Regulating the Acid Sites Distribution in ZSM-5 Zeolite and Its Catalytic Performance in the Conversion of Methanol to Olefins

doi:10.7503/cjcu20200413

Abstract

Abstract:

The catalytic performance and reaction mechanism of ZSM-5 zeolite in the conversion of methanol to olefins（MTO） is closely related to the distribution of acid sites in framework. In this work， it was demonstrated that adding proper content of Na⁺ ions during synthesis can increase the proportion of acid sites in the intersection cavity of ZSM-5； the concentration of acid sites in the intersection cavity can promote the formation of higher polymethylbenzene（polyMBs） and the propagation of aromatic cycle， forming more ethene. In contrast， in the Na⁺ ions free synthesis system， more acid sites are distributed in the sinusoidal and straight channels of ZSM-5， which is more encouraging for the alkene cycle and conduces to producing more propene and higher alkenes（C₃₊）.

Key words: Methanol to olefins, ZSM-5 zeolite, Acid sites distribution, Regulation

CLC Number:

O643.3

TrendMD:

GUO Shujia, WANG Sen, ZHANG Li, QIN Zhangfeng, WANG Pengfei, DONG Mei, WANG Jianguo, FAN Weibin. Regulating the Acid Sites Distribution in ZSM-5 Zeolite and Its Catalytic Performance in the Conversion of Methanol to Olefins[J]. Chem. J. Chinese Universities, 2021, 42(1): 227.

Figures/Tables 14

Table 1 Chemical composition and textural properties of all ZSM-5 zeolites*

Zeolite	Crystallinity (%)	n(Si)/n(Al)	Surface area/(m²·g^-1)		Pore volume/(cm³·g^-1)
Zeolite	Crystallinity (%)	n(Si)/n(Al)	Total	Micro	Total	Micro
ZSM-5-0Na	100	36.1	430.2	294.1	0.37	0.11
ZSM-5-0.2Na	93.5	35.0	364.6	275.6	0.24	0.12
ZSM-5-0.4Na	92.9	35.6	399.5	312.6	0.25	0.10
ZSM-5-0.6Na	92.4	33.5	351.4	277.0	0.22	0.08

Fig.1 XRD patterns(A), NH3?TPD profiles(B), Py?IR spectra collected at 423 K(C) and 27Al solid?state MAS NMR spectra(D) of ZSM?5?0Na(a), ZSM?5?0.2Na(b), ZSM?5?0.4Na(c) and ZSM?5?0.6Na(d)

Table 2 Acid property of different ZSM-5 zeolites determined by Py-IR*

Zeolite	Acidity(423 K)/(μmol·g^-1)			Acidity(523 K)/(μmol·g^-1)			Acidity(623 K)/(μmol·g^-1)
Zeolite	Total	Br?nsted	Lewis	Total	Br?nsted	Lewis	Total	Br?nsted	Lewis
ZSM?5?0Na	220.0	178.4	41.6	186.0	158.5	27.5	154.5	132.3	22.2
ZSM?5?0.2Na	206.4	150.9	55.5	158.5	131.3	27.2	129.0	105.6	23.4
ZSM?5?0.4Na	204.0	162.6	41.4	160.5	135.9	24.6	132.7	113.1	19.6
ZSM?5?0.6Na	241.1	200.3	40.8	201.3	169.9	31.4	158.9	133.9	25.0

Fig.2 Deconvolution of the 27Al MAS NMR spectra of ZSM?5?0Na(A), ZSM?5?0.2Na(B), ZSM?5?0.4Na(C) and ZSM?5?0.6Na(D)The experimental spectra are shown in black lines and the fitted ones in red lines. The Al atoms at different T sites were assigned by referring the chemical shifts estimated by the DFT computation[11].

Table 3 Proportion of integrated peak area obtained by the deconvolution of 27Al MAS NMR spectra of ZSM-5 zeolites*

Zeolite	Al_EF(%)	Al_F(%)	Al distribution(%)
Zeolite	Al_EF(%)	Al_F(%)	δ 50.0	δ 53.2	δ 56.5	δ 57.9
ZSM?5?0Na	2.4	97.6	7.6	28.7	50.7	13.0
ZSM?5?0.2Na	9.0	91.0	4.4	60.6	22.1	12.9
ZSM?5?0.4Na	8.2	91.8	9.4	57.5	22.0	11.1
ZSM?5?0.6Na	5.7	94.3	16.0	60.2	18.8	5.0

Fig.3 Deconvolution of the DR UV?Vis spectra of ZSM?5?0Na(A), ZSM?5?0.2Na(B), ZSM?5?0.4Na(C) and ZSM?5?0.6Na(D) and the region of 25000—33000 cm-1 of various Co2+?exchanged ZSM?5 zeolites(E)The experimental spectra are shown in black lines and the fitted ones in red lines.

Table 4 Distributions of different Al species in the ZSM-5 zeolite as measured by DR UV-Vis spectra of Co2+-exchanged ZSM-5 zeolites*

Zeolite	n(Si)/n(Al)	Al_pairs(%)	Al_single(%)	Al distribution(%)
Zeolite	n(Si)/n(Al)	Al_pairs(%)	Al_single(%)	α type	β type	γ type
ZSM?5?0Na	37.2	75.4	24.6	26.4	43.3	30.3
ZSM?5?0.2Na	35.9	83.1	16.9	21.1	58.6	20.3
ZSM?5?0.4Na	35.5	72.2	37.8	16.3	62.3	21.4
ZSM?5?0.6Na	37.1	80.0	20.0	14.0	77.0	9.0

Fig.4 Variation of the methanol conversion and product selectivity with time on stream for MTO over the ZSM?5?0Na(A), ZSM?5?0.2Na(B), ZSM?5?0.4Na(C) and ZSM?5?0.6Na(D) zeolites under atmospheric pressure and 723 K, with a methanol WHSV of 3.8 h-1

Table 5 Catalytic test results for MTO over the ZSM-5 zeolites with different acid sites distributions*

Zeolite	Conv. (%)	Product selectivity(%)					HTI		Lifetime /h	10^?4TON	(P-E)/E	2MB/E
Zeolite	Conv. (%)	C $2 =$	C $3 =$	C $3 + =$	C₁—C₅	BTX	C_4-HTI	C_5-HTI	Lifetime /h	10^?4TON	(P-E)/E	2MB/E
ZSM?5?0Na	99.8	13.8	29.1	20.0	30.3	6.8	0.48	0.55	74.4	4.92	1.11	1.00
ZSM?5?0.2Na	99.9	15.5	19.2	12.6	43.0	9.7	0.69	0.67	22.9	1.77	0.23	0.67
ZSM?5?0.4Na	99.9	15.6	20.0	15.1	39.6	8.8	0.66	0.63	18.0	1.30	0.28	0.87
ZSM?5?0.6Na	99.9	14.8	19.6	14.2	41.5	9.9	0.67	0.63	21.6	1.27	0.32	0.82

Table 5 Catalytic test results for MTO over the ZSM-5 zeolites with different acid sites distributions*

Zeolite	Conv. (%)	Product selectivity(%)					HTI		Lifetime /h	10^?4TON	(P-E)/E	2MB/E
Zeolite	Conv. (%)	C $2 =$	C $3 =$	C $3 + =$	C₁—C₅	BTX	C_4-HTI	C_5-HTI	Lifetime /h	10^?4TON	(P-E)/E	2MB/E
ZSM?5?0Na	99.8	13.8	29.1	20.0	30.3	6.8	0.48	0.55	74.4	4.92	1.11	1.00
ZSM?5?0.2Na	99.9	15.5	19.2	12.6	43.0	9.7	0.69	0.67	22.9	1.77	0.23	0.67
ZSM?5?0.4Na	99.9	15.6	20.0	15.1	39.6	8.8	0.66	0.63	18.0	1.30	0.28	0.87
ZSM?5?0.6Na	99.9	14.8	19.6	14.2	41.5	9.9	0.67	0.63	21.6	1.27	0.32	0.82

Fig.5 A comparison in the selectivities to ethene(C2???=), propene(C3???=), butene(C4???=), alkenes higher than butene(C5+=), C1―C5 alkanes, and benzene, toluene and xylenes(BTX) as well as the (P-E)/E and 2MB/E(P for propene, E for ethene, and 2MB for 2?methylbutane and 2?methyl?2?butene) for MTO over the ZSM?5?0Na and ZSM?5?0.6Na under atmospheric pressure and 623 K, with a WHSV of 48 h-1 and a methanol conversion of 75%, reported at 30 min on stream

Fig.6 Time?resolved IR spectra of p?xylene isomerization over ZSM?5?0Na(A) and ZSM?5?0.6Na(B) at 473 K as well as the relative fraction of m?xylene(C)(C) Obtained with the peak area of m?xylene divided by the total peak areas of p?, o?, and m?xylenes in situ IR spectra. p?Xylene with a partial pressure of 300 Pa was continuously introduced into the reaction cell and the pressure was kept constant during the whole reaction process.

Fig.7 Time?dependent DR UV?Vis spectra for MTO at 573 K over ZSM?5?0Na(A) and ZSM?5?0.6Na(B) zeolites

Fig.8 GC?MS chromatograms(A) and 13C CP/MAS NMR spectra(B) of the retained species for MTO over ZSM?5?0Na and ZSM?5?0.6Na zeolites

Fig.9 13C contents in the effluent olefins(ethene to pentene) and in the retained aromatics(polyMBs) for MTO over ZSM?5?0Na(A) and ZSM?5?0.6Na(B) zeolites at 553 K

References 43

1	Haw J.， Song W.， Marcus D.， Nicholas J.， Acc. Chem. Res.， 2003， 36， 317—326
2	Olsbye U.， Svelle S.， Bjørgen M.， Beato P.， Janssens T. V. W.， Joensen F.， Bordiga S.， Lillerud K. P.， Angew. Chem. Int. Ed.， 2012， 51（24）， 5810—5831
3	Tian P.， Wei Y.， Ye M.， Liu Z.， ACS Catal.， 2015， 5（3）， 1922—1938
4	Xu S.， Zhi Y.， Han J.， Zhang W.， Wu X.， Sun T.， Wei Y.， Liu Z.， Adv Catal.， 2017， 61， 37—122
5	Wang C.， Chu Y.， Zheng A.， Xu J.， Wang Q.， Gao P.， Qi G.， Gong Y.， Deng F.， Chem. Eur. J.， 2014， 20（39）， 1—13
6	Dai W.， Wan C.， Dyballa M.， Wu G.， Guan N.， Li L.， Xie Z.， Hunger M.， ACS Catal.， 2015， 5（1）， 317—326
7	Dedecek J.， Sobalik Z.， Wichterlova B.， Catal. Rev. Sci. Eng.， 2012， 54， 135—223
8	Knott B.， Nimlos C.， Robichaud D.， Nimlos M.， Kim S.， Gounder R.， ACS Catal.， 2018， 8（2），770—784
9	Wang S.， He Y.， Jiao W.， Wang J.， Fan W.， Curr. Opin. Chem. Eng.， 2019，23， 146—154
10	Chen J.， Liang T.， Li J.， Wang S.， Qin Z.， Wang P.， Huang L.， Fan W.， Wang J.， ACS Catal.， 2016， 6（4）， 2299—2313
11	Wang S.， Wang P.， Qin Z.， Chen Y.， Dong M.， Li J.， Zhang K.， Liu P.， Wang J.， Fan W.， ACS Catal.， 2018， 8（6）， 5485—5505
12	Liang T.， Chen J.， Qin Z.， Li J.， Wang P.， Wang S.， Wang G.， Dong M.， Fan W.， Wang J.， ACS Catal.， 2016， 6（11）， 7311—7325
13	Dedecek J.， Balgova V.， Pashkova V.， Klein P.， Wichterlova B.， Chem. Mater.， 2012， 24（16）， 3231—3239
14	Yokoi T.， Mochizuki H.， Namba S.， Kondo J. N.， Tatsumi T.， J. Phys. Chem. C， 2015， 119（27）， 15303—15315
15	Pashkovava V.， Sklenak S.， Klein P.， Urbanova M.， Dedecek J.， Chem. Eur. J.， 2016， 22（12）， 3937 —3941
16	Di Iorio J.， Gounder R.， Chem. Mater.， 2016， 28（7），2236—2247
17	Zhao X.， Wang L.， Li J.， Xu S.， Zhang W.， Wei Y.， Guo X.， Tian P.， Liu Z.， Catal. Sci. Technol.， 2017， 7（4）， 5882—5892
18	Sazama P.， Dedecek J.， Gabova V.， Wichterlova B.， Spoto G.， Bordiga S.， J. Catal.， 2008， 254（2）， 180—189
19	Wang S.， Zhang L.， Li S.， Qin Z.， Shi D.， He S.， Yuan K.， Wang P.， Zhao T.， Fan S.， Dong M.， Li J.， Fan W.， J. Catal.， 2019， 377， 81—97
20	Price G.， Iglesia E.， Ind. Eng. Chem. Res.， 1989， 28（6）， 839—844
21	Vjunov A.， Fulton J. L.， Huthwelker T.， Pin S.， Mei D. H.， Schenter G. K.， Govind N.， Camaioni D. M.， Hu J. Z.， Lercher J. A.， J. Am. Chem. Soc.， 2014， 136（23）， 8296-8306
22	Liu Z.， Dong X.， Zhu Y.， Emwas A.， Zhang D.， Tian Q.， Han Y.， ACS Catal.， 2015， 5（10）， 5837—5845
23	Dedecek J.， Lucero M. J.， Li C. B.， Gao F.， Klein P.， Urbanova M.， Tvaruzkova Z.， Sazama P.， Sklenak S.， J. Phys. Chem. C， 2011， 115（22）， 11056—11064
24	Sklenak S.， Dedecek J.， Li C. B.， Wichterlova B.， Gabova V.， Sierka M.， Sauer J.， Angew. Chem. Int. Ed.， 2007， 46（38）， 7286—7289
25	Zhao R.， Zhao Z.， Li S.， Zhang W.， J. Phys. Chem. Lett.， 2017， 8（10）， 2323—2327
26	Pashkovava V.， Sklenak S.， Klein P.， Urbanova M.， Dedecek J.， Chem. Eur. J.， 2016， 22（12）， 3937—3941
27	Ilias S.， Khare R.， Malek A.， Bhan A.， J. Catal.， 2013， 303， 135—140
28	Bleken F.， Janssens T. V. W.， Svelle S.， Olsbye U.， Microporous Mesoporous Mater.， 2012， 164， 190—198
29	Shen Y.， Le T.， Fu D.， Schmidt J.， Filez M.， Weckhuysen B.， Rimer J.， ACS Catal.， 2018， 8（12）， 11042—11053
30	Gomez⁃Hortiguela L.， Pinar A.， Cora F.， Perea⁃Pariente J.， Chem. Commun.， 2010， 46（12）， 2073—2075
31	Pinar A.， Marquez⁃Alvarez C.， Grande⁃Casas M.， Perez⁃Pariente J.， J. Catal.， 2009， 263（2）， 258—265
32	Zheng S.， Jentys A.， Lercher J. A.， J. Catal.， 2006， 241（2）， 304—311
33	Bjørgen M.， Bonino F.， Kolboe S.， Lillerud K.， Zecchina A. Bordiga S.， J. Am. Chem. Soc.， 2003， 125（51）， 15863—15868
34	Dai W.， Wu G.， Li L.， Guan N.， Hunger M.， ACS Catal.， 2013， 3（4）， 588—596
35	Borodina E.， Meirer F.， Lezcano⁃Gonzalez I.， Mokhtar M.， Asiri A.， Al⁃Thabaiti S.， Basahel S.， Ruiz⁃Martinez J.， Weckhuysen B.， ACS Catal.， 2015， 5（2）， 992—1003
36	Goetze J.， Meirer F.， Yarulina I.， Gascon J.， Kapteijn F.， Ruiz⁃Martinez J.， Weckhuysen B.， ACS Catal.， 2017， 7（6）， 4033—4046
37	Van Speybroeck V.， Hemelsoet K.， De Wispelaere K.， Qian Q.， Van der Mynsbrugge J.， De Sterck B.， Weckhuysen B.， Waroquier M.， ChemCatChem， 2013， 5（1）， 173—184
38	Wang S.， Chen Y.， Qin Z.， Zhao T.， Fan S.， Dong M.， Li J.， Fan W.， Wang J.， J. Catal.， 2019， 369， 382—395
39	Xu T.， Barich D.， Goguen P.， Song W.， Wang Z.， Nicholas J.， Haw J.， J. Am. Chem. Soc.， 1998， 120（16）， 4025—4026
40	Haw J.， Nicholas J.， Song W.， Deng F.， Wang Z.， Xu T.， Heneghan C.， J. Am. Chem. Soc.， 2000， 122（19）， 4763—4775
41	Li J.， Wei Y.， Chen J.， Tian P.， Su X.， Xu S.， Qi Y.， Wang Q.， Zhou Y.， He Y.， Liu Z.， J. Am. Chem. Soc.， 2012， 134（2）， 836— 839
42	Wang C.， Xu J.， Qi G.， Gong Y.， Wang W.， Gao P.， Wang Q.， Feng N.， Liu X.， Deng F.， J. Catal.， 2015， 332， 127—137
43	Zhang W.， Chen J.， Xu S.， Chu Y.， Wei Y.， Zhi Y.， Huang J.， Zhang A.， Wu X.， Meng X.， Xiao F.， Deng F.， Liu Z.， ACS Catal.， 2018， 8（12）， 10950—10963

[1]	PENG Haiyue, WANG Ting, LI Guorui, HUANG Jing. Synthesis of Melanin and Its Function Regulation by Small Molecules [J]. Chem. J. Chinese Universities, 2021, 42(11): 3357.
[2]	LIN Ningqin, YAO Ke, CHEN Xiangjun. Research Progress of Molecular Recognition and Interaction of Crystallins Linking Cataract [J]. Chem. J. Chinese Universities, 2021, 42(11): 3379.
[3]	HUANG Ling, ZHUANG Zijian, LI Xiang, SHI Muling, LIU Gaoqiang. Advances in Molecular Recognition of Exosomes Based on Aptamers [J]. Chem. J. Chinese Universities, 2021, 42(11): 3493.
[4]	WANG Qing, HE Yuqiu, WANG Fuan. Advances of Multifunctional Deoxyribozyme in Biomedical Analysis [J]. Chem. J. Chinese Universities, 2021, 42(11): 3334.
[5]	LIU Xuejiao, YANG Fan, LIU Shuang, ZHANG Chunjuan, LIU Qiaoling. Progress in Aptamer-targeted Membrane Protein Recognition and Functional Regulation [J]. Chem. J. Chinese Universities, 2021, 42(11): 3277.
[6]	YU Xia, SONG Chenhai, GUO Xiangke, XUE Nianhua, DING Weiping. Cooperative Catalysis of Adjacent Acid Sites in Zeolite HZSM-5 [J]. Chem. J. Chinese Universities, 2021, 42(1): 239.
[7]	LI Jingying, CHEN Chen, LI Juan, YANG Huanghao. Artificial Regulation of Receptor Clustering and Function on Cell Surface ^† [J]. Chem. J. Chinese Universities, 2020, 41(5): 892.
[8]	WANG Xia, LIU Yanji, JIA Yongfeng, JI Lei, HU Quanli, DUAN Limei, LIU Jinghai. Preparative Chemistry of N-containing Porous Carbon Nanofibers for Capacity Improvement in Lithium-sulfur Battery ^† [J]. Chem. J. Chinese Universities, 2020, 41(4): 829.
[9]	WANG Wu, LAI Hua, CHENG Zhongjun, LIU Yuyan. Reversible Regulation of Droplet Directional/anti-directional Rolling on Superhydrophobic Shape Memory Microarray Surface [J]. Chem. J. Chinese Universities, 2020, 41(11): 2538.
[10]	WANG Lin, ZHANG Yanhui, Arzugul Muslim, LAN Haidie. Morphology and Size Regulation of Polyaniline Induced by PS-b-P2VP as Template and Its Electrochemical Characters [J]. Chem. J. Chinese Universities, 2019, 40(8): 1748.
[11]	ZHANG Wenli,NIE Yao,JING Xiaoran,XU Yan. Synthesis of 4-Hydroxyisoleucine Catalyzed by Recombinant Escherichia coli Expressing Fe(Ⅱ)/2-Ketoglutarate-dependent Dioxygenase^† [J]. Chem. J. Chinese Universities, 2019, 40(6): 1172.
[12]	BIAN Kai, HOU Zhanggui, DUAN Xinrui, LI Xiaoguo, CHANG Yang, CAO Hui, ZHANG Anfeng, GUO Xinwen. Synthesis and Catalytic Performance of 2D HZSM-5 Nano-sheet for Ethylbenzene Production from Benzene with Dilute Ethylene [J]. Chem. J. Chinese Universities, 2019, 40(4): 784.
[13]	ZHANG Zhang,WANG Dong,WANG Xiaolei,XU Yan. Regulation of Ester Synthesis Activity of Rhizopus chinensis Lipase^† [J]. Chem. J. Chinese Universities, 2019, 40(4): 747.
[14]	Siqi SUN,Ying WANG,Chuanyin SUN,Runwei WANG,Zhendong ZHANG,Zongtao ZHANG,Shilun QIU. Preparation and Catalytic Performance of Bowl-shaped Amphiphilic ZSM-5 Zeolites Supported Gold Nanoparticles ^† [J]. Chem. J. Chinese Universities, 2019, 40(12): 2436.
[15]	WAN Hai, ZHANG Xiaoyu, ZHANG Ruojie, ZHANG Xiaotong, SONG Lijuan. Synthesis of High Performance ZSM-5-L Composite Zeolite and Its Catalytic Properities for n-Pentane Aromatization^† [J]. Chem. J. Chinese Universities, 2014, 35(10): 2220.