MCM-41分子筛膜的制备、改性及其在酯交换反应中的应用

doi:10.3969/j.issn.0253-2417.2015.01.001

摘要/Abstract

摘要： 采用原位水热合成法在氧化铝陶瓷膜(CM)表面原位合成出了孔道规则有序的MCM-41/CM分子筛膜。再采用浸渍法将SO₄^2-/ZrO₂负载在MCM-41/CM分子筛膜上对MCM-41进行酸改性,制得负载型固体酸催化剂SO₄^2-/ZrO₂/MCM-41/CM,并用于催化棕榈油与甲醇的酯交换反应制备生物柴油。结果表明,当Zr(NO₃)₄的浓度为0.4 mol/L、硫酸浓度为2 mol/L、焙烧温度为550 ℃时,制备出的负载型固体酸催化剂SO₄^2-/ZrO₂/MCM-41/CM活性最高。通过考察反应条件对酯交换反应的影响,得出最佳的反应条件,即当催化剂用量5%(以活性组分负载率计)、反应时间为60 min、反应温度为100 ℃、醇油物质的量之比为10:1时,脂肪酸甲酯的收率可达92%以上,重复使用5次后,脂肪酸甲酯收率仍达80%以上。

关键词: MCM-41, 分子筛膜, SO₄^2-/ZrO₂, 酯交换反应, 脂肪酸甲酯

Abstract: MCM-41 with long range ordered hexagonal mesostructures was loaded on the surface of ceramic membranes (CM) successfully by in situ synthetic method. Then, the MCM-41/CM was modified by loading SO₄^2-/ZrO₂ in order to prepare solid acid catalyst SO₄^2-/ZrO₂/MCM-41/CM. The catalytic performance of the synthesized catalyst was evaluated by transesterification using palm oil and methanolas reactants. The results showed that the SO₄^2-/ZrO₂/MCM-41/CM had good catalytic activity with Zr(NO₃)₄ solution concentration of 0.4 mol/L, H₂SO₄ solution concentration of 2 mol/L, and calcination temperature of 550 ℃. The optimal reaction conditions for transesterification were as follows: catalyst amount (active components loaded ratio) 5%, reaction time 60 min, reaction temperature 100 ℃, methanol/palm oil molar ratio 10:1. The yield of fatty acid methyl ester (FAME) is up to 92% under this condition.

Key words: MCM-41, zeolite membrane, SO₄^2-/ZrO₂, transesterification, fatty acid methyl ester (FAME)

中图分类号:

TQ35

陈丽华, 李遵陕, 高李璟, 徐威, 肖国民. MCM-41分子筛膜的制备、改性及其在酯交换反应中的应用[J]. 林产化学与工业, 2015, 35(1): 1-8.

CHEN Li-hua, LI Zun-shan, GAO Li-jing, XU Wei, XIAO Guo-min. Transesterification Performance of Acidic Group Modified Mesoporous MCM-41 Membrane[J]. Chemistry and Industry of Forest Products, 2015, 35(1): 1-8.

参考文献

[1] 周志华.MCM-48/ZSM-5复合分子筛及膜的制备研究[D].大连:大连理工大学硕士学位论文,2009. ZHOU Zhi-hua.Research on synthesis of MCM-48/ZSM-5 composite molecular sieve and membrane[D].Dalian:Master Degree Thesis of Dalian University of Technology,2009.
[2] 宋艳.MCM-41介孔分子筛及分子筛膜的制备[D].天津:天津大学硕士学位论文,2006. SONG Yan.Synthesis of MCM-41 mesoporous molecular sieve and zeolite membranes[D].Tianjin:Master Degree Thesis of Tianjin University,2006.
[3] 王连洲,施剑林,禹剑,等.介孔氧化硅材料的研究进展[J].无机材料学报,1999,14(3):333-342. WANG Lian-zhou,SHI Jian-lin,YU Jian,et al.Recent progress of mesoporous silica materials[J].Journal of Inorganic Materials,1999,14(3):333-342.
[4] IWASAKI A,SANO T,KIYOZUMI Y.Direct observation of the formation process of silicalite films on various substrates[J].Microporous and Mesoporous Materials,2000,38(1):75-83.
[5] JUNG K T,SHUL Y G.Preparation of ZSM-5 zeolite film and its formation mechanism[J].Journal of Membrane Science,2001,191(1):189-197.
[6] CHON H,WOO S I,PARK S E.Recent Advances and New Horizons in Zeolite Science and Technology[M].New York:Elsevier Science,1996:102.
[7] 任立国,高文艺,张晓丽.SO₄^2-/ZrO₂固体超强酸催化剂上的酯化反应机理[J].抚顺石油学院学报,2003,23(1):33-36. REN Li-guo,GAO Wen-yi,ZHANG Xiao-li.Esterification reaction mechanism on the surface of SO₄^2-/ZrO₂ solid superacid catalysts[J].Journal of Fushun Petroleum Institute,2003,23(1):33-36.
[8] 赵强,孟双明,王俊丽,等.固体超强酸SO₄^2-/ZrO₂和S₂O^2-₈/ZrO₂催化合成环己烯[J].应用化工,2010,39(10):1510-1513. ZHAO Qiang,MENG Shuang-ming,WANG Jun-li,et al.Synthesis of cyclohexene by solid super acid catalyst SO₄^2-/ZrO₂ and S₂O^2-₈/ZrO₂[J].Applied Chemical Industry,2010,39(10):1510-1513.
[9] XIA Q H,HIDAJAT K,KAWI S.Synthesis of SO₄^2-/ZrO₂/MCM-41 as a new superacid catalyst Electronic supplementary information (ESI) available:Characterization data for catalysts[J].Chemical Communications,2000(22):2229-2230.
[10] 俞卫华.Ti、Co和Mn修饰的介孔分子筛制备、表征与催化氧化性能研究[D].杭州:浙江工业大学博士学位论文,2007. YU Wei-hua.Studies on Preparation,Characterization and Catalytic Oxidation Performance of Titanium,Cobalt and Manganese-modified Mesostructured Molecular Sieves[D].Hangzhou:Doctoral Dissertation of Zhejiang University of Technology,2007.
[11] 杨雪岗.温和条件下介孔分子筛Co-MCM-41的烷基修饰和表征[J].中国石油和化工,2012(9):29-30. YANG Xue-gang.Alkylation modification and characterization of mesopore molecular sieve Co-MCM-41 under mild conditings[J].China Petroleum and Chemical Industry,2012(9):29-30.
[12] 白海鑫,刘小花,王喜云,等.SBA-15负载MgO催化大豆油与甲醇酯交换反应制备生物柴油的研究[J].河南农业大学学报,2010,44(6):656-659. BAI Hai-xin,LIU Xiao-hua,WANG Xi-yun,et al.Study on catalyzing transesterification of soybean oil with methanol for biodiesel using supported MgO on SBA-15[J].Journal of Henan Agricultural University,2010,44(6):656-659.
[13] 黄艳芹.分子筛负载杂多酸催化大豆油制备生物柴油[J].大豆科学,2011,30(3):488-492. HUANG Yan-qin.Preparation of biodiesel from soybean oil catalyzed by molecular sieve catalyst with heteropoly acid[J].Soybean Science,2011,30(3):488-492.
[14] CIESLA U,SCHVTH F.Ordered mesoporous materials[J].Microporous and Mesoporous Materials,1999,27(2):131-149.
[15] GRVN M,LAUER I,UNGER K K.The synthesis of micrometer and submicrometer size spheres of ordered mesoporous oxide MCM-41[J].Advanced Materials,1997,9(3):254-257.
[16] 郝成伟,吴伯麟,李继彦.聚乙二醇分散剂对高纯超细α-Al₂O₃制备的影响[J].材料导报,2007,21(S1):163-164. HAO Cheng-wei,WU Bo-lin,LI Ji-yan.Influence of polyethylene glycol dispersants on preparing high purity ultrafine α-Al₂O₃[J].Materials Review,2007,21(S1):163-164.
[17] 申延明,戎梅竹,刘宏伟,等.SO₄^2-/ZrO₂固体超强酸的制备及其催化合成ETBE的研究[J].石油炼制与化工,2006,37(8):12-15. SHEN Yan-ming,RONG Mei-zhu,LIU Hong-wei,et al.Study on the preparation of SO₄^2-/ZrO₂ solid superacid catalyst and its catalytic performance in ETBE synthesis[J].Petroleum Processing and Petrochemicals,2006,37(8):12-15.
[18] 周丽绘,胡军,张利中,等.新型介孔分子筛MCM-41的超微结构观察和表征[J].电子显微学报,2004,23(4):428-428. ZHOU Li-hui,HU Jun,ZHANG Li-zhong,et al.Observation and characterization of ultrasructure of novel mesopore molecular sieve MCM-41[J].Journal of Chinese Electron Microscopy Society,2004,23(4):428-428.
[19] 黄文氢,张颖,张友稳,等.扫描电镜研究分子筛形貌中制样方法及试验条件对图像质量的影响[J].现代科学仪器,2008(1):21-26. HUANG Wen-qing,ZHANG Ying,ZHANG You-wen,et al.SEM in molecular sieve morphology research:The effect on photograph quality by sample preparation and apparatus parameter settings[J].Modern Scientific Instruments,2008(1):21-26.
[20] CORMA A,FORNES V,NAVARRO M T,et al.Acidity and stability of MCM-41 crystalline aluminosilicates[J].Journal of Catalysis,1994,148(2):569-574.
[21] SHEK C H,LAI J K L,GU T S,et al.Transformation evolution and infrared absorption spectra of amorphous and crystalline nano-Al₂O₃ powders[J].Nanostructured Materials,1997,8(5):605-610.
[22] RICHARD A N,RONALD O K.Infrared Spectra of Inorganic Compounds[M].New York:Academic Press,1971:125-147.
[23] OMOTA F,DIMIAN A C,BLIEK A.Fatty acid esterification by reactive distillation.part 2:Kinetics-based design for sulphated zirconia catalysts[J].Chemical Engineering Science,2003,58(14):3175-3185.