酸碱复合处理制备多级孔ZSM-5分子筛及其甲醇制汽油反应性能

doi:10.15541/jim20180034

无机材料学报 ›› 2018, Vol. 33 ›› Issue (11): 1193-1200.DOI: 10.15541/jim20180034 CSTR: 32189.14.10.15541/jim20180034

酸碱复合处理制备多级孔ZSM-5分子筛及其甲醇制汽油反应性能

王有和^1,2, 王晓东², 徐经纬², 孙洪满², 吴成成¹, 阎子峰², 季生福¹

1. 北京化工大学化工资源有效利用国家重点实验室, 北京 100029;
2. 中国石油大学重质油国家重点实验室, 青岛 266580

收稿日期:2018-01-29 修回日期:2018-03-26 出版日期:2018-11-16 网络出版日期:2018-10-20
作者简介:王有和(1976-), 男, 博士, 副教授. E-mail: yhewang@upc.edu.cn
基金资助:
国家自然科学基金(21776311);中央高校基本科研业务费专项资金(15CX05030A);应用表面与胶体化学教育部重点实验室(陕西师范大学)开放课题基金(2017026)

Hierarchical ZSM-5 Zeolite: Preparation by Sequential Desilication-dealumination and Catalytic Performance in Methanol to Gasoline Reaction

WANG You-He^1,2, WANG Xiao-Dong², XU Jing-Wei², SUN Hong-Man², WU Cheng-Cheng¹, YAN Zi-Feng², JI Sheng-Fu¹

1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China;
2. State Key Laboratory for Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China

Received:2018-01-29 Revised:2018-03-26 Published:2018-11-16 Online:2018-10-20
About author:WANG You-He. E-mail: yhewang@upc.edu.cn
Supported by:
National Natural Science Foundation of China (21776311);Fundamental Research Funds for the Central Universities (15CX05030A);Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University) (2017026)

摘要/Abstract

摘要：

以商业ZSM-5分子筛为原料, 分别采用碱处理和酸碱复合处理法制备了多级孔ZSM-5分子筛。利用XRD、FT-IR、SEM、TEM以及氮气吸-脱附等手段对样品进行了表征, 并评价了样品的MTG反应性能。结果表明: 利用单纯碱处理或酸碱复合处理商业ZSM-5分子筛均可制备晶体内富含介孔和大孔的多级孔ZSM-5分子筛。与商业ZSM-5原料相比, 多级孔ZSM-5分子筛催化剂的介孔比表面积、介孔孔容以及酸性位“可接近性指数”等显著增加, 酸量明显减少, 酸强度降低。催化评价结果显示, 多级孔ZSM-5分子筛催化剂在大幅提高汽油产品收率、延长使用寿命的同时降低了芳烃收率。与碱处理样品相比, 酸处理能够进一步调节样品的酸性质和孔结构, 因此酸碱复合处理所得多级孔ZSM-5分子筛催化剂的物化性质和催化性能得以进一步提升。

关键词: 多级孔ZSM-5分子筛, 碱处理脱硅, 酸碱复合处理, 甲醇制汽油

Abstract:

Hierarchical ZSM-5 zeolites were prepared by desilication and sequential desilication-dealumination using commercial ZSM-5 zeolite as raw material. The samples were characterized with XRD, FT-IR, SEM, TEM, and N₂ adsorption-desorption isotherms. The catalytic performance was investigated in methanol to gasoline (MTG) reaction. The results indicated that the hierarchical ZSM-5 zeolite catalysts with abundant intracrystalline meso- and macropores could be prepared by desilication or sequential desilication-dealumination treatment. Compared with commercial ZSM-5 zeolite, the hierarchical ZSM-5 zeolites had higher mesopore surface area, larger mesopore volume and higher accessibility index, but with less acid amount and lower acid strength. The results of catalytic performance evaluation showed that the gasoline yield and lifetime of hierarchical ZSM-5 zeolite catalysts were significantly enhanced after modification. Simultaneously, the yield of aromatic hydrocarbon was reduced. Compared with the sample prepared by the desilication treatment, physicochemical properties and catalytic performance of the hierarchical ZSM-5 zeolite prepared by sequential desilication-dealumination treatment were improved.

Key words: hierarchical ZSM-5 zeolite, desilication by alkali treatment, sequential desilication-dealumination, methanol to gasoline

中图分类号:

O611

王有和, 王晓东, 徐经纬, 孙洪满, 吴成成, 阎子峰, 季生福. 酸碱复合处理制备多级孔ZSM-5分子筛及其甲醇制汽油反应性能[J]. 无机材料学报, 2018, 33(11): 1193-1200.

WANG You-He, WANG Xiao-Dong, XU Jing-Wei, SUN Hong-Man, WU Cheng-Cheng, YAN Zi-Feng, JI Sheng-Fu. Hierarchical ZSM-5 Zeolite: Preparation by Sequential Desilication-dealumination and Catalytic Performance in Methanol to Gasoline Reaction[J]. Journal of Inorganic Materials, 2018, 33(11): 1193-1200.

图/表 10

图1 样品的XRD图谱

Fig. 1 XRD patterns of samples

表1 样品的孔结构参数

Table 1 Textural properties of samples

Samples	RC^a/%	S_BET^b/(m²•g^-1)	S_micro^c/(m²•g^-1)	S_meso^d/(m²•g^-1)	V_total^e/(cm³•g^-1)	V_micro^f/(cm³•g^-1)	V_meso^g/(cm³•g^-1)	SAR^h
C-ZSM-5	100	242	231	11	0.148	0.123	0.054	27.4
BT-ZSM-5	85.3	213	133	80	0.287	0.070	0.219	19.5
BAT-ZSM-5	85.6	305	160	145	0.423	0.085	0.345	20.1

图2 样品的N2吸附-脱附曲线(a)以及BJH孔径分布曲线(b)

Fig. 2 N2 adsorption-desorption isotherms (a) and pore size distribution curves calculated from the BJH adsorption branch (b) of samples

图3 C-ZSM-5(a)~(b), BT-ZSM-5(c)~(d)和BAT-ZSM-5(e)~(f)样品的SEM(a)、(c)、(e)和TEM(b)、(d)、(f)照片

Fig. 3 SEM (a, c, e) and TEM (b, d, f) images of C-ZSM-5 (a, b), BT-ZSM-5 (c, d) and BAT-ZSM-5 (e, f)

图4 样品的NH3-TPD图谱

Fig. 4 NH3-TPD pattern of samples

表2 样品的酸性和酸量分布

Table 2 Acidity and acid distribution of samples

Sample	C_w/(μmol•g^-1)	C_s/(μmol•g^-1)	(C_w+C_s)/(μmol•g^-1)	C_s/C_w
C-ZSM-5	304.5	222.2	526.7	0.73
BT-ZSM-5	233.4	206.0	439.5	0.88
BAT-ZSM-5	237.9	214.0	451.9	0.90

图5 样品的吡啶吸附红外光谱图

Fig. 5 IR spectra of pyridine adsorption of samples

表3 样品的酸量、酸类型分布和酸性位可接近性指数

Table 3 Total acidity, acid distribution and acid site accessibility of samples

Sample	Pyridine adsorbed /(μmol•g^-1)				Collidine adsorbed/ (μmol•g^-1)
Sample	C_BP^a	C_LP^b	C_BP+C_LP	C_BP/C_LP	C_BC^c	ACI
C-ZSM-5	378.3	148.3	526.7	2.55	58.9	0.156
BT-ZSM-5	284.1	155.4	439.5	1.83	67.9	0.239
BAT-ZSM-5	306.4	145.5	451.9	2.11	126.3	0.412

图6 不同MTG催化剂上的汽油(a)和芳烃(b)收率随时间的变化

Fig. 6 Change of yield of gasoline (a) and aromatic hydrocarbon (b) on different MTG catalysts with time

表4 MTG反应烃类产物含量分布表

Table 4 Product distributions of MTG reaction

Y_i/wt%	C-ZSM-5^a	BT-ZSM-5^b	BAT-ZSM-5^c
C₁	3.47	2.82	2.35
C₂	2.08	2.46	2.24
C₃	23.62	13.04	12.29
C₄	14.55	15.22	15.25
C₅	19.23	32.43	33.24
C₆	2.99	2.35	2.55
C₇	12.03	5.34	4.93
C₈	15.22	13.65	12.71
C₉₊	6.81	12.69	14.44
C₅₊/Gasoline	56.28	66.46	67.87
Aromatic hydrocarbon^d	37.05	34.03	34.63
Conversion	100	100	100

参考文献 17

[1]	PANG XIAO-WEN, MENG FAN-HUI, LU JIAN-JUN, et al.Recent advances in methanol-to-gasoline technology and related catalysts.Chemical Industry and Engineering Progress, 2013, 32(5): 1014-1019.
[2]	KEIL F J.Methanol-to-hydrocarbons: process technology.Microporous and Mesoporous Materials, 1999, 29: 49-66.
[3]	HE YING-PING, LIU MIN, DAI CHENG-YI, et al.Modification of nanocrystalline HZSM-5 zeolite with tetrapropylammonium hydroxide and its catalytic performance in methanol to gasoline reaction.Chinese Journal of Catalysis, 2013, 34: 1148-1158.
[4]	STOCKER M.Methanol-to-hydrocarbons: catalytic materials and their behavior.Microporous and Mesoporous Materials, 1999, 29(1/2): 3-48.
[5]	CHANG JIANG-WEI, FU TING-JUN, ZHANG HONG-JIAN, et al.Effect of alkaline concentration on mesopore formation in acid pre-treated HZSM-5 zeolite and its catalytic performance in the methanol-to-gasoline reaction.Chinese Journal of Inorganic Chemistry, 2015, 31(11): 2119-2127.
[6]	LV REN-QING, LUO LI-WEN, XIANG SHOU-HE, et al.Pore texture and cracking activity of HZSM-5 zeolites treated with steam.Journal of the University of Petroleum, China(Edition of Natural Science), 2002, 26(3): 97-100.
[7]	SCHWIEGER W, MACHOKE A G, WEISSENBERGER T, et al.Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity.Chemical Society Reviews, 2016, 45: 3353-3376.
[8]	SUN H, PENG P, WANG Y, et al.Preparation, scale-up and application of meso-ZSM-5 zeolite by sequential desilication- dealumination.Journal of Porous Materials, 2017, 24(6): 1513-1525.
[9]	BJORGEN M, JOENSEN F, HOLM S M, et al.Methanol to gasoline over zeolite H-ZSM-5: improved catalyst performance by treatment with NaOH.Applied Catalysis A: General, 2008, 345: 43-50.
[10]	VENNESTROM P N R, GRILL M, KUSTOVA M, et al. Hierarchical ZSM-5 prepared by guanidinium base treatment: understanding microstructural characteristics and impact on MTG and NH3-SCR catalytic reactions.Catalysis Today, 2011, 168: 71-79.
[11]	FATHI S, SOHRABI M, FALAMAKI C.Improvement of HZSM-5 performance by alkaline treatments: comparative catalytic study in the MTG reactions.Fuel, 2014, 116: 529-537.
[12]	FU T, QI R, WAN W, et al.Fabrication of hollow mesoporous nanosized ZSM-5 catalyst with superior methanol-to-hydrocarbons performance by controllable desilication.ChemCatChem, 2017, 9(22): 4212-4224.
[13]	THIBAULT-STARZYK F, STAN I, ABELLO S, et al.Quantification of enhanced acid site accessibility in hierarchical zeolites-the accessibility index.Journal of Catalysis, 2009, 264(1): 11-14.
[14]	WANG W, LI G, LI W, et al.Synthesis of hierarchical TS-1 by caramel templating.Chemical Communications, 2011, 47: 3529-3531.
[15]	PENG P, WANG Y H, ROOD M J, et al.Effects of dissolution alkalinity and self-assembly on ZSM-5-based micro-/mesoporous composites: a study of the relationship between porosity, acidity, and catalytic performance.CrystEngComm, 2015, 17: 3820-3828.
[16]	HU JIN-XIAN, HU JING-WEN, WANG JUN-JIE, et al.Study of MTG process with ZSM-5 zeolites which have different acid properties.Natural Gas Chemical Industry, 2001, 26(6): 1-3.
[17]	OLSBYE U, SVELLE S, BJORGEN M, et al.Conversion of methanol to hydrocarbons: how zeolite cavity and pore size controls product selectivity.Angewandte Chemie International Edition, 2012, 51(24): 5810-5831.

酸碱复合处理制备多级孔ZSM-5分子筛及其甲醇制汽油反应性能

Hierarchical ZSM-5 Zeolite: Preparation by Sequential Desilication-dealumination and Catalytic Performance in Methanol to Gasoline Reaction

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