Synthesis of mesoporous high-silica zeolite Y and their catalytic cracking performance

doi:10.1016/S1872-2067(21)64043-3

Abstract

Abstract:

Mesoporous high-silica zeolite Y with advantages of improved accessibility of acid sites and mass transport properties is highly desired catalytic materials for oil refinery, fine chemistry and emerging biorefinery. Here, we report the direct synthesis of mesoporous high-silica zeolite Y (named MSY, SiO₂/Al₂O₃ ≥ 9.8) and their excellent catalytic cracking performance. The obtained MSY materials are mesoporous single crystals with octahedral morphology, abundant mesoporosity and excellent (hydro)thermal stability. Both the acid concentration and acid strength of H-form MSY are obviously higher than those of commercial ultra-stable Y (USY), which should be attributed to the uniform Al distribution of MSY zeolite. The H-MSY displays an obviously reduced deactivation rate and improved catalytic activity in the cracking reaction of bulky 1,3,5-triisopropylbenzene (TIPB), as compared with its mesoporogen-free counterpart and USY. In addition, H-MSY was investigated as catalyst for the cracking of industrial heavy oil. The MSY-based catalyst (after aging at 800 ^oC in 100% steam for 17 h) exhibits superior conversion (7.64% increase) and gasoline yield (16.37% increase) than industrial fluid catalytic cracking (FCC) catalyst under the investigated conditions.

Key words: Mesoporous zeolite, FAU, Synthesis, High-silica zeolite Y, Fluid catalytic cracking

Wenhao Cui, Dali Zhu, Juan Tan, Nan Chen, Dong Fan, Juan Wang, Jingfeng Han, Linying Wang, Peng Tian, Zhongmin Liu. Synthesis of mesoporous high-silica zeolite Y and their catalytic cracking performance[J]. Chinese Journal of Catalysis, 2022, 43(7): 1945-1954.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64043-3

https://www.cjcatal.com/EN/Y2022/V43/I7/1945

Figures/Tables 10

Table 1 Synthesis conditions, product phases, compositions and textural properties of the high-silica zeolite Y samples.

Sample	Starting gel ^a			Product		Surface area ^c(m²/g)			Pore volume ^c(cm³/g)		Relative crystallinity % ^e
Sample	x	y	Time (day)	Phase	SAR ^b	S_BET	S_micro	S_exter	V_micro	V_meso	Relative crystallinity % ^e
SY_9.5	20	0	3.5	FAU	9.5 (10.0) [9.8]	644	585	59	0.27	0.06	100
1	20	0.005	3.5	FAU	9.8	692	567	125	0.26	0.13	94.9
2	20	0.01	3.8	FAU	10.2	702	524	178	0.27	0.16	85.1
3 (MSY_10.7)	20	0.015	4.5	FAU	10.7 (9.4) [10.7]	779	568	211	0.26	0.22	84.8
4	20	0.02	5.2	FAU+β (trace)	11.3	770	570	200	0.27	0.18	128.3
5	30	0.01	5.4	FAU	12.6	770	587	183	0.27	0.17	125.1
6^d	40	0.01	8.0	FAU+β+ MOR	17.5	—	—	—	—	—	—
USY	—	—	—	FAU	12.9 (8.1) [17.2]	632	537	95	0.25	0.14	98.8
NaY_5.6	—	—	—	FAU	5.6	540	504	36	0.24	0.03	68.1

Fig. 1. (a) XRD patterns of the as-synthesized MSY10.7 and SY9.5. (b) SEM images of MSY10.7. (c,d) High-magnification SEM images to show the surface of MSY10.7 crystals.

Fig. 2. N2 sorption isotherms (a) and BJH pore size distribution curves (b) of the samples.

Fig. 3. TEM images and SAED pattern of the mesoporous high-silica zeolite Y (sample MSY10.7). (a,c) Low magnification images. (b) SAED pattern taken from selected circle region in (a). (d) High-resolution image corresponds to the rectangle region in (c).

Fig. 4. 13C CP MAS NMR (a) and 29Si CP MAS NMR (b) spectra of the as-synthesized high-silica zeolite Y.

Fig. 5. Thermal and hydrothermal stability of the samples. TG (a) and DSC (b) curves of the as-synthesized high-silica zeolite Y. (c) The micropore volume retention of H-form samples after hydrothermal treatment. The micropore volume of each fresh sample is defined as 100%.

Fig. 6. Acidity of the H-form high-silica zeolite Y. (a) NH3-TPD profiles. (b,c) FTIR spectra of pyridine ring-related vibration regions on the H-form samples after pyridine desorption at 150 and 300 °C.

Table 2 Framework SAR of the H-form samples and the amounts of Brønsted and Lewis acid sites determined by FT-IR spectra of pyridine adsorption at 150 °C a.

Sample	SAR ^b	BAS (mmol/g)	LAS (mmol/g)	BAS+LAS (mmol/g)	BAS/LAS
H-SY_9.5	11.9	0.90	0.26	1.16	3.53
H-MSY_10.7	13.6	0.70	0.26	0.97	2.71
H-USY	20.9	0.30	0.11	0.41	2.88

Fig. 7. Catalytic cracking performance of the H-form high-silica zeolite Y. (a) N-octane cracking versus time on stream. Reaction conditions: T = 460 °C, WHSVn-octane = 3.88 h-1. (b) TIPB cracking versus time on stream. Reaction conditions: T = 200 °C, WHSVTIPB = 3.08 h-1.

Table 3 Heavy oil cracking on MSY10.7-based catalyst and industrial FCC catalyst.

Items (wt%)	MSY_10.7-based catalyst	Industrial FCC catalyst
Conversion	93.11	85.47
Dry gas	1.02	1.23
Gasoline	61.46	45.09
Diesel	13.07	14.14
Gasoline + Diesel	74.53	59.23
Diesel/Gasoline ratio	0.21	0.31
Liquid petroleum gas (LPG)	12.13	20.41
LPG+Gasoline+Diesel	86.66	79.64
Heavy oil	6.89	14.53
Coke	5.42	4.59

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