Towards Thermally Reversible Networks Based on Furan-Functionalization of Jatropha Oil

A novel biobased monomer for the preparation of thermally reversible networks based on the Diels-Alder reaction was synthesized from jatropha oil. The oil was epoxidized and subsequently reacted with furfurylamine to attach furan groups via an epoxide ring opening reaction. However, furfurylamine also reacted with the ester groups of the triglycerides via aminolysis, thus resulting in short-chain molecules that ultimately yielded brittle thermally reversible polymers upon cross-linking via a Diels-Alder reaction. A full-factorial experimental design was used in finding the optimum conditions to minimize ester aminolysis and to maximize the epoxide ring opening reaction as well as the number of furans attached to the modified oil. The optimum conditions were determined experimentally and were found to be 80 °C, 24 h, 1:1 molar ratio, with 50 mol % of LiBr with respect to the modified oil, resulting in 35% of ester conversion, 99% of epoxide conversion, and an average of 1.32 furans/triglyceride. Ultimately, further optimization by a statistical approach led to an average of 2.19 furans per triglyceride, which eventually yielded a flexible network upon cross-linking via a Diels-Alder reaction instead of the brittle one obtained when the furan-functionalization reaction was not optimized

A Systematic Study on the Utilization of Inorganic Salts as Catalyst for the Conversion of Xylose to Furfural

The utilization of biomass-waste such as sugar-bagasse,water-hyacynth and palm-oil-fiber as alternative sources for transportation fuels and platform-chemicals is a very active research field. Furfural(FF) is one-of-the-13top platform-chemicals that may be converted to derivatives such as furfuryl-alcohol,furoic-acid and furan with wide applications in the gasoline,diesel and jet-fuel blending-pool. Many studies have been conducted in the mechanism and the kinetics of FF-formation from xylose since the 1940s to maximize FF-yield and to reduce FF-decomposition to undesired-products. Previous studies showed that inorganic-salt gives positive effects on the FF-yield but systematic studies are lacking. Based on it, 60salts were screened in the hydrolysis of 0.1M xylose-aqueous-solution (T=180°C,90minutes,batch). The maximum FF-yield was 53mol% using 5mM-Fe2(SO4)3. The highest FF-selectivity was at 84mol% using 5mM-NaCl, though at low xylose-conversion(35 mol%-FF-yield). Some transition metal-chloride i.e.FeCl2,CuCl2,SnCl2 showed interesting FF-yields(48-50%) and selectivity(58-65%) indicating interesting roles of ion Fe3+ and Cl-. Subsequent studies of two salts i.e.Fe2(SO4)3 and FeCl3(5mM) in combination with HCl and H2SO4(0.1M) were investigated(0.1M-xylose,T=150°C,0-270 min). The result shows that salts increase no FF-yields for H2SO4 but increase the reaction-rate. In contrast, Fe2(SO4)3 increase no yield nor reaction-rate for HCl-catalyzed-system. In conclusion, the inorganic-salts catalyse xylose-conversion to furfural but best results were obtained using HCl without additional salts

Bio-Based Aromatic Polyesters Reversibly Crosslinked via the Diels–Alder Reaction

Diphenolic acid is functionalized with furfuryl amine and subsequently incorporated in a (partly) bio-based polyester through interfacial polycondensation with terepthalic chloride. The furan groups present in the resulting polyester are able to form a thermoreversible covalent network with different bismaleimide moieties via the Diels–Alder (DA) reaction. Our analysis of the polymer network by1H-NMR clearly shows the formation of both possible stereoisomers (endo and exo) from the Diels–Alder coordination of furan and maleimide. Furthermore, it was found that these isomers can be reversibly interchanged at temperatures below the reported retro Diels–Alder reaction temperature, a phenomenon often claimed but, until present, never directly observed, for thermally reversible polymeric systems. Finally, a proof of principle for reversibility and recyclability is shown

Chiral separation by enantioselective liquid–liquid extraction

The literature on enantioselective liquid–liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid–liquid extraction is a technology of interest for a wide range of chemists and chemical engineers in the fields of fine chemicals, pharmaceuticals, agrochemicals, fragrances and foods. In this review the principles and advances of resolution through enantioselective liquid–liquid extraction are discussed, starting with an introduction on the principles of enantioselective liquid–liquid extraction including host–guest chemistry, extraction and phase transfer mechanisms, and multistage liquid–liquid extraction processing. Then the literature on enantioselective liquid–liquid extraction systems is reviewed, structured on extractant classes. The following extractant classes are considered: crown ether based extractants, metal complexes and metalloids, extractants based on tartrates, and a final section with all other types of chiral extractants.

Biomethanol from Glycerol

Medical bioinformatic

An improved catalytic pyrolysis concept for renewable aromatics from biomass involving a recycling strategy for co-produced polycyclic aromatic hydrocarbons

Catalytic pyrolysis of crude glycerol over a shaped H-ZSM-5 zeolite catalyst with (partial) recycling of the product oil was studied with the incentive to improve benzene, toluene, and xylene (BTX) yields. Recycling of the polycyclic aromatic hydrocarbon (PAH) fraction, after separation from BTX by distillation and co-feeding with the crude glycerol feed, was shown to have a positive effect on the BTX yield. Further improvements were achieved by hydrogenation of the PAH fraction using a Ru/C catalyst and hydrogen gas prior to co-pyrolysis, and BTX yields up to 16 wt% on feed were obtained. The concept was also shown to be beneficial to other biomass feeds such as e.g., Kraft lignin, cellulose, and Jatropha oil

Pyrolysis of plastic waste: effect of feedstock pretreatment and fate of contaminants

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Selective Demethoxylation of Guaiacols to Phenols using Supported MoO 3 Catalysts

Lignin-derived monomers with methoxy substituents are abundantly present in bioliquids derived from lignocellulosic biomass. Examples are the products obtained from the reductive catalytic fractionation of lignin (RCF) and pyrolysis of lignocellulosic biomass and hydrotreated products thereof. An attractive valorization step for these liquids involves demethoxylation to obtain alkylated phenols through selective catalytic hydrodeoxygenation (HDO). Within the context of sustainable chemistry, there is a strong drive to use cheap, non-precious metal catalysts for this purpose. In this study, the HDO of guaiacol (5 wt% in toluene) was investigated in a continuous fixed-bed reactor at 380 °C, 20 bar over supported MoO3 catalysts. MoO3 (5 %) supported on TiO2 (P25) was shown to give superior performance compared with MoO3 supported on anatase TiO2, Al2O3, SiO2, Nb2O5, CeO2, and ZrO2. Additional studies involving variation of the Mo loading and process conditions were performed, and the highest selectivity to demethoxylated phenolics like phenol and methylated phenols was 82 % at 97 % conversion of guaiacol. Both 4-n-propylguaiacol and a realistic guaiacols-rich feed isolated from a representative pyrolysis oil were also successfully demethoxylated with the 5 % MoO3/TiO2 catalyst

Multifunctional Heterogeneous Catalysts for the Selective Conversion of Glycerol into Methyl Lactate

Multifunctional catalytic systems consisting of physical mixtures of Au nanoparticles (2–3 nm) supported on metal oxides and Sn-MCM-41 nanoparticles (50–120 nm) were synthesized and investigated for the selective conversion of glycerol to methyl lactate. The Au catalyst promotes the oxidation of glycerol to trioses, whereas the solid acid Sn-MCM-41 catalyzes the rearrangement of the intermediate trioses to methyl lactate. Among the supported Au nanoparticles, Au/CuO led to the highest yield and selectivity toward methyl lactate, while the Sn-MCM-41 nanoparticles showed much better catalytic performance than a benchmark solid acid catalyst (USY zeolite). The activity of the multifunctional catalytic system was further optimized by tuning the calcination temperature, the gold loading in the Au/CuO catalyst, and the Au/Sn molar ratio, reaching 63% yield of methyl lactate (ML) at 95% glycerol conversion. This catalytic system also showed excellent reusability. The catalytic results were rationalized on the basis of a detailed characterization by means of TEM, N₂-physisorption, UV–vis spectroscopy, and by FT-IR using probe molecules (CO and ethanol)

The Effect of Molecular Weight on the (Re)-Processability and Material Properties of Bio-Based, Thermoreversibly Cross-Linked Polyesters

A (partially) bio-based short-chain polyester is prepared through interfacial polycondensation of furan-functionalized diphenolic acid with terephthalic chloride. The furan groups along the backbone of the obtained polyester are able to form a covalent network (PE-fur/Bism) with various ratios of 1,1′-(methylenedi-4,1-phenylene)bismaleimide via the thermoreversible Diels–Alder (DA) reaction. Several techniques have been employed to characterize the polyester network, including 1H-NMR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). The polyester base polymer displays a glass transition temperature of 115 °C, whereas the temperatures at which the retro-Diels–Alder (rDA) reaction takes place lie above 130 °C for the various polyester/bismaleimide networks. Excellent thermoreversibility and recyclability of the polyester resin have been shown through DSC and DMTA measurements