Characterization and catalytic behavior of EDTA modified silica nanosprings (NS)-supported cobalt catalyst for Fischer-Tropsch CO-hydrogenation

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Environmental Science, University of Idaho, Moscow, ID 83844-3006, United States
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Renewable Materials Program, Department of Forest, Rangeland and Fire Sciences, University of Idaho, Moscow, ID 83844-1133, United States
3.
Department of Physics, Oklahoma State University, Stillwater, OK 74078-3072, United States

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Corresponding author: Armando G. McDonald, E-mail: armandm@uidaho.edu

摘要

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Abstract: The effect of ethylene diamine tetraacetic acid (EDTA) modification on the physico-chemical properties and catalytic performance of silica nanosprings (NS) supported cobalt (Co) catalyst was investigated in the conversion of syngas (H₂ + CO) to hydrocarbons by Fischer-Tropsch synthesis (FTS). The unmodified Co/NS and modified Co/NS-EDTA catalysts were synthesized via an impregnation method. The prepared Co/NS and Co/NS-EDTA catalysts were characterized before the FTS reaction by BET surface area, X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), differential thermal analysis (DTA) and thermogravimetric analysis (TGA) in order to find correlations between physico-chemical properties of catalysts and catalytic performance. FTS was carried out in a quartz fixed-bed microreactor (H₂/CO of 2:1, 230℃ and atmospheric pressure) and the products trapped and analyzed by GC-TCD and GC-MS to determine CO conversion and reaction selectivity. The experimental results indicated that the modified Co/NS-EDTA catalyst displayed a more-dispersed phase of Co₃O₄ nanoparticles (10.9%) and the Co₃O₄ average crystallite size was about 12.4 nm. The EDTA modified catalyst showed relatively higher CO conversion (70.3%) and selectivity toward C_6-18 (JP-8, Jet A and diesel) than the Co/NS catalyst (C_6-14) (JP-4).
- silica nanosprings /
- Fischer-Tropsch synthesis /
- EDTA /
- cobalt catalyst

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Figure 1 H₂-TPR profiles of calcined Co/NS and Co/NS-EDTA catalysts

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Figure 2 X-ray diffractograms of calcined Co/NS and Co/NS-EDTA catalysts

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Figure 3 Transmission electron micrographs of calcined catalysts (a)-(c) Co/NS and (d)-(f) Co/NS-EDTA

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Figure 4 Survey XPS spectra of the calcined Co/NS and Co/NS-EDTA catalysts

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Figure 5 High resolution XPS spectra of the Co 2p of calcined Co/NS and Co/NS-EDTA catalysts

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Figure 6 (a) TGA and (b) DTA thermograms of Co/NS, Co/NS-EDTA and virgin style="class:table_top_border2"

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Figure 7 FT-IR spectra of unmodified Co/NS, modified Co/NS-EDTA catalysts and virgin style="class:table_top_border2"

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Figure 8 Total ion current chromatograms of condensable FTS products from the (a) Co/NS and (b) Co/NS-EDTA catalysts

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Figure 9 Production distribution of FT hydrocarbons (C_6-18) from Co/NS and Co/NS-EDTA catalysts

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Figure 10 CO conversion with time on stream Co/NS and Co/NS-EDTA catalysts

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Table 1 Physical characteristics of unmodified Co/NS, modified Co/NS-EDTA catalysts, and virgin NS

Catalyst	Co w/%	S_BET /(m²·g^-1)	Size of Co₃O₄ particles d/nm		d_XRD(Co⁰) /nm	Co dispersion/%
Catalyst	Co w/%	S_BET /(m²·g^-1)	d_XRD	d_TEM	d_XRD(Co⁰) /nm	Co dispersion/%
NS	-	314	-	-	-	-
Co/NS	15	193	12.4	9.4	9.3	10.3
Co/NS-EDTA	15	94.5	11.8	14.6	8.8	10.9

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Table 2 Catalytic performance and major components of synthesized liquid F-T fuel over Co/NS and Co/NS-EDTA catalysts at 230 ℃, H₂/CO of 2:1 and at atmospheric pressure

Catalyst	Co/NS	Co/NS-EDTA
CO conversion x/%	65.5	70.3
H₂ conversion x/%	61.2	73.2
Products selectivity s/%
CO₂ select. s/%	5.3	3.4
CH₄ select. s/%	6.7	12.7
∑ < C₅	17.1	16.6
Product distribution w_m/%
∑ C_6-11 (naphtha range fuel)	59.3	34.4
∑ C_12-15 (jet range fuel)	11.6	21.3
∑ > C₁₅(diesel range fuel)	-	11.6
∑ > C₆	70.9	67.3
C_6-18 paraffins	18.4	28.7
C_6-18 olefins	26.6	16.5
C_6-18 naphthenes	17.3	13.8
C_6-18 oxygenates	8.6	8.3
Paraffins/olefins (P/O)	0.69	1.72

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