Highly dispersed MgInCe-mixed metal oxides catalyzed direct carbonylation of glycerol and CO_(2)into glycerol carbonate

Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.

Layer-by-layer fabrication of montmorillonite coating immobilizing Cu_(2)O nanoparticles for continuously catalyzing glycerol to dihydroxyacetone

Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.

Complete kinetic model for esterification reaction of lauric acid with glycerol to synthesize glycerol monolaurate

Glycerol monolaurate(GML)is a widely used industrial chemical with excellent emulsification and antibacterial effect.The direct esterification of glycerol with lauric acid is the main method to synthesize GML.In this work,the kinetic process of direct esterification was systematically studied using p-toluenesulfonic acid as catalyst.A complete kinetic model of consecutive esterification reaction has been established,and the kinetic equation of acid catalysis was deduced.The isomerization reactions of GML and glycerol dilaurate were investigated.It was found that the reaction was an equilibrium reaction and the reaction rate was faster than the esterification reaction.The kinetic equations of the consecutive esterification reaction were obtained by experiments as k_(1)=(276+92261Xcat)exp(-37720/RT)and k_(2)=(80+4413Xcat)exp(-32240/RT).The kinetic results are beneficial to the optimization of operating conditions and reactor design in GML production process.

Understanding the catalytic performance and deactivation behaviour of second-promoter doped Pt/WO_(χ)/γ-Al_(2)O_(3) catalysts in the glycerol hydrogenolysis for selective and cleaner production of 1,3-propanediol

The selective aqueous-phase glycerol hydrogenolysis is a promising reaction to produce commercially useful 1,3-propanediol(1,3-PDO).The Pt-WOx bifunctional catalyst can catalyse the glycerol hydrogenol-ysis but the catalyst deactivation via sintering,metal leaching,and coking can predominantly occur in the aqueous phase reaction.In this work,the effect of reaction temperature,pressure and second promoter(Cu,Fe,Rh,Mn,Re,Ru,Ir,Sn,B,and P)on catalytic performance and deactivation behaviour of Pt/WOx/-Al2O3 was investigated.When doped with Rh,Mn,Re,Ru,Ir,B,and P,the second promoter boosts catalytic activity by promoting great dispersion of Pt on support and increasing Pt surface area.The increased Bronsted acid sites lead to selective synthesis of 1,3-PDO than 1,2-propanediol(1,2-PDO).The characterization studies of fresh and spent catalysts reveal that the main cause of catalyst deactivation is the Pt sintering,as interpreted based on XRD,CO chemisorption,and TEM analyses.The Pt sintering is affected depending on the second promoter that can either or reduce the interaction between Pt,WO_(χ)/γ and Al_(2)O_(3).As an electron acceptor of Pt in Pt/WO_(χ)/γ-Al_(2)O_(3),Re and Mn as second promoters resulted in increased Pt^(2+) on the catalytic surface,which strengthens the contact between Pt andγ-Al_(2)O_(3) and WO_(χ),resulting in a decrease in Pt sintering.The metal leaching and coking are not affected by the presence of second promoter.The catalyst modified with a second promoter possesses improved catalytic activity and 1,3-PDO production,however the stability continues to remain a challenge.The present work unrav-elled the determining parameters of catalytic activity and deactivation,thus providing a promising pro-tocol toward effective catalysts for glycerol hydrogenolysis.

Selective glycerol oxidation using platinum nanoparticles supported on multi-walled carbon nanotubes and nitrogen-doped graphene hybrid

Selective oxidation of glycerol is a hot topic.Increased biodiesel production has led to glycerol oxidation over Au- and Pt-based catalysts being widely studied.However,Pt catalysts suffer from deactivation because of weak metal-support interactions.In this study,multi-walled carbon nanotube（MWCNTs）-pillared nitrogen-doped graphene（NG） was prepared by direct pyrolysis of melamine on MWCNTs,and the synthesized NG-MWCNT composite was used as the support for Pt.Characterization results showed that the surface area（173 m^2/g） and pore volume of the NG-MWCNT composite were greater than those of bare MWCNTs and the separated melamine pyrolysis product（CH_x）.Pt（1.4±0.4 nm） dispersion on the NG-MWCNTs was favorable and the Pt/NG-MWCNT catalyst was highly active and selective in the oxidation of glycerol to glyceric acid（GLYA） in base-free aqueous solution.For example,the conversion of glycerol reached 64.4% with a GLYA selectivity of 81.0%,whereas the conversions of glycerol over Pt/MWCNTs and Pt/CN_x were 29.0% and 31.6%,respectively.The unique catalytic activity of the Pt/NG-MWCNTs is attributed to well-dispersed Pt clusters on the NG-MWCNTs and the electron-donating effect of the nitrogen dopant in the NG-MWCNTs.

Selective oxidation of glycerol to lactic acid over activated carbon supported Pt catalyst in alkaline solution

Pt/activated carbon （Pt/AC） catalyst combined with base works efficiently for lactic acid production from glycerol under mild conditions. Base type （LiOH, NaOH, KOH, or Ba（OH）2） and base/glycerol molar ratio significantly affected the catalytic performance. The corresponding lactic acid selectivity was in the order of LiOH〉NaOH〉KOH〉Ba（OH）2. An increase in LiOH/glycerol molar ratio ele‐vated the glycerol conversion and lactic acid selectivity to some degree, but excess LiOH inhibited the transformation of glycerol to lactic acid. In the presence of Pt/AC catalyst, the maximum selec‐tivity of lactic acid was 69.3% at a glycerol conversion of 100% after 6 h at 90 °C, with a Li‐OH/glycerol molar ratio of 1.5. The Pt/AC catalyst was recycled five times and was found to exhibit slightly decreased glycerol conversion and stable lactic acid selectivity. In addition, the experimental results indicated that reaction intermediate dihydroxyacetone was more favorable as the starting reagent for lactic acid formation than glyceraldehyde. However, the Pt/AC catalyst had adverse effects on the intermediate transformation to lactic acid, because it favored the catalytic oxidation of them to glyceric acid.

Urchin-like CoCu Bimetallic Nanocomposites for Catalytic Hydrogenolysis of Glycerol to Propanediols

Bimetallic CoCu nanocomposites were synthesized in polyol by using Ru as heterogeneous nucleation agent and stearic acid as surfactant, and their catalytic properties were investi- gated by hydrogenolysis of glycerol to propanediols. It was found that the surfactant could induce Co nanocrystals to form nanowires as structure-directing agent, while it＇s ineffective for Cu because only spherical Cu particles were produced under the same condition. When Co2＋ and Cu2＋ coexist in polyol, Cu2＋ is firstly reduced and forms the spherical particles, and then the Cu particles afford surface for the subsequential reduction of Co2＋ and growth of Co nanocrystals to form the nanorods, obtaining the urchin-like CoCu nanocomposites. The catalytic performance in selective hydrogenolysis of glycerol to propanediols proposed that the CoCu urchin-like nanocomposites was superior to the Co nanowires possibly due to that the synergistic effect between Co and Cu component promoted conversion of glyc- erol and obtained the higher propanediol yields based on the specific surface areas of the catalysts.

Dose Analysis of Methanol, Ethanol, Acetone and Glycerol to PC-12 Tumor Cells' Morphology and Growth

The morphologic changes and growth status of PC12 cells were observed after intervened by different concentrations of methanol, ethanol, acetone, glycerol and the toxic concentrations were ascertained. Four kinds of organic solvents al showed certain cytotoxicity to PC12 cells. Compared with other three kinds of or-ganic solvents, ethanol showed the most obvious cytotoxicity to PC12 cells and the cellviability would be reduced to 60% if the concentration of ethanol was 20 ml/L and the intervention lasted for 24 h. Under the same condition, the reduced per-centages of cellviability for acetone and ethanol were 20% and 15% respectively. Glycerol also showed cytotoxicity to PC12 cells, especial y as the concentration was raised gradual y, but the toxicity was relatively mild. This study would provide refer-ence material for subsequent pharmacological studies.

Alcohol-treated SiO_2 as the support of Ir-Re/SiO_2 catalysts for glycerol hydrogenolysis

The surface of SiO2 support was pretreated by C1-C4 normal alcohols before the impregnation of iridium and rhenium precursors.These catalysts were applied in high concentration glycerol aqueous solution hydrogenolysis.The catalysts prepared from the pretreated supports exhibited high catalytic activity because of the formation of more active sites from a high dispersion of iridium oxide and rhenium oxide.The catalysts with the support pretreated by 1-propanol showed the highest glycerol conversion of 59.5%.The supports and catalysts were characterized by FT-IR,nitrogen adsorption,TPR,XRD,TEM,H2-chemisorption and NH3-TPD.

Sustainable value-added C3 chemicals from glycerol transformations:A mini review for heterogeneous catalytic processes

It is of importance to convert glycerol,the primary by-product from biodiesel manufacturing,to various valuable C3 chemicals,such as acrolein via dehydration,lactic acid,1,3-dihydroxyacetone via oxidation,and 1,3-propanediol,allyl alcohol via hydrogenolysis.As compared to petroleum-based resources,C3 chemicals from glycerol provide a benign,sustainable and atomically economic feature.Extensive heterogeneous catalysts have been designed,prepared and tested for these transformations.In recent five years,great progress,including high yields to target products over appropriate catalysts,insight into reaction mechanism and network,has been achieved.The present review systematically covers recent research progress on sustainable C3 chemical production from catalytic glycerol transformations.We hope that it will benefit future research on transformations of glycerol as well as other polyols.

Catalytic conversion of cellulose-based biomass and glycerol to lactic acid

Catalytic transformation of cellulose into value-added chemicals is of great importance for utilization of renewable and abundant biomass. Due to the high oxygen content, cellulose serves as an ideal candidate for the production of oxygenates, in particular lactic acid which is a versatile building block in chemical industry. The efficient conversion of cellulose to lactic acid generally requires selective activation of specific C-O and C-C bonds, and therefore multifunctional catalysts that combine several key reactions including hydrolysis, isomerization and retro-aldol fragmentation are highly desirable. This review article highlights the recently developed catalytic systems and catalysts for the selective transformation of cellulose and cellulose-derived carbohydrates into lactic acid, lactates and/or its esters. Emphases will be put on the reaction mechanism and key factors that exert effects on the catalytic performances. In addition, the catalytic transformation of glycerol, a C3 compound over-supplied from biodiesel industry, will also be surveyed. Recent advances in the development of new catalysts or strategies are analyzed and discussed to gain insight into the transformation of C3 compound to lactic acid.

Selective synthesis of triacetin from glycerol catalyzed by HZSM-5/MCM-41 micro/mesoporous molecular sieve

HZSM-5/MCM-41 molecular sieve (H-ZM) catalysts with well-defined micro/mesoporous structures were synthesized and showed high performance for selective synthesis of triacetin via the esterification reaction of glycerol with acetic acid. The conversion of glycerol was demonstrated to be 100% and the triacetin selectivity was over 91%, which can be attributed to the synergistic effect regarding suitable acidic property, excellent diffusion efficiency and good stability derived from the combined advantages of microporous molecular sieve HZSM-5 and mesoporous molecular sieve MCM-41.

Glycerol carbonate synthesis from glycerol and dimethyl carbonate using guanidine ionic liquids

A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate. In this paper, a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate. The tunable basicity and the anion–cation cooperative effect were responsible for the obtained results. The [TMG][TFE] showed the best activity turnover frequency(TOF)of 1754.0 h^(-1), glycerol(GL) conversion of 91.8%, glycerol carbonate(GC) selectivity of 95.5%) at 80 °C with 0.1 mol% catalyst for 30 min. The reaction mechanism of the transesterification was also proposed.

Glycerol steam reforming over calcium hydroxyapatite supported cobalt and cobalt-cerium catalysts

Calcium hydroxyapatite（HAp） supported cobalt and cobalt-cerium catalysts were examined for hydrogen production in glycerol steam reforming. The catalysts were synthesized by incipient wetness impregnation method and characterized through X-ray diffraction, adsorption-desorption isotherms of N2 and temperature-programmed reduction of H2. Catalytic properties were examined in terms of glycerol conversion, selectivity toward hydrogen and C-containing products in temperature range of 650-800 ℃.The effect of active metal reduction and residence time（thereby flow feed rate） was analysed. It was found that the growth of residence time increased the hydrogen selectivity in the whole temperatures range whereas the catalyst reduction, before the catalytic process, decreased the hydrogen selectivity at temperatures lower than 750 ℃. The cerium addition improved the catalytic behaviour for hydrogen production via glycerol steam reforming. Cerium oxide suppressed the sintering of cobalt particles and as a result Co-Ce/HAp ensured higher stability and H2 selectivity than Co/HAp. Under reaction conditions investigated in this study, the highest selectivity toward hydrogen at 650 ℃ was obtained for 7.5 Co-Ce/HAp catalyst.

Syngas production by dry reforming of the mixture of glycerol and ethanol with CaCO3

The reduction of CO2 emission is crucial for the mitigation of climate change.A considerable amount of industrial CO2 can be absorbed in the form of carbonates through high-temperature sorption processes.In this regard,the efficient conversion of carbonates to value-added products will provide an economically viable method for the sustainable usage of carbon compounds.Herein,we report a promising solution involving the use of a glycerol and ethanol mixture as a hydrogen donor in the dry reforming process with CaCO3 to produce syngas.A series of metal active components,including Ni,Fe,Co,Cu,Pt,Pd,Ru,and Rh,was used to promote this reaction.Ni showed comparable performance with that of Pd,but outperformed Co,Fe,Cu,Rh,Ru,and Pt.Approximately 100%conversion of glycerol and ethanol,~92%selectivity of synthesis gas(H2 and CO),and a H2/CO ratio of^1.2 were achieved over CaCO3 containing10 wt%Ni(10Ni-CaCO3).Meanwhile,the CO2 concentration was less than 5 vol%,indicating that most of the CO2 captured by the carbonate can be transformed into chemicals;however,they cannot simply be emitted.The CO2 released from the decomposition of CaCO3 not only adjusted the ratio of H2 to CO but also eliminated cokes to guarantee the CO2 absorption-conversion cyclic stability in the absence of steam and at high temperatures.

Zeolite-assisted etherification of glycerol with butanol for biodiesel oxygenated additives production

This research was focused on the valorisation of glycerol,exploring the feasibility of an efficient route for oxygenated additives production based on its etherification with bio-butanol.A home-made BEA zeolite sample with a tuneable acidity has been proposed as the catalytic system,being tested in a stirred reactor under different etherification conditions.Although a reaction temperature as high as 200℃resulted to be beneficial in terms of glycerol conversion(-90%),only by operating at milder conditions the product selectivity to glycerol-ethers can be better controlled,in order to obtain a bio-fuel complying with the requirements for mixing with fossil diesel or biodiesel,without any need of purification from large amount of by-products.A comprehensive identification of all the compounds formed during the reaction was performed by a GC-MS analysis,on the basis of the complex network of consecutive and parallel reaction paths leading not only to the desired ethers,but also to many side products not detected in similar acid-catalyzed reactions in liquid phase and not available in the most used mass-spectra libraries.

Aquaporin-3 Deletion Reduces Glycerol and ATP Content in Mouse Sciatic Nerve

We reported the expression and function of aquaglyceroporin AQP3 in mouse peripheral nervous system.AQP3 mRNA was identified in freshly isolated mouse sciatic nerve by RT-PCR.Immunofluorescence using AQP3 antibody localized the protein expression in the myelin sheathe of sciatic nerve fibers.Although primary morpholo-gical evaluation of sciatic nerves from AQP3-knockout and wildtype mice revealed no significant difference,biochemical analysis demonstrated remarkably decreased glycerol and ATP contents in freshly isolated AQP3-knockout sciatic nerve.The study indicates an important role of facilitated glycerol transport mechanism in peripheral nerve energy metabolism.

Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al2O3 Catalysts

A series of Cu-ZnO-Al2O3 catalysts with various metal compositions of Cu/Zn/Al were prepared by the co-precipitation method,and screened for glycerol hydrogenolysis to propylene glycol.The catalyst with a Cu/Zn/Al molar ratio of 1:1:0.5 exhibited the best performance for glycerol hydrogenolysis,and thus selected for kinetic investigation.Under elimination of external and internal diffusion limitation,kinetic experiments were performed in an isothermal fixed-bed reactor at a hydrogen pressure range of 3.0-5.0 MPa and a temperature range of 493-513 K. Based on a dehydration-hydrogenation two-step hydrogenolysis mechanism,a two-site Langmuir-Hinshelwood kinetic model taking into account competitive adsorption of glycerol,acetol and propylene glycol was proposed and successfully fitted to the experimental data.The average relative errors between observed and predicted outlet concentrations of glycerol and propylene glycol were 6.3%and 7.6%,respectively.The kinetic and adsorption parameters were estimated by using the fourth-order Runge-Kutta method together with the Rosenbrock algorithm.The activation energies for dehydration and hydrogenation reactions were 86.56 and 57.80 kJ·mol-1,respectively.

Selective oxidation of glycerol in a base-free aqueous solution: A short review

Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.

Selective hydrogenolysis of glycerol to 1,3-propanediol over Pt-W based catalysts

The selective hydrogenolysis of glycerol to 1,3-propanediol(1,3-PDO)is an attractive reaction due to the high demand for valorization of huge excess amounts of glycerol supply as well as the important application of 1,3-PDO in polyester industry.Nevertheless,the formation of 1,3-PDO is thermodynamically less favorable than 1,2-PDO,which necessitates the development of efficient catalysts to manipulate the reaction kinetics towards the 1,3-PDO formation.Among others,Pt-W based catalysts have shown promising activities and selectivities of 1,3-PDO although the reaction mechanism is not well addressed at the molecular level.In this short review,we have compared the performances of different Pt-W based catalysts and discussed the key factors influencing the activity and selectivity.Three possible reaction mechanisms have been discussed in terms of the synergy between Pt and WO_x and the origin of acid sites.Finally,the long-term stability of the Pt-W catalysts has been discussed.We hope this review will provide useful information for the development of more efficient catalysts for this important reaction.