Adjusting Al location in the framework of ITH zeolites for catalytic conversion of methanol to olefins

doi:10.1016/S1872-2067(23)64574-7

Abstract

Abstract:

Adjusting location and distribution of Al sites in the zeolite framework is critical for catalysis, and typical strategies include using zeolites as starting Al source. However, this approach is still challenging for aluminosilicate ITH zeolite. Herein, the distribution of Al species in the framework of ITH was efficiently regulated by implementing LTA zeolite as the aluminum source added in the starting gels (LTA-ITH). The obtained LTA-ITH zeolites have similar nanosheet morphology, textual parameters, and acidic properties to those of conventional ITH synthesized from boehmite (C-ITH), while the results of ²⁷Al MAS NMR spectra and 1-hexene cracking indicate that they have a different Al distribution. The use of LTA zeolite in starting gel is favorable for the formation of more Al species in sinusoidal and straight channels, compared with the C-ITH. Catalytic tests in the conversion of methanol to light olefin showed that LTA-ITH exhibited enhanced catalyst lifetime and propene selectivity compared with the C-ITH, which is reasonably attributed to the different locations of Al species in their respective ITH frameworks.

Key words: Al location in the framework, Aluminosilicate ITH zeolite, Methanol to olefins, ²⁷Al MAS NMR spectroscopy

Kai Fan, Qinming Wu, Shuo Liu, Haiyu Kong, Sen Wang, Eduard Kunkes, Trees De Baerdemaeker, Andrei-Nicolae Parvulescu, Nils Bottke, Toshiyuki Yokoi, Dirk E. De Vos, Xiangju Meng, Weiping Zhang, Feng-Shou Xiao. Adjusting Al location in the framework of ITH zeolites for catalytic conversion of methanol to olefins[J]. Chinese Journal of Catalysis, 2024, 56: 114-121.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64574-7

https://www.cjcatal.com/EN/Y2024/V56/I1/114

Figures/Tables 9

Fig. 1. XRD patterns of the as-synthesized ITH zeolites (A) and H-form ITH zeolites (B), and SEM images (C) of the as-synthesized ITH zeolites with C-ITH-50 (a), LTA-ITH-50 (b), C-ITH-75 (c), LTA-ITH-75 (d), C-ITH-100 (e) and LTA-ITH-100 (f).

Table 1 Chemical compositions, textual parameters and acid properties of H-form LTA-ITH and C-ITH zeolites.

Zeolite	Si/Al ^a	Surface area ^b(m²/g)		Pore volume ^b(cm³/g)		Acidity by NH₃-TPD ^c(mmol/g)
Zeolite	Si/Al ^a	Total	Micro	Micro	Meso	Total	Weak	Strong
C-ITH-50	42	393	310	0.14	0.21	0.89	0.55	0.34
LTA-ITH-50	44	394	313	0.14	0.21	0.83	0.50	0.33
C-ITH-75	66	388	305	0.14	0.22	0.51	0.29	0.22
LTA-ITH-75	65	395	316	0.15	0.21	0.47	0.27	0.20
C-ITH-100	89	399	320	0.15	0.21	0.39	0.21	0.18
LTA-ITH-100	93	400	322	0.15	0.19	0.34	0.19	0.15

Fig. 2. Deconvoluted and simulated 27Al MAS NMR spectra of H-form C-ITH (A) and LTA-ITH (B) zeolites. The experimental spectra are shown in pink solid lines and the fitted ones are shown in yellow dashed lines.

Table 2 Deconvolutional data of the 27Al MAS NMR spectra of H-form ITH zeolites.

Zeolite	Al distribution (%)
Zeolite	Al_S 56 and 61 ppm	Al_I 48 and 53 ppm
C-ITH-100	47.9	52.1
C-ITH-75	42.7	57.3
C-ITH-50	39.6	60.4
LTA-ITH-100	62.8	37.2
LTA-ITH-75	51.5	48.5
LTA-ITH-50	40.8	59.2

Table 3 Catalytic data in 1-hexene cracking over the LTA-ITH-100 and C-ITH-100 zeolites.

Sample	Selectivity (C%)			C₂⁼/C₄⁼	C₄⁼/C₃⁼	Conversion (%)
Sample	C₂⁼	C₃⁼	C₄⁼	C₂⁼/C₄⁼	C₄⁼/C₃⁼	Conversion (%)
C-ITH-100	4.2	35.9	15.6	0.27	0.43	98.1
LTA-ITH-100	3.8	40.4	12.8	0.30	0.32	97.6

Fig. 3. MTO performance of the H-form ITH zeolites. The MTO reactions were carried out at atmospheric pressure, 480 ?°C and a methanol weight hourly space velocity (WHSVMethanol) of 2 h?1.

Table 4 Catalytic performances of various H-form ITH zeolites in the steady stage.

Zeolite	Selectivity (C%)					(P-E)/E	Lifetime (h)
Zeolite	C₂⁼	C₃⁼	C₄⁼	C₁^‒‒C₄^‒	BTX	(P-E)/E	Lifetime (h)
C-ITH-50	14.0	34.0	13.6	15.8	11.0	1.43	26.6
LTA-ITH-50	13.3	34.1	15.4	15.0	8.4	1.56	31.3
C-ITH-75	14.2	37.6	14.5	14.8	7.9	1.65	38.9
LTA-ITH-75	11.8	40.8	16.5	13.0	4.4	2.46	44.7
C-ITH-100	12.2	40.1	15.3	13.6	4.9	2.29	50.4
LTA-ITH-100	10.1	43.5	16.2	12.5	2.2	3.31	58.7

Fig. 4. Proposed schematic diagram of aromatic and alkene cycle mechanism for the MTO reaction.

Fig. 5. Dependences of (P-E)/E ratios in the MTO reaction (complete methanol conversion) on (A) AlS and (B) AlI percentages in the ITH zeolites.

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