生物基化工与材料产业技术的开发与探索

本文阐述了中国石油化工集团公司(中国石化)在生物基化工与材料领域的探索路径和发展战略,介绍了中国石化近年来在生物基单体、生物基材料与可降解材料等领域开展的创新实践及取得的阶段性成果,主要包括乳酸—聚乳酸、丁二酸/二元醇—生物可降解材料、长链二元酸—生物基尼龙以及生物质芳烃—聚对苯二甲酸乙二酯(PET)等技术领域.提出了建立生物基化工与材料科学技术平台、突破关键技术、发展新兴产业等建议.     

生物质利用新途径:多元醇催化合成可再生燃料和化学品

日益严重的全球性能源和环境问题促使开发利用可再生的生物质资源成为当前研究的一个热点.本文概述了生物质基多元醇合成燃料和化学品来实现生物质转化利用的一些最新进展,特别是集中介绍了甘油和山梨醇等多元醇催化水相重整合成氢气和液体烃等燃料、催化选择氢解和氧化合成高附加值化学品或化学中间体等方面的进展,分析了存在的问题和可能的解决措施以及今后的发展趋势,指出生物质基多元醇将成为今后合成可再生燃料和化学品的新型平台分子.     

生物质利用新途径:多元醇催化合成可再生燃料和化学品

日益严重的全球性能源和环境问题促使开发利用可再生的生物质资源成为当前研究的一个热点。本文概述了生物质基多元醇合成燃料和化学品来实现生物质转化利用的一些最新进展,特别是集中介绍了甘油和山梨醇等多元醇催化水相重整合成氢气和液体烃等燃料、催化选择氢解和氧化合成高附加值化学品或化学中间体等方面的进展,分析了存在的问题和可能的解决措施以及今后的发展趋势,指出生物质基多元醇将成为今后合成可再生燃料和化学品的新型平台分子。     

Derivation and synthesis of renewable surfactants

This critical review focuses on the origins and preparation of bio-based surfactants, defined here as non-soap, amphiphilic molecules in which the carbon atoms are derived from annually renewable feedstocks. Environmental concerns and market pressures have led to greater relevance of these chemicals in commercial applications in recent years and extensive research has gone into exploring new classes of surfactants. Highlighted here are examples of bio-based surfactants that are produced on an industrial scale and/or are based on abundant starting materials. The trend of increasing use of renewable resources as starting materials for surfactants is introduced, followed by extensive discussion of the major classes of bio-derived hydrophobes and hydrophiles. Also discussed is the status of research and development with regard to biosynthetically produced surfactants. Finally, concluding remarks address the potential for new surfactant molecular structures as a result of ongoing development in the chemistry of biorefineries, i.e., that the transformation of lignocellulose into fuels is likely to support the manufacturing of new bio-based coproducts (238 references).     

FDCA基聚酯的合成、性能及应用研究进展

生物质资源是一种储量丰富的可再生资源。生物质资源的高效利用不仅具有非常巨大的经济和生态价值,而且对新能源与生物基合成材料的可持续发展战略具有重大意义。由植物纤维素等生物质材料经生物或者简单化学过程处理,可获得丰富的生物基单体2,5-呋喃二甲酸(FDCA)。FDCA可用于生物基聚酯材料的合成。FDCA系列聚酯材料性能优异,可作为由石油基单体对苯二甲酸(PTA)而合成的芳香族聚酯材料(例如PET)的一种潜在的高性能生物可降解替代材料。本文简要说明了生物基单体FDCA的物性及制备方法,并重点阐述了包括聚呋喃二甲酸乙二酯(PEF)与聚呋喃二甲酸丁二酯(PBF)等一系列FDCA基聚酯材料的合成及性质,同时对FDCA基聚酯材料的应用进展进行了简要介绍,最后对FDCA基聚酯生物基合成材料的发展前景作了初步展望。     

Methanol – die Basischemikalie

Today methanol is produced from synthesis gas derived from coal and natural gas. However carbon dioxide and hydrogen obtained from water electrolysis with renewable energy have the potential to play a leading role as fuel, energy raw material and chemical feedstock. As a liquid energy storage system it can be used to easily transport electric power conserved in chemical bonds with unparalleled efficiency. Homologisation making use of the Mobil zeolite processes (MTG, MTO, MTA) for instance, or via the methanol derived platform chemicals methyl formate and dimethyl ether, the majority of organic chemicals established in chemical industry is available. Through its diverse of applications methanol has the potential to substitute crude oil and natural gas as the leading feedstock for organic chemicals.     

Renewability is not Enough: Recent Advances in the Sustainable Synthesis of Biomass‐Derived Monomers and Polymers

Taking advantage of the structural diversity of different biomass resources, recent efforts were directed towards the synthesis of renewable monomers and polymers, either for the substitution of petroleum‐based resources or for the design of novel polymers. Not only the use of biomass, but also the development of sustainable chemical approaches is a crucial aspect for the production of sustainable materials. This review discusses the recent examples of chemical modifications and polymerizations of abundant biomass resources with a clear focus on the sustainability of the described processes. Topics such as synthetic methodology, catalysis, and development of new solvent systems or greener alternative reagents are addressed. The chemistry of vegetable oil derivatives, terpenes, lignin, carbohydrates, and sugar‐based platform chemicals was selected to highlight the trends in the active field of a sustainable use of renewable resources.     

生物基环氧树脂及固化剂研究现状

生物基高分子材料以可再生资源为主要原料,它在减少塑料行业对石油资源消耗的同时,也减少了石油化工原料在生产过程中对环境的污染,具有节约石油资源和保护环境的双重功效。桐油和松香是我国两种重要的天然可再生资源,在目前将化工原料逐步转向可再生资源的时代背景下,它们已被广泛应用于高分子材料的合成和改性。生物基热固性树脂是一个意义重大且前景广阔的研究领域,本文就桐油和松香在生物基环氧树脂和固化剂方面的应用进行了系统的综述和展望。     

用于生物质水相加氢多相负载型金属催化剂的稳定策略

生物质是天然的可再生能源和资源,具有来源广泛、储量丰富、价格低廉的优点以及可转化为高附加值化学品的多功能性,因此作为传统化石能源替代材料受到广泛关注和研究.将生物质通过催化转化为平台化合物再进一步利用是生物质利用的重要途径,其中催化加氢是常用的反应之一.由于绝大多数生物质平台化合物分子中都含氧元素,其加氢过程中会不可避免的产生水,同时水作为绿色环保,价廉易得的溶剂,可以溶解绝大多数生物质平台化合物,因此选择水做溶剂具有重要意义.负载型纳米金属催化剂(如Au、Rh、Pt、Pd、Ru、Cu和Co等)在生物质水相加氢反应中具有广泛的应用,但其在水相反应条件下(通常为高温、高压、强酸性等苛刻条件)容易在反应过程中发生纳米金属粒子的团聚、流失以及载体的坍塌、结构转变等引起失活.因此,发展可以在水相体系中稳定的金属多相催化剂对生物质资源化利用非常必要.本文首先综述了溶剂水对反应的影响以及负载型金属催化剂在水相体系中的失活类型与机理,内容包括:(1)溶剂水对催化剂及催化加氢反应的积极作用,包含提高转化率和影响产物选择性;(2)溶剂水引起催化剂失活的原因,如引起金属纳米粒子发生团聚、氧化、流失以及载体发生溶解、坍塌、结构转变等.从负载型金属催化剂的失活机理入手,分别从提高金属纳米粒子的稳定性和载体的稳定性两个方向综述了提高负载型金属催化剂稳定性的普适性策略,内容包括:(1)通过界面限域策略增强金属-载体相互作用的方式提高金属纳米粒子在载体上的稳定性,包括有机基团配位、杂原子配位、镶嵌法等;(2)通过空间限域策略将金属纳米颗粒封装的方式提高金属纳米粒子的稳定性,包括利用一维的空心管状材料、二维的超薄材料以及三位的空心球(笼)材料等;(3)通过提高载体(主要为氧化物载体)的稳定性以提高催化剂整体稳定性,包括对载体进行修饰、包覆、杂化等方式.本工作所综述的提高生物质水相加氢金属催化剂稳定性的策略为高稳定性催化剂的设计指出了方向.     

有关“环境友好塑料”几个概念的澄清

生物塑料、生物降解塑料、生物基塑料统称为环境友好塑料,但它们三者的侧重点各有不同,既有区别,也有联系,本文对以上三个概念的意义做了详细的解释和澄清。生物塑料注重于生产原料的生物来源性和制造过程的生物技术性;生物降解塑料则注重于它是否可以被生物降解,其原料可以来自于可再生资源,也可来自于石油资源;生物基塑料则关注其生产原料是否来自于可再生资源,而对其是否可以生物降解没有特别要求。     

Molybdenum-Catalyzed Deoxygenation Coupling of Lignin-Derived Alcohols for Functionalized Bibenzyl Chemicals

With the growing demand for sustainability and reducing CO₂ footprint, lignocellulosic biomass has attracted much attention as a renewable, carbon-neutral and low-cost feedstock for the production of chemicals and fuels. To realize efficient utilization of biomass resource, it is essential to selectively alter the high degree of oxygen functionality of biomass-derivates. Herein, we introduced a novel procedure to transform renewable lignin-derived alcohols to various functionalized bibenzyl chemicals. This strategy relied on a short deoxygenation coupling pathway with economical molybdenum catalyst. A well-designed H-donor experiment was performed to investigate the mechanism of this Mo-catalyzed process. It was proven that benzyl carbon-radical was the most possible intermediate to form the bibenzyl products. It was also discovered that the para methoxy and phenolic hydroxyl groups could stabilize the corresponding radical intermediates and then facilitate to selectively obtain bibenzyl products. Our research provides a promising application to produce functionalized aromatics from biomass-derived materials.     

光电解水制氢耦合生物质醇/醛氧化的研究进展

生物质醇/醛是一类重要的生物基平台化合物, 通过催化氧化重整可将其进一步转化为高值含氧化学品或燃料. 太阳能驱动的光电催化技术是实现生物质醇/醛氧化最为绿色高效的途径之一. 与传统光电解水制氢相比, 利用生物质醇/醛氧化来替代阳极析氧过程不仅可以提高阳极产物的附加值, 同时可以提升太阳能到氢能的转化效率. 因此, 光电解水制氢耦合生物质醇/醛氧化对绿氢提效降本和高值化学品合成具有重要意义. 本文综合评述了光电解水制氢耦合生物质醇/醛的氧化反应机理, 总结了目前光电催化技术在生物质醇/醛氧化方面的研究进展, 最后对该领域所面临的机遇和挑战进行了展望.     

Recent Advances in C5 and C6 Sugar Alcohol Synthesis by Hydrogenation of Monosaccharides and Cellulose Hydrolytic Hydrogenation over Non-Noble Metal Catalysts

A new reality of the 21st century is the transition to a new type of economy and energy concepts characterized by the replacement of existing petrochemical routes to a bio-based circular economy. The needs for new strategies in obtaining basic products from bio-based resources with minimum CO₂ traces has become mandatory. In this review, recent trends in the conversion of biomass-derived molecules, such as simple monomeric sugars and cellulose, to industrially important C₅ and C₆ sugar alcohols on heterogeneous catalysts based on non-noble metals are discussed focusing on the influence of catalyst structures and reaction conditions used on the substrate conversion and product selectivity. The challenges and prominent ideas are suggested for the further development of catalytic hydrogenation of naturally abundant carbohydrates to value-added chemicals on non-noble metal catalysts.     

Green synthesis of carbon solid acid catalysts using methane sulfonic acid and its application in the conversion of cellulose to platform chemicals

Cellulose - Levulinic acid (LA) is an important platform chemical and used for the production of various biofuels and bio-based chemicals. Formic acid (FA) is a major product of biomass conversion...     

A One-Pot Approach for Bio-Based Arylamines via a Combined Photooxidative Dearomatization-Rearomatization Strategy

The synthesis of arylamines from renewable resources under mild reaction conditions is highly desired for the sustainability of the chemical industry, where the production of hazardous waste is a prime concern. However, to date, there are very few tools in chemists’ toolboxes that are able to produce arylamines in a sustainable manner. Herein, a robust one-pot approach for constructing bio-based arylamines via a combined photooxidative dearomatization-rearomatization strategy is presented. The developed methodology enables the synthesis of structurally complex amines in moderate-to-good isolated yields using biomass-derived phenols, natural α-amino acids, and naphthols under remarkably mild reaction conditions. For the photooxygenation of phenols, a novel chrysazine-based catalyst system was introduced, demonstrating its efficiency for the synthesis of natural products – hallerone, rengyolone, and the pharmaceutically relevant prodrug DHED.     

Circularity in green chemical products,processes and services: Innovative routes based on integrated eco-design and solution systems

Understanding the current drivers, potentialities and challenges related to the role of chemical sciences in a circular economy is of fundamental importance when bioresources are taken into account. Particularly, after launching the European Commission action plan in 2015, the creation, development and use of green chemicals derived from renewable materials can be seen as more than simple opportunities in research and innovation. In this paper, the latest trends related to green chemical products, processes and services concerning eco-design and solution approaches will be focused on, using an orange waste biorefinery as a case study. Emphasis will be given to establishing new relationships with goods, materials, energy and, mostly, long-term cooperation and integration models among all partners involved.     

Recent advances in paired electrolysis of biomass-derived compounds toward cogeneration of value-added chemicals and fuels

Pairing the electrocatalytic hydrogenation reaction with different anodic reactions driven by renewable electricity offers a greener way for producing value-added chemicals and fuels. In particular, replacing the sluggish water oxidation with a biomass-based upgrading reaction can reduce the overall energy cost, thus allowing for the simultaneous generation of high-value products at both electrodes. This mini-review summarized the recent progress in paired electrolysis of biomass-derived compounds, particularly the furanic chemicals. Some perspectives and outlooks were proposed for further improvements in this research area.     

Recent development on bio-based thermosetting resins

Due to the rapid depletion of crude oil and serious environmental pollution, the synthesis of polymers from renewable resource is becoming more and more important. Up to now, a great variety of biomass and bio-based platform compounds have been taken to prepare the polymers. However, as two representative thermosetting resins, epoxy and benzoxazine resin derived from renewable feedstocks only obtain limited attention compared with the popular bio-based plastics, including PLA, PBAT and PHBV etc. The reason might be that the properties of previously reported thermosetting resins directly obtained from biomass are usually unsatisfied, and their application fields are limited. In this paper, the latest development on the synthesis of high-performance bio-based epoxy and polybenzoxazine resins are reviewed. In addition, to further broaden their applications, the functionalization strategies are also summarized. The objective of this work is to help us fully aware the present situation of bio-based thermosetting resins and then promote their faster development, especially practical application.     

Transformations of biomass-derived platform molecules: from high added-value chemicals to fuels via aqueous-phase processing

Global warming issues and the medium-term depletion of fossil fuel reserves are stimulating researchers around the world to find alternative sources of energy and organic carbon. Biomass is considered by experts the only sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum in the production of chemicals and liquid transportation fuels. However, the transition from a petroleum-based economy to one based on biomass requires new strategies since the petrochemical technologies, well-developed over the last century, are not valid to process the biomass-derived compounds. Unlike petroleum feedstocks, biomass derived platform molecules possess a high oxygen content that gives them low volatility, high solubility in water, high reactivity and low thermal stability, properties that favour the processing of these resources by catalytic aqueous-phase technologies at moderate temperatures. This tutorial review is aimed at providing a general overview of processes, technologies and challenges that lie ahead for a range of different aqueous-phase transformations of some of the key biomass-derived platform molecules into liquid fuels for the transportation sector and related high added value chemicals.     

Overcoming Thermodynamically Driven Retro-Diels–Alder Reaction through a Cascade One-Pot Process Exemplified for a Bio-Based Platform Chemical

In this contribution, we describe a new approach to apply thermodynamically unfavored reactions in synthetic chemistry and to integrate them in cascade processes. By means of a new developed procedure for multi-step one-pot syntheses, we succeeded in nearly completely converting a thermodynamically labile Diels–Alder adduct, which strongly tends to react back, to the target product with high conversion of >99 % and in excellent yield by coupling with a rapid subsequent hydrogenation reaction. In detail, the process is based on the use of a rotating reaction vessel to form a thin product film of the thermodynamically labile Diels–Alder product from 2-methylfuran and maleic acid anhydride (as two bio-based raw materials), which then slowly dissolves into solution and is immediately converted by hydrogenation to the target product. Such a combination of Diels–Alder reaction and hydrogenation in a sequential one-pot process without by-product formation enables the efficient production of the product, which represents a valuable bio-based platform chemical. In addition, this process concept generally opens a perspective for the integration of thermodynamically unfavorable reaction steps in multi-step one-pot cascade processes while obtaining the desired target products in high yields.