Production of acetol and lactic acid from cellulose hydrogenolysis over Sn-Fe@C catalysts
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摘要: 丙酮醇和乳酸都是具有很高利用价值的化学品,充分利用可再生的纤维素资源制备丙酮醇和乳酸,具有重要的意义。本研究采用溶胶-凝胶法并结合惰性气氛高温退火方法制备了Sn-Fe@C系列催化剂,探讨了该催化剂上纤维素水相体系一步氢解制备丙酮醇和乳酸的催化性能。研究发现,丙酮醇和乳酸的收率与催化剂的Sn/Fe比以及焙烧温度具有显著的相关性。以3Sn1Fe@C600为催化剂,在240 ℃,5 MPa H2压力和1 h的反应条件下,丙酮醇和乳酸的总收率为45.4%。催化剂物理化学性质的表征结果表明,催化剂的酸、碱性位及金属活性位点之间的协同催化作用,是纤维素选择性氢解制备丙酮醇和乳酸的关键。Abstract: Acetol and lactic acid are valuable platform chemicals that have a broad range of industrial applications and their production from renewable cellulose is of scientific and practical significance. A series of Sn-Fe@C catalysts were prepared by sol-gel and high-temperature annealing method in an inert atmosphere and then used for preparing acetol and lactic acid by one-step hydrogenolysis of cellulose in aqueous system. 3Sn1Fe@C600 as catalyst, the total acetol and lactic acid yield of 45.4% were obtained at 240 ℃ for 1 h under H2 atmosphere, of which the yields of acetol and lactic acid were 24.3% and 21.1%, respectively. The results indicated that the yield of acetol and lactic acid was strongly dependent on the Sn/Fe ratio of the catalyst as well as the annealing temperature. The characterizations including BET, XRD, XPS, Py-FTIR and CO2-TPD were carried out to explore the relationship between the structure of catalysts and catalytic activity. The strong L acid sites, basic sites and the metal active sites of the catalyst were the key factors affecting the selective production of acetol and lactic acid from cellulose hydrogenolysis.
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Key words:
- biomass /
- hydrogenolysis /
- acetol /
- lactic acid /
- catalysis
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图 6 不同催化剂对纤维素转化的影响
Figure 6 Influences of different catalysts on cellulose conversion
reaction condition: 0.2 g cellulose; 0.1 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 1 h and 4 MPa H2 a: 0.1 g cellulose; 0.05 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 1 h and 5 MPa H2 La, lactic acid; 1-HB, 1-hydroxy-2-butanone; EG, ethylene glycol; Eth, ethanol; 3-HB, 3-hydroxy-2-butanone; Gly, glycerol; C6, fructose and glucose, the main product is fructose
图 7 (a)焙烧温度,(b)Sn含量和(c)Fe含量对纤维素转化的影响
Figure 7 Effect of (a) annealing temperature, (b) Sn content and Fe content on cellulose conversion
Reaction condition: 0.2 g cellulose; 0.08 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 1 h and 4 MPa H2;La, lactic acid; 1-HB, 1-hydroxy-2-butanone; EG, ethylene glycol; Eth, ethanol; 3-HB, 3-hydroxy-2-butanone; Gly, glycerol; C6, fructose and glucose, the main product is fructose
图 8 (a)催化剂用量,(b)底物用量对纤维素转化的影响
Figure 8 Effect of (a) catalyst amount, (b) substrate amount on cellulose conversion
Reaction condition: (a) 0.2 g cellulose, 0.01–0.06 g catalyst; (b) 0.4–2.0 g cellulose, 0.08 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 1 h and 4 MPa H2;La, lactic acid; 1-HB, 1-hydroxy-2-butanone; EG, ethylene glycol; Eth, ethanol; 3-HB, 3-hydroxy-2-butanone; Gly, glycerol; C6, fructose and glucose, the main product is fructose
表 1 不同催化剂的孔结构参数
Table 1 Pore structural parameters of different catalysts
Catalyst SBET /(m2·g−1) v /(cm3·g−1) d /nm 1Sn1Fe@C600 223.7 0.24 3.83 2Sn1Fe@C600 249.9 0.07 3.83 4Sn1Fe@C600 375.5 0.16 3.81 5Sn1Fe@C600 365.7 0.11 3.83 3Sn1Fe@C400 125.1 0.04 3.85 3Sn1Fe@C500 73.5 0.08 3.82 3Sn1Fe@C600 266.1 0.09 3.76 3Sn1Fe@C700 293.6 0.11 3.79 3Sn1Fe@C800 347.4 0.15 3.80 SBET,BET surface area;v,pore volume;d,pore diameter 表 2 不同焙烧温度催化剂的B酸位和L酸位表征
Table 2 Characterization results of B sites and L sites on catalysts with different annealing temperatures
t /℃ Catalyst Acid /(µmol·g−1) B/L B L 50 3Sn1Fe@C400 5.44 56.47 0.0964 3Sn1Fe@C500 3.05 44.04 0.0691 3Sn1Fe@C600 2.04 69.74 0.0293 3Sn1Fe@C700 2.13 46.16 0.0461 3Sn1Fe@C800 4.59 34.25 0.134 200 3Sn1Fe@C400 4.31 16.04 0.269 3Sn1Fe@C500 1.95 18.40 0.106 3Sn1Fe@C600 1.19 31.98 0.0372 3Sn1Fe@C700 1.28 15.59 0.0818 3Sn1Fe@C800 2.30 17.02 0.135 250 3Sn1Fe@C400 0.73 11.43 0.0638 3Sn1Fe@C500 0.83 6.66 0.125 3Sn1Fe@C600 0.70 11.99 0.0576 3Sn1Fe@C700 0.81 4.72 0.172 3Sn1Fe@C800 1.35 7.05 0.191 amount of acid sites was determined by quantifying the area of the characteristic diffraction peak. B acid, Brönsted acid; L acid, Lewis acid 表 3 其他催化剂对纤维素转化的影响
Table 3 Influence of other catalysts on cellulose conversion
Catalyst Conv. /% Yield wmoL/% acetol LA 1-HB 3-HB Gly EG Eth C6 total CA-L Sn@C600 56.2 17.1 0.1 6.3 0 0 0 7.7 0 17.2 Fe@C600 31.9 4.3 7.9 0 0 0 0 0 0 12.1 Sn@C600+Fe@C600 86.7 17.7 11.5 1.3 0 0 0 0 0 29.1 SnO 63.4 23.3 4.2 3.8 0 0 0 4.0 0 27.5 SnO2 24.3 0 0 1.0 0 0 0 0 7.0 0 Reaction condition: 0.2 g cellulose; 0.08 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 1 h and 4 MPa H2; La, lactic acid; 1-HB, 1-hydroxy-2-butanone; 3-HB, 3-hydroxy-2-butanone; Gly, glycerol; EG, ethylene glycol; Eth, ethanol; C6, fructose and glucose, the main product is fructose; total CA-L, total yield of acetol and lactic acid 表 4 一系列不同催化剂对不同底物转化的影响
Table 4 Influences of a series of different catalysts on different substrates conversion
Catalyst Substrate Conv. /% Yield wmoL/% acetol LA 1-HB 3-HB Gly EG Eth C6 total CA-L 3Sn-1Fe@C600 glucose 100 16.9 3.1 2.3 3.3 0 0 0 0 20.0 3Sn-1Fe@C600 fructose 100 12 6.8 0 4.7 0 0 0 0 18.8 3Sn-1Fe@C600 glyceraldehyde 100 21.8 5.9 0 0 0 0 2.0 0 27.7 3Sn-1Fe@C600 1,3-dihydroxyacetone 100 0 17.1 0 0 0 0.1 0 0 17.1 3Sn-1Fe@C600 acetol 0 0 0 0 0 0 0 0 0 0 3Sn-1Fe@C600 lactic acid 0 0 0 0 0 0 0 0 0 0 Fe@C600 glucose 100 13.6 18.1 0 0 0.1 0 0 0 31.7 Fe@Ca600 fructose 100 0 19.3 6.2 13.4 0 0 0 0 19.3 Fe@C600 glyceraldehyde 100 20.5 21.0 0 0 0 0 0 0 41.5 Fe@C600 1,3-dihydroxyacetone 100 0 21.3 0 0 0 0 0 0 21.3 Sn@Ca600 glucose 100 7.2 4.5 1.9 0 0 0 0 0 11.7 Sn@Ca600 fructose 100 7.2 4.1 0 0 0 0 0 0 11.3 Sn@Ca600 glyceraldehyde 100 26.5 13.4 0 0 0 0 0 0 39.9 Sn@Ca600 1,3-dihydroxyacetone 100 49.7 24.6 0 0 0 0 0 0 74.3 SnO glucose 100 5.6 0.8 0 0 0 0 0 0 6.4 SnO fructose 100 8.1 1.7 0 5.14 0 0 0 0 9.8 SnO glyceraldehyde 100 15.0 16.1 0 0 0 0 0 0 31.1 SnO 1,3-dihydroxyacetone 100 13.4 23.3 0 0 0 0 0 0 36.7 SnO2 glucose 100 0 0 1.6 0 0 0 0 8.6 0 Reaction condition: 0.2 g cellulose; 0.08 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 1 h and 4 MPa H2; a: 0.2 g cellulose; 0.08 g catalyst; 20 mL deionized water; reaction temperature 240 ℃; reaction time 10 min and 4 MPa H2;
La, lactic acid; 1-HB, 1-hydroxy-2-butanone; 3-HB, 3-hydroxy-2-butanone; Gly, glycerol; EG, ethylene glycol; Eth, ethanol; C6, fructose and glucose, the main product is fructose; total CA-L, total yield of acetol and lactic acid -
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