Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH3-SCR†

doi:10.7503/cjcu20160360

Abstract

Abstract:

A new type of SAPO-35 zeolite was synthesized utilizing hexamethyleneimine(HMI) as template. It was found that the acidity of SAPO-35 firstly increased and then decreased along with the increasing of SiO₂/Al₂O₃ molar ratio(0.3, 0.5, 0.7). With the molar ratio of SiO₂/Al₂O₃ = 0.7, the SM3 substitution mode occurred for the atomic Si during the SAPO-35 synthesis process, which could decrease the related acidity. The impregnation and wet ion exchange(WIE) method were applied to produce Cu modified SAPO-35 samples of Cu/SAPO-35, which were further evaluated in NH₃-SCR reaction system. According to various characterization results of XRF, NH₃-TPD, and H₂-TPR, it was revealed that the cationic Cu²⁺ constituted the main copper species on WIE method prepared Cu/SAPO-35, which displayed much better NH₃-SCR catalytic performance with respect to that of Cu/SAPO-35 prepared by impregnation method. Finally, various Cu/SAPO-35 with different SiO₂/Al₂O₃ molar ratio(0.3, 0.5, 0.7) were prepared by WIE and further evaluated for NH₃-SCR, wherein the influences of the acidities of parent SAPO-35 were thereafter investigated. It was revealed that the higher acidity of parent SAPO-15 could produce higher amount of exchanged Cu²⁺ cations, which resulted in superior NH₃-SCR activity and N₂ selectivity.

Key words: Cu/SAPO-35, NH3-SCR, Acidity, Si/Al ratio, Wet ion exchange method

CLC Number:

O643.3

TrendMD:

LIU Ning, WANG Jiqiong, CHEN Biaohua, LI Yingxia, ZHANG Runduo. Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR^†[J]. Chem. J. Chinese Universities, 2016, 37(10): 1817.

Figures/Tables 14

Fig.1 XRD patterns of SAPO-35 zeolites with the Si/Al molar ratios of 0.3(a), 0.5(b) and 0.7(c)

Fig.2 SEM image of 0.5Si-SAPO-35 zeolite

Table 1 N2 adsorption-desorption test results of SAPO-35 samples with different Si/Al molar ratios

Zeolite	Specific surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Pore diameter/nm	Crystallite size^*/nm
0.3Si-SAPO-35	398.8	0.14	4.4	1.9
0.5Si-SAPO-35	443.4	0.10	3.4	2.1
0.7Si-SAPO-35	597.4	0.09	3.8	2.2

Table 2 XRF element analysis data of SAPO-35 samples

Zeolite	Molar ratio		Si substitution method
Zeolite	Al/Si/P		(Si+P)/Al
0.3Si-SAPO-35	1/0.15/0.83	0.98	SM2
0.5Si-SAPO-35	1/0.25/0.82	1.07	SM2
0.7Si-SAPO-35	1/0.36/0.81	1.17	SM2+SM3

Fig.3 Si NMR profiles of SAPO-35 zeolitesa. 0.3Si-SAPO-35; b. 0.5Si-SAPO-35; c. 0.7Si-SAPO-35.

Fig.4 NH3-TPD curves of SAPO-35 zeolitesa. 0.3Si-SAPO-35; b. 0.5Si-SAPO-35; c. 0.7Si-SAPO-35.

Table 3 XRF element analysis data of SAPO-35 samples

Catalyst	Molar ratio of SiO₂/Al₂O₃	Molar fraction of (Si+P)	Mass fraction of Cu(%)
Cu/0.3Si-SAPO-35	0.3	0.98	1.8
Cu/0.5Si-SAPO-35	0.5	1.07	3.1
Cu/0.7Si-SAPO-35	0.7	1.17	2.5

Fig.5 NH3-SCR activities of Cu/SAPO-35 zeolites prepared by ion exchange methodReaction conditions: 1 g/m3 NO, 1 g/m3 NH3, 10%O2 balanced by Ar, GHSV=3×104 h-1.

Fig.6 Comparison of H2-TPR test result between the samples prepared by rotating impregnation method and ion exchange methoda. 3.1%Cu/0.5Si-SAPO-35;b. 4%Cu/0.5Si-SAPO-35.

Fig.7 XPS test result of the 3.1%Cu/0.5Si-SAPO-35 zeolite prepared by ion exchange method

Fig.8 NH3-SCR activities of Cu/SAPO-35 zeolites prepared by ion exchange method with different Si/Al molar ratios Reaction conditions: 1 g/m3 NO, 1 g/m3 NH3, 10%O2 balanced by Ar, GHSV=3×104 h-1.

Fig.9 H2-TPR profiles of Cu/SAPO-35 zeolites prepared by ion exchange methoda. Cu/0.3Si-SAPO-35; b. Cu/0.5Si-SAPO-35; c. Cu/0.7Si-SAPO-35.

Table 4 H2-Consumption of Cu/SAPO-35 zeolites calculated by H2-TPR test result

Catalyst	H₂ Consumption/(mmol·g^-1)	H₂/Cu^*
Cu/0.3Si-SAPO-35	0.185	0.65
Cu/0.5Si-SAPO-35	0.213	0.44
Cu/0.7Si-SAPO-35	0.190	0.49

Fig.10 Possible location site of Cu2+ ions on Cu-SAPO-35 zeolite

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Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR^†

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