磺化聚醚砜/聚醚砜共混膜的制备及膜催化酯化反应动力学研究
|
摘要
以聚醚砜(PES)为基体,磺化聚醚砜(SPES)为催化活性成分,通过溶剂挥发法制备SPES/PES共混膜,用于酸化油(酸值153 mg KOH/g)酯化反应制备生物柴油,并研究了SPES/PES共混型催化膜酯化反应动力学。结果表明,在不同反应温度(45,55,65,75℃),不同的催化剂用量(0.68%,1.35%和2.70%)以及醇油质量比(1∶1,2∶1,5∶1,8∶1和10∶1)条件下,通过反应动力学计算出相应的反应速率以及反应级数。随着催化剂用量和醇油质量比的增加,反应速率逐渐增加,反应级数也增大,平均反应级数为n=2.2,而指前因子和活化能逐渐减小,说明由反应控制逐渐转为混合控制和反应控制。建立了SPES/PES共混型催化膜酯化反应动力学模型。得到实验值与理论值吻合程度较高(误差在±5%左右),验证了动力学模型的正确性。
A blend membrane from sulfonated polyethersulfone(SPES) as the catalyst and polyethersulfone(PES) as the carrier were prepared by the solvent evaporation method.The SPES/PES blend membrane was used as a heterogeneous catalyst in the esterification of the acidified oil(acid value 153 mg KOH/g) for producing biodiesel.The results showed that the reaction rate and reaction order were calculated by reaction kinetics at different reaction temperatures(45,55,65,75 ℃),the amount of catalyst(0.68%,1.35%,2.70%) and the mass ratio of methanol/oil(1∶ 1,2∶ 1,5∶ 1,8∶ 1 and 10∶ 1).With the increase of the amount of catalyst and the mass ratio of methanol/oil,the reaction rate gradually increases and the reaction order increases and the average reaction order is n = 2.2.The frequency factor and activation energy are gradually reduced.It implies that the esterification is not reaction controlled but both kinetically controlled and diffusively controlled.The kinetic model of the esterification reaction of SPES/PES blend catalytic membrane was established.The experimental values are in good agreement with the theoretical values(the error is about 5%),and the correctness of the dynamic model is verified.
A blend membrane from sulfonated polyethersulfone(SPES) as the catalyst and polyethersulfone(PES) as the carrier were prepared by the solvent evaporation method.The SPES/PES blend membrane was used as a heterogeneous catalyst in the esterification of the acidified oil(acid value 153 mg KOH/g) for producing biodiesel.The results showed that the reaction rate and reaction order were calculated by reaction kinetics at different reaction temperatures(45,55,65,75 ℃),the amount of catalyst(0.68%,1.35%,2.70%) and the mass ratio of methanol/oil(1∶ 1,2∶ 1,5∶ 1,8∶ 1 and 10∶ 1).With the increase of the amount of catalyst and the mass ratio of methanol/oil,the reaction rate gradually increases and the reaction order increases and the average reaction order is n = 2.2.The frequency factor and activation energy are gradually reduced.It implies that the esterification is not reaction controlled but both kinetically controlled and diffusively controlled.The kinetic model of the esterification reaction of SPES/PES blend catalytic membrane was established.The experimental values are in good agreement with the theoretical values(the error is about 5%),and the correctness of the dynamic model is verified.
引文
[1]常飞琴,张黎,李华锋,等.丙烯酸甲酯改性氧化钙催化制备生物柴油的研究[J].应用化工,2017,46(3):532-536.
[2]石文英,李红宾,周蓉.聚合物膜催化接触器研究进展[J].化工进展,2015,34(2):312-318.
[3]Shi W Y,He B Q,Li J X,et al.Continuous esterification to produce biodiesel by SPES/PES/NWF composite catalytic membrane in flow-through membrane reactor:Experimental and kinetics studies[J].Bioresource Technology,2013,129(2):100-107.
[4]Avellaneda F,Salvado J.Continuous transesterification of biodiesel in ahelicoidal reactor using recycled oil[J].Fuel Processing Technology,2011,92(1):83-91.
[5]曾繁涤,李建新,石文英.膜技术在生物柴油制备中的应用研究进展[J].功能材料信息,2010,7(2):11-18.
[6]梁孟珠,邵译萱,何本桥,等.响应面法优化HTCC/Na2SiO3/ECH杂化膜催化制备生物柴油[J].膜科学与技术,2015,35(4):54-64.
[7]夏海平,陈小艾,彭赛群,等.硫酸铁掺杂聚乙烯醇复合膜的催化酯化作用[J].化学通报,2000(3):39-40.
[8]Zhang S,Zu Y G,Fu Y J,et al.Rapid microwave-assisted transesterification of yellow horn oil to biodiesel using a heteropolyacid solid catalyst[J].Bioresource Technology,2010,101(3):931-936.
[9]Banerjee A,Chakraborty R.Parametric sensitivity in transesterification of waste cooking oil for biodiesel production---A review[J].Resources Conservation and Recycing,2009,53(9):490-497.
[10]朱木兰,何本桥,石文英.响应面法优化PSSA/PVA共混膜催化酯化制备生物柴油[J].膜科学与技术,2011,31(4):89-93.
[2]石文英,李红宾,周蓉.聚合物膜催化接触器研究进展[J].化工进展,2015,34(2):312-318.
[3]Shi W Y,He B Q,Li J X,et al.Continuous esterification to produce biodiesel by SPES/PES/NWF composite catalytic membrane in flow-through membrane reactor:Experimental and kinetics studies[J].Bioresource Technology,2013,129(2):100-107.
[4]Avellaneda F,Salvado J.Continuous transesterification of biodiesel in ahelicoidal reactor using recycled oil[J].Fuel Processing Technology,2011,92(1):83-91.
[5]曾繁涤,李建新,石文英.膜技术在生物柴油制备中的应用研究进展[J].功能材料信息,2010,7(2):11-18.
[6]梁孟珠,邵译萱,何本桥,等.响应面法优化HTCC/Na2SiO3/ECH杂化膜催化制备生物柴油[J].膜科学与技术,2015,35(4):54-64.
[7]夏海平,陈小艾,彭赛群,等.硫酸铁掺杂聚乙烯醇复合膜的催化酯化作用[J].化学通报,2000(3):39-40.
[8]Zhang S,Zu Y G,Fu Y J,et al.Rapid microwave-assisted transesterification of yellow horn oil to biodiesel using a heteropolyacid solid catalyst[J].Bioresource Technology,2010,101(3):931-936.
[9]Banerjee A,Chakraborty R.Parametric sensitivity in transesterification of waste cooking oil for biodiesel production---A review[J].Resources Conservation and Recycing,2009,53(9):490-497.
[10]朱木兰,何本桥,石文英.响应面法优化PSSA/PVA共混膜催化酯化制备生物柴油[J].膜科学与技术,2011,31(4):89-93.