催化一步转化木质素单体为苯酚:建立木质素到高附加值化学品的通道

doi:10.1016/S1872-2067(18)63132-8

催化学报 ›› 2018, Vol. 39 ›› Issue (9): 1445-1452.DOI: 10.1016/S1872-2067(18)63132-8

催化一步转化木质素单体为苯酚:建立木质素到高附加值化学品的通道

张佳光^a,b, Loris Lombardoa^c, Gökalp Gözaydin^a, Paul J. Dyson^c, 颜宁^a

a 新加坡国立大学化学与生物分子工程系, 新加坡;
b 林肯大学化学学院, 英国;
c 瑞士洛桑联邦理工化学科学与工程所, 瑞士

收稿日期:2018-06-28 修回日期:2018-07-04 出版日期:2018-09-18 发布日期:2018-07-19
通讯作者: 颜宁
基金资助:
新加坡教育部资助项目（R-279-000-479-112，R-279-000-462-112）.

Single-step conversion of lignin monomers to phenol: Bridging the gap between lignin and high-value chemicals

Jiaguang Zhang^a,b, Loris Lombardo^c, Gökalp Gözaydin^a, Paul J. Dyson^c, Ning Yan^a

a Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585 Singapore;
b School of Chemistry, University of Lincoln, Joseph Banks Laboratories, Green Lane, Lincoln, LN6 7DL, United Kingdom;
c Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne(EPFL), CH-1015, Switzerland

Received:2018-06-28 Revised:2018-07-04 Online:2018-09-18 Published:2018-07-19
Contact: 10.1016/S1872-2067(18)63132-8
Supported by:
This work was supported by the Ministry of Education in Singapore Tier-1 (R-279-000-479-112) and Tier-2 (R-279-000-462-112) Projects.

摘要/Abstract

摘要：

木质素是地球上产量最大的芳香类有机高分子，其有效转化利用在近年来备受关注.催化降解木质素制备酚类单体在过去十年取得了长足进步，目前已开发出氢解、水解、热解、氧化、光解等一系列方法.通过加氢脱氧法可以将木质素的降解产物转化为烃类燃料，但该过程耗氢量大，并且芳香环在加氢气氛下被破坏.另一个可能的应用是将木质素衍生物进一步转化为高附加值的芳香族化合物，但解聚产物成分复杂，成为木质素高效转化为单一高附加值化学品的瓶颈.
在加氢条件下，木质素解聚产物主要为酚类混合物，多在羟基临位带有一至两个甲氧基，并在对位带有C2或C3的取代基（多为烷基）.针对这一结构特点，我们设计了新反应路径，通过分别去除甲氧基和烷基得到苯酚.该过程保留了苯酚的基本结构而将其他取代基去除，原理上可以有效的将木质素降解的混合物转化为单一产物苯酚.通过催化剂的筛选和优化，Pt/C催化剂对脱甲氧基显示出最好的活性和选择性，在400℃，常压下脱除效率>80%.在流动气氛下连续工作4h，Pt/C催化剂无失活迹象.H-ZSM-5为最有效的脱烷基催化剂，最优效率83%左右.H-ZSM-5在反应过程中逐渐失活.通过热重差热及红外光谱分析，失活主要原因为积碳.在400℃空气中煅烧后，催化剂可以再生.
通过简单的物理混合，Pt/C和H-ZSM-5一步将木质素单体转化为60%的苯酚，显示了该方法直接转化木质素到高附加值苯酚的巨大潜力.这是同时将木质素中甲氧基、烷基选择性脱除的首例报道.经过估算，从原生木质素出发，通过加氢解聚，耦合本文开发的一步脱甲氧基、烷基路径，可将木质素转化为约25%的苯酚.木质素中的甲氧基、烷基将分别转化为甲醇和烯烃，提高了木质素碳资源的利用效率.

关键词: 木质素, 苯酚, 分子筛催化剂, 脱甲氧基, 脱烷基

Abstract:

Transformation of lignin into high-value chemicals is hampered by the complexity of monomers obtained from lignin depolymerization. Here we report a strategy, composed of hydro-demethoxylation and de-alkylation reactions, that is able to chemically converge various lignin-derived phenolic monomers into phenol in a single-step. Using 2-methoxy-4-propylphenol as a model compound, Pt/C exhibited the best performance in hydro-demethoxylation reaction affording >80% 4-propylphenol from 2-methoxy-4-propylphenol, while H-ZSM-5 was identified as the most suitable catalyst for de-alkylation, achieving 83% yield of phenol from 4-propylphenol. Since the two catalysts operate under compatible conditions, combining the two catalysts to simultaneously promote both hydro-demethoxylation and de-alkylation reactions was achieved. Configuration of how to organize the catalysts is a critical parameter, where the physical mixture of the two was most effective, providing over 60% phenol from 2-methoxy-4-propylphenol in a single-step.

Key words: Lignin, Phenol, Zeolite, De-alkylation, Hydro-demethoxylation

张佳光, Loris Lombardoa, Gökalp Gözaydın, Paul J. Dyson, 颜宁. 催化一步转化木质素单体为苯酚:建立木质素到高附加值化学品的通道[J]. 催化学报, 2018, 39(9): 1445-1452.

Jiaguang Zhang, Loris Lombardo, Gökalp Gözaydın, Paul J. Dyson, Ning Yan. Single-step conversion of lignin monomers to phenol: Bridging the gap between lignin and high-value chemicals[J]. Chinese Journal of Catalysis, 2018, 39(9): 1445-1452.

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催化一步转化木质素单体为苯酚:建立木质素到高附加值化学品的通道

Single-step conversion of lignin monomers to phenol: Bridging the gap between lignin and high-value chemicals

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