SCM-36 zeolite nanosheets applied in the production of renewable p-xylene from ethylene and 2,5-dimethylfuran

doi:10.1016/S1872-2067(22)64200-1

Abstract

Abstract:

Zeolites as solid acid materials have played important roles in industrial catalysis. The attempts to obtain new zeolite framework structures and related chemical compositions have never stopped, and may expand the application thereof. Using renewable bioderived molecules as starting feedstocks would be of great help in building a more circular carbon cycle. However, zeolites have only shown limited efficiency in the conversion or production of bioderived chemicals. In this work, we report on the synthesis of a new aluminosilicate zeolite named SCM-36 (Sinopec Composite Material No. 36) using tetramethylammonium hydroxide (TMAOH) with the presence of hexadecylpyridinium bromide hydrate (C₁₆PyBr) or octyltrimethylammonium chloride (OTMAC). The pore opening of this new zeolite material is about 0.6 nm, which is consistent with the size of 10 to 12 membered ring channel. SCM-36 possesses a nanoflower-like morphology with a thickness of ~20 nm. The SiO₂/Al₂O₃ molar ratio of the SCM-36 material is ranging from 21.2 to 36.6, with most Al incorporated into the zeolite framework structure. The acid strength of SCM-36 is not strong, as confirmed by various techniques, including NH₃-TPD, pyridine FT-IR, ex-situ confocal fluorescence microscopy and in-situ UV-Vis micro-spectroscopy. In the catalytic conversion of bio-derived 2,5-dimethylfuran (DMF) and ethylene into para-xylene (PX), H-SCM-36 zeolite showed better performance than the more traditional zeolites. The highest selectivity towards PX reached a value of ~93%. Besides, SCM-36 zeolite showed remarkable recyclability in the reaction.

Key words: Zeolite, Aluminosilicate, SCM-36, In-situ spectroscopy, Para-xylene, Biomass

Duozheng Ma, Xiangcheng Li, Chuang Liu, Caroline Versluis, Yingchun Ye, Zhendong Wang, Eelco T. C. Vogt, Bert M. Weckhuysen, Weimin Yang. SCM-36 zeolite nanosheets applied in the production of renewable p-xylene from ethylene and 2,5-dimethylfuran[J]. Chinese Journal of Catalysis, 2023, 47: 200-213.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64200-1

https://www.cjcatal.com/EN/Y2023/V47/I4/200

Figures/Tables 12

Fig. 1. (a) XRD patterns of as-made SCM-36 (bottom) and calcined SCM-36 at 550 °C (top); In-situ XRD patterns were recorded while heating the synthesized material from 30 to 700 °C (b) and its corresponding ‘heatmap’ (c). The patterns were recorded with Cu Kα-radiation.

Fig. 2. SEM images of as-synthesized (a) and calcined (b) SCM-36(35) zeolite. TEM-EDX mapping of all chemical elements (c) and its Al element (d). HRTEM images of calcined SCM-36(35) (e?g) and its FFT pattern (h).

Fig. 3. AFM topography image of the layers deposited from ethanol solution of calcined SCM-36(35) zeolite (a) and its corresponding 3D AFM mountain image (b), cross-section profiles extracted from (a) or (b) marked by the dashed red line (c). Statistical distribution of thickness of SCM-36(35) by the AFM measurements from a total of 62 valid nanosheet thickness data (d).

Fig. 4. N2 (a) and Ar (b) adsorption-desorption isotherms and micropore size distribution (by the Horvath-Kawazoe method of calcined SCM-36(35); (c) SiO2/Al2O3 ratios in synthetic gels and in SCM-36 solid products. 29Si (d) and 27Al (e) NMR spectra of calcined SCM-36(35) zeolite.

Table 1 Structural features of SCM-36(n) zeolites a.

Sample	SiO₂/Al₂O₃		Yield (%)	A_BET^e (m²/g)	A_ext.^e (m²/g)	A_micro.^e (cm²/g)	V_total^f (cm³/g)	V_micro.^f (cm³/g)
Sample	Gel	Bulk ^d	Yield (%)	A_BET^e (m²/g)	A_ext.^e (m²/g)	A_micro.^e (cm²/g)	V_total^f (cm³/g)	V_micro.^f (cm³/g)
SCM-36(25) ^b	25	21.2	85	355	121	234	0.62	0.10
SCM-36(35) ^c	35	27.3	80	348	138	210	0.57	0.09
SCM-36(45) ^c	45	29.1	76	319	105	214	0.49	0.093
SCM-36(60) ^c	60	36.6	64	296	92	204	0.45	0.089

Fig. 5. (a) 13C liquid NMR spectra of C16PyBr and TMAOH, 13C solid-state MAS NMR of SCM-36(25). (b) TG/DTA curves of SCM-36(25). (c) 13C liquid NMR of OTMAC and TMAOH, 13C solid-state MAS NMR of SCM-36(35). (d) TG/DTA curves of SCM-36(35).

Fig. 6. (a) NH3-TPD profiles of H-SCM-36(35). (b) Pyridine-adsorbed FT-IR spectra (measured at 150 °C) of SCM-36 zeolites synthesized with starting SiO2/Al2O3 gel compositions of ratios of 25 (1), 35 (2), 45 (3), and 60 (4). OH-stretch region (c) and CO-stretch region (d) of FT-IR spectra of SCM-36(35) zeolite. In (c) and (d), the sample was measured at 300 °C at PCO = 10.0 under pressure of PCO = 10.0 (1), 1.0 (2), 0.5 (3), 0.1 (4), 0.05 (5), 0.01(6) and 0.001 (7) mbar.

Table 2 Acidic properties of SCM-36 given by NH3-TPD and pyridine adsorbed FT-IR spectroscopy.

Sample	NH₃-TPD^a(μmol/g)		Brönsted acid^b(μmol/g)			Lewis acid^b(μmol/g)
Sample	Weak+Medium	Total	150 °C	250 °C	350 °C	150 °C	250 °C	350 °C
SCM-36(25)	657	872	40	19	5	36	19	6
SCM-36(35)	512	674	85	73	44	24	15	9
SCM-36(45)	495	635	89	46	17	19	9	7
SCM-36(60)	477	605	97	58	19	15	13	8

Fig. 7. In-situ UV-Vis time-resolved absorption spectra measured during the oligomerization of styrene derivatives over SCM-36(35) and ZSM-5 at 373 K for 3 min (a, c, e, and g). CFM images of spent SCM-36(35) and ZSM-5 zeolite after oligomerization (b, d, f, h). Where (a, b, e, f) were used 4-methoxystyrene, and (c, d, g, and h) were used 4-fluorostyrene as probe molecule. (i, j) Schematic illustration of the fluorescence microscopy selective staining approach. (k) Real cross-sectional slice CFM image of SCM-36 zeolite nanospheres. (l) CFM Image of 3D stacked cross-sectional slices of SCM-36. The probe molecules were excited at 488, 561 and 638 nm and the detection wavelength range was between 480-720 nm.

Scheme 1. Schematic illustration of the conversion of DMF to PX, including the main and side chemical reactions of the catalytic process.

Table 3 Catalytic performances of some conventional zeolites and the newly synthesized SCM-36 zeolite in conversion of DMF and ethylene to produce PX.

Catalyst	SiO₂/Al₂O₃^a	DMF conversion (%)	Selectivity (%)
Catalyst	SiO₂/Al₂O₃^a	DMF conversion (%)	PX	OAB	HDO	MCP	Oligomers
SCM-1 (MWW)	15	>99	63	18	4	4	11
Beta	20	>99	75	9	5	3	8
USY	23	>99	81	5	3	2	9
ZSM-5	40	93	72	11	3	2	12
SAPO-34	0.5^b	>99	56	6	23	7	8
SCM-36(25)	21.2	>99	86	3	3	2	6
SCM-36(35)	27.3	95	91	1	2	1	5
SCM-36(45)	29.1	>99	89	2	3	2	4
SCM-36(60)	36.6	98	93	1	2	0	4

Fig. 8. (a) Acid distribution of zeolites with different structures as a function of PX selectivity. (b) Weak and strong acid ratios of different zeolite materials as demonstrated by the NH3-TPD profile deconvolution procedure. PX selectivity (left axis) and DMF conversion (right axis) over various catalysts (c) and over SCM-36 zeolites with different bulk SiO2/Al2O3 molar ratios (d). Reaction conditions: ~1.2±0.1 mol/L of DMF (1.0 g), n-heptane (20 ml) and zeolite (1.0 g) enclosed in the reactor and then heated to 250 °C for 24 h at 2.0 MPa with ethylene.

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