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  • 1
    Publication Date: 2018-05-03
    Description: A heterogeneous catalyst (ZnO/SFCCR) composed of ZnO supported on spent fluid cracking catalyst by wet impregnation was synthesized and applied to the esterification of colophony acids with methanol under subcritical CO 2 conditions. The catalyst was characterized by SEM-EDS, BET, ICP, FTIR, XRD and Py-IR. An experimental set-up involving a new injection technique was designed to promote the heterogeneous methyl esterification, and the subcritical CO 2 played a role in auxiliary acid catalysis (a pH range of 3.54–3.91), increasing the lifespan of ZnO/SFCCR, reducing the viscosity of the system to promote gas–liquid mass transfer. A maximum conversion rate of 97.01% was obtained in a relatively short time of 5 h. Kinetic experiments were performed from 190 to 220°C using a special high-temperature sampling device and analysing aliquots with high-performance liquid chromatography. A new reaction pathway, involving methyl abietate, methyl dehydroabietate, methyl neoabietate and methyl palustrate along with other kinds of colophony acids, was developed. The kinetic parameters were obtained using the Levenberg–Marquardt nonlinear least-squares method, and the activation energies for the isomerizations of neoabietic and palustric acids and for the methyl esterification of neoabietic, abietic, palustric and dehydroabietic acids were found to be 107.09, 113.95, 68.99, 49.85, 75.43 and 59.20 kJ mol –1 , respectively. The results from the kinetic model were in good agreement with experimental values.
    Keywords: synthetic chemistry, chemical engineering
    Electronic ISSN: 2054-5703
    Topics: Natural Sciences in General
    Published by Royal Society
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  • 2
    Publication Date: 2018-05-24
    Description: A Ni-based catalyst (Ni-PVP/PFC3R) with polyvinyl pyrrolidone (PVP) as a dispersant supported in a pretreated fluid catalytic cracking catalyst residue (PFC3R) was synthesized and applied to C9 petroleum resin (C9 PR) hydrogenation. For comparison, a Ni catalyst without PVP (Ni/PFC3R) was prepared in the same way. Ni-PVP/PFC3R exhibited higher activity and better stability. The catalysts were characterized by X-ray diffraction, scanning electron microscope, H 2 -temperature programmed reduction/temperature programmed desorption, Fourier transform infrared spectroscopy and the Brunauer–Emmett–Teller method. The catalysts had a smaller crystallite size and stronger interactions between the Ni species and the PFC3R support in the presence of PVP. The effects of nickel loading, H 2 pressure, temperature and reaction time for C9 PR hydrogenation over Ni-PVP/PFC3R were investigated. The bromine number was reduced to 1.25 under the following conditions: nickel content of 12 wt%, PVP amount of 1.5 wt%, temperature of 270°C, H 2 pressure of 8 MPa and reaction time of 240 min.
    Keywords: chemical engineering
    Electronic ISSN: 2054-5703
    Topics: Natural Sciences in General
    Published by Royal Society
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  • 3
    Publication Date: 2018-07-05
    Description: Rosin esters are widely applied as masticatory substances and beverage stabilizers, while classical acid-catalysed processes will lead to metal residue or environmental issues. Super/subcritical CO 2 –enriched high temperature liquid water (HTLW) as a green acid catalyst in the esterification reaction of rosin with glycerol was investigated. The pH of CO 2 –H 2 O binary system, as calculated based on gas–liquid equilibrium, charge balance and chemical equilibrium equations, ranged from 3.49 to 3.70 depending on the reaction conditions, indicating effective acid catalysis. Response surface methodology experiments showed the optimum conditions were 3.5 h, 3.9 MPa CO 2 pressure, a rosin-to-glycerol molar ratio of 1.32 and 269°C, and an enhanced esterification yield of 94.74% was achieved, which was superior to that obtained using a ZnO catalyst. It was found that the esterification kinetics was a pseudo first-order reaction, and the enthalpy and entropy of activation were calculated using the Arrhenius–Polanyi equation. The presence of super/subcritical CO 2 -enriched HTLW catalyst can decrease the activation energy and significantly accelerate the reaction rate.
    Keywords: chemical engineering, green chemistry
    Electronic ISSN: 2054-5703
    Topics: Natural Sciences in General
    Published by Royal Society
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  • 4
    Publication Date: 2018-10-18
    Description: The work investigated the effect of sepiolite nanofibres on mechanical properties and sintering behaviour of shellfish porcelain. Samples of shellfish porcelain reinforced by sepiolite nanofibres were fired in an electric furnace at 1150, 1200 and 1250°C for a period of 80, 100, 120 and 140 min. Sintered samples were characterized by flexural strength, fracture toughness, scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The results showed that 2 wt% sepiolite nanofibres could increase the flexural strength and fracture toughness of the porcelain bodies through the fibre pullout and the weak interface mechanisms. Sintering activation energies were determined according to the linear shrinkage results. It is found that the liquid-phase sintering mechanism of shellfish porcelain with sepiolite nanofibres is a diffusion mechanism. Porcelain without sepiolite is controlled by volume diffusion, and eventually, the grain boundary diffusion began to appear with the increase of sepiolite addition.
    Keywords: inorganic chemistry, materials science
    Electronic ISSN: 2054-5703
    Topics: Natural Sciences in General
    Published by Royal Society
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  • 5
    Publication Date: 2018-11-15
    Description: Starch films are developed as the biodegradable packaging materials to replace the petroleum-based materials in recent years. Thus, it is extremely beneficial to improve the hydrophobicity and mechanical strength of starch films, through a novel approach of co-cross-linking in neutral conditions, with glyoxal and AZC. In this work, systematic studies have been conducted to assess the performance of the co-cross-linked starch along with the control starch and starch cross-linked by glyoxal or AZC alone. Results showed that the co-cross-linked starch films exhibited significantly improved hydrophobicity and strength and the wet stress reached 1.53 MPa, compared to the control, glyoxal or AZC cross-linked starch films. More interestingly, the co-cross-linked film also demonstrated excellent UV shielding capacity and transmittance at visible wavelength range. The reaction mechanism was revealed based on the findings from UV, FT-IR and NMR spectra. This work established an innovative approach to improving the performance of starch film in neutral conditions for packaging applications.
    Keywords: materials science, chemical engineering
    Electronic ISSN: 2054-5703
    Topics: Natural Sciences in General
    Published by Royal Society
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