短轴纳米ZSM-23的合成及异构化性能

doi:10.7503/cjcu20160577

摘要/Abstract

摘要：

分别以异丙胺和二甲胺为模板剂, 通过控制合成配比和反应条件, 合成了硅铝比相近、酸分布一致, 但晶体形貌不同的ZSM-23分子筛. 表征结果表明, 以异丙胺为模板剂合成的ZSM-23具有长径比<5、纳米尺寸均一及外比表面积更高的特点. 正十二烷异构化性能测试结果表明, 具有短轴形貌的ZSM-23分子筛具有更高的异构烷烃选择性和产品收率, 并在实际原油评价测试中取得了更好的降凝效果. 润滑油基础油的收率及其低温流动性能得到进一步改善, 并为加氢异构催化剂的研发提供了指导方向.

关键词: ZSM-23, 分子筛, 形貌, 加氢异构化

Abstract:

Rod-like ZSM-23 zeolites with different length/diameter values(L/D) were synthesized using dimethylamine(DMA) and isopropylamine(IPA) as templates, respectively. The samples were characterized by means of XRD, SEM, XRF, N₂ sorption and NH₃-TPD. The crystals(ZSM-23-IPA) shows special nanoscaled and uniformed morphology with L/D<5, and more external surface areas by controlling the initial gel composition and hydrothermal reaction parameters. On n-dodecane hydroisomerization reaction, it also shows high conversion, selectivity and i-C₁₂ yield, which is associated with the more exposed active sites. Furthermore, Pt-ZSM-23-IPA catalyst also shows very good performance on real crude oil test. It indicates that ZSM-23 catalyst with low L/D value would be applied in the future for improving the low-temperature fluidity of lubricant oil in industry.

Key words: ZSM-23, Zeolite, Morphology, Hydroisomerization

中图分类号:

O643

TrendMD:

张瑀健, 翟绪丽, 付凯妹, 姜涛. 短轴纳米ZSM-23的合成及异构化性能. 高等学校化学学报, 2017, 38(2): 231.

ZHANG Yujian, ZHAI Xuli, FU Kaimei, JIANG Tao. Synthesis of Nano ZSM-23 Zeolites with Low L/D Value Morphology and Their Hydroisomerization Performance^†. Chem. J. Chinese Universities, 2017, 38(2): 231.

图/表 9

Table 1 Products crystallized at various alkalinity

n(Na₂O)/n(SiO₂)	Product	n(Na₂O)/n(SiO₂)	Product
0.03	Amorphous	0.125	ZSM-23
0.05	ZSM-23+Amorphous	0.15	ZSM-23+ZSM-5
0.075	ZSM-23	0.20	ZSM-5
0.10	ZSM-23

Fig.1 XRD patterns of ZSM-23-DMA(a) and ZSM-23-IPA(b)

Fig.2 SEM images of ZSM-23 with different templates of DMA(A, B) and IPA(C, D)

Fig.3 Crystallization curves of ZSM-23-DMA(a) and ZSM-23-IPA(b)

Table 2 Physico-chemical characteristics of ZSM-23-DMA and ZSM-23-IPA

Sample	Molar ratio of SiO₂/Al₂O₃	Na₂O(%)	S_BET/ (m²·g^-1)	S_Micropore/ (m²·g^-1)	S_External/ (m²·g^-1)	V_Micropore / (cm³·g^-1)
ZSM-23-DMA	90	0.32	165	126	39	0.06
ZSM-23-IPA	88	0.34	243	149	94	0.07

Fig.4 NH3-TPD profiles of ZSM-23-DMA(a) and ZSM-23-IPA(b)

Fig.5 Dependences of conversion of n-C12(A), yield of i-C12(B) on temperature and yield of i-C12 vs. conversion of n-C12(C) a. Pt-ZSM-23-DMA; b. Pt-ZSM-23-IPA.

Fig.6 Hydroisomerization processes of n-C12 on ZSM-23 with different L/D values

Table 3 Reaction parameters and lubricant base oil properties

Item	Pt-ZSM-23-DMA	Pt-ZSM-23-IPA
Reaction temperature/℃	345	335
$V H 2$ :V_Oil	500:1	500:1
LHSV/h^-1	0.75	0.75
Total yield of product(%)	86	87
Yield of 10cSt base oil(%)	54.6	63.4
Kinematic viscosity/(mm·s^-1)	9.54	9.61
Viscosity index	126	127
Pour point/℃	-15	-21

Table 3 Reaction parameters and lubricant base oil properties

Item	Pt-ZSM-23-DMA	Pt-ZSM-23-IPA
Reaction temperature/℃	345	335
$V H 2$ :V_Oil	500:1	500:1
LHSV/h^-1	0.75	0.75
Total yield of product(%)	86	87
Yield of 10cSt base oil(%)	54.6	63.4
Kinematic viscosity/(mm·s^-1)	9.54	9.61
Viscosity index	126	127
Pour point/℃	-15	-21

参考文献 36

[1]	Corma A., Chem. Rev., 1995, 95, 559—614
[2]	Davis M. E., Nature, 2002, 417, 813—821
[3]	Cundy C. S., Cox P. A., Chem. Rev., 2003, 103, 663—702
[4]	Seo Y., Lee S., Jo C., Ryoo R., J. Am. Chem. Soc., 2013, 135, 8806—8809
[5]	Meng X. J., Xiao F. S., Chem. Rev., 2014, 114, 1521—1543
[6]	Mériaudeau P., Tuan V. A., Nghiem V. T., Lai S. Y., Hung L. N., Naccache C., J. Catal., 1997, 169, 55—66
[7]	Guo L., Fan Y., Bao X. J., Shi G., Liu H. Y., J. Catal., 2013, 301, 162—173
[8]	Liu W. Q., Liu P., Jiang H. Y., Shang T. M., Ren J., Sun Y. H., Chinese J. Inorg. Chem., 2010, 26(7), 1218—1224
	(刘维桥, 刘平, 蒋海燕, 尚通明, 任杰, 孙予罕. 无机化学学报, 2010, 26(7), 1218—1224)
[9]	Choudhury I. R., Hayasaka K., Thybaut J. W., Narasimhan C. S. L., Denayer J. F., Martens J. A., Marin G. B., J. Catal., 2012, 290, 165—176
[10]	Batalha N., Pinard L., Morisset S., Lemberton J. L., Pouilloux Y., Guisnet M., Lemos F., Ribeiro F. R., Reac. Kinet. Mech. Cat., 2012, 107, 285—294
[11]	Chi K. B., Zhao Z., Tian Z. J., Hu S., Yan L. J., Li T. S., Wang B. C., Meng X. B., Gao S. B., Tan M. W., Liu Y. F., Pet. Sci., 2013, 10, 242—250
[12]	Santilli D. S., Zones S. I., Process for Producing Heavy Lubricating Oil Having a Low Pour Point, US 5376260,1994-12-27
[13]	Narasimhan C. S. L., Thybaut J. W., Marin G. B., Jacobs P. A., Martens J. A., Denayer J. F., Baron G. V., J. Catal., 2003, 220, 399—413
[14]	Huybrechts W., Vanbutsele G., Houthoofd K. J., Bertinchamps F., Narasimhan C. S. L., Gaigneaux E. M., Thybaut J. W., Marin G. B., Denayer F. M., Baron G. V., Jacobs P. A., Martens J. A., Catal. Lett., 2005, 100, 235—242
[15]	Hu Y. F., Wang X. S., Guo X. W., Li S., Hu S., Sun H. B., Bai L., Catal. Lett., 2005, 100, 59—65
[16]	Lee S. W., Ihm S. K., Ind. Eng. Chem. Res., 2013, 52, 15359—15365
[17]	Zhang M., Chen Y. J., Wang L., Zhang Q. M., Tsang C. W., Liang C. H., Ind. Eng. Chem. Res., 2016, 55, 6069—6078
[18]	Elia C., Kalyanaraman M., Zhang L., Acharya M., Daage M. A., Sinclair D., Kowalski J. A., Santiesteban J. G., Dandekar A. B., Hydroprocessing Catalysts with Low Surface Area Binders, US 8263517,2012-09-11
[19]	Elia C., Kalyanaraman M., Daage M. A., Brown S. H., Zhang L., Crane R. A., Sokolovskii V., Lowe D. M., Han J., Ohler N., Giaquinta D., Volpe J., Anthony F., Sour Service Dewaxing Catalyst without Separate Hydrogenation Function, US 8263519,2012-09-11
[20]	Philip K. E., Stefano R. M., Anne S. J. R., Process to Prepare Middle Distillates and Base Oils WO 2014/001552, 2014-01-03
[21]	Mehla S., Krishnamurthy K. R., Viswanathan B., John M., Niwate Y., Kumar K., Pai S. M., Newalkar B. L., J. Porous Mater., 2013, 20(5), 1023—1029
[22]	Parmar S., Pant K., John M., Kumar K., Pai S. M., Gupta S., Newalkar B. L., J. Porous Mater., 2014, 21(5), 849—857
[23]	Souverijns W., Martens J. A., Froment G. F., Jacobs P. A., J. Catal., 1998, 174, 177—184
[24]	Claude M. C., Martens J. A., J. Catal,2000, 190, 39—48
[25]	Martens J. A., Vanbutsele G., Jacobs P. A., Denayer J., Ocakoglu R., Baron G., Muñoz Arroyo J. A., Marin G. B., Catal. Today,2001, 65, 111—116
[26]	Zones S. I., Darton R. J., Morris R., Hwang S. J., J. Phys. Chem. B,2005, 109, 652—661
[27]	Zones S. I., Burton A. W., Lee G. S., Olmstead M. M., J. Am. Chem. Soc., 2007, 129, 9066—9079
[28]	Burton A. W., J. Am. Chem. Soc., 2007, 129, 7627—7637
[29]	Liu Y., Wang Z. D., Ling Y., Liu Y. M., Wu P., Chinese Journal of Catalysis,2009, 30(6), 525—530
	(刘烨, 王振东, 凌云, 刘月明, 吴鹏. 催化学报, 2009, 30(6), 525—530)
[30]	Wang B. C., Tian Z. J., Li P., Wang L., Xu Y. P., Qu W., He Y. L., Ma H. J., Xu Z. S., Lin L. W., Micropours Mesopours Mater., 2010, 134, 203—209
[31]	Wu Q. M., Wang X., Meng X. J., Yang C. G., Liu Y., Jin Y. Y., Yang Q., Xiao F. S., Micropours Mesopours Mater., 2014, 186, 106—112
[32]	Muraza O., Ind. Eng. Chem. Res., 2015, 54, 781—789
[33]	Liu Y., Qu W., Chang W. W., Pan S. X., Tian Z. J., Meng X. J., Rigutto M., Made A., Zhao L., Zheng X. M., Xiao F. S., J. Colloid Interf. Sci., 2014, 418, 193—199
[34]	Yang J., Wu W., Zhou Y. J., Wu G., Zhao A. J., Kikhtyanin O. V., Toktarev A. V., Echevskii G. V., Chinese Journal of Catalysis,2011, 32(7), 1234—1241
	(杨杰, 吴伟, 周亚静, 武光, 赵爱娟, 基赫佳宁 O. V., 托克塔列夫 A. V., 伊切夫斯基 G. V. 催化学报, 2011, 32(7), 1234—1241)
[35]	Guo L., Bao X. J., Fan Y., Shi G., Liu H. Y., Bai D. J., J. Catal., 2012, 294, 161—170
[36]	Zhang S. Z., Chen S. L., Dong P., Ji Z. Y., Zhao J. Y., Xu K. Q., Chinese Journal of Catalysis,2007, 28(10), 857—864
	(张胜振, 陈胜利, 董鹏, 纪智勇, 赵俊颖, 徐克琪. 催化学报, 2007, 28(10), 857—864)