Abstract
Benzene carboxylic acid (BCAs) are common and useful chemical blocks, which can be derived from the abundant low rank coals (LRCs) via oxidative degradation. In this work, we proposed a novel strategy to utilize BCAs as raw materials to prepare catalysts with transition metal zirconium, and the prepared catalysts were applied into the conversion of the renewable biomass resources. Typical model BCAs in the oxidative products of LRCs, including pyromellitic acid, trimesic acid (TMSA), trimellitic acid, and benzoic acid, were used as the block to construct the Zr-BCAs catalysts. The chemoselective conversion of furfural into furfuryl alcohol (FAL), an important reaction in the biomass conversion chain, is chosen to evaluate the activity of the catalysts. The preparation conditions of the catalysts and experiment factors during the reaction were systematically investigated. The prepared catalysts were characterized by SEM, TEM, XRD and TG-DTG. The results showed that the prepared catalysts were efficient for the conversion of furfural into FAL, among which Zr-TMSA gave the highest activity. Zr-TMSA could be recycled for ten times without obvious deactivation, indicating an excellent stability. The strategy proposed in this work may be beneficial for the value-added utilization of both LRCs and biomass resources.Graphical Zr-BCAs catalysts prepared using benzene carboxylic acids and Zr are very efficient and stable for hydrogenation of biomass-derived furfural to furfuryl alcohol at mild conditions.
Highlights
Low rank coals (LRCs), with large abundance on earth, become important carbon resources especially with the fast depletion of high quality fossil resources
For the conditions that all the carboxylic groups in benzene carboxylic acids (BCAs) molecules were totally neutralized for the four kinds of BCAs, Zr-trimesic acid (TMSA) possessed the highest activity (Entries 1, 5, 7, 9)
For pyromellitic acid (PMA) (Entries 1–4), TMSA (Entries 5–6), and trimellitic acid (TMLA) (Entries 7–8), similar potentials could be found that the activity generally increased with the increasing of the usage of alkali, coming to the highest value when all the carboxylic groups in BCAs were totally neutralized
Summary
Low rank coals (LRCs), with large abundance on earth, become important carbon resources especially with the fast depletion of high quality fossil resources. We reported a novel Zr catalyst using the LRCs derived humic acids (HAs) as the building block, and the Zr-HAs catalysts were highly efficient for the production of gamma-valerolactone (GVL) from ethyl levulinate (EL) (Xiao et al 2017). These reported catalysts are efficient for the hydrogenation of carbonyl groups, they suffer some drawbacks, such as severe reaction conditions and limited sources of the skeleton materials used in the preparation. The proposed strategy is beneficial for both the efficient and clean utilization of LRCs and promoting the conversion of biomass-derived furfural
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