Effect of additive on CuO-ZnO/SBA-15 catalytic performance of CO2 hydrogenation to methanol
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摘要: 以硅质骨架结构介孔分子筛SBA-15为载体，采用浸渍法合成CuO-ZnO/SBA-15（CZ/SBA-15）、CuO-ZnO-MnO2/SBA-15（CZM/SBA-15）、CuO-ZnO-ZrO2/SBA-15（CZZ/SBA-15）三组多孔催化剂，在固定床反应器上评价了各组催化剂催化CO2加氢合成甲醇的性能，同时结合N2吸附-脱附（BET）、X射线衍射（XRD）、H2程序升温还原（H2-TPR）、程序升温脱附（H2-TPD、CO2-TPD）、N2O滴定、X射线光电子能谱（XPS）、透射电子显微镜（TEM）等表征研究了不同助剂对CO2催化加氢制甲醇的影响。结果表明，催化剂中的金属氧化物改变了SBA-15分子筛载体的孔径大小和比表面积；催化剂CuO-ZnO-MnO2/SBA-15、CuO-ZnO-ZrO2/SBA-15中铜的分散度（DCu）和比表面积（ACu）更大，表面CuO粒径更小，更易被还原；相比Mn-O簇，Zr-O簇为增强了碱性位点，提高了甲醇选择性。此外，CuO-ZnO-ZrO2/SBA-15具有更高的氧空位浓度，催化活性更好，其甲醇选择性为25.02%，与CuO-ZnO/SBA-15、CuO-ZnO-MnO2/SBA-15相比分别提高了28%和136.9%，催化效果最好。Abstract: Three kinds of porous catalysts CuO-ZnO/SBA-15 (CZ/SBA-15), CuO-ZnO-MnO2/SBA-15 (CZM/SBA-15) and CuO-ZnO-ZrO2/SBA-15 (CZZ/SBA-15) were synthesized by impregnation method with a siliceous framework mesoporous molecular sieve SBA-15. The performance of all catalysts for catalytic hydrogenation of CO2 to methanol was evaluated on a fixed bed reactor, combined with N2 adsorption-desorption (BET), X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR), temperature programmed desorption (H2-TPD, CO2-TPD), N2O titration, X-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM). The results show that the introduction of metal oxide in the catalyst changes the pore size and specific surface area of the SBA-15 molecular sieve support. The CuO-ZnO-MnO2/SBA-15 and CuO-ZnO-ZrO2/SBA-15 have high copper dispersion (DCu%), large specific surface area (SCu), small surface CuO particle size, and easy to be reduced. Compared with the Mn-O cluster, the Zr-O cluster enhances the basic site and improves the methanol selectivity. In addition, CuO-ZnO-ZrO2/SBA-15 has the highest oxygen vacancy concentration and better catalytic activity among three catalysts. The methanol selectivity of CuO-ZnO-ZrO2/SBA-15 is 25.02%, which is 28% and 136.9% higher than those of CuO-ZnO/SBA-15 and CuO-ZnO-MnO2/SBA-15, respectively.
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Key words:
- molecular sieve SBA-15 /
- oxygen vacancy /
- alkaline sites /
- methanol
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图 1 催化剂的XRD谱图
Figure 1 XRD patterns of the catalyst
(a): low-angle XRD pattern of SBA-15; (b): wide-angle XRD patterns of SBA-15; (c): wide-angle XRD patterns of the catalysts; (d): wide-angle XRD of the catalysts after reduction
图 5 催化剂的XPS谱图
Figure 5 XPS spectra of the catalyst
(a): full spectra; (b): O 1s; (c): Cu 2p; (d): Zn 2p; (e): Mn 2p; (f): Zr 3d
图 6 催化剂的TEM照片
Figure 6 TEM images of the catalyst
(a): C/SBA-15; (b): CZ/SBA-15; (c): CZM/SBA-15; (d): CZZ/SBA-15; (e): energy spectrum of CZM/SBA-15; (f): energy spectrum of CZZ/SBA-15
表 1 还原后催化剂中Cu的晶粒粒径
Table 1 Grain size of Cu in the catalyst after reduction
Sample C/SBA-15 CZ/SBA-15 CZM/SBA-15 CZZ/SBA-15 dCua/nm 19.8 18.9 17.8 15.4 a: the crystallite size of Cu NPs was calculated by Scherrer′s equation, where 2θ= 43.3°, 50.5°, 74.2° 
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表 2 催化剂的物性参数表
Table 2 Physical property parameter table of the catalyst
Sample ABET/(m2·g-1) vporea/(cm3·g-1) dpore/nm DCu/% ACu/(m2·g-1) SBA-15 863.25 1.17 7.41 - - CZ/SBA-15 382.96 0.60 6.27 7.80 52.6 CZM/SBA-15 412.87 0.65 6.24 11.4 77.3 CZZ/SBA-15 387.60 0.54 5.57 19.6 133.2 a: total pore volume obtained from p/p0= 0.99
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表 3 催化剂的吸附性能参数
Table 3 Catalysts adsorption performance parameters
Sample H2-TPD CO2-TPD maximum desorption temperature t/℃ area maximum desorption temperature t/℃ area CZ/SBA-15 479 6415 149 183 470 1736 CZM/SBA-15 476 7485 138 118 473 1988 CZZ/SBA-15 480 7262 141 159 488 2253
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表 4 催化剂中各元素的XPS分峰数据
Table 4 XPS peak data of each element in the catalyst
Sample E /eV E /eV E /eV O 1s /% OⅢ/(OⅠ+ OⅡ) Cu 2p3/2 Cu 2p1/2 Mn 2p3/2 Mn 2p1/2 Zr 2p5/2 Zr 2p3/2 OⅠ OⅡ OⅢ CZ/SBA-15 933.1 953.1 - - - - 22.8 42.2 35 0.53 CZM/SBA-15 933.1 953.1 641.6 654.1 - - 22.4 47.4 30.2 0.43 CZZ/SBA-15 933.1 953.1 - - 182.4 184.8 20 42.4 37.6 0.60
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表 5 催化剂的催化性能评价
Table 5 Catalytic performance evaluation of catalysts
Catalyst xCO2/% sCH3OH/% sCO/% wCH3OH/(mmol·g-1·h-1) CZ/SBA-15 8.7 19.54 80.46 0.42 CZM/SBA-15 8.2 10.56 89.40 0.25 CZZ/SBA-15 8.1 25.02 74.97 0.99 reaction condition: t=250 ℃, p=3 MPa, H2/CO2 (volume ratio)=3:1, SV=6000 mL/(g·h)
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