High Aluminum Content Beta Zeolite as an Active Lewis Acid Catalyst for γ-Valerolactone Decarboxylation

Abstract

Butene plays an essential role in the area of petrochemical industry. The production of butene from the biomass-derived platform molecule γ-valerolactone (GVL) is of great interest. GVL decarboxylation reaction occurred under high temperature because the catalytic activity of the catalysts used before was not efficient for this reaction. In this work, beta zeolite with Si:Al = 5 was synthesized and used for GVL decarboxylation. It exhibited a higher catalytic performance than other commercial zeolites due to a large number of Lewis acid sites and relatively large micropore size. At 300 °C, 99.5% GVL conversion and 98% butene yield were obtained after condition optimizing. For further research, the influence of the Brønsted/Lewis acid ratio was investigated, and it turned out that Lewis acid was more active than Brønsted acid in crystalline material on GVL decarboxylation for the first time.

Synthesis of High-Molecular-Weight Biobased Aliphatic Polyesters by Acyclic Diene Metathesis Polymerization in Ionic Liquids

“…Ionic liquids (ILs) are thus the ideal solvents due to their lack of (or extremely low) vapor pressure, miscibility with polymers as well as organic compounds and metal catalysts (which makes most homogeneous catalytic reactions feasible), and high stability ranging from −30 to 300 °C. − These promising characteristics of ILs enable us to consider them as desirable solvents for synthesis of high-molecular-weight polyesters in the ADMET condensation polymerization. − Although olefin metathesis reactions in ILs have been known, − the reported examples of ADMET polymerization have been limited so far. − ,− For instance, the polymerization of 1,9-decadiene in 1- n -butyl-3-methyl imidazolium hexafluorophosphate ([Bmim]­PF 6 ,) in the presence of RuCl 2 (PCy 3 ) 2 (CHPh) ( G1 ) at 50 °C afforded rather high molecular weight polymers (Scheme , M n = 1.08–1.92 × 10 4 ) . The polymerization of 1,4-bis­(undec-10-en-1-yloxy)-triptycene conducted at 100 °C using G2 (initially 80 °C for 24 h, total of seven days) also gave a rather high molecular weight polymer ( M n = 1.15 × 10 4 ) .…”

Selective Synthesis of Butadiene from γ-Valerolactone over ZSM-35 Zeolite

“…Pentanoic acid , and 1,4-pentanediol − could be obtained from the hydrogenation of GVL. Moreover, the decarboxylation of GVL could produce a high yield of butenes over solid acid catalyst such as ZSM-5, Na-BETA, SiO 2 –Al 2 O 3 , − and Al-SBA-15 . Recently, Lin et al found that a yield of >99% butenes could be achieved over a heteroatomic MFI-type zeolite (NbAlS-1) at ambient pressure under continuous flow conditions .…”

Synthesis of Porous Amorphous SiO2−Al2O3 Solid Acid Catalyst for Efficiently Catalyzing GVL Decarboxylation to Butene

“…They found that 98 % butene yield could be obtained over the Nabate-5 catalyst after reacting 4.5 h at 300 °C. [10] Lin et al prepared a novel NbAlS-1 catalyst with both Lewis acids and Brønsted acid, 99 % butene yield can be obtained from 30 % GVL aqueous solution at 300 °C. [11] The same year, Ding and coworker prepared an amorphous SiO 2 À Al 2 O 3 (Si/Al = 4 : 1) catalyst, it also exhibits excellent catalytic performance.…”

“…found that a high butene yield can be obtained only under the action of catalyst with large specific surface area and suitable amount of Brønsted acid sites [8b] . Subsequently, Bond, [9] Zhang, [10] Lin, [11] Ding, [8a] and their team all put forward their ideas on the reaction of catalyzing GVL to butene. Bond et al suggested that the ring‐open of GVL, cyclization and decarboxylation of pentanoic acids occur in parallel at Brønsted sites through a sequence of proton‐mediated elementary steps [9] .…”