Study on the synthesis of propylene glycol through cellulose hydrogenation using alkaline promoted Ni-W/β-zeolite catalysts
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摘要: 为提高纤维素催化氢解产醇类产物中1,2-丙二醇(1,2-PG)的收率,采用等体积浸渍法制备了以β分子筛为载体负载Ni和W的催化剂。结果表明,当7Ni-20W/β分子筛作为催化剂时,在240℃反应温度和6.0 MPa H2的条件下反应30 min后,纤维素实现完全转化,1,2-PG和乙二醇(EG)产率分别达到19.3%和45.3%;不同于其他载体催化剂,β分子筛可以明显提高1,2-PG选择性。当不同碱催化剂加入到Ni-W/β分子筛催化剂反应体系后,可以进一步提高1,2-PG的选择性。尤其是当加入Ba(OH)2后,1,2-丙二醇产率从19.3%提高了32.5%。为了探究碱催化剂在反应中的作用,以葡萄糖为底物进行了一系列的碱催化反应。结果表明,碱催化剂主要作用是有助于将葡萄糖异构化为果糖,从而促进纤维素转化为1,2-PG。催化剂在两次回收重复利用之后1,2-PG的收率只下降3.9%,乙二醇产率收率下降4.1%。Abstract: A series of Ni-W/β zeolite catalysts were prepared via incipient impregnation method in order to improve the yield of 1, 2-propylene glycol (1, 2-PG) in the alcohol products of cellulose hydrogenation. Under the reaction conditions of 240℃ and 6.0 MPa H2 for 30 min, the complete conversion of cellulose was obtained and the yields of 1, 2 propylene glycol and ethylene glycol (EG) were 19.3% and 45.3%, respectively. Different from other supports, the selectivity of 1, 2-PG was highly improved when β zeolite was used. The selectivity of 1, 2-PG was further improved after the addition of alkaline, and the yield of 1, 2-PG was up to 32.5% especially for Ba (OH)2. The function of alkaline catalysts in the reaction was also discussed based on a series of reactions using glucose as the substrate, indicating that alkaline was favorable for the isomerization of glucose to fructose and thus promoted the conversion of cellulose into 1, 2-PG. After two cycles of reuse, the yield of 1, 2-PG and EG slightly decreased (3.9% and 4.1%, respectively).
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Key words:
- Ni-W/β zeolite /
- cellulose /
- 1, 2-propylene glycol /
- alkaline catalysts /
- hydrogenation
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表 1 催化剂的孔结构
Table 1 Pore structure of the catalyst
Catalyst BET surface area
A/(m2·g-1)Pore volume
v/(cm3·g-1)Pore size
d/nm1Ni-20W/β 368 0.11 11.1 3Ni-20W/β 357 0.09 9.5 5Ni-20W/β 342 0.08 8.4 7Ni-20W/β 329 0.07 7.8 9Ni-20W/β 313 0.06 7.2 15Ni-20W/β 287 0.06 6.9 7Ni-5W/β 371 0.10 10.1 7Ni-15W/β 348 0.07 7.5 7Ni-25W/β 277 0.05 6.7 表 2 碱催化剂种类和用量对葡萄糖异构化为果糖的影响
Table 2 Effect of type and amount of base catalyst on glucose isomerization
Catalyst Conversion x/% Yield w/% mannose fructose No base 6 trace 4 5 mmol/L NaOH 33 6 26 10 mmol/L NaOH 41 5 28 15 mmol/L NaOH 47 4 27 5 mmol/L Ca (OH)2 41 6 29 10 mmol/L Ca (OH)2 44 5 28 15 mmol/L Ca (OH)2 50 3 27 5 mmol/L Ba (OH)2 36 6 26 10 mmol/L Ba (OH)2 42 5 27 15 mmol/L Ba (OH)2 45 4 24 reaction conditions: 30 min,6 MPa H2,518 K,40 mL H2O,0.5 g glucose,0.15 g catalyst -
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