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Pentanoic acid from γ-valerolactone and formic acid using bifunctional catalysis
Green Chemistry ( IF 9.3 ) Pub Date : 2019-11-22 , DOI: 10.1039/c9gc02627d Majd Al-Naji 1, 2, 3, 4, 5 , Joost Van Aelst 5, 6, 7, 8, 9 , Yuhe Liao 5, 6, 7, 8, 9 , Martin d'Hullian 5, 6, 7, 8, 9 , Zhipeng Tian 10, 11, 12, 13 , Chenguang Wang 10, 11, 12, 13 , Roger Gläser 4, 14, 15, 16 , Bert F. Sels 5, 6, 7, 8, 9
Green Chemistry ( IF 9.3 ) Pub Date : 2019-11-22 , DOI: 10.1039/c9gc02627d Majd Al-Naji 1, 2, 3, 4, 5 , Joost Van Aelst 5, 6, 7, 8, 9 , Yuhe Liao 5, 6, 7, 8, 9 , Martin d'Hullian 5, 6, 7, 8, 9 , Zhipeng Tian 10, 11, 12, 13 , Chenguang Wang 10, 11, 12, 13 , Roger Gläser 4, 14, 15, 16 , Bert F. Sels 5, 6, 7, 8, 9
Affiliation
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Pentanoic acid (PA) is an industrially relevant chemical used in several applications, currently manufactured from fossil feedstock. Conversion of γ-valerolactone (GVL), a stable platform chemical from cellulosic biorefineries, into PA is studied here in the presence of aqueous formic acid (FA), as a sustainable and available reducing agent. For this purpose, bifunctional catalyst comprising Pt supported on acidic zeolites were utilized. Pt has a dual role, decomposing FA into hydrogen in the fastest step occuring in the initial stage of the reaction, and hydrogenating pentenoic acids (PEAs) intermediates, which are formed through acid-catalyzed ring opening of GVL, to PA. Since ring-opening is thermodynamically disfavored under hydrothermal conditions at high temperature (543 K), hydrogenation on Pt is rate limiting and thus fast provision of hydrogen is a prerequisite to PA formation from GVL. Strong acidity such as on ZSM-5 is required to catalyze the dehydration/ring-opening step in the reaction cascade from GVL to PA. High surface area of Pt improves GVL conversion rate, whereas no dependency of rate on Brønsted acidity is observed in the applied conditions. Strong interaction of the Pt/ZSM-5 catalyst with FA and its decomposition side-products, e.g. CO, retards the hydrogenation step, and therefore may better be added stepwise. The temperature dependency of this cascade reaction was determined, showing an apparent activation energy for GVL conversion and FA dehydrogenation of 73 kJ mol−1 and 19 kJ mol−1, respectively. Finally, the selective one-pot process of levulinic (LA) instead of GVL, to PA using FA as reducing agent was pioneered successfully.
中文翻译：
γ-戊内酯中的戊酸和甲酸的双功能催化
戊酸（PA）是一种工业相关的化学品，用于多种应用，目前由化石原料生产。γ-戊内酯（GVL）是一种稳定的平台化学物质，由纤维素生物精炼厂转化为PA，在甲酸（FA）作为可持续和可用的还原剂存在的情况下，在此进行了研究。为此目的，使用了包含负载在酸性沸石上的Pt的双功能催化剂。Pt具有双重作用，即在反应初始阶段发生的最快步骤中将FA分解成氢，然后将通过GVL的酸催化开环形成的戊烯酸（PEA）中间体氢化成PA。由于开环在高温（543 K）的水热条件下在热力学上是不利的，在Pt上加氢是速率限制，因此快速提供氢是从GVL形成PA的先决条件。在从GVL到PA的级联反应中，需要强酸（例如ZSM-5）来催化脱水/开环步骤。Pt的高表面积可提高GVL转化率，而在所施加的条件下未观察到速率对布朗斯台德酸度的依赖性。Pt / ZSM-5催化剂与FA及其分解副产物之间有很强的相互作用，例如CO，会延迟氢化步骤，因此最好逐步添加。确定了该级联反应的温度依赖性，显示出用于GVL转化和FA脱氢的表观活化能分别为73kJ mol -1和19kJ mol -1。最后，成功地探索了以FA为还原剂的乙酰丙氨酸（LA）取代GVL的选择性一锅法。
更新日期：2019-11-22
中文翻译：
γ-戊内酯中的戊酸和甲酸的双功能催化
戊酸（PA）是一种工业相关的化学品，用于多种应用，目前由化石原料生产。γ-戊内酯（GVL）是一种稳定的平台化学物质，由纤维素生物精炼厂转化为PA，在甲酸（FA）作为可持续和可用的还原剂存在的情况下，在此进行了研究。为此目的，使用了包含负载在酸性沸石上的Pt的双功能催化剂。Pt具有双重作用，即在反应初始阶段发生的最快步骤中将FA分解成氢，然后将通过GVL的酸催化开环形成的戊烯酸（PEA）中间体氢化成PA。由于开环在高温（543 K）的水热条件下在热力学上是不利的，在Pt上加氢是速率限制，因此快速提供氢是从GVL形成PA的先决条件。在从GVL到PA的级联反应中，需要强酸（例如ZSM-5）来催化脱水/开环步骤。Pt的高表面积可提高GVL转化率，而在所施加的条件下未观察到速率对布朗斯台德酸度的依赖性。Pt / ZSM-5催化剂与FA及其分解副产物之间有很强的相互作用，例如CO，会延迟氢化步骤，因此最好逐步添加。确定了该级联反应的温度依赖性，显示出用于GVL转化和FA脱氢的表观活化能分别为73kJ mol -1和19kJ mol -1。最后，成功地探索了以FA为还原剂的乙酰丙氨酸（LA）取代GVL的选择性一锅法。
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