Keli Chen

Synthesis, isolation and characterization of methyl levulinate from cellulose catalyzed by extremely low concentration acid

Abstract A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition (180–210 °C) catalyzed by extremely low concentration sulfuric acid (≤0.01 mol/L) and the product isolation were developed in this study. Effects of different process variables towards the catalytic performance were performed as a function of reaction time. The results indicated that sulfuric acid concentration, temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate. An optimized yield of around 50% was achieved at 210 °C for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L. The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n -dodecane was added to help distill the heavy fraction. The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate. The chemical composition and structural of lower heavy fraction were characterized by GC/MS, FTIR, 1 H-NMR and 13 C-NMR techniques. Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%. This pathway is efficient, environmentally benign and economical for the production of pure levulinate esters from cellulose.

Formation of Humin and Alkyl Levulinate in the Acid-catalyzed Conversion of Biomass-derived Furfuryl Alcohol

To avoid undesired polymerization and maximize the selectivity of alkyl levulinate from the acid-catalyzed conversion of biomass-derived furfuryl alcohol, the effects of catalyst and reaction parameters on the formations of humin and alkyl levulinate were investigated. The results show that Amberlyst 15, of moderate acidic strength, was more favorable for the selective conversion of furfuryl alcohol to alkyl levulinate, and heteropolyacids of strong acidic strength tended to promote furfuryl alcohol polymerization. Compared with water as a reaction medium, alcohol significantly lowered humin formation and enhanced the yield of the resulting products. The formations of humin and alkyl levulinate were both favored at high catalyst loadings and reaction temperatures. An augmentation in initial furfuryl alcohol concentration caused an increase in humin formation and a decrease in alkyl levulinate yield. A high alkyl levulinate yield of up to 94% (100% furfuryl alcohol conversion) was achieved at 110 °C for 4 h with 5 g/L Amberlyst 15 catalyst and an initial furfuryl alcohol concentration of 0.1 mol/L. At this point, about 5% furfuryl alcohol was polymerized to form the humin, and its polymerization occurred mainly during the initial reaction stage.

One-step fabrication of carbonaceous solid acid derived from lignosulfonate for the synthesis of biobased furan derivatives

An eco-friendly and low-cost lignosulfonate-based acidic carbonaceous catalyst (LS-SO3H) was effectively fabricated using the sulfite pulping by-product of sodium lignosulfonate as a precursor by facile one-step simultaneous carbonization and sulfonation, and employed for the synthesis of promising biofuel furan derivatives from biorenewable feedstocks. The catalyst preparation conditions significantly affected the preparation and properties of LS-SO3H. A relatively high catalyst preparation yield (40.4%) with strong –SO3H density (1.33 mmol g−1) were achieved when the lignosulfonate was treated in concentrated H2SO4 solution at 120 °C for 6 h. The preparation yield of LS-SO3H was nearly twice as much as that of one-step prepared catalyst using alkaline lignin (another technical lignin from pulping) as a precursor. The as-prepared LS-SO3H had similar textural characteristics to the frequently-used two-step prepared carbonaceous catalyst involving pyrolysis carbonization and sulfonation. LS-SO3H was found to show good catalytic activity for the synthesis of 5-ethoxymethylfurfural (EMF) in ethanol medium, affording around 86%, 57% and 47% yields from 5-hydroxymethylfurfural (HMF), fructose and inulin, respectively. Also, a high HMF yield of 83% could be obtained from fructose when DMSO was replaced as reaction medium. The used LS-SO3H was readily recovered by filtration, and remained active in recycle runs.

Removal of heavy metal and sulfate ions by cellulose derivative-based biosorbents

A series of environmentally-friendly bagasse pith cellulose-based adsorbents were prepared in an attempt to retain Cu2+ and SO42− from aqueous solutions. The proof of ion adsorption on the biosorbents was identified from Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy-scanning electron microscope. The adsorption capacities were highly dependent on pH and the maximum uptakes of both ions were obtained at pH 5. An increase of solution temperature resulted in decreasing Cu2+ removal but enhancing SO42− adsorption. The kinetic studies showed that the adsorptions of copper and sulfate ions followed the pseudo-second-order kinetics. The analysis of isotherm data indicated that the Langmuir and Freundlich models were in good agreement with the sorptions of Cu2+ and SO42−, respectively. The proportion of carboxylate cellulose and quaternary ammonium-functionalized cellulose in biosorbents influenced on adsorption capacity of the above ions. The adsorption mechanism was mainly governed by ion exchange, complexation and electrostatic association.

Thermo-sensitive and swelling properties of cellouronic acid sodium/poly (acrylamide-co-diallyldimethylammonium chloride) semi-IPN

In current study, cellouronic acid sodium (CAS), obtained from bagasse pith, has been introduced into poly(acrylamide-co-diallyldimethylammonium chloride) (poly(AM-co-DAC)) network to form novel thermo-sensitive semi-IPNs. The structure and morphology of the hydrogels were proved by Fourier transformation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The effects of CAS content, initiator charge, cross-linker dosage and swelling-medium property on the thermo-responsive water absorptivity were investigated in detail. The results elucidated that the prepared gels exhibited a thermo-sensibility with an upper critical solution temperature (UCST) and a high water-absorbency. And the values of UCST and equilibrium swelling ratio largely depended on the inner structure of the semi-IPNs and the external solvent property. It was also revealed that the swelling process conformed to the Schotts pseudo second order model and diffusion type was non-Fickian diffusion. The value of activation energy for this polyelectrolyte was found to be 8.74kJ/mol.

Reinforcement of the bio-gas conversion from pyrolysis of wheat straw by hot caustic pre-extraction

BackgroundPyrolysis has attracted growing interest as a versatile means to convert biomass into valuable products. Wheat straw has been considered to be a promising biomass resource due to its low price and easy availability. However, most of the products obtained from wheat straw pyrolysis are usually of low quality. Hot soda extraction has the advantage of selective dissolution of lignin whilst retaining the carbohydrates. This can selectively convert biomass into high-quality desired products and suppress the formation of undesirable products. The aim of this study was to investigate the pyrolysis properties of wheat straw under different hot caustic pretreatment conditions.ResultsCompared with the untreated straw, a greater amount of gas was released and fewer residues were retained in the extracted wheat straw, which was caused by an increase in porosity. When the NaOH loading was 14%, the average pore size of the extracted straw increased by 12% and the cumulative pore volume increased by 157% compared with the untreated straw. The extracted straw obtained from the 14% NaOH extraction was clearly selective for pyrolysis products. On one hand, many lignin pyrolysis products disappeared, and only four main lignin-unit-pyrolysis products were retained. On the other hand, polysaccharide pyrolysis products were enriched. Both propanone and furfural have outstanding peak intensities that could account for approximately 30% of the total pyrolysis products. However, with the excessive addition of NaOH (i.e. > 22% w/w) during pretreatment, the conversion of bio-gas products decreased. Thermogravimetric and low-temperature nitrogen-adsorption analysis showed that the pore structure had been seriously destroyed, leading to the closing of the release paths of the bio-gas and thus increasing the re-polymerisation of small bio-gas molecules.ConclusionsAfter suitable extraction (14% NaOH loading extraction), a considerable amount (25%) of the soluble components dissolved out of the straw. This resulted in an increase in both pore size and volume. This condition appeared to be optimally selective for the release of value-added pyrolysis products such as furfural, ketones and lignin monomer units. However, excessive addition of alkali (22%) for extraction could change the original interior structure, resulting in a decrease in both pore size and volume. This interior structure modification limited the release of pyrolysis products, and greater carbonisation occurred.