Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2024-12-12 , DOI: 10.1002/adsc.202401446 Joseph J. Bozell
Terrestrial raw materials, whether petrochemical or renewable, can be converted into small families of building blocks from which other chemicals can be derived. Nonrenewable feedstocks afford a group of olefins, aromatics, CH4 or syngas, which serve as platforms for further conversion into the thousands of products that make up the modern chemical industry.
The analogous fractionation of renewables provides a ready supply of carbohydrates, lignin or long chain hydrocarbons. However, the polymeric nature and structural complexity of the materials from this fractionation precludes their immediate assignment as platforms. As a result, the challenge becomes determining whether there are small, low molecular weight structures, derived from these biomass fractions, that can be employed in the same manner as the petrochemical industry's olefins and aromatics.
The concept of using biobased feedstocks for the production of platform chemicals is not new. As a response to the oil crises of the time, efforts were made to define renewable platforms as far back as the mid-1970s and early 1980s.1-5 These initial studies normally focused on “picking winners”, a process of pre-identifying specific, structural targets, frequently hydrocarbon based, against which research should be directed, but sometimes regardless of whether these targets could be reasonably sourced from an initial group of renewable feedstocks.6, 7 It was often observed that transforming highly oxygenated carbohydrates or lignin to petrochemical-like platforms was an economic non-starter.
Thus, the importance of identifying technology, rather than structures, tailored to the unique features of biomass became critical to realizing a credible suite of biobased platforms for the chemical industry. What building blocks would be most easily and inexpensively derived from carbohydrates, lignin or plant oils? What processes were needed to make these materials? How can the structural features of biomass be accommodated by the chemical industry? Which of these materials will be true analogs to the petrochemical industry's olefins and aromatics?
Accordingly, investigations evolved to understand and develop bespoke transformations best suited to provide the interface between renewable feedstocks and the chemical industry. An early US Department of Energy evaluation appeared in 1994, which, while still describing pre-identification of targets, also began to acknowledge the need for technology development.8 With the DOE's release of their “Top Ten” report in 2004, the need for new technology was more strongly established.9 Finally, a highly cited and technology-based revisiting of the Top Ten was published in 2010, providing rationale and background for evaluating new building blocks.10 Their potential was illustrated with multiple examples of available platforms serving as starting materials for a wide array of chemical products. Since that time, many excellent reviews have continued to appear.11-14
We felt it appropriate to provide an opportunity for examining some of the more recent developments in technology development for converting renewables to platform chemicals. A portion of this issue of Advanced Synthesis and Catalysis, builds on these foundations and provides a “mini-review” of several advances in the field. Here, the reader will find new studies describing the utility and transformation of the very well recognized renewable platforms, 1,3-propanediol and levulinic acid. Less frequently exploited renewable raw materials as sources of new platforms are also examined through the use of chitin for the production of 3-acetamidofuran and difuropyridines. Developing catalysis tailored for the structures of biomass is critical for preparing new platforms and is illustrated with the Mo-catalyzed conversion of 1,2-diols into terminal alkenes. Finally, the potential of renewables to provide novel and perhaps underexamined platforms is considered in the production of families of bioactive materials.
Interest in converting biomass to platforms and diverse families of chemicals continues to grow. We hope the reader finds these articles useful and informative, and that they are able to provide inspiration for further inclusion of renewables within the chemical industry.
中文翻译:
将可再生能源转化为平台化学品的发展
陆地原材料,无论是石化还是可再生能源,都可以转化为小系列的组成部分,从中可以衍生出其他化学品。不可再生原料提供了一组烯烃、芳烃、CH4 或合成气,这些原料可作为进一步转化为构成现代化工工业的数千种产品的平台。
可再生能源的类似分馏提供了碳水化合物、木质素或长链碳氢化合物的现成供应。然而,这种分馏产生的材料的聚合物性质和结构复杂性排除了它们作为平台的直接分配。因此,挑战变成了确定是否有来自这些生物质馏分的小而低分子量的结构可以像石化行业的烯烃和芳烃一样使用。
使用生物基原料生产平台化学品的概念并不新鲜。作为对当时石油危机的回应,早在 1970 年代中期和 1980 年代初就努力定义可再生能源平台。这些初步研究通常侧重于“挑选赢家”,这是一个预先确定具体的结构性目标的过程,通常是基于碳氢化合物的,研究应该针对这些目标,但有时无论这些目标是否可以合理地来自初始可再生原料组。6、7人们经常观察到,将高含氧碳水化合物或木质素转化为类似石化的平台是一种经济上的失败。
因此,确定针对生物质独特特征的技术而不是结构的重要性,对于为化工行业实现一套可靠的生物基平台至关重要。哪些构建块最容易且最便宜地从碳水化合物、木质素或植物油中提取?制造这些材料需要哪些工艺?化学工业如何适应生物质的结构特征?这些材料中哪些是石化工业的烯烃和芳烃的真正类似物?
因此,研究不断发展,以了解和开发最适合在可再生原料和化学工业之间提供接口的定制转型。1994 年,美国能源部 (Department of Energy) 进行了早期评估,该评估虽然仍然描述了目标的预先识别,但也开始承认技术开发的必要性。8 随着美国能源部在 2004 年发布其“十大”报告,对新技术的需求更加强烈。9 最后,2010 年发表了一篇被高度引用且基于技术的对前十名的回顾,为评估新的构建块提供了基本原理和背景。10 通过多个可用平台作为各种化学产品的起始材料的例子来说明它们的潜力。从那时起,许多优秀的评论不断出现。11-14
我们认为提供一个机会来研究将可再生能源转化为平台化学品的技术开发的一些最新发展是合适的。本期《高级合成与催化》的一部分建立在这些基础上,并提供了该领域几项进展的“迷你回顾”。在这里,读者将找到新的研究,这些研究描述了非常公认的可再生平台(1,3-丙二醇和乙酰丙酸)的效用和转型。通过使用甲壳素生产 3-乙酰氨基呋喃和二呋喃吡啶,还研究了作为新平台来源的不太经常开发的可再生原材料。开发为生物质结构量身定制的催化对于制备新平台至关重要,并以 Mo 催化将 1,2-二醇转化为末端烯烃来说明。最后,在生物活性材料系列的生产中考虑了可再生能源提供新颖且可能未被充分研究的平台的潜力。
将生物质转化为平台和各种化学品的兴趣不断增长。我们希望读者发现这些文章有用且信息丰富,并且它们能够为进一步将可再生能源纳入化工行业提供灵感。