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This document is a compilation of contributions to a special issue on catalysts published in the journal Catalysts. The contributions cover various topics related to catalysis, including the hydrodeoxygenation of lignin-derived compounds, the synthesis of bifunctional catalysts, transfer hydrogenation of biomass-like compounds, and the development of multifunctional catalytic systems. Each contribution presents research findings and discusses the implications and potential applications of the respective catalysts. The authors express their gratitude to the editorial team and reviewers for their support and contributions. [Extracted from the article]

Copper (I, II) oxide powders were tested for glycerol conversion to lactic acid under alkaline conditions. Fresh and spent catalysts were characterized using powder X-ray diffraction, Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy, the BET-nitrogen adsorption method and FTIR spectroscopy. In all cases, an almost complete in situ reduction of Cu (I, II) oxides into metallic Cu was observed, even after one catalytic run. Moreover, all the samples of spent catalysts showed similar catalytic activity regardless of their initial form and particle size. Commercial copper powders, prepared copper powders and in situ reduced copper catalysts were tested under the same conditions to compare their catalytic activity. It was shown that the in situ reduced copper catalyst had similar activity to the specially prepared copper powders and much higher activity compared to the commercial copper powders. The in situ reduced copper catalyst exhibited rather high stability. The glycerol conversion and lactic acid selectivity were about 98% and 70%, respectively, after ten catalytic cycles. [ABSTRACT FROM AUTHOR]

In the last decades, environmental crises and increasing energy demand have motivated researchers to investigate the practical techniques for the production of clean fuels through renewable energy resources. It is essential to develop technologies to utilize glycerol as a byproduct derived from biodiesel. Glycerol is known as a sustainable and clean source of energy, which can be an alternative resource for the production of value-added chemicals and hydrogen. The hydrogen production via steam reforming (SR) of glycerol using Ni-based catalysts is one of the promising approaches for the entry of the hydrogen economy. The purpose of this review paper is to highlight the recent trends in hydrogen production over Ni-based catalysts using the SR of glycerol. The intrinsic ability of Ni to disperse easily over variable supports makes it a more viable active phase for the SR catalysts. The optimal reaction conditions have been indicated as 650–900 °C, 1 bar, and 15 wt% Ni in catalysts for high glycerol conversion. In this review paper, the effects of various supports, different promoters (K, Ca, Sr, Ce, La, Cr, Fe), and process conditions on the catalytic performance have been summarized and discussed to provide a better comparison for the future works. It was found that Ce, Mg, and La have a significant effect on catalytic performance as promoters. Moreover, SR of glycerol over hydrotalcite and perovskite-based catalysts have been reviewed as they suggest high catalytic performance in SR of glycerol with improved thermal stability and coke resistance. More specifically, the Ni/LaNi0.9Cu0.1O3 synthesized using perovskite-type supports has shown high glycerol conversion and sufficient hydrogen selectivity at low temperatures. On the other hand, hydrotalcite-like catalysts have shown higher catalytic stability due to high thermal stability and low coke formation. It is vital to notice that the primary concern is developing a high-performance catalyst to utilize crude glycerol efficiently. [ABSTRACT FROM AUTHOR]

Higher tert-Butyl glycerol ethers (tBGEs) are interesting glycerol derivatives that can be produced from tert-butyl alcohol (TBA) and glycerol using an acid catalyst. Glycerol tert-butylation is a complex reaction that leads to the formation of five tBGEs (two monoethers, two diethers, and one triether). In order to gain insight into the reaction progress, the present work reports on the monitoring of glycerol etherification with TBA and p-toluensulfonic acid (PTSA) as homogeneous catalysts. Two analytical techniques were used: gas chromatography (GC), which constitutes the benchmark method, and 1H nuclear magnetic resonance (1H NMR), whose use for this purpose has not been reported to date. A method for the quantitative analysis of tBGEs and glycerol based on 1H NMR is presented that greatly reduced the analysis time and relative error compared with GC-based methods. The combined use of both techniques allowed for a complete quantitative and qualitative description of the glycerol tert-butylation progress. The set of experimental results collected showed the influence of the catalyst concentration and TBA/glycerol ratio on the etherification reaction and evidenced the intrinsic difficulties of this process to achieve high selectivities and yields to the triether. [ABSTRACT FROM AUTHOR]

β-cyclodextrin derivative intercalated MgAl-hydrotalcites (β-CD-Ca/LDH) was synthesized to convert glycerol into high value-added glycerol carbonate(GC) by transesterification of dimethyl carbonate (DMC) and glycerol in this paper. β-cyclodextrin-metal complexes and β-CD-Ca/LDH was characterized by XRD, FT-IR, SEM, XPS and nitrogen adsorption-desorption. The enrichment of organic reactants in the hydrophobic cavity of β-cyclodextrin improved the collision probability of reactants. The intercalation of β-cyclodextrin-calcium complex (β-CD-Ca) increased the pore size and basic strength of catalyst. The experiment results showed that the glycerol conversion was 93.7% and the GC yield was 91.8% catalyzed by β-CD-Ca/LDH when the molar ratio of DMC and glycerol was 3:1, the catalyst dosage was 4 wt.%, the reaction temperature was 75 °C and the reaction time was 100 min while the glycerol conversion was 49.4% and the GC yield was 48.6% catalyzed by MgAl-LDH under the same conditions. [ABSTRACT FROM AUTHOR]

Three types of CuO with different micro–structures were applied to catalyze the conversion of glycerol to lactic acid. The structure–activity relationship between CuO and its catalytic performance was investigated by combining experiments and theoretical calculations. We demonstrated that two CuO samples (CuO–BCC and CuO–CA), as prepared by calcining copper salts, show larger lattice spacing than that of commercial CuO (CuO–COM). In the catalytic experiments, CuO–BCC, which had the largest lattice spacing (d = 0.2480 nm), exhibited the highest yield of 78.54% for lactic acid. The lattice strain caused by lattice expansion was considered more favorable for CuO–BCC in adsorbing glycerol molecules, thereby improving the conversion of glycerol to lactic acid. The DFT simulation calculation results further prove that CuO–BCC has a larger adsorption energy for glycerol and a smaller thermodynamic energy barrier for the dehydrogenation of glycerol to form the key intermediate products (glyceraldehyde and 1,3-dihydroxyacetone) than CuO–COM. This study demonstrates the role of lattice strain effects in the development of catalysts and provides ideas for catalytic glycerol-selective oxidation studies. [ABSTRACT FROM AUTHOR]

Oxidative coupling of alcohols using methanol and ethanol, which can both be made renewable, is an attractive route to produce acrolein (propenaldehyde) in a single-step process. Currently acrolein is produced by direct oxidation of fossil propylene, and catalytic double dehydration of glycerol has been also investigated up to pilot scale. Although glycerol is an attractive feedstock, it suffers of several drawbacks. Addressing the limitations of both routes, the oxidative coupling of alcohols combines an exothermic oxidation and cross-aldolization. The best performing catalysts so far combine redox and acid/base sites. Reviewing the academic and patent literature, the present paper also addresses the economic analysis, to highlight the potential of this reaction at a yield from 70%, and at two different plant scales. The analysis has been made to guide further research, with the remaining technical problems to solve. Improved selectivity contributing to reduce the amount of equipment and the investment cost should be the prime target. [ABSTRACT FROM AUTHOR]

The glycerol hydrogenolysis to produce 1,2-propanediol without using externally supplied hydrogen was investigated using methanol present in crude glycerol to provide in situ hydrogen via its steam reforming reaction. This paper focuses on the promoting effect of Pd on the reactivity of a Cu/Zn/Al2O3 catalyst. Adding 2 wt% Pd onto a Cu/ZnO/Al2O3 catalyst significantly improved the selectivity to 1,2-propanediol from 63.0% to 82.4% and the glycerol conversion from 70.2% to 99.4%. This enhancement on the catalytic activity by Pd is mainly due to the improved hydrogenation of acetol, which is the intermediate formed during the glycerol dehydration. The rapid hydrogenation of acetol can shift the reaction equilibrium of glycerol dehydration forward resulting in a higher glycerol conversion. The improved reducibility of the catalyst by Pd allows the catalyst to be reduced in situ during the reaction preventing any loss of catalyst activity due to any potential oxidation of the catalyst. The catalyst was slightly deactivated when it was firstly recycled resulting in a 5.4% loss of glycerol conversion due to the aggregation of Cu and the deactivation became less noticeable upon further recycling. [ABSTRACT FROM AUTHOR]

In this work, we show that finding and controlling optimum pH environments with Pt-based alloy catalysts can create high catalytic performances for electrocatalytic glycerol oxidation reaction (EGOR). Compared to a Pt/C catalyst, the PtCu/C alloy catalyst has higher reaction rate and turnover frequency (TOF) values by increasing the pH. Specifically, the reaction rate and TOF of the PtCu/C catalyst at pH 13 were 2.93 and 6.65 times higher than those of Pt/C, respectively. The PtCu/C catalyst also showed lower onset potential value and higher mass and specific activities than the Pt/C by increasing the pH. This indicates that the Cu in the PtCu alloy improves the catalytic activity for the EGOR in an OH− group-rich environment. In the case of the PtCu/C catalyst at a high pH condition, the selectivities of tartronic acid and oxalic acid tended to increase as the selectivity of lactic acid decreased. This result means that the PtCu alloy follows primary alcohol oxidation pathways, which are more favorable in an OH− group-rich environment than with only Pt. This study proposes that it is critical to optimize and control the reaction conditions for developing efficient EGOR catalysts. [ABSTRACT FROM AUTHOR]

In this work we demonstrate one-pot glycidol synthesis, via trans-esterification between glycerol and dimethyl carbonate, by making use of commercially available sodium methoxide as a catalyst. An excellent glycerol conversion (99%) and remarkable glycidol yield (75%) was obtained using dimethyl carbonate/glycerol (molar ratio 2:1) in the presence of 3 wt% catalyst amount (with respect to glycerol weight) at 85 °C for a reaction time of 120 min. Sodium methoxide was recycled and reused twice with only a slight decrease in glycerol conversion. The water content of the glycerol reached 2.5 wt%; this did not reduce the glycerol conversion efficiency of the catalyst. A plausible mechanism for the trans-esterification involved in the preparation of glycidol was proposed. [ABSTRACT FROM AUTHOR]

Tungstophosphoric acid (H3PW12O40) supported on silica-coated magnetite nanoparticles has been prepared and used as a heterogeneous acid catalyst (Fe3O4@SiO2@HPW) in the condensation of benzaldehyde (B) with glycerol (Gly) for the production of cyclic acetals. Physicochemical techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectrometry (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and N2 physisorption were used to characterize the prepared catalyst. The effect of glycerol/benzaldehyde molar ratio (1/1 to 1/1.2), temperature (80–120 °C), and catalyst amount (1–5%) on glycerol conversion and the selectivity in main reaction products: benzoic acid, 2-phenyl-1,3-dioxolan-4-yl)methanol, 2-Phenyl-1,3-dioxan-5-ol, 2-phenyl-1,3-dioxolane, and methyl 2-hydroxy-3-phenylpropanoate was studied to evaluate the catalytic activity of the prepared Fe3O4@SiO2@HPW catalyst. The optimization of these process parameters was conducted using Box–Behnken design (BBD). Using the BBD methodology, the optimal parameters (120 °C, 1:1.15 glycerol: benzaldehyde, 5% catalyst) were determined, for a glycerol conversion of and cyclic acetals yield of 85.95% and 78.36%, respectively. The catalyst also exhibits excellent activity for glycerol acetalization with other aromatic aldehydes such as cinnamaldehyde, p-methyl-benzaldehyde, p-hydroxy-benzaldehyde, and vanillin. [ABSTRACT FROM AUTHOR]

Polyglycerols (PGs) are biocompatible and highly functional polyols with a wide range of applications, such as emulsifiers, stabilizers and antimicrobial agents, in many industries including cosmetics, food, plastic and biomedical. The demand increase for biobased PGs encourages researchers to develop new catalytic systems for glycerol polymerization. This review focuses on alkaline homogeneous and heterogeneous catalysts. The performances of the alkaline catalysts are compared in terms of conversion and selectivity, and their respective advantages and disadvantages are commented. While homogeneous catalysts exhibit a high catalytic activity, they cannot be recycled and reused, whereas solid catalysts can be partially recycled. The key issue for heterogenous catalytic systems, which is unsolved thus far, is linked to their instability due to partial dissolution in the reaction medium. Further, this paper also reviews the proposed mechanisms of glycerol polymerization over alkaline-based catalysts and discusses the various operating conditions with an impact on performance. More particularly, temperature and amount of catalyst are proven to have a significant influence on glycerol conversion and on its polymerization extent. [ABSTRACT FROM AUTHOR]

It is of interest to study not only the fundamental behavior of catalysts and reactors but also to ensure that they can be scaled up in size. This paper investigates the scale-up of a glycerol-to-propane process starting from fundamental laboratory data from micro-reactor testing to the kilogram scale. The process is described in detail and consist of the use of design documents and computer simulations for determining the sizes of the unit operations involved. The final design included a vaporizer section for a glycerol/water mixture, four reactors in tandem with subsequent dehydration and hydrogenation reactions, a flash vessel to separate the excess hydrogen used, and a compressor for recycling the excess hydrogen with additional light components. The system was commissioned in a linear fashion, which is described, and operated for more than 3000 h and more than 1000 h in the final operating mode including recycle. The major results were that no catalyst deactivation was apparent aside from the slow build-up of carbonaceous material in the first dehydration reactor. That the system design calculations proved to be quite close to the results achieved and that the data generated is believed to be sufficient for up-scaling the process into the 1000 to 10,000 tonnes-per-annum range. [ABSTRACT FROM AUTHOR]

In this paper, liquefaction of sodium lignosulfonate (SL) over SO42−/TiO2 catalyst in methanol/glycerol was investigated. Effects of temperature, time, the ratio of methanol to glycerol and catalyst dosage were also studied. It was indicated that optimal reaction condition (the temperature of 160 °C, the time of 1 h, solvent ratio (methanol/glycerol) of 2:1, catalyst dosage of 5 wt % (based on lignin input)) was obtained after sets of experiments. The maximum yields of liquefaction (89.8%) and bio-oil (86.8%) were gained under the optimal reaction conditions. Bio-oil was analyzed by elemental analysis, FT-IR and gas chromatogram and mass spectrometry (GC/MS). It was shown that the functional groups of bio-oil were enriched and calorific value of bio-oil was increased. Finally, it can be seen from GC/MS analysis that the type of products included alcohols, ethers, phenols, ketones, esters and acids. Phenolic compounds mainly consisted of G (guaiacyl)-type phenols. [ABSTRACT FROM AUTHOR]

The rapid growth of global biodiesel production requires simultaneous effective utilization of glycerol obtained as a by-product of the transesterification process. Accumulation of the byproduct glycerol from biodiesel industries can lead to considerable environment issues. Hence, there is extensive research focus on the transformation of crude glycerol into value-added products. This paper makes an overview of the nature of crude glycerol and ongoing research on its conversion to value-added products. Both chemical and biological routes of glycerol valorization will be presented. Details of crude glycerol conversion into microbial lipid and subsequent products will also be highlighted. [ABSTRACT FROM AUTHOR]

In this paper, the first biphasic photoreactor was introduced and utilized for the conversion of glycerol to glyceraldehyde (GAD) and dihydroxyacetone (DHA) using water and ethyl acetate as dispersed (active) and continuous (inactive) phases, respectively. Increasing the ethyl acetate content in the reactor improved the DHA yield; however, the optimal DHA selectivity was obtained at an ethyl acetate to water ratio of 90:10 (vol/vol). Compared to a monophasic photoreactor containing only water and identical amounts of glycerol and photocatalyst, the biphasic reactor containing 90 vol % ethyl acetate increased the DHA yield by a factor of 2.9 (from 4.5% to 13%) and the concentration of DHA by approximately 14 times (from 0.08 mM to 1.1 mM) after 240 min. Additionally, photocatalytic conversion of crude glycerol extracted using a 90:10 (vol/vol) ethyl acetate-water mixture showed a similar DHA conversion and yield to that of pure glycerol. [ABSTRACT FROM AUTHOR]

Production of green chemicals using a biomass derived feedstock is of current interest. Among the processes, the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PD) using externally supplied molecular hydrogen has been studied quite extensively. The utilization of methanol present in crude glycerol from biodiesel production can avoid the additional cost for molecular hydrogen storage and transportation, as well as reduce the safety risks due to the high hydrogen pressure operation. Recently the hydrogenolysis of glycerol with a Cu/ZnO/Al2O3 catalyst using in situ hydrogen generated from methanol steam reforming in a liquid phase reaction has been reported. This paper focusses on the effect of added Ni on the activity of a Cu/ZnO/Al2O3 catalyst prepared by an oxalate gel-co-precipitation method for the hydrogenolysis of glycerol using methanol as a hydrogen source. It is found that Ni reduces the conversion of glycerol but improves the selectivity to 1,2-PD, while a higher conversion of methanol is observed. The promoting effect of Ni on the selectivity to 1,2-PD is attributed to the slower dehydration of glycerol to acetol coupled with a higher availability of in situ hydrogen produced from methanol steam reforming and the higher hydrogenation activity of Ni towards the intermediate acetol to produce 1,2-PD. [ABSTRACT FROM AUTHOR]

The direct alcohol fuel cell is a kind of power generation device that directly converts the chemical energy of small molecule alcohols into electric energy. In this paper, the electro-oxidation behaviors of some typical alcohols (methanol, ethanol, ethylene glycol, n-propanol, 2-propanol, and glycerol) over Pt, Pd, and Au electrodes were investigated in acidic, neutral, and alkaline media, respectively. By analyzing the activity information from a cyclic voltammetry (CV) method and some dynamic tests, several regularities were revealed in those electro-oxidation behaviors. Firstly, alkaline media is the best for the electro-oxidation of all these alcohols over Pt, Pd, and Au catalysts. Secondly, the hydrogen bond donation abilities (HBD) of different alcohols were found have a great relationship with the catalytic performance. In alkaline media, on Pt electrodes, the solute HBD is positively correlated with the ease of electrooxidation within the scope of this experiment. Contrarily, it is negatively correlated on Pd and Au electrodes. Additionally, for Pt catalysts in acidic and neutral media, the relationship becomes negative again as the HBD increases. Finally, the alcohol's molecular structure properties were found to have a remarkably influence on the activity of different catalysts. Over the Pt electrode in alkaline media, the activation energy of methanol oxidation is 44.1 KJ/mol, and is obviously lower than the oxidation of other alcohols. Under similar conditions, the lowest activation energy was measured in the oxidation of n-propanol (14.4 KJ/mol) over the Pd electrode, and in the oxidation of glycerol (42.2 KJ/mol) over the Au electrode. Totally, among all these electrodes, Pt electrodes showed the best activities on the oxidation of C1 alcohol, Pd electrodes were more active on the oxidation of C2-3 monobasic alcohols, and Au electrodes were more active on the oxidation of polybasic alcohols. [ABSTRACT FROM AUTHOR]

The depletion of fossil fuels has heightened research and utilization of renewable energy such as biodiesel. However, this has thrown up another challenge of significant increase in its byproduct, glycerol. In view of the characteristics and potentials of glycerol, efforts are on the increase to convert it to higher-value products, which will in turn improve the overall economics of biodiesel production. These high-value products include biofuels, oxygenated fuel additives, polymer precursors and other industrial bio-based chemicals. This review gives up-to-date research findings in the conversion of glycerol to the above high-value products, with a special focus on the performance of the catalysts used and their challenges. The specific products reviewed in this paper include hydrogen, ethanol, methanol, acetin, glycerol ethers, solketal, acetal, acrolein, glycerol carbonate, 1,3-propanediol, polyglycerol and olefins. [ABSTRACT FROM AUTHOR]

Production of 1,2-propanediol and 1,3-propanediol are identified as methods to reduce glycerol oversupply. Hence, glycerol hydrogenolysis is identified as a thermochemical conversion substitute; however, it requires an expensive, high-pressure pure hydrogen supply. Studies have been performed on other potential thermochemical conversion processes whereby aqueous phase reforming has been identified as an excellent substitute for the conversion process due to its low temperature requirement and high H2 yields, factors which permit the process of in-situ glycerol hydrogenolysis which requires no external H2 supply. Hence, this manuscript emphasizes delving into the possibilities of this concept to produce 1,2-propanediol and 1,3-propanediol without "breaking the bank" with expenses. Various heterogenous catalysts of aqueous phase reforming (APR) and glycerol hydrogenolysis were identified, whereby the combination of a noble metal, support, and dopant with a good amount of Brønsted acid sites are identified as the key factors to ensure a high yield of 1,3-propanediol. However, for 1,2-propanediol, a Cu-based catalyst with decent basic support is observed to be the key for good yield and selectivity of product. The findings have shown that it is possible to produce high yields of both 1,2-propanediol and 1,3-propanediol via aqueous phase reforming, specifically 1,2-propanediol, for which some of the findings achieve better selectivity compared to direct glycerol hydrogenolysis to 1,2-propanediol. This is not the case for 1,3-propanediol, for which further studies need to be conducted to evaluate its feasibility. [ABSTRACT FROM AUTHOR]

This study presented an optimisation study of two-stage vapour-phase catalytic glycerol reforming (VPCGR) using response surface methodology (RSM) with a central composite experimental design (CCD) approach. Characterisation through Brunauer–Emmett–Teller analysis (BET), small-angle X-ray scattering (SAXS), scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX), atomic force microscopy (AFM) and particle X-ray diffraction (PXRD) were carried out to understand the physiochemical activity of the honeycomb morphology CuO/CeO2 catalyst. Notably, in this study, we achieved the desired result of glycerol conversion (94%) and H2 production (81 vol.%) under the reaction condition of Cu species loading (10 wt.%), reaction temperature (823 K), WHSV (2 h−1) and glycerol concentration (15 wt.%). From the RSM analysis, an optimum predicted model for VPCGR was obtained and further integrated into Microsoft Excel and Aspen Plus to perform an energy analysis of the VPCGR plant at a scale of 100 kg h−1 of glycerol feed. As a whole, this study aimed to provide an overview of the technical operation and energy aspect for a sustainable frontier in glycerol reforming. [ABSTRACT FROM AUTHOR]

The valuable products produced from glycerol transformation have become a research route that attracted considerable benefits owing to their huge volumes in recent decades (as a result of biodiesel production as a byproduct) as well as a myriad of chemical and biological techniques for transforming glycerol into high-value compounds, such as fuel additives, biofuels, precursors and other useful chemicals, etc. Biodiesel has presented another challenge in the considerable increase in its byproduct (glycerol). This review provides a recent update on the transformation of glycerol with an exclusive focus on the various catalysts' performance in designing reaction operation conditions. The different products observed and cataloged in this review involved hydrogen, acetol, acrolein, ethylene glycol, and propylene glycol (1,3-propanediol and 1,2-propanediol) from reforming and dehydration and hydrogenolysis reactions of glycerol conversions. The future prospects and critical challenges are finally presented. [ABSTRACT FROM AUTHOR]

Activated bentonites are low-cost acid catalysts used in several reactions. However, their application at an industrial scale is affected by the formation of colloidal suspensions when these bentonites are in aqueous solutions. In order to overcome these limitations, this work proposes obtaining a catalyst based on a composite containing natural bentonite within a silica–resin structure, which allows separating and re-utilizing the catalyst more easily and without centrifugal filtration requirements. By means of characterization techniques, the present study determined that the activated bentonite composite presented a total specific surface area of ~360 m2 g−1, ~4 mmol of acid sites per gram of bentonite, and sites with strong acid strength, all of which bestowed activity and selectivity in the solketal synthesis reaction from glycerol and acetone, reaching equilibrium conversion within a short reaction time. Furthermore, the present work developed a Langmuir–Hinshelwood–Hougen–Watson kinetic model, achieving an activation energy of 50.3 ± 3.6 kJ mol−1 and a pre-exponential factor of 6.4 × 106 mol g−1 L−1 s−1, which are necessary for reactor design. [ABSTRACT FROM AUTHOR]

A morphological strategy consisting of nanocasting synthesis of nickel aluminate spinel precursor was addressed. Two nanocasted catalysts were synthesized involving different template-removal procedures (i.e., Teflon-assisted calcination vs. NaOH washing) for spinel recovery. As a reference, spinel NiAl2O4 supported by SBA-15 and bare nickel aluminate spinel were selected. The obtained solids were characterized in detail, examining their textural, acid–base, structural and compositional characteristics, either in the calcined or reduced forms. The as-obtained catalysts' performance was evaluated in the aqueous-phase reforming of glycerol at 235 °C and 35 bar. Exhausted samples were also characterized to enlighten changes in catalyst properties during the aqueous-phase reaction. NiAl/SBA-15 and NiAl-NCF catalyst showed very poor catalytic performance for the glycerol transformation. NiAl-NCN catalyst presented improved activity with respect to NiAl, with a 20% higher hydrogen production rate but, as a drawback, higher methane formation for a whole range of glycerol conversions. Exhausted catalyst indicated nickel oxidized in liquid phase reaction. [ABSTRACT FROM AUTHOR]

In this review, the authors believed that base-catalyzed glycerol etherification via a solvent-free reaction route is a desired way to improve glycerol conversion and product selectivity [[12]]. Gull and co-workers reported the utilization of glycerol for the synthesis of glycerol phosphate esters which could be used as a model molecule to study the origin and evolution of life [[10]]. Meanwhile, the study proved that glycerol concentration influenced the 1,2-PD selectivity greatly, and higher glycerol concentration led to lower 1,2-PD selectivity [[4]]. The glycerol etherification mechanisms in different solvent systems including alcohol solvent, olefin solvent, and solvent-free were investigated. [Extracted from the article]

Natural zeolite clinoptilolite CLIN with a framework ratio of Si/Al ≥ 4 containing mainly potassium and calcium ions in its internal channel system was used as a starting material. The acidic HCLIN catalysts were prepared under soft conditions avoiding the use of environmental less-benign mineral acids. The starting material was ion exchanged using a 0.2 M aqueous ammonium nitrate solution at a temperature 80 °C for 2 h. The obtained NH4CLIN was converted into the acid HCLIN catalyst by calcination at 300–600 °C. The obtained samples were characterized by XRD, FTIR, SEM/TEM, AAS, and EDX element mapping. The state of aluminium and silicon was studied by 27Al- and 29SiMAS NMR spectroscopy. The textural properties of the catalysts were investigated by nitrogen adsorption and desorption measurements. The Brønsted acidity of the HCLIN catalysts was studied by temperature-programmed decomposition of the exchanged ammonium ions releasing ammonia as well as 1H MAS NMR, {1H–27Al} Trapdor, and {1H–27Al} Redor experiments. The strongly agglomerated samples were crystalline and thermally stable up to >500 °C. Although a part of the clinoptilolite framework is maintained up to 600 °C, a loss of crystallinity is already observed starting from 450 °C. The specific surface areas of the starting CLIN and ammonium exchanged NH4CLIN are low with ca. 26 m2/g. The pores are nearly blocked by the exchangeable cations located in the zeolite pores. The thermal decomposition of the ammonium ions by calcination at 400 °C causes an opening of the pore entrances and a markable increase in the specific micropore area and micropore volume to ca. 163 m2/g and 0.07 cm3/g, respectively. It decreases with further rising calcination temperature indicating some structural loss. The catalysts show a broad distribution of Brønsted acid sites (BS) ranging from weak to strong sites as indicated the thermal decomposition of exchanged ammonium ions (TPDA). The ammonium ion decomposition leaving BS, i.e., H+ located at Al–O–Si framework bridges, starts at ≥250 °C. A part of the Brønsted sites is lost after calcination specifically at 500 °C. It is related to the formation of penta-coordinated aluminium at the expense of tetrahedral framework aluminium. The Brønsted sites are partially recreated after repeated ammonium ion exchange. The catalytic performance of the acidic HCLIN catalysts was tested in the etherification of glycerol as a green renewable resource with different C1-C4 alcohols. The catalysts are highly active in the etherification of glycerol, especially with alcohols containing the branched, tertiary alkyl groups. Highest activity is observed with the soft activated catalyst HCLIN300 (300 °C, temperature holding time: 1 min). A total of 78% conversion of glycerol to mono and di ether were achieved with tert-butanol at 140 °C after 4 h of reaction. The mono- and di-ether selectivity were 75% and 25%, respectively. The catalyst can be reused. [ABSTRACT FROM AUTHOR]

Keywords: sustainable fuels and chemicals; hydrogenolysis; deoxygenation; desulfurization and denitrogenation; CO2 utilization; hydroprocessing; pyrolysis and cracking; syngas and hydrogen; light olefins; biomass and bio-oil; catalysis EN sustainable fuels and chemicals hydrogenolysis deoxygenation desulfurization and denitrogenation CO2 utilization hydroprocessing pyrolysis and cracking syngas and hydrogen light olefins biomass and bio-oil catalysis 388 1 05/20/20 20200401 NES 200401 The emission of green-house gases and environmental concerns have led to recent research in the use of renewable feedstocks derived from biomass, waste oils and fats as a source for fuels and chemicals. Processing these feedstocks generally requires esterification and transesterification, deoxygenation, hydrogenation, hydrogenolysis, aldol condensation and cracking reactions. The properties of fuel blend, such as viscosity, density, and cold filter plugging point, confirmed that the hydrotreated vegetable oil blend with fuel can meet the fuel standard for engines without modification. [Extracted from the article]

As the main by-product obtained from biomass, glycerol could be converted into valuable chemicals. Tunable propylsulfonic acid functionalized SBA-15 and KIT-6 with different structural parameters have been prepared by different methods while using 3-mercaptopropyltrimethoxysilane (MPTMS) as the source of sulfur. The composition and structure of the synthesized catalysts have been well-characterized by N2 adsorption-desorption (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The catalytic performance of the prepared catalysts have been evaluated and compared in glycerol acetalization with formaldehyde to the mixture of 1,3-dioxane-5-ol and 1,3-dioxolane-4-methanol. Optimum reaction parameters were investigated to enhance the yield of products and control the distribution of glycerol formals. More than 90% yield of cyclic acetals were obtained with the ratio of two isomers 5R to 6R of 42:58. [ABSTRACT FROM AUTHOR]

Bimetallic AuPt nanoparticles with different Au:Pt ratios (molar ratio: 9-1, 8-2, 6-4, 2-8, 1-9) and the corresponding Au and Pt monometallic ones were prepared by sol immobilization and immobilized on commercial TiO2 (P25). The catalytic activity was evaluated in the liquid phase glycerol oxidation in presence and absence of a base (NaOH). It was found that the Au:Pt molar ratio and reaction conditions strongly influence the catalytic performance. In the presence of NaOH, Au-rich catalysts were more active than Pt-rich ones, with the highest activity observed for Au9Pt1/TiO2 (6575 h-1). In absence of a base, a higher content of Pt is needed to produce the most active catalyst (Au6Pt4/TiO2, 301 h-1). In terms of selectivity, in presence of NaOH, Au-rich catalysts showed a high selectivity to C3 products (63-72%) whereas Pt-rich catalysts promote the formation of formic and glycolic acids. The opposite trend was observed in absence of a base with Pt-rich catalysts showing higher selectivity to C3 products (83-88%). [ABSTRACT FROM AUTHOR]

The performance of boron oxide (B2O3)-promoted Cu/Al2O3 catalyst in the selective hydrogenolysis of glycerol and crude glycerol (a by-product or waste stream from the biodiesel industry) to produce 1,2-propanediol (1,2-PDO) was investigated. The catalysts were characterized using N2-adsorption-desorption isotherm, Inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), ammonia temperature programmed desorption (NH3-TPD), thermogravimetric analysis (TGA), temperature programmed reduction (TPR), and transmission electron microscopy (TEM). Incorporation of B2O3 to Cu/Al2O3 was found to enhance the catalytic activity. At the optimum condition (250 °C, 6 MPa H2 pressure, 0.1 h-1 WHSV (weight hourly space velocity), and 5Cu-B/Al2O3 catalyst), 10 wt% aqueous solution of glycerol was converted into 1,2-PDO at 98 ± 2% glycerol conversion and 98 ± 2% selectivity. The effects of temperature, pressure, boron addition amount, and liquid hourly space velocity were studied. Different grades of glycerol (pharmaceutical, technical, or crude glycerol) were used in the process to investigate the stability and resistance to deactivation of the selected 5Cu-B/Al2O3 catalyst. [ABSTRACT FROM AUTHOR]

Herein, an optimized method for 100 g scale synthesis of glycerol oligomers using a microwave multimode source and the low priced K2CO3 as catalyst is reported. This method allows the complete conversion of glycerol to its oligomers in only 30 min, yielding molecular weights up to 1000 g mol-1. Furthermore, a simple iterative purification process, involving the precipitation of the crude product in acetone and methanol, affords a final product composed of larger oligomers with a narrow dispersity (D < 1.5). [ABSTRACT FROM AUTHOR]

Glycerol steam reforming (GSR) is a promising alternative to obtain renewable hydrogen and help the economics of the biodiesel industry. Nickel-based catalysts are typically used in reforming reactions. However, the choice of the catalyst greatly influences the process, so the development of bimetallic catalysts is a research topic of relevant interest. In this work, the effect of adding Cu, Co, and Cr to the formulation of Ni/SBA-15 catalysts for hydrogen production by GSR has been studied, looking for an enhancement of its catalytic performance. Bimetallic Ni-M/SBA-15 (M: Co, Cu, Cr) samples were prepared by incipient wetness co-impregnation to reach 15 wt % of Ni and 4 wt % of the second metal. Catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), N2-physisorption, X-ray powder diffraction (XRD), hydrogen temperature programmed reduction (H2-TPR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TGA), and tested in GSR at 600 °C and atmospheric pressure. The addition of Cu, Co, and Cr to the Ni/SBA-15 catalyst helped to form smaller crystallites of the Ni phase, this effect being more pronounced in the case of the Ni-Cr/SBA-15 sample. This catalyst also showed a reduction profile shifted towards higher temperatures, indicating stronger metal-support interaction. As a consequence, the Ni-Cr/SBA-15 catalyst exhibited the best performance in GSR in terms of glycerol conversion and hydrogen production. Additionally, Ni-Cr/SBA-15 achieved a drastic reduction in coke formation compared to the Ni/SBA-15 material. [ABSTRACT FROM AUTHOR]

A series of transition metal sulphonato-Schiff base complexes were intercalated into Mg-Al layered-double hydroxides (LDHs). The obtained catalysts were characterized by FTIR, XRD, N2 sorption, SEM and elemental analysis, and then were used in the selective oxidation of glycerol (GLY) using 3% H2O2 as an oxidant. It was found that their catalytic performances were closely related to the loading of active complexes, the Schiff base ligands and the metal centers of the catalysts, as well as the reaction conditions. The optimal conversion of GLY was 85.0%, while the selectivity of 1,3-dihydroxyacetone (DHA) was 56.5%. Moreover, the catalysts could be reused at least 10 times. [ABSTRACT FROM AUTHOR]

The effect of formulations and procedures to deposit thin active layers based on low surface area powders on complex geometry substrates (open-cell foams) was experimentally assessed. An acid-free liquid medium based on water, glycerol, and polyvinyl alcohol was used for powder dispersion, while a dip-coating technique was chosen for washcoat deposition on 30 PPI ceramic open-cell foams. The rheological behavior was explained on the bases of both porosity and actual powder density. It was proved that the use of multiple dippings fulfills flexibility requirements for washcoat load management. Multiple depositions with intermediate flash drying steps at 350 °C were carried out. Washcoat loads in the 2.5 to 22 wt. % range were obtained. Pore clogging was seldom observed in a limited extent in samples with high loading (>20 wt. %). Adhesion, evaluated by means of accelerated stress test in ultrasound bath, pointed out good results of all the deposited layers. [ABSTRACT FROM AUTHOR]

A series of layered double hydroxides (LDHs) -hosted sulphonato-salen Cr(III) complexes were prepared and characterized by various physico-chemical measurements, such as Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-Vis), powder X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM) and elemental analysis. Additionally, their catalytic performances were investigated in the selective oxidation of glycerol (GLY) using 3% H2O2 as an oxidant. It was found that all the LDH-hosted Cr(III) complexes exhibited significantly enhanced catalytic performance compared to the homogeneous Cr(III) complex. Additionally, it was worth mentioning that the metal composition of LDH plates played an important role in the catalytic performances of LDH-hosted Cr(III) complex catalysts. Under the optimal reaction conditions, the highest GLY conversion reached 85.5% with 59.3% of the selectivity to 1,3-dihydroxyacetone (DHA). In addition, the catalytic activity remained after being recycled five times. [ABSTRACT FROM AUTHOR]

Ni-based catalysts as replacement for noble metal catalysts are of particular interest in the catalytic conversion of biomass due to their cheap and satisfactory catalytic activity. The Ni/SiO2 catalyst has been studied for the hydrogenolysis of glycerol, and doping with phosphorus (P) found to improve the catalytic performance significantly because of the formation of Ni2P alloys. However, in the present work we disclose a different catalytic phenomenon for the P-doped Ni/Al2O3 catalyst. We found that doping with P has a significant effect on the state of the active Ni species, and thus improves the selectivity to 1,2-propanediol (1,2-PDO) significantly in the hydrogenolysis of glycerol, although Ni-P alloys were not observed in our catalytic system. The structure and selectivity correlations were determined from the experimental data, combining the results of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR) and ammonia temperature-programmed desorption (NH3-TPD). The presence of NiO species, formed from P-doped Ni/Al2O3 catalyst, was shown to benefit the formation of 1,2-PDO. This was supported by the results of the Ni/Al2O3 catalyst containing NiO species with incomplete reduction. Furthermore, the role the NiO species played in the reaction and the potential reaction mechanism over the P-doped Ni/Al2O3 catalyst is discussed. The new findings in the present work open a new vision for Ni catalysis and will benefit researchers in designing Ni-based catalysts. [ABSTRACT FROM AUTHOR]

Bimetallic AuPd supported on different carbonaceous materials and TiO2 was tested in the liquid phase oxidation of commercial grade and raw glycerol. The latter was directly obtained from the base-catalyzed transesterification of edible rapeseed oil using KOH. The best catalytic results were obtained using activated carbon and nitrogen-functionalized carbon nanofibers as supports. In fact, the catalysts were more active using pure glycerol instead of the one obtained from rapeseed, where strong deactivation phenomena were present. Fourier transform infrared (FT-IR) and TEM were utilized to investigate the possible reasons for the observed loss of activity. [ABSTRACT FROM AUTHOR]

In recent years, the development of renewable energy alternatives to traditional fossil fuels has become one of the major challenges all over the world, due to the decline of fossil fuel reserves and their effect on global warming. Biodiesel has become a popular alternative energy source to reduce gas emissions compared to traditional fossil fuels. According to statistics, a nine-fold increase in global biofuel production between 2000 and 2020 was observed. However, its production generates a large amount of glycerol as a by-product, posing an environmental problem when disposed directly in landfills or by incineration. Therefore, low-value glycerol should be converted into high value-added derivatives. As glycerol carbonate is one of the most important derivatives of glycerol, this review aims to discuss the studies over the last ten years about glycerol carbonate synthetic methods, including the typical routes such as phosgene, esterification reaction, urea, oxidative and direct carbonylation as well as several rare synthetic procedures. At the same time, it summarizes the different catalytic reaction systems of each route comparing the advantages and disadvantages of various catalysts and evaluating their catalytic activity. Finally, the future development of glycerol carbonate synthesis is prospected from the point of view of development, technology research and industrialization. [ABSTRACT FROM AUTHOR]

In this research, a solid acid catalyst was synthesized to catalyse glycerol acetylation into acetins. The sulphated-titania catalysts were prepared via the wet impregnation method at different sulfuric acid concentrations (5%, 10%, 15%, and 20%) and denoted as 5SA, 10SA, 15SA, and 20SA, respectively. The synthesized catalysts were characterized using FTIR, XRD, TGA, BET, NH3-TPD, XRF, and SEM-EDX. The synthesized catalysts were tested on glycerol acetylation reaction at conditions: 0.5 g catalyst loading, 100–120 °C temperature, 1:6 glycerol/acetic acid molar ratios, and 2–4 h reaction time. The final product obtained was analysed using GC-FID. An increment in sulfuric acid concentration reduces the surface area, pore volume, and particles size. However, the increment has increased the number of active sites (Lewis acid) and strong acid strength. 15SA catalyst exhibited excellent glycerol conversion (>90%) and the highest selectivity of triacetin (42%). Besides sufficient surface area (1.9 m2 g−1) and good porosity structure, the great performance of the 15SA catalyst was attributed to its high acid site density (342.6 µmol g−1) and the high active site of metal oxide (95%). [ABSTRACT FROM AUTHOR]

The emergence of biological phosphate esters of glycerol could have been a crucial step in the origin and evolution of life on the early Earth as glycerol phosphates today play a central role in biochemistry. We investigate here the formation of the glycerol phosphates by employing various rock samples, salts, and minerals as potential catalysts to aid the phosphorylation process. We report the synthesis of various phosphate esters of glycerol including glycerol-1-phosphate, glycerol-2-phosphate, cyclic glycerol-monophosphate as well as various diphosphate esters. Furthermore, the decomposition rates of glycerol phosphate under mild heating were also studied while keeping the pH constant. It was observed that glycerol phosphate starts decomposing quickly under mild heating conditions into inorganic orthophosphate and pyrophosphate, and a steady state concentration of ~0.5 M of glycerol phosphate may have been reasonable in ponds with abundant glycerol, phosphate, urea, and catalytic minerals. [ABSTRACT FROM AUTHOR]

Recently, an in vitro enzymatic cascade was constructed to transform glycerol into the high-value platform chemical pyruvate. However, the low activity of dihydroxy acid dehydratase from Sulfolobus solfataricus (SsDHAD) limited the efficiency. In this study, the enzymatic reduction of pyruvate catalyzed by d-lactate dehydrogenase from Pseudomonas aeruginosa PAO1 was used to assay the activities of dihydroxy acid dehydratases. Dihydroxy acid dehydratase from Paralcaligenes ureilyticus (PuDHT) was identified as the most efficient candidate for glycerate dehydration. After the optimization of the catalytic temperature for the enzymatic cascade, comprising alditol oxidase from Streptomyces coelicolor A3, PuDHT, and catalase from Aspergillus niger, 20.50 ± 0.27 mM of glycerol was consumed in 4 h to produce 18.95 ± 0.97 mM of pyruvate with a productivity 12.15-fold higher than the previous report using SsDHAD. The enzymatic cascade was further coupled with the pyruvate decarboxylase from Zymomonas mobile for the production of another platform compound, acetoin. Acetoin at a concentration of 8.52 ± 0.12 mM was produced from 21.62 ± 0.19 mM of glycerol with a productivity of 1.42 ± 0.02 mM h−1. [ABSTRACT FROM AUTHOR]

Calcium-based catalysts are of high interest for glycerol polymerization due to their high catalytic activity and large availability. However, their poor stability under reaction conditions is an issue. In the present study, we investigated the stability and catalytic activity of Ca-hydroxyapatites (HAps) as one of the most abundant Ca-source in nature. A stochiometric, Ca-deficient and Ca-rich HAps were synthesized and tested as catalysts in the glycerol polymerization reaction. Deficient and stochiometric HAps exhibited a remarkable 100% selectivity to triglycerol at 15% of glycerol conversion at 245 °C after 8 h of reaction in the presence of 0.5 mol.% of catalyst. Moreover, under the same reaction conditions, Ca-rich HAp showed a high selectivity (88%) to di- and triglycerol at a glycerol conversion of 27%. Most importantly, these catalysts were unexpectedly stable towards leaching under the reaction conditions based on the ICP-OES results. However, based on the catalytic tests and characterization analysis performed by XRD, XPS, IR, TGA-DSC and ICP-OES, we found that HAps can be deactivated by the presence of the reaction products themselves, i.e., water and polymers. [ABSTRACT FROM AUTHOR]

2-Methylquinoxaline derivatives are widely used as intermediates in the synthesis of pharmaceuticals, natural products, and dyes; however, their syntheses usually require excess reagents, making them environmentally burdensome. Meanwhile, glycerol can be sustainably obtained in large quantities as a by-product in the production of biodiesel fuel using waste oil as a raw material. Thus, it is worthwhile to develop a new catalytic system that utilizes glycerol as a C3 source. In this study, an efficient catalytic system was developed to obtain 2-methylquinoxaline derivatives from glycerol and 1,2-phenylenediamines. This system is beneficial because it is environmentally friendly and has excellent atom efficiency. [ABSTRACT FROM AUTHOR]

The aqueous phase reforming (APR) of glycerol was studied using sonochemically synthesized 10%Ni-x%Ca/ZrO2 catalysts (where x = 0, 0.5, 3, and 5) for the production of value-added liquid products. The APR reaction was performed in a batch reactor under the following conditions: 20 bar, 230 °C 450 rpm, and 1 h of reaction time. The synthesized catalysts were characterized using XRD, FESEM, BET, and H2-TPR to observe the effect of Ca doping on the physio-chemical properties of the catalysts. The results revealed that, at higher Ca loading, the catalysts experienced serious particles' agglomeration, which resulted in a larger particles' size, smaller surface area, and smaller pore volume owing to uneven distribution of the particles. The characterization results of the catalysts confirmed that the Us catalysts have a slightly higher surface area, pore volume, and pore size, as well as highly reducible and fine crystalline structure, compared with WI catalysts. The catalytic performance of the catalysts shows that 1,3-propanediol (1,3-PDO) and 1,2-propanediol (1,2-PDO) were the two main liquid products produced from this reaction. The highest selectivity of 1,3-PDO (23.84%) was obtained over the 10%Ni/ZrO2 catalyst, while the highest selectivity of 1,2-PDO (25.87%) was obtained over the 10%Ni-5%Ca/ZrO2 catalyst. [ABSTRACT FROM AUTHOR]

Biodiesel is one of the most significant and valuable alternatives to fossil fuels. In the process of transesterification to produce biodiesel from various feedstocks, glycerol is one of the side products obtained, in a high glycerol: biodiesel weight ratio (1:10). Therefore, the growing world demand for biodiesel prompted a glycerol surplus. It is, thus, of interest to find new and added-value paths for the transformation of this abundant chemical. One of the most auspicious glycerol applications is the production of fuel additives, namely cyclic acetals and ketals, from aldehydes and ketones, respectively. In this work, coordination polymers based on nitrile (trimethylphosphonic acid) and Ln3+/Eu3+ are used as catalysts for the acetalization of the bio-renewable glycerol into oxygenated fuel additives. Solketal is the major product obtained from the reaction of glycerol with acetone. This product improves the cold flow properties, lowering the viscosity of biodiesel, improving combustion, and boosting the octane number. The stability of the materials is studied as well as their recovery and reuse. [ABSTRACT FROM AUTHOR]

The continuous oligomerization of glycerol for the formation of polyglycerol was carried out for the first time under microwave activation. In the presence of potassium carbonate, we studied the ease of handling, effects of temperature, flow rate and residence time of an inexpensive homogeneous commercial catalyst. The main linear and branched-chain diglycerol and triglycerol regioisomers were characterized and the quantification of the different isomers was realized. Successive cyclic mode processes followed by short distance distillation allowed the mixture to be enriched with glycerol ethers and thus to obtain a mixture of diglycerol (50.2 wt%), triglycerol (22.1 wt%), tetraglycerol (9.5 wt%), and pentaglycerol (4.3 wt%). [ABSTRACT FROM AUTHOR]

Diols, such as 1,2 propanediol, are important commodities for the food, cosmetic, chemical and pharma industries, while 1-propanol is an important chemical and solvent that can be also obtained from glycerol [[11]]. As for ketones, dihydroxyacetone can not only be obtained as one of the main byproducts on the route to biomethanol from glycerol [[10]], but is also very selectively produced by several bacteria such as I Gluconobacter oxidans i out of crude and pure glycerol. 10.3390/catal10060615 12 Ji Y. Recent development of heterogeneous catalysis in the transesterification of glycerol to glycerol carbonate. 10.3390/catal9070581 13 Esteban J., Fuente E., González-Miquel M., Blanco A., Ladero M., Garcia-Ochoa F. Sustainable joint solventless coproduction of glycerol carbonate and ethylene glycol via thermal transesterification of glycerol. [Extracted from the article]

The emergence and evolution of prebiotic biomolecules on the early Earth remain a question that is considered crucial to understanding the chemistry of the origin of life. Amongst prebiotic molecules, glycerol is significant due to its ubiquity in biochemistry. In this review, we discuss the significance of glycerol and its various derivatives in biochemistry, their plausible roles in the origin and evolution of early cell membranes, and significance in the biochemistry of extremophiles, followed by their prebiotic origin on the early Earth and associated catalytic processes that led to the origin of these compounds. We also discuss various scenarios for the prebiotic syntheses of glycerol and its derivates and evaluate these to determine their relevance to early Earth biochemistry and geochemistry, and recapitulate the utilization of various minerals (including clays), condensation agents, and solvents that could have led to the successful prebiotic genesis of these biomolecules. Furthermore, important prebiotic events such as meteoritic delivery and prebiotic synthesis reactions under astrophysical conditions are also discussed. Finally, we have also highlighted some novel features of glycerol, including glycerol nucleic acid (GNA), in the origin and evolution of the life. [ABSTRACT FROM AUTHOR]

In the last few years, the depletion of the fossil sources and their negative effect on the environment has led to find new alternatives; among these, biodiesel is considered one of the most promising for this purpose. Biodiesel can be produced from the transesterification of vegetable oils or animal fats, obtaining glycerol as a by-product. Glycerol can be used in different processes and one of the most interesting is the condensation with acetone to produce solketal. Among its applications, plasticizers, solvents, and pharmaceutical formulations are the most common. In this work, the attention was focused on the reaction between glycerol and acetone to give solketal promoted by an iron(III) complex. The reaction mechanism was hypothesized, and the kinetics was studied in a batch reactor. Finally, the thermodynamic and kinetic parameters were determined with a reliable model investigating the phenomena that occurred in the reaction network. [ABSTRACT FROM AUTHOR]

An unprecedented two-step sequence was designed by combining batch and continuous flow (CF) protocols for the upgrading of two aminodiol regioisomers derived from glycerol, i.e., 3-amino-1,2-propanediol and 2-amino-1,3-propanediol (serinol). Under batch conditions, at 80–90 °C, both substrates were quantitatively converted into the corresponding amides through a catalyst-free N-acetylation reaction mediated by an innocuous enol ester as isopropenyl acetate (iPAc). Thereafter, at 30–100 °C and 1–10 atm, the amide derivatives underwent a selective CF-acetalisation in the presence of acetone and a solid acid catalyst, to afford the double-functionalized (amide-acetal) products. [ABSTRACT FROM AUTHOR]