Catarina N. Dias

The development of sustainable catalysts from renewable resources is a key challenge for reducing the cost of industrial catalytic processes and waste valorization. In this work, low-cost heterogeneous active catalysts were prepared based on pyrolyzed forest residues, forming valuable porous support materials (Biochar) able to efficiently accommodate the highly active heteropolyacid HPW₁₂. Further, magnetic functionality was incorporated in the novel catalytic materials by the impregnation of NiFe₂O₄. The resulting magnetic composites were characterized by FTIR-ATR, SEM-EDS, ICP-OES, BET, XRD, potentiometric titration and magnetometry. The novel HPW₁₂@NiFe₂O₄@Biochar composites were able to valorize the glycerol to produce the fuel additive solketal with high conversion and high selectivity after only 3 h of reaction via acetalization reaction with acetone. The biochar catalytic composite prepared from cork presented higher pore size than the same prepared from forest biomass. This property was crucial to achieve the best conversion (89%) and the highest solketal selectivity (96%). Additionally, reusability capacity was verified, supporting the potential of the cork-pyrolyzed-based composites as potential low-cost catalytic material to produce fuel additives, such as solketal, under sustainable conditions. This may contribute one step further toward a future with greener energy, increasing the viability of biodiesel industry waste.

The valorization of the large amount of crude glycerol formed from the biodiesel industry is of primordial necessity. One possible direction with high interest to the biorefinery sector is the production of fuel additives such as solketal, through the acetalization of glycerol with acetone. This is a chemical process that conciliates high sustainability and economic interest, since solketal contributes to the fulfillment of a Circular Economy Model through its use in biodiesel blends. The key to guarantee high efficiency and high sustainability for solketal production is the use of recovery and recyclable heterogeneous catalysts. Reported works indicate that high yields are attributed to catalyst acidity, mainly the ones containing Brönsted acidic sites. On the other hand, the catalyst stability and its recycling capacity are completely dependent of the support material and the acidic sites incorporation methodology. This review intends to conciliate the information spread on this topic and indicate the most assertive strategies to achieve high solketal production in short reaction time during various reaction cycles.

A binuclear dioxomolybdenum catalyst [(MoO₂Cl₂)₂(L)] (1) (with L (1S,2S)-N,N′-bis(2-pyridinecarboxamide)-1,2-cyclohexane) was prepared and used as catalyst for the desulfurization of a multicomponent model fuel containing the most refractory sulfur compounds in real fuels. This complex was shown to have a high efficiency to oxidize the aromatic benzothiophene derivative compounds present in fuels, mainly using a biphasic 1:1 model fuel/MeOH system. This process conciliates catalytic oxidative and extractive desulfurization, resulting in the oxidation of the sulfur compounds in the polar organic solvent. The oxidative catalytic performance of (1) was shown to be influenced by the presence of water in the system. Using 50% aq. H₂O₂, it was possible to reuse the catalyst and the extraction solvent, MeOH, during ten consecutive cycles without loss of desulfurization efficiency.

The composites of heteropolyacids (H₃PW₁₂, H₃PMo₁₂) incorporated into amine-functionalized silica materials were used for the first time as heterogeneous catalysts in the valorization of glycerol (a major waste from the biodiesel industry) through acetalization reaction with acetone. The polyoxotungstate catalyst H₃PW₁₂@AptesSBA-15 exhibited higher catalytic efficiency than the phosphomolybdate, achieving 97% conversion and 97% of solketal selectivity, after 60 min at 25 °C, or 91% glycerol conversion and the same selectivity, after 5 min, performing the reaction at 60 °C. A correlation between catalytic performance and catalyst acidity is presented here. Furthermore, the stability of the solid catalyst was investigated and discussed.

The composites of heteropolyacids (H3PW12, H3PMo12) incorporated into amine-functionalized silica materials, were used for the first time as heterogeneous catalysts in the valorisation of glycerol (a large waste from biodiesel industry) by acetalization reaction with acetone. The polyoxotungstate catalyst H3PW12@AptesSBA-15 presented higher catalytic efficiency than the phosphomolybdate, with 97% of conversion with 97% of solketal selectivity, after 60 min at 25 °C, or 91% of glycerol conversion and the same selectivity, after 5 min, performing the reaction at 60 ºC. A relation of catalytic performance and acidity of the catalyst is here presented. Furthermore, the stability of the solid catalyst was investigated and discussed.

Glycerol is the main residue in the biodiesel production industry; therefore, their valorization is crucial. The acetalization of glycerol toward fuel additives such as solketal (2,2-dimethyl-1,3-dioxolan-4-methanol) is of high interest, promoting circular economy since it can be added to biodiesel or even fossil diesel to improve their quality and efficiency. Straightforward-prepared metal–organic framework (MOF) materials of the MOF-808 family were applied to the valorization of glycerol for the first time. In particular, MOF-808(Hf) was revealed to be an effective heterogeneous catalyst to produce solketal under moderate conditions: a small amount of the MOF material (only 4 wt% of glycerol), a 1:6 ratio of glycerol/acetone, and a temperature of 333 K. The high efficiency of MOF-808(Hf) was associated with the high amount of acid centers present in its structure. Furthermore, its structural characteristics, such as window opening cavity size and pore diameters, were shown to be ideal for reusing this material for at least ten consecutive reaction cycles without losing activity (conversion > 90% and selectivity > 98%). Remarkably, it was not necessary to wash or activate the MOF-808(Hf) catalyst between cycles (no pore blockage occurred), and it maintained structural integrity after ten cycles, confirming its ability to be a sustainable heterogeneous catalyst for glycerol valorization.

Glycerol is the main residue in the biodiesel production industry; therefore, their valorisation is crucial. Acetalization of glycerol towards fuel additives as solketal (2,2-dimethyl-1,3-dioxolan-4-methanol) is of high interest, promoting circular economy since it can be added to the biodiesel or even fossil-diesel to improve their quality and efficiency. Straightforward prepared metal-organic framework (MOF) materials of MOF-808 family were applied to the valorisation of glycerol for the first time. In particular, MOF-808(Hf) revealed to be an effective heterogeneous catalyst to produce solketal under moderate conditions: small amount of the MOF material (only 4wt% of glycerol), ratio 1:6 of glycerol/acetone and temperature of 60 ºC. The high efficiency of MOF-808(Hf) was associated with the high amount of acid centres present in its structure. Furthermore, its structural characteristics such as window opening cavities size and pore diameters showed to be ideal to reuse this material during at least ten consecutive reaction cycles without losing activity (conversion > 90% and selectivity > 98%). Remarkably, it was not necessary the washing or other activation treatment of the MOF-808(Hf) catalyst between cycles (no pore blockage occurred) and it maintained structural integrity after the ten cycles, confirming to be a sustainable heterogeneous catalyst to the glycerol valorisation.