Co nanoparticles confined in mesopores of MFI zeolite for selective syngas conversion to heavy liquid hydrocarbon fuels

doi:10.1016/S1872-2067(24)60166-X

Abstract

Abstract:

Designing Fischer-Tropsch synthesis (FTS) catalysts to selectively produce liquid hydrocarbon fuels is a crucial challenge. Herein, we selectively introduced Co nanoparticles (NPs) into the micropores and mesopores of an ordered mesoporous MFI zeolite (OMMZ) through impregnation, which controlled the carbon number distribution in the FTS products by tuning the position of catalytic active sites in differently sized pores. The Co precursors coordinated by acetate with a size of 9.4 × 4.2 × 2.5 Å and by 2,2'-bipyridine with a size of 9.5 × 8.7 × 7.9 Å, smaller and larger than the micropores (ca. 5.5 Å) of MFI, made the Co species incorporated in OMMZ's micropores and mesopores, respectively. The carbon number products synthesized with the Co NPs confined in mesopores were larger than that in micropores. The high jet and diesel selectivities of 66.5% and 65.3% were achieved with Co NPs confined in micropores and mesopores of less acidic Na-type OMMZ, respectively. Gasoline and jet selectivities of 76.7% and 70.8% were achieved with Co NPs confined in micropores and mesopores of H-type OMMZ with Brönsted acid sites, respectively. A series of characterizations revealed that the selective production of diesel and jet fuels was due to the C-C cleavage suppressing of heavier hydrocarbons by the Co NPs located in mesopores.

Key words: Fischer-Tropsch synthesis, Heavy liquid hydrocarbon fuel, Co nanoparticle, Ordered mesoporous MFI zeolite, C-C cleavage

Neng Gong, Quanzheng Deng, Yujiao Wang, Zitao Wang, Lu Han, Peng Wu, Shun’ai Che. Co nanoparticles confined in mesopores of MFI zeolite for selective syngas conversion to heavy liquid hydrocarbon fuels[J]. Chinese Journal of Catalysis, 2025, 68: 246-258.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60166-X

https://www.cjcatal.com/EN/Y2025/V68/I1/246

Figures/Tables 12

Fig. 1 Strategy for confining the Co NPs in micropores and mesopores of OMMZ for selective FTS of liquid fuels with controlled carbon number distribution, which would be realized by impregnation with smaller precursor of Co-acet (9.4 × 4.2 × 2.5 ?) and larger precursor of Co-bpy (9.5 × 8.7 × 7.9 ?) than the 10-MR micropores (ca. 5.5 ?) of MFI, respectively. (a) shows the low- and high-angle XRD patterns of Na-OMMZ, Co-acet/Na-OMMZ and Co-bpy/Na-OMMZ. Na-OMMZ show well-resolved diffraction peaks centered at 2θ = 1.50° due to the presence of ordered mesostructure with a d-spacing of 5.9 nm. The mesostructured-related peaks are invisible in Co-acet/Na-OMMZ and Co-bpy/Na-OMMZ (Fig. 1(a1)), which is possibly due to that the mesopores are partially occupied by Co NPs. The high-angle XRD patterns indicate all samples possess the pure MFI

Fig. 1. Morphology and structure of Na-OMMZ, Co-acet/Na-OMMZ and Co-bpy/Na-OMMZ. Low- and high-angle XRD patterns (a1,2), N2 adsorption-desorption isotherms and pore size distributions (b1,2). SEM images, HAADF-STEM images, elemental mappings and structural models of Na-OMMZ (c1-4), Co-acet/Na-OMMZ (d1-4) and Co-bpy/Na-OMMZ (e1-4).

Table 1 Textural properties, element composition and acidity amounts of different zeolites before and after Co loading.

Sample	A_BET^a (m² g^-1)	A_ext^b (m² g^-1)	Pore size^c (nm)	V_micro^d (cm³ g^-1)	V_total^e (cm³ g^-1)	Si/Al ratio^f	Loading Co^f (wt%)	Amounts of acid sites^g
Sample	A_BET^a (m² g^-1)	A_ext^b (m² g^-1)	Pore size^c (nm)	V_micro^d (cm³ g^-1)	V_total^e (cm³ g^-1)	Si/Al ratio^f	Loading Co^f (wt%)	B (μmol g^-1)	L (μmol g^-1)
Na-bulky ZSM-5	362	37	3.2	0.15	0.44	112	—	—	102.2
Na-meso-ZSM-5	388	168	3.5	0.09	0.46	111	—	—	106.0
Na-OMMZ	856	505	3.6	0.21	0.67	90	—	—	112.4
H-bulky ZSM-5	366	49	3.4	0.15	0.41	109	—	65.8	40.5
H-meso-ZSM-5	408	165	3.5	0.09	0.49	110	—	50.4	50.9
H-OMMZ	863	503	3.6	0.21	0.70	98	—	22.0	73.8
Co-acet/Na-bulky ZSM-5	317	63	3.5	0.12	0.38	105	9.9	—	84.4
Co-acet/Na-meso-ZSM-5	371	126	3.5	0.13	0.46	111	9.4	—	74.0
Co-bpy/Na-meso-ZSM-5	370	136	3.5	0.10	0.44	112	9.3	—	76.3
Co-acet/Na-OMMZ	508	334	4.3	0.12	0.50	81	9.1	—	79.8
Co-bpy/Na-OMMZ	574	388	4.4	0.12	0.55	84	8.8	—	78.3
Co-acet/H-bulky ZSM-5	355	81	3.5	0.13	0.36	102	9.6	25.8	48.3
Co-acet/H-meso-ZSM-5	369	131	3.7	0.11	0.47	116	9.6	22.3	48.9
Co-bpy/H-meso-ZSM-5	345	154	3.5	0.09	0.47	115	9.5	28.1	52.2
Co-acet/H-OMMZ	534	345	4.1	0.14	0.54	104	9.5	18.2	56.4
Co-bpy/H-OMMZ	585	391	4.2	0.12	0.54	106	9.3	15.1	60.4

Table 2 Chemical adsorptions and Co sizes of various samples of zeolites supported Co NPs.

Sample	H₂ consumption^a (mmol g^-1)	Reduction degree^a (%)	Adsorbed H₂^b (cm³ g^-1)	Dispersity^b (%)	Mean Co size^c (nm)
Sample	H₂ consumption^a (mmol g^-1)	Reduction degree^a (%)	Adsorbed H₂^b (cm³ g^-1)	Dispersity^b (%)	fresh	used^e
Co-acet/Na-bulky ZSM-5	3.7	83.1	1.7	9.0	18.4	23.3
Co-acet/Na-meso-ZSM-5	3.4	80.6	4.2	23.5	13.6	19.3
Co-bpy/Na-meso-ZSM-5	3.6	84.6	5.2	29.4	10.6	14.3
Co-acet/Na-OMMZ	1.5	35.9	0.3	1.7	0.9^d	3.6(3.8)
Co-bpy/Na-OMMZ	1.6	39.7	0.9	5.4	2.5^d	3.8(4.0)
Co-acet/H-bulky ZSM-5	3.6	83.2	4.3	23.5	17.9	22.7
Co-acet/H-meso-ZSM-5	3.8	87.4	4.0	21.9	9.0	13.6
Co-bpy/H-mes-ZSM-5	3.8	87.2	5.0	27.7	6.5	10.2
Co-acet/H-OMMZ	1.4	33.4	0.3	1.7	—	3.4(3.5)
Co-bpy/H-OMMZ	1.2	27.7	0.2	1.1	—	3.6(3.8)

Fig. 2. Co 2p XPS spectra of Co catalysts supported on Na-type MFI (a) and H-type MFI zeolites (b). H2-TPR of Co based catalysts supported on Na-type MFI (c) and H-type MFI zeolites (d).

Fig. 3. Acidity of Na-MFI and H-MFI zeolites and Co based catalysts measured by NH3-TPD profiles (a1?a3) and pyridine-IR spectra (b1?b3).

Fig. 4. FTS performance over Co-based catalysts with Na- and H-type MFI zeolites supports. CO Conversion and selectivity of gasoline (C5-C11), jet (C8-C16) and diesel (C10-C20) (a); and distributions of carbon number in the products on different Na-(b1,2) and H-type MFI zeolites supports (c1,2). Co loading = 10 wt%, Si/Al = 100. Reaction conditions: T = 513?K, P = 2.0?MPa, H2/CO = 1.0, flow rate = 20 mL min-1, GHSV = 3600 mL gcat-1 h-1, time on stream = 10?h. The hydrocarbon selectivity was calculated by the weight fraction of target product with respect to the total hydrocarbons.

Fig. 5. Catalytic performance syngas conversion on Co-bpy/Na-OMMZ (8.8 wt% Co) at different reaction temperature (a) and different GHSVs (b). Reaction conditions: H2/CO = 1, P = 2.0 MPa; (a) GHSV = 3600 mL gcat-1 h-1; (b) T = 513 K; time on stream = 10 h.

Table 3 Catalytic performances of Co based catalysts supported on different MFI zeolites.

Catalyst	CO conv.^a (%)	Hydrocarbon selectivity (%)				C_iso/C_n^a	C_olefins^b (%)	CO₂	Alcohols	CTY (mol_CO kg_Co^-1 h^-1)
Catalyst	CO conv.^a (%)	CH₄	C₂-C₄	C₅-C₂₀	C₂₁₊	C_iso/C_n^a	C_olefins^b (%)	(%)	(%)	CTY (mol_CO kg_Co^-1 h^-1)
Co-acet/Na-bulky ZSM-5	10.1	5.2	13.1	66.3	15.4	0.3	27.7	4.3	7.6	78
Co-acet/Na-meso-ZSM-5	21.9	3.1	6.4	64.7	25.8	0.1	30.8	6.5	4.6	178
Co-bpy/Na-meso-ZSM-5	22.5	2.6	4.9	65.9	26.6	0.04	28.0	4.1	4.5	185
Co-acet/Na-OMMZ	35.9	7.5	6.9	80.4	5.2	1.1	32.7	2.1	1.0	301
Co-bpy/Na-OMMZ	38.2	5.8	5.1	77.3	11.8	0.6	28.0	3.6	0.9	331
Co-acet/H-bulky ZSM-5	29.7	10.2	7.7	70.3	11.8	0.4	35.6	2.4	1.4	236
Co-acet/H-meso-ZSM-5	35.1	8.5	7.9	76.4	7.2	1.1	38.0	5.5	0.7	279
Co-bpy/H-meso-ZSM-5	37.7	7.6	7.7	77.3	7.4	0.9	31.3	1.6	0.7	303
Co-acet/H-OMMZ	34.0	7.1	6.4	86.5	—	3.0	35.2	1.5	0.1	273
Co-bpy/H-OMMZ	31.5	5.7	5.5	88.8	—	3.8	22.1	0.6	0.1	258

Fig. 6. Time on stream (a) and products distribution (b) of Co based catalysts supported on OMMZ after 120 h. Reaction conditions: H2/CO = 1, P = 2.0 MPa, T = 513 K, GHSV = 3600 mL gcat-1 h-1, time on stream = 120 h.

Fig. 7. HAADF-SETM images of used Co based catalysts for syngas conversion. Used Co-acet/Na-OMMZ after 10 h (a1) and 120 h (a2), used Co-bpy/Na-OMMZ after 10 h (b1) and 120 h (b2).

Fig. 8. XRD patterns (a1,b1) and Co 2p XPS spectra (a2,b2) of used Co based catalysts supported on Na-OMMZ and H-OMMZ for syngas conversion after 10 and 120 h.

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