基于间苯三酚的磺化碳基固体酸催化剂的制备及其催化油酸甲酯的合成
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摘要
采用间苯三酚与对苯二甲醛缩聚得到的树脂为碳前驱体,分别以1,4-二氧六环与去离子水为溶剂,以溶剂热和水热法、氯磺酸为磺化试剂制备两种磺化碳基固体酸催化剂。SEM、XPS和TGA等分析表明,以1,4-二氧六环为溶剂合成的TP-A-S催化剂为形貌规整、高酸密度、良好稳定性的球形,并表现出良好的催化性能。将其用于油酸与甲醇的酯化反应,最适宜的条件为:醇油物质的量比10∶1,催化剂用量占原料总质量的2. 0%,反应温度70℃,反应时间4 h,油酸最高转化率达98. 3%。且催化剂循环使用5次后,油酸转化率仍达84. 4%。将制备的TP-A-S催化剂用于长链游离脂肪酸与甲醇的酯化反应,转化率高于90%,表现出良好的催化效果。
With resin from polycondensation of phloroglucinol and terephthaladehyde as precursor,using1,4-dioxane and deionized water as different solvents,chlorosulfonic acid as sulfonated reagent,two catalysts were prepared by solvothermal and hydrothermal methods. Characterization results of SEM,XPS,TGA and so on showed that the spherical catalyst prepared by 1,4-dioxane as solvent with regular morphology,high acid density and good stability exhibited excellent catalytic avtivity. Highest oleic acid conversion reached 98. 3% under the optimum esterification conditions of oleic acid and methanol which were MeOH/OA molar ratio of 10∶ 1,catalyst dosage of 2. 0% of raw material total mass,reaction temperature of 70 ℃,reaction time of 4 h. After 5 times of reuse,conversion of oleic acid was 84. 4%. The prepared catalyst TP-A-S was tested in esterification of long chain free fatty acids with methanol and showed good activity,conversion was higher than 90%.
With resin from polycondensation of phloroglucinol and terephthaladehyde as precursor,using1,4-dioxane and deionized water as different solvents,chlorosulfonic acid as sulfonated reagent,two catalysts were prepared by solvothermal and hydrothermal methods. Characterization results of SEM,XPS,TGA and so on showed that the spherical catalyst prepared by 1,4-dioxane as solvent with regular morphology,high acid density and good stability exhibited excellent catalytic avtivity. Highest oleic acid conversion reached 98. 3% under the optimum esterification conditions of oleic acid and methanol which were MeOH/OA molar ratio of 10∶ 1,catalyst dosage of 2. 0% of raw material total mass,reaction temperature of 70 ℃,reaction time of 4 h. After 5 times of reuse,conversion of oleic acid was 84. 4%. The prepared catalyst TP-A-S was tested in esterification of long chain free fatty acids with methanol and showed good activity,conversion was higher than 90%.
引文
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[3]Su F,Guo Y. Advancements in solid acid catalysts for biodiesel production[J]. Green Chemistry,2014,16(6):2934-2957.
[4]范明明,刘延磊,张萍波,等. Ca O-MgO@Co Fe2O4磁性固体碱的制备及其大豆油酯交换反应催化性能[J].燃料化学学报,2016,44(4):422-427.Fan Mingming,Liu Yanlei,Zhang Pingbo,et al. Preparation of magnetic core-shell Ca O-MgO@Co Fe2O4solid base and its catalytic performance in the transesterification of soybean oil to biodiesel[J]. Journal of Fuel Chemistry and Technology,2016,44(4):422-427.
[5]Clark J H. Solid acids for green chemistry[J]. Accounts of chemical research,2002,35(9):791-797.
[6]胡仁国.碳基固体酸催化柠檬酸三丁酯的合成[J].化工时刊,2013,(1):25-27.Hu Renguo. Catalytic synthesis of tributyl citrate by carbon based solid acid[J]. Chemical Industry Times,2013,(1):25-27.
[7]Zuo C,Pan L,Cao S,et al. Catalysts,kinetics,and reactive distillation for methyl acetate synthesis[J]. Industrial&Engineering Chemistry Research,2014,53(26):10540-10548.
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[9]Lu W,Bosch M,Yuan D,et al. Cost-effective synthesis of amine-tethered porous materials for carbon Ca cure[J].Chem Sus Chem,2015,8(3):433-438.
[10]Kang D W,Lim K S,Lee K J,et al. Cost-effective,highperformance porous-organic-polymer conductors functionalized with sulfonic acid groups by direct postsynthetic substitution[J]. Angewandte Chemie International Edition,2016,55(52):16123-16126.
[11]Katsoulidis A P,Dyar S M,Carmieli R,et al. Copolymerization of terephthalaldehyde with pyrrole,indole and carbazole gives microporous POFs functionalized with unpaired electrons[J]. Journal of Materials Chemistry A,2013,1(35):10465-10473.
[12]Upare P P,Yoon J W,Mi Y K,et al. Chemical conversion of biomass-derived hexose sugars to levulinic acid over sulfonic acid-functionalized graphene oxide catalysts[J].Green Chemistry,2013,15(10):2935-2943.
[13]Zhang B H,Ren J W,Liu X H,et al. Novel sulfonated carbonaceous materials from p-toluenesulfonic acid/glucose as a high-performance solid-acid catalyst[J]. Catalysis Communnications,2010,11:629-632.
[14]Kanokwan N,James G G J,Piyasan P. A green sulfonated carbon-based catalyst derived from coffee residue for ester ification[J]. Renew Energ,2016,86:262-269.
[15]Malins K,Kampars V,Brinks J,et al. Synthesis of activated carbon based heterogenous acid catalyst for biodiesel preparation[J]. Applied Catalysis B:Environmental,2015,176:553-558.
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[17]李梦天.磺酸基碳基固体酸催化剂的制备及其催化酯化研究[D].无锡:江南大学,2018.Li Mengtian. synthesis of sulfonic carbon-bassed solid acid catalyst and its catalytic study of esterification[D].Wuxi:Jiangnan University,2018.
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[19]Shu Q,Hou X P,Zhu L H,et al. Preparation of a novel solid acid catalyst SO24-/Nd2O3/C and study of its performance for the synthesis of biodiesel from esterification reaction of oleic acid and methanol[J]. Journal of Fuel Chemistry&Technology,2016,44(2):209-216.
[20]Wang J L,Wang L L,Liu X J,et al. Catalytic synthesis of methyl oleate by morpholine basic ionic liquid[J]. Journal of Fuel Chemistry&Technology,2013,41(1):85-90.
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