CO2-assisted oxidative dehydrogenation of ethane to ethylene over the ZnO-ZrO2 catalyst
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摘要: 以焙烧商用氢氧化锆（Zr(OH)4）得到的ZrO2为载体，通过沉积-沉淀法制备了ZnO-ZrO2催化剂，并在873 K下对该催化剂上CO2辅助的乙烷氧化脱氢反应（CO2-ODHE）的催化性能进行了评价。利用X射线衍射（XRD）、扫描电镜（SEM）、拉曼光谱（Raman）、高分辨透射电镜（HRTEM）、X射线光电子能谱（XPS）、CO2程序升温脱附（CO2-TPD）等技术对ZnO-ZrO2催化剂的表面物理化学性质和形貌进行了表征。结果表明，在5%ZnO-ZrO2催化剂上，ZnO掺入到了ZrO2的表面晶格之中，在催化剂表面产生了高度分散的ZnO物种和氧缺陷区域。5%ZnO-ZrO2催化剂可以选择性地剪裁乙烷C−H键，抑制C−C键的断裂，具备良好的催化性能。210 µmol/(gcat·min)的C2H4形成率可以与贵金属和过渡金属碳化物催化剂的报道数据接近。此外，还对ZnO-ZrO2催化剂上CO2-ODHE反应可能的反应机制进行了讨论。
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关键词:
- 乙烯 /
- 乙烷氧化脱氢 /
- CO2辅助 /
- ZnO-ZrO2催化剂
Abstract: The ZnO-ZrO2 catalyst was prepared by the deposition-precipitation method using ZrO2 as the carrier obtained from calcining commercial zirconium hydroxide (Zr(OH)4). And the catalytic performance was evaluated at 873 K in CO2-assisted ethane oxidative dehydrogenation reaction (CO2-ODHE). The physical-chemical properties and morphology were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectra, High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectra (XPS), CO2 temperature-programmed desorption (CO2-TPD). The results show that ZnO were doped into the surface lattice of ZrO2 on the 5%ZnO-ZrO2 catalyst, generating highly dispersed ZnO species and oxygen-deficient regions on catalyst surface. 5%ZnO-ZrO2 catalyst could selectively breaking C−H bond instead of C−C bond, delivering excellent catalytic performance. 210 μmol/(gcat·min) of C2H4 formation rate could compare favorably with the data reported on noble metal and transition metal carbides. Additionally, the possible mechanism is discussed.-
Key words:
- ethylene /
- ethane oxidative dehydrogenation /
- CO2-assisted /
- ZnO-ZrO2 catalyst
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Figure 1 (a) XRD patterns of ZrO2, ZnO, and 5%ZnO-ZrO2 catalysts; (b) partially enlarged XRD patterns of ZrO2 and 5%ZnO-ZrO2 catalysts
Figure 3 SEM images of ZrO2 (a) and 5%ZnO-ZrO2 (b); Elemental mapping of 5%ZnO-ZrO2 ((c), (d))
Figure 5 XPS spectra of the ZrO2, ZnO, and 5%ZnO-ZrO2 catalysts: Zr 3d (a); Zn 2p (b); O 1s (c)
Figure 7 (a) Ethane conversion of ZrO2 and 5%ZnO-ZrO2 catalysts; (b) Products yield, selectivity and CO2 conversion of ZrO2 and 5%ZnO-ZrO2 catalysts Reaction conditions: for all catalyst, test in a flow of C2H6/CO2/N2 = 1∶1∶2, the total flow of 60 mL/min, reaction temperature of 600 °C and atmospheric pressure, GHSV = 12000 mL/(gcat·h)
Table 1 Binding energy of Zr 3d, Zn 2p and O 1s spectra and surface oxygen-deficient region (OII) concentration on ZrO2, ZnO and 5%ZnO-ZrO2 catalysts
Catalyst Zr 3d Zn 2p OII/
(OI + OII)a /%Zr 3d5/2 Zr 3d3/2 Zn 2p3/2 Zn 2p1/2 ZrO2 182.40 184.80 − − 20 5%ZnO-ZrO2 182.06 184.46 1021.51 1044.62 30 ZnO − − 1021.26 1044.37 − a: relative content of surface oxygen-deficient regions calculated from XPS spectra 
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Table 2 Details of catalytic performance over the ZrO2 and 5%ZnO-ZrO2 catalysts in CO2-ODHE and EDH reaction
Catalyst
CO2-ODHEa
EDHbC2H6
conversion
/%C2H4
selectivity
/%C2H4
yield
/%C2H4 STY /
(μmol·gcat−1·min−1)COtotal STYc /
(μmol·gcat−1·min−1)Carbon
balance
/%C2H6
conversion
/%C2H4
selectivity
/%C2H4
yield
/%ZrO2 3.2 93.5 3.0 − − 98.0 − − − 5%ZnO-ZrO2 11.2 84.0 9.4 210 195 96.6 8.6 91.3 7.8 a: reaction of ethane oxidative dehydrogenation with CO2 (CO2-ODHE), reaction conditions: for all catalyst, test in a flow of C2H6/CO2/N2 = 1∶1∶2, the total flow of 60 mL/min, reaction temperature of 873 K and atmospheric pressure, GHSV = 12000 mL/(gcat·h), b: reaction of ethane dehydrogenation without CO2 (EDH), reaction conditions: for 5%ZnO-ZrO2 catalyst, test in a flow of C2H6/N2 = 1∶3, the total flow of 60 mL/min, reaction temperature of 873 K and atmospheric pressure, GHSV = 12000 mL/(gcat·h), c: total CO formation rate from RWGS reaction, dry reforming reaction, and etc
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Table 3 Catalytic performance of various catalysts evaluated in CO2-ODHE reaction
Catalyst Mass /g T /K C2H6 flow rate /
(mL·${\rm{h}}^{- 1}\cdot{\rm{g}}_{\rm{cat}}^{-1} $)C2H6 conversion
/%C2H4 selectivity
/%STY /
(μmol·${\rm{g}}_{\rm{cat}}^{-1} \cdot {\rm{min}}^{-1} $)This work 0.3 873 3000 11 84 210 NiFe/CeO2[45] 0.1 873 6000 9.1 31 100 PtCe@MZ[17] 0.1 873 1500 39.4 84 326 CsRu/CeO2[46] 1.0 973 1080 33 60 163 1% Fe/Mo2C[47] 0.3 873 6000 7.3 75 235 Ni1.5Fe0.5/ZrO2-M[22] 0.2 873 3000 11 68 167 MoxCy[48] 0.1 873 3750 6.5 60 101 5% Cr-D-ERB-1[49] 0.5 973 600 35.6 94.5 150 Zn9.18/K0.74/NaS50[50] 2.0 923 180 57 79 61 Ga/TiSi-15[51] 0.2 923 270 46 84.9 78 3Cr/NaZSM-5-160[52] 0.2 923 270 61.3 78.9 89
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