Investigation on production of dimethyl carbonate from propylene carbonate and methanol on calcium cerium-based catalysts
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摘要: 采用溶胶凝胶法制备了不同比例的钙铈基催化剂，并研究了其对于碳酸丙烯酯和甲醇制备碳酸二甲酯的酯交换反应性能。结果表明， Ca∶Ce=9的催化剂在反应时间2 h，温度40 ℃，甲醇与碳酸丙烯酯物质的量比为15∶1，催化剂用量为碳酸丙烯酯用量4%的条件下，碳酸丙烯酯转化率达到91.1%，碳酸二甲酯选择性达到91.7%。采用XRD、N2吸附-脱附、FT-IR、XPS和CO2-TPD对催化剂进行了表征。结果表明，催化剂表面的氧空穴越多，中等碱性位数量越多，越有利于甲醇的活化，催化剂的活性越好。Abstract: Calcium cerium-based catalysts with different Ca:Ce molar ratio prepared by sol-gel method were characterized by XRD, N2 adsorption-desorption, FT-IR, XPS and CO2-TPD, and evaluated the activity for dimethyl carbonate (DMC) synthesis from propylene carbonate (PC) and methanol. The results indicated that more surface oxygen vacancies and more moderate basic sites are beneficial for methanol activation and thus leading to better catalytic activity. The PC conversion was 91.1% with DMC selectivity of 91.72% over 0.9CaCe under the reaction conditions-reaction time of 2 h, reaction temperature of 40 °C, methanol to propylene carbonate molar ratio of 15:1 and catalyst amount of 4% relative to the amount of PC.
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Key words:
- calcium-cerium based catalysts /
- dimethyl carbonate /
- transesterification /
- solid base
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图 1 不同比例钙铈基催化剂的XRD谱图
Figure 1 XRD patterns of the catalysts with different Ca∶Ce molar ratio
图 2 不同比例钙铈基催化剂的N2吸附-解吸等温线和孔径分布
Figure 2 N2 adsorption-desorption isotherms and pore size distribution of CaxCe1−xOz with different Ca∶Ce molar ratio
图 3 不同比例钙铈基催化剂的红外光谱谱图
Figure 3 FT-IR spectra of the catalysts with different Ca:Ce molar ratio
图 4 不同比例钙铈基催化剂的XPS谱图
Figure 4 XPS spectra of the catalysts with different Ca∶Ce molar ratio
图 5 不同比例钙铈基催化剂的CO2-TPD谱图
Figure 5 CO2-TPD profiles of the catalysts with different Ca∶Ce molar ratio
图 6 0.9CaCe催化剂反应条件优化及循环使用性能
Figure 6 Optimization of reaction conditions and recyclability for 0.9CaCe catalyst
图 7 氧空穴占比与PC转化率的关系(a)，中强碱性位点占比与PC转化率的关系(b)
Figure 7 Relationship between oxygen defect proportion and PC conversion (a); Relationship between medium-strong basic site proportion and PC conversion (b)
表 1 不同比例钙铈基催化剂的织构参数
Table 1 Textural parameters of the catalysts with different Ca∶Ce molar ratio
Catalyst SBET/
(m2·g−1)Pore volumea/
(cm3·g−1)Average pore
sizeb/nm0.9CaCe 10.9 0.03 13.0 0.7CaCe 1.8 0.02 60.1 0.5CaCe 5.9 0.02 26.9 0.3CaCe 1.6 0.01 48.7 0.1CaCe 0.7 0.01 39.4 a: Measured at p/p0=0.99; b: Calculated from isothermal desorption branches using the BJH method. 
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表 2 催化剂中Ca和O的结合能值
Table 2 Binding energy values of the catalysts
Catalyst Binding energy/eV Ca 2p O 1s 0.9CaCe 346.86, 350.41 528.89, 531.3, 532.42 0.7CaCe 346.64, 350.2 528.77, 531.13, 532.07 0.5CaCe 346.58, 350.13 528.61, 531.03, 532.25 0.3CaCe 346.64, 350.19 528.69, 531.14, 532.87 0.1CaCe 346.51, 350.1 528.51, 531.01, 532.42
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表 3 催化剂表面氧物种的相对含量
Table 3 Relative content of oxygen species of the catalysts
Catalyst O 1s/% O1 O2 O3 0.9CaCe 5.92 80.30 13.79 0.7CaCe 20.01 63.04 16.95 0.5CaCe 31.34 57.33 11.33 0.3CaCe 41.61 52.32 6.07 0.1CaCe 51.90 40.33 7.76
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表 4 催化剂的总碱位数量和各碱性位点所占比例
Table 4 The total number and the proportion of each basic site of the catalysts
Catalyst α peak/% β peak/% Total basicity/(mmol·g−1) 0.9CaCe 3.96 96.04 1.85 0.7CaCe 22.76 77.24 0.35 0.5CaCe 23.98 76.02 0.52 0.3CaCe 44.81 55.19 0.12 0.1CaCe 53.31 46.69 0.04
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表 5 钙铈基催化剂的反应性能评价
Table 5 Catalytic performance of the catalysts
Catalyst Reaction conditions PC
conv./%DMC
sel./%temp./℃ time/h CH3OH/PC mcat./mPC
/%0.1CaCe 60 2 15 4 32.0 6.3 0.3CaCe 60 2 15 4 61.3 45.7 0.5CaCe 60 2 15 4 74.3 87.5 0.7CaCe 60 2 15 4 88.9 87.4 0.9CaCe 60 2 15 4 89.4 87.4 CeO2 60 2 15 4 43.7 0.0
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