Performance and Improvement of Ni-based Catalysts for Ethane Dehydrogenation

doi:10.6023/A21100451

Abstract

Ethylene is one of the largest chemical products in the world, and its global demand increases significantly every year. At present, ethylene is mainly produced commercially through steam cracking of naphtha or alkane feedstocks. Catalytic dehydrogenation of ethane can effectively reduce energy loss of steam cracking. The transition metal Ni is a metal element with abundant reserves on the earth. It is widely used in the catalytic fields of hydrodesulphurization and reforming hydrogen production. However, there are few studies on Ni-based catalysts in alkanes dehydrogenation; therefore, three kinds of Ni-based supported catalysts, namely spinel decomposition-type, impregnation-type and perovskite precipitation-type, were prepared by different methods and explored for their performance in ethane dehydrogenation at 700 ℃ in C₂H₆-N₂ atmosphere at 50 mL•min^-1. The results show that the spinel decomposition-type catalyst Ni_1-_xCu_xCr₂O₄ prepared by glycine combustion method formed Ni-Cu alloy particles on the surface of Cr₂O₃ after reduction, which effectively passivated the C—C bond breaking activity of Ni and improved the selectivity of ethylene. The effect of Cu addition can be explained in geometric effect and electronic effect. When the Ni content was too high, the Ni particles could not be effectively dispersed, forming large metal clusters and resulting in excessive cracking of ethane and low ethylene selectivity. The impregnation-type catalyst Ni_xM_y/Al₂O₃ (M=Cu or Ag) had a large specific surface area and dispersed surface active sites, but the active metal particles were weakly interacted with the support and unstable at high temperatures; Cu or Ag forming an alloy with Ni effectively improved the selectivity of ethylene with Ag superior to Cu. The perovskite precipitation-type catalyst LaCr_1-_xNi_xO₃ (LCNi-100x) precipitated uniform and fine Ni particles in a reducing atmosphere, which were strongly bonded to the support and demonstrated high carbon deposition resistance and high stability; the reduced LCNi-15 (R-LCNi-15 containing 15% Ni) showed the best catalytic performance with the highest ethylene yield (24%), and high carbon deposition resistance and stability compared to commercial 13% CrO_x/Al₂O₃. Moreover, carbon-deposited R-LCNi-15 can restore catalytic activity by oxidation regeneration.

Key words: Ni-based catalysts, dehydrogenation, conversion of ethane, selectivity of ethylene, alloy

Cite this article

Jun Luo, Lichao Jia, Dong Yan, Jian Li. Performance and Improvement of Ni-based Catalysts for Ethane Dehydrogenation[J]. Acta Chimica Sinica, 2022, 80(3): 317-326.

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Fig. & Tab. 15

Figure 1. Ethane dehydrogenation (V(C2H6)/V(N2)=1/1) and ethylene polymerization decomposition under blank condition (without catalyst): (a) changes in ethane conversion and ethylene selectivity with temperature (solid line: 50 mL•min-1, dashed line: 20 mL•min-1); (b) the effect of temperature on ethylene polymerization decomposition (50 mL•min-1)

Figure 2. XRD patterns and microstructure of Ni1-xCuxCr2O4 catalyst before and after reduction: XRD patterns of before (a) and after (b) reduction; (c) microstructure of NiCr2O4 before and after reduction

Figure 3. Performance of ethane dehydrogenation for Ni1-xCux/Cr2O3, Cr2O3 and blank condition: (a) dehydrogenation performance changes with time; (b) the highest ethylene yield under the 90 min test. Test condition: 700 ℃, V(C2H6)/V(N2)=1/1, 50 mL•min-1. Ethane conversion (red), ethylene selectivity (blue)

Figure 4. The microstructure of tested Ni1Cu0/Cr2O3 (a) and Ni0.1Cu0.9/Cr2O3 (b)

Figure 5. Performance of ethane dehydrogenation for 13% CrOx/γ-Al2O3 (circle) and Cr2O3 (square)

Figure 6. Performance of ethane dehydrogenation for NixMy/γ-Al2O3: (a) catalytic activity of different Ni loadings (y=0); (b) alloying Ni5 and Ni7 (y=2), gray square Ni, blue triangle NiCu, red circle NiAg, ethane conversion (solid line), ethylene selectivity (dashed line)

Figure 7. Ni 2p3/2 XPS spectra of Ni5, Ni5Cu2 and Ni5Ag2

Figure 8. XRD patterns of LaCr1-xNixO3 catalyst before (a) and after (b) reduction

Figure 9. Microstructure of LaCr0.85Ni0.15O3 catalysts before (a) and after (b) reduction and EDS elemental mappings (c~f)

Figure 10. Performance of ethane dehydrogenation for Perovskite-precipitation type: (a) catalytic activity of R-LCNi-05, R-LCNi-10 and R-LCNi-15; (b) the highest yield of different catalysts under 180 min of testing; (c) comparison of performance between R-LCNi-15 (square) and commercial 13% CrOx/Al2O3 (circle)

催化剂	乙烷转化率/%	乙烯选择性/%	碳平衡/%
R-LCNi-15	29.4	83.2	94.3
13% CrO_x/Al₂O₃	20.4	87.6	90.4

Table 1. The dehydrogenation performance of R-LCNi-15 and 13% CrOx/Al2O3 tested for 90 min

Figure 11. Characterization of tested catalysts: (a) XRD patterns and (b) microstructure of tested R-LCNi-15 catalyst; (c) Raman spectra, (d) TG curves and (e) O2-TPO profiles of R-LCNi-15 and 13% CrOx/Al2O3

Figure 12. Catalytic performance of carbon-deposited R-LCNi-15 after oxidation regeneration

Figure 13. Cu or Ag doped Perovskite-type: catalytic results (a) of Cu doped LCNi-05 and LCNi-10; (b) of Cu doped LCNi-15; (c) XRD patterns of Ag doped LCNi-15 calcined at 900 ℃ or 1000 ℃; (d) catalytic result of Ag doped LCNi-15

Figure 14. H2-TPR profiles of three kinds of Ni-based catalysts

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Ni基乙烷脱氢催化剂的性能及其改进