An integrated approach to the key parameters in methanol-to-olefins reaction catalyzed by MFI/MEL zeolite materials

doi:10.1016/S1872-2067(21)63990-6

Abstract

Abstract:

Identification of the catalyst characteristics correlating with the key performance parameters including selectivity and stability is key to the rational catalyst design. Herein we focused on the identification of property-performance relationships in the methanol-to-olefin (MTO) process by studying in detail the catalytic behaviour of MFI, MEL and their respective intergrowth zeolites. The detailed material characterization reveals that both the high production of propylene and butylenes and the large MeOH conversion capacity correlate with the enrichment of lattice Al sites in the channels of the pentasil structure as identified by ²⁷Al MAS NMR and 3-methylpentane cracking results. The lack of correlation between MTO performance and other catalyst characteristics, such as crystal size, presence of external Brønsted acid sites and Al pairing suggests their less pronounced role in defining the propylene selectivity. Our analysis reveals that catalyst deactivation is rather complex and is strongly affected by the enrichment of lattice Al in the intersections, the overall Al-content, and crystal size. The intergrowth of MFI and MEL phases accelerates the catalyst deactivation rate.

Key words: Structure-performance relationship, Zeolite catalysis, Methanol-to-olefin conversion, Al-distribution, Acidity, Intergrowth MFI/MEL, Pentasil

Chuncheng Liu, Evgeny A. Uslamin, Sophie H. van Vreeswijk, Irina Yarulina, Swapna Ganapathy, Bert M. Weckhuysen, Freek Kapteijn, Evgeny A. Pidko. An integrated approach to the key parameters in methanol-to-olefins reaction catalyzed by MFI/MEL zeolite materials[J]. Chinese Journal of Catalysis, 2022, 43(7): 1879-1893.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63990-6

https://www.cjcatal.com/EN/Y2022/V43/I7/1879

Figures/Tables 10

Fig. 1. XRD data comparing patterns for investigated samples (a), and a highlighted 21°-26° range (b).

Table 1 Summarized textural and acidic properties of studied catalysts.

Catalyst	Si/Al ^a	Size ^b	V_total^c	V_micro^c	S_ext^c	S_BET^d	BAS ^e	LAS ^e
Catalyst	(mol mol^-1)	(Å)	(cm³/g)	(cm³/g)	(m²/g)	(m²/g)	(µmol/g)	(µmol/g)
MEL-25-S	27	419	0.31	0.14	85	439	543	90
MFI/MEL-25-S	25	463	0.31	0.15	81	448	556	139
MFI-25-M	26	613	0.22	0.17	56	414	575	94
MFI-25-S	25	428	0.27	0.16	67	453	530	74
MFI/MEL-50-L	48	830	0.19	0.16	27	423	376	72
MFI-50-S	50	428	0.29	0.16	77	471	338	91

Fig. 2. MeOH conversion as a function of cumulative MeOH throughput (a) and cumulative carbon yields of different hydrocarbons until MeOH conversion is at 50% (color bars) and estimated conversion capacity (symbols to right axis) (b) for all studied catalysts in MTO tests. Reaction conditions: T = 450 °C, mcat = 40 mg (150-212 µm), 1 bar, WHSV = 5.2 gMeOH/gcat/h, carrier gas N2 = 50 mL/min. The full picture of MeOH conversion and product selectivity curves as a function of TOS are presented in Fig. S5.

Fig. 3. Carbon selectivity to propylene (a) and ethylene (b) as a function of MeOH conversion over studied materials. Reaction conditions: Reaction conditions: T = 450 °C, mcat = 40 mg (150-212 µm), 1 bar, WHSV = 5.2 gMeOH/gcat/h, carrier gas N2 = 50 mL/min. Similar graphs of other product groups are presented in Fig. S6.

Fig. 4. Time-resolved operando UV-vis spectra during MeOH conversion at 450 °C over studied catalysts. All spectra were collected during TOS within 0-1 h with 1 min interval. Band Assignments in the 40000-12500 cm-1 are displayed in UV-vis spectra for MFI-25-M [58,59].

Fig. 5. MeOH conversion capacity as a function of 1,3,5-TIPB conversion over catalysts at 200 °C. Cracking conditions: T = 200 °C, mcat = 20 mg (150-212 µm), 1 bar, P1,3,5-TIPB = 0.3 kPa, carrier gas N2 = 50 mL/min. Cracking conversion was averaged within TOS = 0.1-0.3 h. The full picture of 1,3,5-TIPB conversion as a function of TOS were present in Fig. S9.

Fig. 6. Selectivity to propylene (a) and MeOH conversion capacity (b) versus the proportion of Alpair of tested samples. Alpair is measured based on Co concentration determined by ICP-AES after Co ion exchange.

Fig. 7. 2D 27Al MQ MAS NMR spectrum of MEL-25-S (a), MFI-25-M (b), and MFI/MEL-25-S (c) together with the isotopic projection F1 spectrum at the left and the corresponding 27Al MAS NMR spectrum at the top of the 2D contour profile.

Table 2 The fraction of various peaks obtained from the 27Al MAS NMR spectrum.

Catalyst	Al_intersection/%	Al_channel/%	Characteristic peaks proportion/%
Catalyst	Al_intersection/%	Al_channel/%	58±0.3 ppm	56±0.2 ppm	55±0.5 ppm	53±0.4 ppm	52±0.3 ppm
MEL-25-S	46.4	53.6	11.1	24.0	29.6	24.1	11.2
MFI-25-S	47.9	52.1	9.0	28.6	24.2	23.6	14.7
MFI/MEL-25-S	48.7*	51.3*	14.2	25.0	28.6	24.1	8.2
MFI-25-M	49.3	50.7	11.7	25.5	24.8	25.3	12.7
MFI-50-S	47.0	53.0	8.0	26.9	25.5	26.1	13.5
MFI/MEL-50-L	45.2*	54.8*	15.3	32.1	31.8	18.3	2.5

Fig. 8. Carbon selectivity to propylene versus selectivity towards hydrogen, methane and ethane of 3-MP monomolecular cracking over samples with Si/Al of 25 (a) and Si/Al of 50 (b). 3-MP cracking conditions: T = 400 °C, mcat = 20 mg (150-212 µm), 1 bar, carrier gas N2 = 50 mL/min, 3-MP partial pressure = 3.8 kPa in the presence of 2,4-DMQ (<0.1 kPa). The product selectivity is averaged values within TOS = 0.1-0.4 h. The full-scale picture along TOS is given in Fig. S13.

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