HY-SBA-15复合分子筛催化苯酚甲醇烷基化
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摘要
采用原位合成法合成了HY-SBA-15复合分子筛,通过XRD、N_2吸附-脱附、NH_3-TPD、Py-FTIR、TG-DTA和SEM表征发现,合成出的样品是具有微介孔结构的HY-SBA-15核壳型复合分子筛,且复合后分子筛的总酸量减少,L酸增多,B酸减少。在温度为440℃,n(苯酚)∶n(甲醇)=1∶4,质量空速为1 h~(-1)条件下,对样品进行苯酚甲醇烷基化性能评价,结果表明,30%HY-SBA-15复合分子筛的催化性能最好,苯酚的转化率为69.9%,邻甲酚的选择性为80.3%。
HY-SBA-15 composite molecular sieve was prepared by in-situ synthesis method and was characterized by XRD, N_2 adsorption-desorption, NH_3-TPD, Py-FTIR, SEM and TG-DTA. The results show that HY-SBA-15 composite molecular sieve has less acid amounts(more Lewis acids and less Bronsted acids) and has both microporous and mesoporous structures. The reaction of phenol with methanol was catalyzed by different zeolites when temperature was 440 ℃, phenol/methanol(molar ratio) was 1 ∶4, and WHSV was 1.0 h~(-1).30% HY-SBA-15 composite molecular sieve shows the best performance of alkylation and the conversation of phenol is 69.9%, and the selectivity of o-cresol is 80.3%.
HY-SBA-15 composite molecular sieve was prepared by in-situ synthesis method and was characterized by XRD, N_2 adsorption-desorption, NH_3-TPD, Py-FTIR, SEM and TG-DTA. The results show that HY-SBA-15 composite molecular sieve has less acid amounts(more Lewis acids and less Bronsted acids) and has both microporous and mesoporous structures. The reaction of phenol with methanol was catalyzed by different zeolites when temperature was 440 ℃, phenol/methanol(molar ratio) was 1 ∶4, and WHSV was 1.0 h~(-1).30% HY-SBA-15 composite molecular sieve shows the best performance of alkylation and the conversation of phenol is 69.9%, and the selectivity of o-cresol is 80.3%.
引文
[1] WANG Y, SONG Y, HUO W, et al. Vaporphaseortho -selectivealkylationofphenolwithmethanoloversilica-manganesemixedoxidecatalysts[J]. Chemical Engineering Journal, 2012, s181/182(2):630-635.
[2] SANTACESARIA E, SERIO M D, CIAMbELLI P, et al. Catalytic alkylation of phenol with methanol: Factors influencing activities and selectivities : Ⅱ. Effect of intracrystalline diffusion and shape selectivity on H-ZSM5 zeolite[J]. Applied Catalysis, 1990, 64(1/2):101-117.
[3] SREEKUMARK, SUGUNANS. A comparison on the catalytic activity of Zn1-xCoxFe2O4(x=0, 0.2, 0.5, 0.8 and 1.0)-type ferrospinels prepared via. a low temperature route for the alkylation of aniline and phenol using methanol as the alkylating agent [J]. Applied Catalysis A General, 2002, 230(1/2):245-251.
[4] SREEKUMAR K, SUGUNAN S. Ferrospinels based on Co and Ni prepared via a low temperature route as efficient catalysts for the selective synthesis of o-cresol and 2,6-xylenol from phenol and methanol [J]. Journal of Molecular Catalysis A Chemical, 2002, 185(1/2):259-268.
[5] 王俊丰, 沈健, 石薇薇. Ce/USY改性分子筛催化苯酚甲醇烷基化的实验研究[J]. 石油学报(石油加工), 2017, 33(4):757-762.
[6] 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.
[7] 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.
[8] 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.
[9] JIANG T, QI L, JI M, et al. Characterization of Y/MCM-41 composite molecular sieve with high stability from Kaolin and its catalytic property[J]. Applied Clay Science, 2012, 62/63:32-40.
[10] 武宝萍, 沈健, 张秋荣. 微孔-介孔复合分子筛HY-SBA-15的表征及应用[J]. 燃料化学学报, 2012, 40(6):732-736.
[11] DU J, SHI C, WU W, et al. Synthesis of core-shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene[J]. Science & Technology of Advanced Materials, 2017, 18(1):939-949.
[12] ZHAO Q, MAO Y, YAN L, et al. Stability of Y/MCM-48 composite molecular sieve with mesoporous and microporous structures[J]. Journal of Asian Ceramic Societies, 2014, 2(4):347-356.
[13] 刘鹏, 沈健. ZSM-5-SBA-15复合分子筛的制备[J]. 硅酸盐学报, 2015(7):875-881.
[14] 吴伟, 吴维果, 李凌飞,等. 氟硅酸铵改性的HZSM-12分子筛催化合成2,6-二甲基萘[J].石油学报(石油加工), 2010, 26(2):189-194.
[15] ULLAH R, BAI P, WU P, et al. Cation-anion double hydrolysis derived mesoporous mixed oxides for reactive adsorption desulfurization[J]. Microporous & Mesoporous Materials, 2017, 238:36-45.
[16] ROSSETTO E, NICOLA B P, SOUZA R F D, et al. Anchoring via covalent binding of β-diimine-nickel complexes in SBA-15 and its application in catalytic reactions[J]. Applied Catalysis A General, 2015, 502(11):221-229.
[2] SANTACESARIA E, SERIO M D, CIAMbELLI P, et al. Catalytic alkylation of phenol with methanol: Factors influencing activities and selectivities : Ⅱ. Effect of intracrystalline diffusion and shape selectivity on H-ZSM5 zeolite[J]. Applied Catalysis, 1990, 64(1/2):101-117.
[3] SREEKUMARK, SUGUNANS. A comparison on the catalytic activity of Zn1-xCoxFe2O4(x=0, 0.2, 0.5, 0.8 and 1.0)-type ferrospinels prepared via. a low temperature route for the alkylation of aniline and phenol using methanol as the alkylating agent [J]. Applied Catalysis A General, 2002, 230(1/2):245-251.
[4] SREEKUMAR K, SUGUNAN S. Ferrospinels based on Co and Ni prepared via a low temperature route as efficient catalysts for the selective synthesis of o-cresol and 2,6-xylenol from phenol and methanol [J]. Journal of Molecular Catalysis A Chemical, 2002, 185(1/2):259-268.
[5] 王俊丰, 沈健, 石薇薇. Ce/USY改性分子筛催化苯酚甲醇烷基化的实验研究[J]. 石油学报(石油加工), 2017, 33(4):757-762.
[6] 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.
[7] 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.
[8] 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.
[9] JIANG T, QI L, JI M, et al. Characterization of Y/MCM-41 composite molecular sieve with high stability from Kaolin and its catalytic property[J]. Applied Clay Science, 2012, 62/63:32-40.
[10] 武宝萍, 沈健, 张秋荣. 微孔-介孔复合分子筛HY-SBA-15的表征及应用[J]. 燃料化学学报, 2012, 40(6):732-736.
[11] DU J, SHI C, WU W, et al. Synthesis of core-shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene[J]. Science & Technology of Advanced Materials, 2017, 18(1):939-949.
[12] ZHAO Q, MAO Y, YAN L, et al. Stability of Y/MCM-48 composite molecular sieve with mesoporous and microporous structures[J]. Journal of Asian Ceramic Societies, 2014, 2(4):347-356.
[13] 刘鹏, 沈健. ZSM-5-SBA-15复合分子筛的制备[J]. 硅酸盐学报, 2015(7):875-881.
[14] 吴伟, 吴维果, 李凌飞,等. 氟硅酸铵改性的HZSM-12分子筛催化合成2,6-二甲基萘[J].石油学报(石油加工), 2010, 26(2):189-194.
[15] ULLAH R, BAI P, WU P, et al. Cation-anion double hydrolysis derived mesoporous mixed oxides for reactive adsorption desulfurization[J]. Microporous & Mesoporous Materials, 2017, 238:36-45.
[16] ROSSETTO E, NICOLA B P, SOUZA R F D, et al. Anchoring via covalent binding of β-diimine-nickel complexes in SBA-15 and its application in catalytic reactions[J]. Applied Catalysis A General, 2015, 502(11):221-229.