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摘要: 超声辅助浸渍法制备了SBA-15分子筛负载三组分非晶态Co-Ni-B，研究了其对1-辛烯氢甲酰化制壬醛反应的催化性能。SBA-15负载纳米非晶态Co-Ni-B，增加了Co-Ni-B的分散；且非晶态Co-Ni-B转化为晶体的温度升高约280 ℃，耐热稳定性增强。Co-Ni-B/SBA-15催化剂，其中Co(wt.) = 17.22%，n(Ni)/n(Co) = 0.157，n(B)/n(Co + Ni) = 0.434，用于120 ℃、5 MPa条件下氢甲酰化反应，间歇反应4 h，1-辛烯完全转化，壬醛选择性91.24%；相比Co-Ni-B，副产物减少1倍。催化剂重复使用5次，活性稳定。Abstract: SBA-15 zeolite supported amorphous Co-Ni-B was prepared by the ultrasonic-assisted impregnation and its catalytic activity for hydroformylation of 1-octene to nonanal studied. Supported by SBA-15, nano amorphous Co-Ni-B became more dispersed. In particular, the crystallization temperature of amorphous Co-Ni-B was elevated and the heat-resisting stability of Co-Ni-B improved. Using Co-Ni-B/SBA-15 with Co(wt.) = 17.22%, n(Ni)/n(Co) = 0.157 and n(B)/n(CO + Ni) = 0.434, in hydroformylation at 120 °C and 5 MPa, the conversion of 1-octene and the selectivity of nonanal reached 100% and 91.24%, respectively. The side-product was reduced by 1 times compared with using Co-Ni-B. The catalytic activity showed stable after 5 cycle use.
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Key words:
- Co-Ni-B /
- SBA-15 /
- 1-octene /
- hydroformylation /
- catalytic activity
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图 2 催化剂的N2吸附-脱附等温曲线和孔分布
Figure 2. N2 adsorption isotherms and pore distribution of catalysts
图 3 催化剂的TEM、SAED图和元素映射图(Co-Ni-B/SBA-15)
Figure 3. TEM/SAED images of catalysts and elemental mapping of Co-Ni-B/SBA-15
图 5 Co-Ni-B和Co-Ni-B/SBA-15的差示扫描量热图谱
Figure 5. DSC profiles of Co-Ni-B and Co-Ni-B/SBA-15
图 7 Co-Ni-B/SBA-15重复使用5次后XRD图
Figure 7. XRD patterns of Co-Ni-B/SBA-15 after 5 repetition use
表 1 催化剂的织构性质
Table 1. Textural properties of catalysts
Catalysts Real bulk (w %) Real loading (w %) ABET(m2·g−1) Vpore (cm3·g−1) Dpore (nm) Co Ni B SBA-15 − − − − 713 1.03 7.8 Co-Ni-B 63.52 10.74 7.25 − 22.9 0.15 26.6 Co-Ni-B/SBA-15 17.22 2.69 1.59 21.50 539 0.64 6.8 Co-B/SBA-15 15.99 − 1.28 17.27 453 0.49 6.6 Ni-B/SBA-15 − 19.03 1.65 20.68 413 0.57 7.3 
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表 2 1-辛烯氢甲酰化催化活性
Table 2. Catalytic activity for hydroformylation of 1-octene
Catalysts Co/1-octene(molar ratio) x (%) Product s (%) Aldehydeyield (%) n/i TON nonanal isononanal isomers others Co-Ni-B/SBA-15 0.018 100 54.89 36.35 8.29 0.47 91.24 1.51 55.5 Co-B/SBA-15 0.019 100 50.64 34.30 10.02 5.04 84.94 1.48 52.3 Ni-B/SBA-15 − 5.81 27.63 11.51 46.28 14.58 2.27 2.40 3.3 Co-Ni-B 0.055 94.63 49.48 32.99 17.53 0 78.04 1.59 17.3 Cat. 0.25 g, toluene 13 g, 1-octene 3.57 g, 120 ℃, 5 MPa, 1200 rpm, 4 h
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表 3 焙烧对催化活性影响
Table 3. Effect of calcination on catalytic activity
Calc. t(℃) x (%) Product s (%) Aldehydeyield (%) n/i TON nonanal isononanal isomers others uncalcined 100 54.89 36.35 8.29 0.47 91.24 1.51 55.5 300 100 47.49 31.85 12.59 8.07 79.34 1.49 55.1 400 97.15 49.86 30.49 17.08 2.57 78.06 1.59 53.2 500 92.67 36.54 24.03 16.97 22.46 56.13 1.52 50.7 600 24.62 35.03 21.23 18.61 25.13 13.85 1.65 13.5 Co-Ni-B/SBA-15 0.25 g, toluene 13 g, 1-octene 3.57 g, 120 ℃, 5 MPa, 1200 rpm, 4 h
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