合成条件对SAPO-11分子筛性质及催化性能的影响

石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (3): 22-30.

合成条件对SAPO-11分子筛性质及催化性能的影响

高敏¹,赵新红¹,向永生²,姚文君²,黄峰³

1. 兰州理工大学石油化工学院
2. 中国石油兰州化工研究中心 3.中国石油大庆石化公司化工一厂

收稿日期:2021-07-13 修回日期:2021-11-18 出版日期:2022-03-12 发布日期:2022-03-03
通讯作者: 高敏 E-mail:gaomincup@163.com
基金资助:
国家自然科学基金

IMPACT OF WATER AMOUNT AND SEED CRYSTAL ON SAPO-11 MOLECULAR SIEVE SYNTHESIS AND ISOMERIZATION PERFORMANCE

#br#

Received:2021-07-13 Revised:2021-11-18 Online:2022-03-12 Published:2022-03-03
Contact: Min GAO E-mail:gaomincup@163.com
Supported by:
National Natural Science Foundation of China

摘要/Abstract

摘要： 通过调变SAPO-11分子筛合成的水/铝比[n(H₂O)/n(Al₂O₃)]、晶种添加量、晶化温度，合成了系列SAPO-11分子筛，研究合成条件对SAPO-11分子筛物化性质及其催化1-己烯临氢异构化性能的影响。结果表明：适当提高体系水/铝比，可使SAPO-11分子筛晶化时产生优先生长现象，从而暴露出更多孔口，提高分子筛的催化性能；加入异质晶种可以缩小SAPO-11分子筛的粒径，提高分子筛的比表面积、孔体积与酸量；与其他条件下合成的分子筛相比，在高水/铝比、添加异质晶种、高晶化温度下合成的SAPO-11-seed-200分子筛的粒径最小、比表面积和孔体积最大、酸量最高，催化1-己烯临氢异构化反应比合成的其他分子筛具有更优的催化活性和更高的骨架异构选择性。

关键词: SAPO-11分子筛, 水热合成, 晶种, 1-己烯异构化

Abstract: A series of SAPO-11 molecular sieves were synthesized by adjusting the n(H₂O)/n(Al₂O₃) ratio, the amount of seed crystals addition and crystallization temperature in the SAPO-11 molecular sieve synthesis process, and the effects of synthesis conditions on the physicochemical properties of molecular sieves and the catalytic performance in 1-hexene hydroisomerization were studied. The results show that the preferential growth of SAPO-11 molecular sieves can be obtained by increasing ratio of n(H2O)/n(Al2O3), thus exposing more pores and improving the catalytic performance, and the size of SAPO-11 molecular sieve can be reduced by adding heterogeneous crystal seeds. Compared with the molecular sieves synthesized under other conditions, the specific surface area, pore volume and acid content were increased. The SAPO-11-seed-200 molecular sieves synthesized at high n(H2O)/n(Al2O3) ratio, heterogeneous seeds and high crystallization temperature had the smallest particle size, the largest specific surface area and pore volume, and the highest acid amount. The catalytic activity and the skeletal isomerization selectivity of 1-hexene isomerization were better than those of other molecular sieves.

Key words: SAPO-11 molecular sieve, hydrothermal synthesis, seed crystal, 1-hexene isomerization

高敏赵新红向永生姚文君黄峰. 合成条件对SAPO-11分子筛性质及催化性能的影响[J]. 石油炼制与化工, 2022, 53(3): 22-30.

参考文献

[1]RAYBAUD P，PATRIGEON A，TOULHOAT H.The origin of the C7-Hydroconversion selectivities on Y,β,ZSM-22,ZSM-23,and EU-1 zeolites[J].Journal of Catalysis, 2001, 197(1):98-112 [2]MERIAUDEAU P, TUAN V A.NGHIEM V T,et alSAPO-11,SAPO-31,and SAPO-41 molecular sieves: Synthesis,characterization,and catalytic properties innoctane hydroisomerizations[J].Journal of Catalysis, 1997, 169(1):55-66 [3]López C M, Machado F J, Goldwasser J, et al.The successive crystallization and characterization of SAPO-31 and SAPO-11 from the same synthesis gel: Influence on the selectivity for 1-butene isomerization[J].Zeolites, 1997, 19(2-3):133-141 [4]CAMPELO J M，LAFONT F，MARINAS J M.Hydroisomerization and hydrocracking of nr heptane on PtSAPO-5 and PtSAP0-11 catalysts[J].Zeolites, 1995, 15(2):97-103 [5]SINHA A K, SIVASANKER s.Hydroisomerization of n-hexane over Pt-SAPO-11 and Pt-SAPO-31 molecular: sieves[J].Catalysis Today, 1999, 49(1-3):293-302 [6]GUO L, BAO X J, FAN Y, et al.Impact of cationic surfactant chain length during SAPO-11 molecular: sievesynthesis on structure,acidity,and n-octane isomerization to di-methyl hexanes[J].Journal of Catalysis, 2012, 294(10):161-170 [7] Zhu G, Qiu S, Gao F, et al.Synthesis of aluminophosphate molecular sieve AIPO4-11 nanocrystals[J]. Microporous and mesoporous materials, 2001, 50: 129-135. [8] Wu Q, Oduro I N, Huang Y, et al.Synthesis of hierarchical SAPO-11 via seeded crystallization[J]. Microporous and Mesoporous Materials, 2015, 218: 24-32.[J].Microporous & Mesoporous Materials, 2015, 218:24-32 [9]Yang X, Lu T, Chen C, et al.Synthesis of hierarchical AIPO-n molecular sieves templated by saccharides[J].Microporous and Mesoporous Materials, 2011, 144(1-3):176-182 [10]Blasco T, Chica A, G A, et al.Changing the Si distribution in SAPO-11 by synthesis with surfactants improves the hydr oisomerizationdewaxing properties[J].Joumal of Catalysis, 2006, 242(1):153-161 [11]Chen Z, Song W, Zhu S, et al.Synthesis of a multi-branched dandelion-like SAPO-11 by an in situ inoculating seed-induced-steam-assisted conversion method (SISAC) as a highly effective hydrois omerization support[J].RSC Advances, 2017, 7(8):4656-4666 [12]T.CHELLAPPA,MJOSé FONSECA COSTA,W.A. NASCIMENTO et al. Synthesis,characterization and catalytic properties of SAPO-11 molecular sieve synthesized in hydrothermal media using di-isopropylamine as template[J].TECHNICAL SCIENCES, 2014, 62(3):481-488 [13] 李莉.SAPO-11的形貌调控及其催化长链烷烃异构化反应性能研究[D].华东师范大学, 2019. [14] Liu P, Ren J, Sun Y.Influence of template on Si distribution of SAPO-11 and their performance for n-paraffin isomerization [J]. Microporous and Mesoporous Materials, 2008, 114: 365-372. [15] Zhang S, Chen S L, Dong P, et al.Characterization and hydroisomerization performance of SAPO-11 molecular sieves synthesized in different media[J]. Applied Catalysis A: General, 2007, 332: 46-55. [16] Yadav R, Sakthivel A.Silicoaluminophosphate molecular sieves as potential catalysts for hydroisomerization of alkanes and alkenes [J]. Applied Catalysis A: General.2014. 481:143-160. [17]Zhe-ming Wang, Zi-feng Yan.Synthesis of SAPO-11 zeolites[J].Joumal of Fuel Chemistry and Technology, 2003, 31(4):360-366 [18]XIAO Han, ZANG Jiazhong, SONG Guoliang, et al.Impact of different alkyl chain lengths on physicochemical properties and hydroisomerization of SAPO-11 molecular sieves synthesized with organic phosphoric acid esters[J].Acta Petrolei Sinica (Petroleum Processing Section), 2017, 33(05):865-872 [19]王潇潇, 郭少青, 张伟.分子筛合成条件对其结晶度与催化性能的影响[J].分子催化, 2013, 27(4):295-306 [20]刘维桥, 雷卫宁, 刘平.对-催化剂物化及异构性能影响[J].化学学报, 2010, 68(18):1781-1786 [21] Martens J A, Vanbutsele G, Jacobs P A, et al.Evidences for pore mouth and key-lock catalysis in hydroisomerization of long n-alkanes over 10-ring tubular pore bifunctional zeolites [J]. Catalysis today, 2001, 65: 111-116. [22]Kazansky V B.Adsorbed carbocations as transition states in heterogeneous acid catalyzed transformations of hydrocarbons[J].Catalysis Today, 1999, 51(3):419-434 [23] Fottinger K, Kinger G Vinek H.1-Pentene isomerization over FER and BEA [J]. Appl. Catal. A: Gen., 2003, 249: 205-212. [24]López C M, Machado F J, Goldwasser J, et al.The successive crystallization and characterization of SAPO-31 and SAPO-11 from the same synthesis gel: Influence on the selectivity for 1-butene isomerization[J].Zeolites, 1997, 19(2-3):133-141 [25] Lin Guo, Xiaojun Bao, Yu Fan, Gang Shi, Haiyan Liu, Danjiang Bai.Impact of cationic surfactant chain length during SAPO-11 molecular sieve synthesis on structure, acidity, and n -octane isomerization to di-methyl hexanes[J]. Journal of Catalysis, 2012, 294. [26] HochtI M, Jentys A, Vinek H.Isomerization of l-pentene over SAPO, CoAPO (AEL, AFD) molecular sieves and HZSM-5[J]. Appl. Catal, A, 2001, 207: 397 405. [27] 吴肖群, 周力, 慎炼, C5全组分异构烯烃化的催化反应原理与催化剂[J].石油炼制与化工, 1995, 26: 19-24. [28] Asensi M A, Corma A, Martinez A.Skeletal isomerization of l-butene on MCM-22 zeolite catalyst [J]. Catal., 1996, 158: 561-569.