弱酸性多级孔MFI沸石上甲醇转化制丙烯

ZHAO Yan-nan; FAN Su-bing; MA Qing-xiang; ZHANG Jian-li; ZHAO Tian-sheng

doi:10.1016/S1872-5813(21)60175-5

弱酸性多级孔MFI沸石上甲醇转化制丙烯

doi: 10.1016/S1872-5813(21)60175-5

宁夏大学, 化学化工学院, 省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏银川 750021

详细信息

中图分类号: O643
计量
- 文章访问数: 262
- HTML全文浏览量: 94
- PDF下载量: 36
- 被引次数: 0
出版历程
- 收稿日期: 2021-05-19
- 修回日期: 2021-06-23
- 网络出版日期: 2021-10-29
- 刊出日期: 2022-02-12

Methanol converting to propylene on weakly acidic and hierarchical porous MFI zeolite

State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the East-West Cooperation Project of Ningxia Key R&D Plan (2017BY063).

More Information

Corresponding author: zhaots@nxu.edu.cn

摘要

摘要: 使用葡萄糖辅助模板合成了H-[B,Al]-ZSM-5 沸石并用于催化甲醇转化制丙烯。优越的丙烯选择性和活性持久性关联于有利于丙烯生成的高的弱酸/强酸比例以及有利于改善反应物扩散的防止快速积炭的高的介孔率。较多的位于MFI沸石直/正弦孔道的骨架铝增加了产物丙烯/乙烯比归因于促进的丙烯生成。低的酸密度有助于高的丙烯/乙烯比。B/Al比为2 且(Al₂+B₂)/Si 比为0.01的HZ5-G-2B 样品用于甲醇制丙烯反应，在原料CH₃OH/H₂O(1∶1.2) 重时空速为1.8 h⁻¹ 、480 °C反应条件下，丙烯选择性为51.6%, ${\rm{C}}_{2-4}^ {=} $烯烃选择性为83.7%，甲醇完全转化。丙烯/乙烯比为2。催化活性保持580 h稳定。
- H-[B /
- Al]-ZSM-5 /
- 弱酸性 /
- 介孔率 /
- MTP
Abstract: H-[B,Al]-ZSM-5 zeolites were synthesized with glucose as assistant template to catalyze methanol converting toward propylene. The superior catalytic performance in terms of the propylene selectivity and the activity longevity was related to high ratio of weak acid to strong acid for favorable production of propylene and to high mesoporosity for improved diffusion of reactants and prevention from fast coking. More framework Al siting in the straight or sinusoidal channels of the MFI zeolite could also enhance the propylene/ethylene ratio due to the promotional effect on propylene formation. Low weak acid density was conducive to the production of high propylene/ethylene ratio. With the B/Al ratio of 2 and the (Al₂+B₂)/Si ratio of 0.01, HZ5-G-2B was applied in the methanol to propylene reaction at CH₃OH/H₂O (1∶1.2) WHSV of 1.8 h⁻¹ and 480 °C. Propylene selectivity of 51.6%, the ${\rm{C}}_{{2-4}}^ {=} $ selectivity of 83.7% and complete conversion of methanol were achieved. The propylene/ethylene ratio was 2. The catalytic activity kept stable for 580 h.
- H-[B /
- Al]-ZSM-5 /
- weak acidity /
- mesoporosity /
- MTP

HTML全文

FIG. 1266. FIG. 1266.

FIG. 1266.

下载: 全尺寸图片幻灯片

Figure 1 SEM and TEM images of synthetic samples

下载: 全尺寸图片幻灯片

Figure 2 XRD patterns of synthetic samples

下载: 全尺寸图片幻灯片

Figure 3 N₂ adsorption isotherms and pore distribution of synthetic samples

下载: 全尺寸图片幻灯片

Figure 4 ¹¹B NMR spectra of synthetic samples

下载: 全尺寸图片幻灯片

Figure 5 ²⁷Al NMR spectra of synthetic samples

下载: 全尺寸图片幻灯片

Figure 6 Curve fitting of ²⁷Al NMR spectra of synthetic samples

下载: 全尺寸图片幻灯片

Figure 7 NH₃-TPD profiles of synthetic samples

下载: 全尺寸图片幻灯片

Figure 8 Py-FTIR spectra of synthetic samples

下载: 全尺寸图片幻灯片

Figure 9 Catalytic activity of synthetic samples for MTP

下载: 全尺寸图片幻灯片

Figure 10 TG curves of spent catalyst samples

下载: 全尺寸图片幻灯片

Table 1 Textural properties of synthetic samples

Sample	Measured molar ratio*			Crysta-llinity/%	BET area/(m²·g⁻¹)			Pore volume/(cm³·g⁻¹)			Mesoporosity/%
Sample	Si/Al₂	B/Al	(Al₂+B₂)/Si	Crysta-llinity/%	micro	meso	total	micro	meso	total	Mesoporosity/%
HZ5-G-9B	220	5.1	0.030	98	279	58	337	0.12	0.14	0.26	53
HZ5-G-2B	230	1.3	0.010	95	254	72	326	0.11	0.30	0.41	73
HZ5-G-1B	224	0.7	0.008	89	295	48	343	0.13	0.23	0.36	63
HZ5-G	218	0	0.005	96	316	57	373	0.14	0.10	0.22	45
HZ5-1B	−	−	−	−	382	33	415	0.17	0.02	0.19	10
HZ5	220	0	0.005	−	−	−	−	−	−	−	−
*: charged Si/Al₂=200, B/Al=9, 2, 1, 0, 0

下载: 导出CSV

Table 2 Percentage of deconvoluted peak areas for synthetic samples

Sample	Percentage/%					Al₅₆/Al₅₄
Sample	52	53	54	56	58	Al₅₆/Al₅₄
HZ5-G-9B	12	13	20	47	8	2.04
HZ5-G-2B	8	12	23	45	9	2.03
HZ5-G-1B	10	13	25	42	10	1.68
HZ5-G	12	14	30	31	12	1.03

下载: 导出CSV

Table 3 Surface acidity of synthetic samples

Sample	Temp./°C		Acid amount/(μmol NH₃·g⁻¹)		W/S ratio	Weak acid density/ (μmol·m⁻²)	Acid/(μmol·g⁻¹)
Sample	weak	strong	weak	strong	W/S ratio	Weak acid density/ (μmol·m⁻²)	B	L
HZ5-G-9B	170	373	213	38	5.6	0.63	130	3
HZ5-G-2B	175	374	167	41	4.1	0.51	126	3
HZ5-G-1B	174	369	139	40	3.5	0.41	94	4
HZ5-G	168	362	92	42	2.2	0.25	80	1

下载: 导出CSV

Table 4 Catalytic activity of synthetic samples for MTP

Sample	TOS/h	Product selectivity/%									P/E	HTI
Sample	TOS/h	C₁	${\rm{C}}_{2}^ {=} $	C₂	${\rm{C}}_{3}^ {=} $	C₃	${\rm{C}}_{4}^ {=} $	C₄	${\rm{C}}_{5+} $	${\rm{C} }_{{2-4}}^ {=}$	P/E	HTI
HZ5-G-9B	480	3.4	25.4	0.3	47.9	3.4	10.4	0.7	7.1	83.7	1.9	0.05
HZ5-G-2B	580	3.7	22.8	0.3	50.1	2.1	11.6	0.7	6.4	84.5	2.2	0.04
HZ5-G-1B	230	4.3	24.1	0.5	44.4	3.3	11.4	0.6	7.6	79.9	1.8	0.05
HZ5-G	80	1.8	25.2	0.6	41.1	4.3	12.6	0.7	13.5	78.9	1.6	0.07
HZ5	23	6.5	24.9	0.5	38.9	4.9	11.5	0.8	15.7	75.3	1.5	0.08

下载: 导出CSV

参考文献(25)

[1]	HAW J F, SONG W, MARCUS D M, NICHOLAS J B. The mechanism of methanol to hydrocarbon catalysis[J]. Acc Chem Res,2003,36:317−326. doi: 10.1021/ar020006o
[2]	INOUE M, DHUPATEMIYA P, PHATANASRI S, INUI T. Synthesis course of the Ni-SAPO-34 catalyst for methanol-to-olefin conversion[J]. Microporous Mesoporous Mater,1999,28(1):19−24. doi: 10.1016/S1387-1811(98)00278-9
[3]	ZHAO T S, TAKEMOTO T, TSUBAKI N. Direct synthesis of propylene and light olefins from dimethyl ether catalyzed by modified H-ZSM-5[J]. Catal Commun,2006,7(9):647−650. doi: 10.1016/j.catcom.2005.11.009
[4]	LEE K Y, LEE S W, IHM S K. Acid strength control in MFI zeolite for the methanol-to-hydrocarbons(MTH) reaction[J]. Ind Eng Chem Res,2014,53(24):10072−10079.
[5]	PALČIČ A, ORDOMSKY V V, QIN Z, GEORGIEVA V, VALTCHEV V. Tuning zeolite properties for highly efficient synthesis of propylene from methanol[J]. Chem-Eur J,2018,24(50):13136−13149. doi: 10.1002/chem.201803136
[6]	UNNEBERG E, KOLBOE S. H--ZSM-5 as catalyst for methanol reactions[J]. Appl Catal A: Gen,1995,124:345−354. doi: 10.1016/0926-860X(95)00005-4
[7]	CHU C T-W, KUEHL G H, LAGO R M, CHANG C D. lsomorphous substitution in zeolite frameworks II catalytic properties ofZSM-5[J]. J Catal,1985,89:1569−1571.
[8]	YANG Y, SUN C, DU J, YUE Y, HUA W, ZHANG C, SHEN W, XU H. The synthesis of endurable B-Al-ZSM-5 catalysts with tunable acidity for methanol to propylene reaction[J]. Catal Commun,2012,24(26):44−47.
[9]	YARIPOUR F, SHARIATINIA Z, SAHEBDELFAR S, IRANDOUKHT A. Effect of boron incorporation on the structure, products selectivities and lifetime of H-ZSM-5 nanocatalyst designed for application in methanol-to-olefins (MTO) reaction[J]. Microporous Mesoporous Mater,2015,203:41−53.
[10]	LIANG T, CHEN J, QIN Z, LI J, WANG P, WANG S, WANG G, DONG M, FAN W, WANG J. Conversion of methanol to olefins over H-ZSM-5 zeolite: Reaction pathway is related to the framework Aluminum siting[J]. ACS Catal,2016,6:7311−7325. doi: 10.1021/acscatal.6b01771
[11]	TAO J, ZHANG J, FAN S, MA Q, GAO X, ZHAO T S. Effects of boron modification on the activity of HZSM-5 toward MTP[J]. J Fuel Chem Technol,2020,48(9):1105−1111. doi: 10.1016/S1872-5813(20)30074-8
[12]	CUI N, GUO H, ZHOU J, LI L, GUO L, HUA Z. Regulation of framework Al distribution of high-silica hierarchically structured ZSM-5 zeolites by boron-modification and its effect on materials catalytic performance in methanol-to-propylene reaction[J]. Microporous Mesoporous Mater,2020,306:110411. doi: 10.1016/j.micromeso.2020.110411
[13]	HU Z, ZHANG H, WANG L, ZHANG H, ZHANG Y, XU H, SHEN W, TANG Y. Highly stable boron-modified hierarchical nanocrystalline ZSM-5 zeolite for the methanol to propylene reaction[J]. Catal Sci Technol,2014,4(9):2891−2895. doi: 10.1039/C4CY00376D
[14]	DING J, JIA Y, CHEN P, ZHAO G, LIU Y, LU Y. Thin-felt hollow-B-ZSM-5/SS-fiber catalyst for methanol-to-propylene: toward remarkable stability improvement from mesoporosity-dependent diffusion enhancement[J]. Chem Eng J, 2019, 361: 588−598.
[15]	KIM J, CHOI M, RYOO R. Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process[J]. J Catal,2010,269(1):219−228.
[16]	TAO J, ZHANG J, FAN S, ZHAO T S. Cocrystalline synthesis of ZSM-5/ZSM-11 and catalytic activity for methanol to propylene[J]. Cryst Res Technol,2020,55:2000027. doi: 10.1002/crat.202000027
[17]	LIU H, ERNST H, FREUDDE D, SCHEFFLER F, SCHWIEGER W. In situ ¹¹B MAS NMR study of the synthesis of a boron-containing MFI type zeolite[J]. Microporous Mesoporous Mater,2002,54(3):319−330. doi: 10.1016/S1387-1811(02)00392-X
[18]	CHEN T H, WOUTERS B H, GROBET P J. Aluminium coordinations in zeolite mordenite by ²⁷Al multiple quantum MAS NMR spectroscopy[J]. Eur J Inorg Chem,2000,2:281−285.
[19]	YOKOI T, MOCHIZUKI H, NAMBA S, KONDO J N, TATSUMI T. Control of the Al distribution in the framework of ZSM-5 zeolite and its evaluation by solid-state NMR technique and catalytic properties[J]. J Phys Chem C,2015,119(27):15303. doi: 10.1021/acs.jpcc.5b03289
[20]	LI J, MA H, CHEN Y, XU Z, LI C, YING W. Conversion of methanol to propylene over hierarchical HZSM-5: Effect of Al spatial distribution[J]. Chem Commun,2018,54:6032−6035. doi: 10.1039/C8CC02042F
[21]	RODRÍGUEZ-GONZÁLEZ L, HERMES F, BERTMER M, RODRÍGUEZ-CASTELLÓN E, JIMÉNEZ-LÓPEZ A, SIMON U. The acid properties of H-ZSM-5 as studied by NH₃-TPD and ²⁷Al-MAS-NMR spectroscopy[J]. Appl Catal A: Gen,2007,328(2):174−182.
[22]	CHU C T-W, CHANG C D. Isomorphous substitution in zeolite frameworks. 1. acidity of surface hydroxyls in [B]-, [Fe]-, [Ga]-, and [AI]-ZSM-5[J]. J Phys Chem,1985,89(30):1569−1571.
[23]	CHANG C D, CHU C T-W, SOCHA R F. Methanol conversion to olefins over ZSM-5 I. effect of temperature and zeolite SiO₂/A1₂O₃[J]. J Catal,1984,86(2):289−296.
[24]	ZHU Q, KONDO J N, SETOYAMA T, YAMAGUCHI M, DOMEN K, TATSUMI T. Activation of hydrocarbons on acidic zeolites: superior selectivity of methylation of ethene with methanol to propene on weakly acidic catalysts[J]. Chem Commun,2008,71(41):5164−5166.
[25]	KIM S, PARK G, WOO M H, KWAK G, KIM S K. Control of hierarchical structure and framework-Al distribution of ZSM-5 via adjusting crystallization temperature and their effects on methanol conversion[J]. ACS Catal,2019,9:2880−2892.