Selective xylose hydrogenolysis to 1,2-diols using Co@NC catalysts
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摘要: 本研究采用bottom-up法,制备了具有加氢和异构活性的碳包裹金属催化剂Co@NC,用于催化木糖氢解制备1,2-二元醇。结合XRD、TEM、XPS等表征手段对比了不同焙烧温度制备的Co@NC催化剂的物理和化学性质。研究发现,600 ℃焙烧的Co@NC催化剂具有最高的二元醇的总收率 (70.1%),其中,乙二醇、1,2-丙二醇和1,2-戊二醇的收率分别达到17.6%、25.1%和27.4%。机理研究表明,N的掺杂为Co@NC提供了碱性位点,在碱的催化作用下促进木糖向木酮糖的异构,再通过Retro-aldol反应得到乙醇醛和丙酮醇中间产物,最后经加氢得到乙二醇和1,2-丙二醇。1,2-戊二醇来源于木糖的加氢脱氧,其产率高于文献报道的最佳结果。本研究工作发展的水热稳定性优异的Co@NC催化剂为生物质高效制备1,2-二元醇提供了新的研究思路。Abstract: Xylose is the predominant component of hemicellulose, and converting xylose to valuable compounds is essential to achieve biomass utilization. Herein, N-doped carbon nanotubes encapsulated metal catalysts (Co@NC) with hydrogenation and isomerization capacities were synthesized via bottom-up method for catalyzing xylose hydrogenolysis into 1,2-diols. The physicochemical properties of Co@NC prepared with different calcination temperature were determined by XRD, TEM, XPS and so on. The Co@NC prepared at 600 ℃ exhibited the optimal catalytic activity, and the yield of diols reached 70.1% with ethylene glycol, 1,2-propylene glycol and 1,2-pentanediol being 17.6%, 25.1% and 27.4%, respectively. The doping N species served as the basic sites which benefited the isomerization of xylose to xylulose. Xylulose was subsequently converted to glycolaldehyde and acetol through Retro-aldol reaction, followed by hydrogenation to produce ethylene glycol and 1,2-propylene glycol. 1,2-Pentanediol derived from the selective hydrodeoxygenation of xylose, the yield of which surpassed the results that had been reported. The Co@NC catalysts with high robustness under harsh hydrothermal conditions provided new insights into the effective conversion of lignocellulosic biomass to 1,2-diols.
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Key words:
- Co@NC /
- xylose /
- hydrogenolysis /
- 1,2-diols /
- 1,2-pentanediol
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图 10 Co@NC-600催化剂上不同反应条件下木糖氢解反应性能
Figure 10 Effect of (a) reaction temperature, (b) reaction time and (c) H2 pressure on the selective hydrogenolysis of xylose over Co@NC-600
Reaction conditions: 0.2 g xylose, 0.07 g catalysts, 20 mL de-ionized water, EG: ethylene glycol; 1,2-PG: 1,2-propylene glycol; 1,2-PeD: 1,2-pentanediol; CPO: cyclopentanone; THFA: tetrahydrofurfuryl alcohol
图 11 Co@NC催化木糖转化的循环使用性能
Figure 11 Cycle test of Co@NC for xylose conversion.
Reaction conditions: 0.2 g xylose, 0.07 g catalysts, 20 mL de-ionized water, reaction temperature: 200 ℃, reaction time: 3 h, H2 pressure: 3 MPa. EG: ethylene glycol; 1,2-PG: 1,2-propylene glycol; 1,2-PeD: 1,2-pentanediol; CPO: cyclopentanone; Ac: acetol; THFA: tetrahydrofurfuryl alcohol
表 1 Co@NC催化剂的BET数据和孔结构参数
Table 1 BET surface area and pores of Co@NC catalysts
Catalyst BET surface area/(m2·g−1) Pore volume/(cm3·g−1) Pore size/nm Co@NC-500 3.4 0.01 – Co@NC-600 194.0 0.50 3.6 Co@NC-700 275.2 0.76 3.3 Co@NC-800 275.3 0.83 3.4 表 2 Co@NC催化剂的表面酸/碱量
Table 2 Surface acid/base amounts of Co@NC catalysts
Catalyst Total acid amount/
(mmol·g−1)Weak base amount/
(mmol·g−1)Strong base amount/
(mmol·g−1)Total base amount/
(mmol·g−1)Co@NC-500 2.132 0.118 8.694 8.812 Co@NC-600 1.142 0.221 3.681 3.902 Co@NC-700 1.104 0.163 1.402 1.565 Co@NC-800 0.586 0.155 0.997 1.152 Ni@NC-600 3.162 0.218 4.649 4.867 表 3 不同N掺杂碳包裹型催化剂在木糖氢解反应中的催化性能
Table 3 Xylose conversion to 1,2-diols over different N-doped carbon encapsulated metal catalysts
Catalyst Conv./% Yield Cmol/% EG 1,2-PG 1,2-PeD CPO Ac THFA Co@NC-500 37.3 0 0 0 0 0 0 Co@NC-600 98.4 17.6 25.1 27.4 2.0 2.9 3.5 Co@NC-700 95.1 12.9 11.8 23.4 9.3 17.4 1.8 Co@NC-800 90.9 6.0 3.5 4.3 3.7 26.1 1.0 Ni@NC-600 82.4 2.4 8.2 0 15.0 20.5 10.3 Fe@NC-600 62.9 0 0 0 0 10.5 0 Reaction conditions: 0.2 g xylose, 0.07 g catalysts, 20 mL de-ionized water, reaction temperature: 200 ℃, reaction time: 3 h, H2 pressure: 3 MPa. EG: ethylene glycol; 1,2-PG: 1,2-propylene glycol; 1,2-PeD: 1,2-pentanediol; CPO: cyclopentanone; Ac: acetol; THFA: tetrahydrofurfuryl alcohol 表 4 不同催化剂上木糖的氢解性能
Table 4 Xylose hydrogenolysis catalyzed by different catalysts
Catalyst Conv./% Yield Cmol/% xylitol cyclopentanone acetol Co@C 97.5 96.5 0 0 Ni@C 93.7 90.7 0 0 Fe@C 96.4 85.0 0 0 Co/C 99.9 99.9 0 0 N-AC 62.1 0 13.8 20.4 Reaction conditions: 0.2 g xylose, 0.07 g catalysts, 20 mL de-ionized water, reaction temperature: 200 ℃, reaction time: 3 h, H2 pressure: 3 MPa, N-AC: N-activated carbon 表 5 1,2-PeD收率与文献对比
Table 5 Comparison of 1,2-PeD yield in this work with reported references
表 6 不同原料下的产物分布
Table 6 Product distribution using various possible intermediates
Substrate Conv./% Yield Cmol/% EG 1,2-PG 1,2-PeD CPO cyclopentanol Ac THFA Xylitol 25.2 1.9 0.8 2.5 0 0 0 0 Xylulose 92.5 24.4 32.9 7.5 1.0 1.1 8.5 0.5 Glycolaldehyde 99.9 93.7 0 0 0 0 0 0 Acetol 98.2 0 95.3 0 0 0 0 0 Methylglyoxal 95.6 0 39.1 0 0 0 19.3 0 Furfural 99.9 0 0 0 86.5 10.1 0 0.3 Furfuryl alcohol 99.9 0 0 0 78.2 13.8 0 3.6 Glucose 93.5 0 0 0 0 0 8.9 0 Fructose 96.7 0 10.4 0 0 0 30.1 0 Reaction conditions: 0.2 g xylose, 0.07 g catalysts, 20 mL de-ionized water, reaction temperature: 200 ℃, reaction time: 3 h, H2 pressure: 3 MPa. EG: ethylene glycol; 1,2-PG: 1,2-propylene glycol; 1,2-PeD: 1,2-pentanediol; CPO: cyclopentanone; Ac: acetol; THFA: tetrahydrofurfuryl alcohol -
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