Catalytic conversion of glucose and cellobiose into ethylene glycol over various tungsten-based catalysts
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摘要: 以葡萄糖和纤维二糖为模型化合物研究了逆羟醛缩合速率与加氢速率之间的匹配对纤维素转化产物分布的影响。葡萄糖和纤维二糖在共浸渍的Ni-WO3/SBA-15催化剂和物理混合的Ni/SBA-15、WO3/SBA-15催化剂上具有不同的产物分布。葡萄糖和纤维二糖在不同钨基催化剂上具有不同的乙二醇收率, 其顺序为WO3 < WO3/SBA-15 < (NH4)6W7O24·6H2O (偏钨酸铵), 这与它们的颗粒粒径成反比。在相同钨基催化剂用量条件下, 葡萄糖转化中乙二醇收率小于纤维二糖。Abstract: Glucose and cellobiose were used as model compounds to investigate the effect of retro-aldol condensation and hydrogenation rates on the product distribution of cellulose conversion. It was shown that the product distribution obtained over the physical mixture of Ni/SBA-15 and WO3/SBA-15 in the glucose and cellobiose conversions were different from that attained on the Ni-WO3/SBA-15 prepared by the co-impregnation method. The ethylene glycol (EG) yield depended on the structures of tungstic compounds, and it increased in the order of WO3 < WO3/SBA-15 < (NH4)6W7O24·6H2O (AMT), while the particle sizes of them decreased in such an order. Regardless of the types of tungstic compounds, the EG yield obtained in the glucose conversion is lower than that attained in the cellobiose conversion at the same amount of catalyst.
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Key words:
- glucose /
- cellobiose /
- hydrogenolysis /
- tungsten-based catalysts /
- ethylene glycol
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Table 1 Catalytic results of different catalysts for conversion of glucose
Catalyst Conversion x/% Yield w /% EG 1, 2-PG glycerol sorbitol mannitol 10%Ni/SBA-15 100 trace trace trace 97.2 no 10%Ni/SBA-15+15%WO3/SBA-15a 100 15.2 1.0 2.3 54.5 7.7 10%Ni-15%WO3/SBA-15 100 29.8 2.4 2.9 36.5 7.5 reaction conditions: 0.5 g glucose, 40 g water, 0.125 g catalyst, 175 ℃, 80 min, 6 MPa H2 pressure
a: 0.125 g of 15%WO3/SBA-15 was used to make sure that it had the same WO3 content as the 10%Ni-15%WO3/SBA-15Table 2 Catalytic results of different catalysts for conversion of cellobiose
Catalyst Conversion x/% Yield w/% EG 1, 2-PG glycerol sorbitol mannitol 10%Ni/SBA-15 97.8 trace trace trace 47.7 no 10%Ni/SBA-15+15%WO3/SBA-15a 100 15.3 1.1 1.8 51.7 4.6 10%Ni-15%WO3/SBA-15 100 40.5 3.4 2.8 18.5 2.0 reaction conditions: 0.5 g cellobiose, 40 g water, 0.125 g catalyst, 190 ℃, 30 min, 6 MPa H2 pressure
a: 0.125 g 15%WO3/SBA-15 was used to make sure that it had the same WO3 content as the 10%Ni-15%WO3/SBA-15Table 3 Catalytic results of different amounts of WO3/SBA-15 for glucose conversion
Catalyst Amount m/g Conversion x/% Yield w/% EG 1, 2-PG glycerol sorbitol mannitol 15%WO3/SBA-15 0.125 100 15.2 1.0 2.3 54.5 7.7 15%WO3/SBA-15 0.190 100 19.6 1.2 2.3 47.0 10.9 15%WO3/SBA-15 0.250 100 23.7 1.8 2.7 38.0 8.1 15%WO3/SBA-15 0.375 100 36.5 2.8 3.8 21.7 5.9 reaction conditions: 0.5 g glucose, 40 g water, 0.125 g 10%Ni/SBA-15, 175 ℃, 80 min, 6 MPa H2 pressure Table 4 Catalytic results of different amounts of WO3/SBA-15 for cellobiose conversion
Catalyst Amount m/g Conversion x/% Yield w/% EG 1, 2-PG glycerol sorbitol mannitol 15%WO3/SBA-15 0.125 100 15.3 1.1 1.8 51.7 4.6 15%WO3/SBA-15 0.190 100 30.8 2.1 2.1 32.2 5.2 15%WO3/SBA-15 0.250 100 37.6 3.4 3.5 23.4 5.4 15%WO3/SBA-15 0.375 100 41.6 3.7 3.6 24.7 5.0 reaction conditions: 0.5 g cellobiose, 40 g water, 0.125 g 10%Ni/SBA-15, 190 ℃, 30 min, 6 MPa H2 pressure Table 5 Catalytic results of different amounts of WO3 for glucose conversion
Catalyst Amounta m/g Conversion x/% Yield w /% EG 1, 2-PG glycerol sorbitol mannitol WO3 0.018 7 100 2.7 0.2 1.3 82.3 4.9 WO3 0.037 5 100 2.6 0.3 1.7 85.6 10.0 WO3 0.056 2 100 8.3 0.3 1.6 71.8 11.0 WO3 0.082 5 100 13.4 0.5 1.9 61.0 6.2 reaction conditions: 0.5 g glucose, 40 g water, 0.125 g 10%Ni/SBA-15, 175 ℃, 80 min, 6 MPa H2 pressure
a: the WO3 amounts listed from the first to the fourth line are the same as those contained in 0.125, 0.250, 0.375 and 0.550 g 15%WO3/SBA-15, respectivelyTable 6 Catalytic results of different amounts of WO3 for cellobiose conversion
Catalyst Amount m/g Conversion x/% Yield w /% EG 1, 2-PG glycerol sorbitol mannitol WO3 0.018 7 100 11.9 0.6 1.8 63.0 6.1 WO3 0.037 5 100 15.8 0.5 2.0 51.6 5.4 WO3 0.056 2 100 23.8 0.5 1.8 44.9 6.4 WO3 0.082 5 100 30.5 0.9 1.8 38.9 5.3 reaction conditions: 0.5 g cellobiose, 40 g water, 0.125 g 10%Ni/SBA-15, 190 ℃, 30 min, 6 MPa H2 pressure
a: the WO3 amounts listed from the first to the fourth line are the same as those contained in 0.125, 0.250, 0.375 and 0.550 g 15%WO3/SBA-15, respectivelyTable 7 Catalytic results of different amounts of AMT for glucose conversion
Catalyst Amounta m/g Conversion x/% Yield w/% EG 1, 2-PG glycerol sorbitol mannitol AMT 0.021 8 100 22.6 1.2 2.4 48.6 4.4 AMT 0.033 1 100 35.9 1.5 2.4 30.5 3.7 AMT 0.043 6 100 41.4 2.5 2.6 22.9 2.6 AMT 0.065 4 100 44.5 2.7 2.9 21.2 2.7 reaction conditions: 0.5 g glucose, 40 g water, 0.125 g 10%Ni/SBA-15, 175 ℃, 80 min, 6 MPa H2 pressure
a: the W amounts listed from the first to the fourth line are the same as those contained in 0.125, 0.190, 0.250 and 0.375 g 15%WO3/SBA-15, respectivelyTable 8 Catalytic results of different amounts of AMT for cellobiose conversion
Catalyst Amount m/g Conversion x/% Yield w/ % EG 1, 2-PG glycerol sorbitol mannitol AMT 0.0218 100 52.4 2.9 2.0 19.6 2.6 AMT 0.0331 100 50.6 2.8 2.0 18.8 2.8 AMT 0.0436 100 51.0 3.1 2.0 20.2 2.4 AMT 0.0654 100 49.6 3.2 1.9 17.6 2.4 reaction conditions: 0.5 g cellobiose, 40 g water, 0.125 g 10%Ni/SBA-15, 190 ℃, 30 min, 6 MPa H2 pressure
a: the W amounts listed from the first to the fourth line are the same as those contained in 0.125, 0.190, 0.250 and 0.375 g 15%WO3/SBA-15, respectively -
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