Study on the synthesis of melem catalyst and its application in synthesis of cyclic carbonate
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摘要: 以纳米二氧化硅 (SiO2) 为模板,以三聚氰胺为前驱体,采用固相反应法制备一系列介孔蜜勒胺 (melem) 材料。通过调控硬模板剂和前驱体的用量,最终得到一系列高比表面积 (40−92 m2/g) 和孔体积 (0.179−0.407 cm3/g)的介孔 melem材料。将其作为催化剂用于1, 4 -丁二醇二缩水甘油醚 (BDODGE) 与CO2的环加成反应中,结果表明,随着比表面积增大,催化剂活性相比未加入模板剂的melem样品有了显著提高。三聚氰胺与纳米SiO2的质量比为2时制备的催化剂,在130 ℃、20 h、2.0 MPa条件下,BDODGE转化率为99.3%,环碳酸酯选择性为99.5%。Abstract: In this paper, a series of mesoporous melem materials were prepared from melamine by solid-phase reaction using nano-silica (SiO2) as the template. The mesoporous melem materials with high specific surface area (40−92 m2/g) and pore volume (0.179−0.407 cm3/g) were obtained by adjusting the ratio of SiO2 template and melamine. The obtained melem was used as catalyst for the cycloaddition reaction between BDODGE and CO2. The results showed that the catalytic activity was greatly improved with the increase of specific surface area of the catalysts. The catalyst mp-CN-450-2 showed the best performance. After 20 h reaction at 130 ºC, 2.0 MPa, 99.3% of BDODGE conversion and 99.5% of cyclic carbonate selectivity were acquired, respectively.
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Key words:
- melamine /
- mesoporous melem materials /
- epoxide /
- cyclic carbonate /
- CO2
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表 1 CN-450-r及mp-CN-450-r材料的织构分析
Table 1 Textual parameters of CN-450-r and mp-CN-450-r materials
Entry Catalyst SBET/ (m2·g−1) Pore volume/ (cm3·g−1) Average pore diameter / nm 1 CN-450 4 0.0157 16.3 2 CN-450-8 7 0.0332 19.1 3 CN-450-4 16 0.0589 14.8 4 CN-450-2 36 0.1394 15.6 5 mp-CN-450-8 40 0.1794 17.7 6 mp-CN-450-4 69 0.3275 18.9 7 mp-CN-450-2 92 0.4072 17.6 8 SiO2 189 0.7826 16.6 表 2 CN-450-r及mp-CN-450-r催化剂对BDODGE与CO2环加成反应的影响
Table 2 Catalytic performance of different CN-450-r and mp-CN-450-r catalysts in the reaction of BDODGE and CO2
Entry Catalyst BDODGE
conversion/%Selectivity/
%1 a CN-450 32.5 91.7 2 a CN-450-8 25.8 99.0 3 a CN-450-4 38.2 99.7 4 a CN-450-2 33.5 94.2 5 b[19] CN-450-W 93.1 99.3 6 c mp-CN-450-8 97.6 98.3 7 c mp-CN-450-4 98.7 98.9 8 c mp-CN-450-2 99.3 99.5 a reaction conditions:W(BDODGE) = 30 g, W(catalyst) = 1.5 g, p(CO2) = 2.0 MPa, t = 140 ℃, t = 20 h; b W(catalyst) = 2.1 g; c t = 130 ℃ 表 3 各种催化剂催化CO2环加成反应对比
Table 3 Comparison of various catalysts for the cycloaddition of CO2
Entry Catalyst Conversion / % Selectivity / % Ref. 1 a m-C3N4 36.1 98.0 [19] 2 a u-C3N4 51.3 98.2 [19] 3 b ZnBr2/u-CN/r-Al2O3 98.9 99.1 [25] 4 c D296 95.8 97.1 [26] 5 d LiBr 94.0 99.1 [27] 6 mp-CN-450-2 99.3 99.5 this work a reaction conditions:W(BDODGE) = 30 g, W(catalyst) = 5.0%, p(CO2) = 1.0 MPa, t = 140 ℃, t = 20 h;b W(catalyst) = 15.1%, t = 30 h;c W(PPGDGE) = 100 g, W(catalyst) = 10%, t = 30 h;d W(E51) = 30 g, W(catalyst) = 1.0%, W(DMF) = 25 g, t = 90 ℃ -
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