-
摘要: 用两步浸渍法制备了Mg-La-HY-SBA-15复合分子筛,在小型固定床反应器上考察了苯酚甲醇烷基化性能;通过SEM-EDS、Py-FTIR等表征手段分析了Mg-La-HY-SBA-15分子筛的孔结构和酸性。结果表明,Mg负载到HY-SBA-15分子筛上且未改变其微介孔结构;Mg改性后降低了载体的总酸量,增加了总Lewis酸,提高了邻甲酚的选择性和收率。
-
关键词:
- Mg-La-HY-SBA-15 /
- 微介孔 /
- 苯酚 /
- 烷基化 /
- 邻甲酚
Abstract: Mg-La-HY-SBA-15 zeolite prepared by separate-step impregnation method was used to catalyze alkylation of phenol with methanol. The porous structure and acid property were characterized by SEM-EDS, Py-FTIR and others.The results found that Mg was successfully supported on La-HY-SBA-15 zeolite. Mg-La-HY-SBA-15 had micro-mesoporous structures. Compared with mono-mental modification, bimental modification reduced the amount of total acid and gained more total Lewis acid. At the same time, the selectivity and yield of o-cresol were increased.-
Key words:
- Mg-La-HY-SBA-15 /
- micro-mesoporous /
- phenol /
- alkylation /
- o-cresol
-
表 1 不同样品的孔结构性质
Table 1 Textural properties of different samples
Sample ABET/(m2·g-1) vt/(cm3·g-1) d/nm 30%HY-SBA-15 643 0.864 5.51 10%La-HY-SBA-15 396 0.705 5.34 2%Mg-10%La-HY-SBA-15 375 0.535 5.37 5%Mg-10%La-HY-SBA-15 342 0.501 5.42 8%Mg-10%La-HY-SBA-15 301 0.453 5.49 表 2 样品的酸量
Table 2 Acid amount of the sample
Sample Acid amount /(mmol·g-1) T TL TB SL SB ML MB WL WB 10%La-HY-SBA-15 2.34 1.47 0.60 0.11 0.08 1.36 0.52 0.12 0.05 2%Mg-10%La-HY-SBA-15 1.94 1.70 0.14 0.10 0.05 1.42 0.05 0.18 0.04 5%Mg-10%La-HY-SBA-15 1.87 1.78 0.09 0.08 0.02 1.50 0.04 0.20 0.03 8%Mg-10%La-HY-SBA-15 1.37 1.23 0.15 0.05 0.02 0.82 0.05 0.36 0.08 T: total acid; TL: total L acid; TB: total B acid; SL: strong L acid; SB: strong B acid; ML: moderate L acid; MB: moderate B acid; WL: weak L acid; WB: weak B acid 表 3 催化剂的烷基化性能
Table 3 Alkylation properties of the zeolites
Sample x/% s/% w/% o-cresol p-cresol m-cresol xylenol anisole others HY-SBA-15 58.2 76.6 5.2 3.5 4.4 4.7 5.6 44.58 10%La-HY-SBA-15 87.8 80.5 3.9 2.6 3.3 4.4 5.3 70.68 2%Mg-10%La-HY-SBA-15 84.2 88.3 2.2 0.8 1.6 2.5 4.6 74.35 5%Mg-10%La-HY-SBA-15 81.5 93.1 1.4 0.3 1.0 1.9 2.3 75.88 8%Mg-10%La-HY-SBA-15 65.3 84.6 2.9 1.7 2.4 3.6 4.8 55.24 reaction conditions: t=440 ℃,n(phenol)/n(methanol)=1:4,WHSV=2 h-1; x: conversion of phenol; s: selectivity of product; w: yield of o-cresol -
[1] ZHAO Q, MAO Y, YAN L, LU L, JIANG T, YIN H. Stability of Y/MCM-48 composite molecular sieve with mesoporous and microporous structures[J]. J Asian Ceram Soc, 2014, 2(4):347-356. doi: 10.1016/j.jascer.2014.07.003 [2] AUTTHANIT C, JONGSOMJIT B. Differences in characteristics of Zr/SBA-15 and bimetallic Zr-La/SBA-15 prepared by sol-gel and hydrothermal methods[J]. J Porous Mater, 2017, 24(1):1-12. doi: 10.1007/s10934-016-0230-z [3] 刘鹏, 沈健. ZSM-5-SBA-15复合分子筛制备及甲苯甲醇烷基化性能研究[J].燃料化学学报, 2015, 43(9):1147-1152. doi: 10.3969/j.issn.0253-2409.2015.09.019LIU Peng, SHEN Jian. Preparation of ZSM-5-SBA-15 composite molecular sieves and its performance for toluene alkylation with methanol[J]. J Fuel Chem Technol, 2015, 43(9):1147-1152. doi: 10.3969/j.issn.0253-2409.2015.09.019 [4] WU W, SHI C, BIAN X, BAI Y. Microwave radiation hydrothermal synthesis and characterization of micro-and mesoporous composite molecular sieve Y/SBA-15[J]. Arabian J Chem, 2013, 13(2):123-126. http://www.sciencedirect.com/science/article/pii/S1878535213003675 [5] DU J, SHI C, WU W, BIAN Y, CHEN P, CUI Q, CUI Z. Synthesis of core-shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene[J]. Sci Technol Adv Mater, 2017, 18(1):939. doi: 10.1080/14686996.2017.1396561 [6] LIU J, LIU Y, YANG W, GUO H, ZHANG H, TANG Z, FANG F. A novel and simple strategy for the direct synthesis bimetallic mesoporous materials Zr-La-SBA-15[J]. Mater Lett, 2014, 128(10):15-18. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=a75c223ef5c60d789a7b5f278efe2c5b [7] SUBBARAMAIAH V, SRIVASTAVA V C, MALL I D. Optimization of reaction parameters and kinetic modeling of catalytic wet peroxidation of picoline by Cu/SBA-15[J]. Ind Eng Chem Res, 2013, 52(26):9021-9029. doi: 10.1021/ie400124d [8] ZHANG H, LI M, XIAO P, LIU D, ZOU C. Structure and catalytic performance of Mg-SBA-15-supported nickel catalysts for CO2 reforming of methane to syngas[J]. Chem Eng Technol, 2013, 36(10):1701-1707. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=79fc4cad9a883f35cb3a491b36575793 [9] 王俊丰, 沈健, 李剑. Mg/Ce-SBA-15的制备及其苯酚甲醇烷基化性能的研究[J].燃料化学学报, 2017, 45(5):633-640. doi: 10.3969/j.issn.0253-2409.2017.05.015WANG Jun-feng, SHEN Jian, LI Jian. Preparation of Mg/Ce-SBA-15 catalyst and its performance on phenol alkylation with methanol[J]. J Fuel Chem Technol, 2017, 45(5):633-640. doi: 10.3969/j.issn.0253-2409.2017.05.015 [10] ZHAO D, FENG J, HUO Q, MELOSH N, FREDRICKSON G, CHMELKA B, STUCKY G. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998, 279(5350):548-552. doi: 10.1126/science.279.5350.548 [11] ZHENG X D, DONG H J, WANG X, SHI L. Study on olefin alkylation of thiophenic sulfur in FCC gasoline using La2O3-modified HY zeolite[J]. Catal Lett, 2009, 127(1/2):70-74. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=9f2590bcdfc0fa56437cc6dc5b6a9bd9 [12] 张闯, 张波, 尉明全.离子改性Y分子筛吸附分离1, 1, 1, 2-四氟乙烷/1, 1-二氟-2-氯乙烯[J].化工学报, 2014, 65(10):3946-3952. doi: 10.3969/j.issn.0438-1157.2014.10.027ZHANG Chuang, ZHANG Bo, YU Ming-quan. Adsorptive separation of 1, 1, 1, 2-tetrafluoroethane/1, 1-difluoro-2-chloroethylene over ion-exchanged Y zeolites[J]. J Chem Ind Eng, 2014, 65(10):3946-3952. doi: 10.3969/j.issn.0438-1157.2014.10.027 [13] 徐新龙, 沈健. β/SBA-15复合分子筛的制备及其催化合成叔丁基苯酚的性能[J].石油化工, 2014, 43(7):767-773. doi: 10.3969/j.issn.1000-8144.2014.07.005XU Xin-long, SHEN Jian. Preparation of β/SBA-15 composite molecular sieves and their catalytic performances of the synthesis of tert-Butyl phenol[J]. Petrochem Technol, 2014, 43(7):767-773. doi: 10.3969/j.issn.1000-8144.2014.07.005 [14] LIU J, LIU Y, YANG W, GUO H, FANG F, TANG Z. Immobilization of phosphortungstic acid on amino-functionalized bimetallic Zr-La-SBA-15 and its highly catalytic performance for acetylation[J]. J Mol Catal A:Chem, 2014, 393(18):1-7. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=2970a90bba00dcb61d9f3b9a790d4d23 [15] KOSUGE K, SATO T, KIKUKAWA N, TAKEMORI M. Morphological control of rod-and fiberlike SBA-15 type mesoporous silica using water-soluble sodium silicate[J]. Chem Mater, 2004, 16(5):899-905. doi: 10.1021/cm030622u [16] CHEN L, DONG H, SHI L. Study on alkylation of toluene with tert-butanol over La2O3-modified HY zeolite[J]. Ind Eng Chem Res, 2010, 49(16):7234-7238. doi: 10.1021/ie100695k [17] 桂建舟, 张晓彤, 胡之德, 孙兆林.正己烷在ZnNi/HZSM-5上芳构化反应的研究[J].兰州大学学报(自科版), 2003, 39(5):61-65. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=lzdxxb200305015GUI Jian-zhou, ZHANG Xiao-tong, HU Zhi-de, SUN Zhao-lin. A study of n-hexane aromatization on the ZnNi/HZSM-5 catalyst[J]. J Univ Lanzhou (Nat Sci), 2003, 39(5):61-65. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=lzdxxb200305015 [18] LI X, XIA Q, NGUYEN V C, PENG K, LIU X, ESSAYEM N, WANG Y. High yield production of HMF from carbohydrates over silica-alumina composite catalysts[J]. Catal Sci Technol, 2016, 6(20):7586-7596. doi: 10.1039/C6CY01628F [19] 王俊丰, 沈健, 任铁强. Ce-SBA-15的制备及其苯酚甲醇烷基化性能[J].分子催化, 2016, 30(6):523-531. http://d.old.wanfangdata.com.cn/Periodical/rlhxxb201705015WANG Jun-feng, SHEN Jian, REN Tie-qiang. Preparation of Ce-SBA-15 catalyst and its performance on phenol alkylation with methanol[J]. J Mol Catal, 2016, 30(6):523-531. http://d.old.wanfangdata.com.cn/Periodical/rlhxxb201705015