summarizes the development and progress of ex situ CFP applications, including the rationale and performances of different catalysts, and the choices of suitable ex situ reactor systems. Due to the complex composition of bio-oil, no single approach was believed to be able to solve the problems completely among all those existing technologies. With the increased understanding of catalyst performances and reaction process, the recent trend toward an integration of biomass or bio-oil fractionation with subsequent thermo/biochemical conversion routes is also discussed.