Esterification of acidified oil with methanol by SPES/PES catalytic membrane

Shi, Wenying; He, Benqiao; Li, Jianxin

doi:10.1016/j.biortech.2010.09.074

Cited by 48 publications

(39 citation statements)

References 35 publications

(35 reference statements)

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“…29 Indeed, there is no water determined in the product mixture with the Karl Fischer water tester with a sensitivity of 500 ppm. The kinetic model was built on the following assumptions: the whole reaction system was taken into account as an ideal solution; k was believed to be far larger than k 0 because the water could be instantly taken out by vacuum pump.…”

Section: Kinetic Studymentioning

confidence: 99%

An innovative auto-catalytic esterification for the production of phytosterol esters: experiment and kinetics

Deng

et al. 2014

RSC Adv.

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An innovative auto-catalytic method was proposed to synthesize phytosterol esters from phytosterols and long-chain fatty acids without adding any catalyst and solvent. The effects of reaction temperature, molar ratio of oleic acid/phytosterols, reaction time and carbon-chain length of the fatty acids on the reaction were investigated. The results showed that the conversion, the yield and the selectivity of the reaction were increased with the increase in reaction temperature, molar ratio and a decrease in the length of carbon chains of fatty acids. The selectivity was decreased on prolonging the reaction time. A high conversion (99.1%) with a high yield (94.9%) and selectivity (95.8%) was achieved under a molar ratio of oleic acid/phytosterols of 3 : 1, a reaction temperature of 220 C and reaction time of 4 h. The properties of the phytosterol oleic esters by autocatalysis conformed to the quality indices of phytosterol esters from the China Ministry of Health and were superior to the commercial product. The kinetics suggested that the reaction order was 2 and the reaction activation energy was 58.75 kJ mol À1 . The auto-catalytic process, omitting the separation step for catalysts and solvents, could be considered as a promising process to synthesize phytosterol esters. 22 83955055; Tel: +86 22 83955055 † Electronic supplementary information (ESI) available. See

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Section: Kinetic Studymentioning

confidence: 99%

An innovative auto-catalytic esterification for the production of phytosterol esters: experiment and kinetics

Deng

et al. 2014

RSC Adv.

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“…5(b), the plot of lnk versus 1/T can be represented by a straight line and E a is determined to be 47.8 kJ mol -1 . According to Shi et al and Singh,42,43 the esterification reaction is not diffusively controlled but kinetically controlled if the apparent activation energy is high enough (e.g., > 20.0 kJ mol -1 ). The high apparent activation energy of esterification catalyzed by s-CER/PVA composite (i.e., 47.8 kJ mol -1 ) further demonstrates that diffusion is not important during our esterification processes.…”

Section: Esterification Kineticsmentioning

confidence: 99%

Esterification of fatty acids from waste cooking oil to biodiesel over a sulfonated resin/PVA composite

Zhang

Gao

Zhao

et al. 2016

Catal. Sci. Technol.

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(2016) Esterification of fatty acids from waste cooking oil to biodiesel over a sulfonated resin/PVA composite. Catalysis Science and Technology, 2016 (6). pp. 5590-5598. ISSN 2044-4761 Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/33644/1/ZhangHL%20Catalysis%20Science %20%26%20Technology%202016%20online.pdf Copyright and reuse:The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the University of Nottingham End User licence and may be reused according to the conditions of the licence. For more details see: http://eprints.nottingham.ac.uk/end_user_agreement.pdf A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. Sulfonated cation exchange resins (s-CER) have been widely studied as a replacement of liquid acids for the catalysis of esterification of free fatty acids (FFAs) to produce biodiesel with water as the only by-product. However, the water produced has strong affinity to sulfonate groups in s-CER, which blocks the reactive sites for esterification and thus reduces the activity of the catalyst. To overcome this technical barrier, we have designed an s-CER/PVA composite by incorporating s-CER fines within a poly (vinyl alcohol) (PVA) matrix. PVA has much stronger absorption preference of water than s-CER and has very low selectivity for the reactants (FFAs and methanol), which enables the continuous removal of the produced water and liberation of reactive sulfonate sites in s-CER for catalysis. With s-CER/PVA, the FFAs conversion was increased from 80.1 % to 97.5 % after 8-hour reaction and the turnover frequency (TOF) was increased more than 3.3 times. The TOF of s-CER/PVA was also 2.6 times of that of sulfuric acid, suggesting that the water less, heterogeneous sulfonate sites are more reactive than water-blocked homogeneous ones. The reusability of the s-CER/PVA was also enhanced due to that the produced water that could cause deactivation of the s-CER was largely removed by PVA.

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“…SPES with different DS as catalytic active component was synthesized in our laboratory according to the literature [17]. Three kinds of SPES samples with the DS of 9.7, 20.3 and 39.1 % were obtained through increasing the amount of chlorosulfonic acid in the reactant during the sulfonation process.…”

Section: Methodsmentioning

confidence: 99%

“…Though the hybrid membranes with DS 39.1 % showed high catalytic performances at the first run, the stabilities of SPES/PWA hybrid membrane were not satisfied at higher DS after the hybrid membrane used three times. This may be due to the hybrid membrane with higher DS was easier to absorb water produced from esterification and PWA particles from hybrid membrane tended to loss [17]. In order to prove this view, water uptakes for SPES/PWA hybrid membranes with three kinds of DS 9.7, 20.3 and 39.1 % were measured as a function of recycling times, as shown in Fig.…”

Section: Catalytic Stability Of Spes/pwa Hybrid Membrane With Differementioning

confidence: 97%

Preparation and Characterization of Sulfonated Poly (Ether Sulfone) (SPES)/Phosphotungstic Acid (PWA) Hybrid Membranes for Biodiesel Production

Shi

Yang

et al. 2015

Catal Lett

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A new kind of organic-inorganic hybrid membrane based on sulfonated poly (ether sulfone) (SPES) with different degree of sulfonation (DS) embedded phosphotungstic acid (PWA) was prepared as a heterogeneous acid catalyst for biodiesel production. Three kinds of hybrid membranes with the DS of SPES 9.7, 20.3 and 39.1 % were obtained. The interactions between SPES and PWA in SPES/PWA hybrid membrane were characterized by Fourier transform infrared (FTIR), thermogravimetric analysis and X-ray diffraction (XRD). The band shift of FTIR spectrum showed that the PWA particles interacted primarily with sulfonic acid groups on the polymer backbone. Compared to pure SPES membrane, the thermal stability of SPES/PWA hybrid membrane was enhanced. The XRD results suggested that the PWA particles were incorporated inside membrane pores and adhered on the walls outside the pores which were due to the interaction between PWA and SPES polymer matrix. The catalytic properties of SPES/PWA membranes were tested by the esterification of the acidified oil with methanol. The reaction conditions were optimized by response surface model and the optimum conditions were obtained as: methanol/oil mass ratio of 1:1, hybrid membrane loading of 1.66 meq/g and reaction time 6 h with the free fatty acids conversion of 95.3 %. The hybrid membrane with SPES/PWA mass ratio of 2:1 and the membrane thicknesses of 0.06 mm were optimal for the esterification. The SPES/PWA membrane of DS 20.3 % exhibited the best catalytic stabilities among the three kinds of hybrid membranes with different DS with a stable conversion of above 90 % in all times. Graphical Abstract 1 2 3 4 5 0 20 40 60 80 100 Conversion (%)Recycling times DS=9.7% DS=20.3% DS=39.1%

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Esterification of acidified oil with methanol by SPES/PES catalytic membrane

Cited by 48 publications

References 35 publications

An innovative auto-catalytic esterification for the production of phytosterol esters: experiment and kinetics

An innovative auto-catalytic esterification for the production of phytosterol esters: experiment and kinetics

Esterification of fatty acids from waste cooking oil to biodiesel over a sulfonated resin/PVA composite

Preparation and Characterization of Sulfonated Poly (Ether Sulfone) (SPES)/Phosphotungstic Acid (PWA) Hybrid Membranes for Biodiesel Production

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