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Sn-Fe@C催化纤维素氢解制备丙酮醇和乳酸

李思婵 邓玉龙 王海永 王晨光 马隆龙 刘琪英

李思婵, 邓玉龙, 王海永, 王晨光, 马隆龙, 刘琪英. Sn-Fe@C催化纤维素氢解制备丙酮醇和乳酸[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60153-6
引用本文: 李思婵, 邓玉龙, 王海永, 王晨光, 马隆龙, 刘琪英. Sn-Fe@C催化纤维素氢解制备丙酮醇和乳酸[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60153-6
LI Si-chan, DENG Yu-long, WANG Hai-yong, WANG Chen-guang, MA Long-long, LIU Qi-ying. Production of acetol and lactic acid from cellulose hydrogenolysis over Sn-Fe@C catalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60153-6
Citation: LI Si-chan, DENG Yu-long, WANG Hai-yong, WANG Chen-guang, MA Long-long, LIU Qi-ying. Production of acetol and lactic acid from cellulose hydrogenolysis over Sn-Fe@C catalysts[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60153-6

Sn-Fe@C催化纤维素氢解制备丙酮醇和乳酸

doi: 10.1016/S1872-5813(21)60153-6
基金项目: 国家重点研发计划项目“纤维素类生物质生物、化学、热化学转化液体燃料机理与调控”(2018YFB1501402);国家自然科学基金青年基金“纤维素水相催化转化制备羟基丁酮的调控机制”(52006225)
详细信息
    作者简介:

    李思婵:lisc@ms.giec.ac.cn

    通讯作者:

    王海永(1989-),男,博士,主要从事生物质转化方面的研究。wanghy@ms.giec.ac.cn

    刘琪英(1975-),男,博士,研究员,主要从事生物质转化方面的研究。liuqy@ms.giec.ac.cn

  • 中图分类号: O643.3

Production of acetol and lactic acid from cellulose hydrogenolysis over Sn-Fe@C catalysts

Funds: National Key R&D Project “mechanism and regulation of liquid fuel conversion from cellulosic biomass by biochemistry and thermochemistry” (2018YFB1501402); The National Natural Science Foundation of China Youth Fund “Regulatory Mechanism of Hydroxybutanone from Cellulose Aqueous Phase Catalytic Conversion” (52006225)
  • 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。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。
  • 图  1  不同Sn/Fe配比以及不同焙烧温度催化剂的N2吸附-脱附等温曲线

    Figure  1  N2 adsorption-desorption isotherms of catalysts with different Sn/Fe ratios and different annealing temperatures

    图  2  不同Sn/Fe配比(A)以及不同焙烧温度(B)催化剂的XRD谱图

    Figure  2  XRD patterns of catalysts with different Sn/Fe ratios (A) and different annealing temperatures (B).

    Sn, PDF#04-0673; SnOx, PDF#13-0111 and PDF#41-1445; Fe3O4, PDF#75-1609; FeSn2, PDF#25-0415.

    图  3  不同Sn/Fe配比以及不同焙烧温度催化剂的Sn 3d(A、B)和Fe 2p(C)的XPS谱图

    Figure  3  Sn 3d(A、B) and Fe 2p(C) XPS spectra of catalysts with different Sn/Fe ratios(A) and different annealing temperatures(B、C). 3Sn1Fea600, used catalyst.

    图  4  不同焙烧温度催化剂的Py-FTIR谱图

    Figure  4  Py-FTIR spectra of catalysts with different annealing temperatures; treatment temperatures: 50 ℃(A); 200 ℃(B); 250 ℃(C).

    图  5  不同催化剂的CO2-TPD谱图

    Figure  5  CO2-TPD profiles of catalysts with different annealing temperatures

    图  6  不同催化剂对纤维素转化的影响

    Figure  6  The influence 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 ℃; 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 ℃; reation 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 g–0.06 g catalyst; (B) 0.4 g–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.

    1  3Sn1Fe@C600催化剂催化纤维素转化为丙酮醇和乳酸的反应路径

    1  Reaction routes for conversion cellulose to acetol and lactic acid over 3Sn1Fe@C600

    图  9  (A)催化剂回收次数对纤维素转化的影响,(B)3Sn1Fe@C600催化剂使用前后的TEM谱图,(C) 反应溶液的ICP分析

    Figure  9  (A) Effect of Recycle times of catalyst on cellulose conversion, (B) TEM Patterns of 3Sn1Fe@C600 catalyst before(a)-after(b) use. (C) ICP-AES analysis of reaction solution.

    表  1  不同催化剂的孔结构参数

    Table  1  Pore structural parameters of different catalysts

    CatalystSBETPvPd
    m2·g−1cm3·g−1nm
    1Sn1Fe@C600223.70.243.83
    2Sn1Fe@C600249.90.073.83
    4Sn1Fe@C600375.50.163.81
    5Sn1Fe@C600365.70.113.83
    3Sn1Fe@C400125.10.043.85
    3Sn1Fe@C50073.50.083.82
    3Sn1Fe@C600266.10.093.76
    3Sn1Fe@C700293.60.113.79
    3Sn1Fe@C800347.40.153.80
    SBET,BET surface area;PV,pore volume;Pd,pore diameter.
    下载: 导出CSV

    表  2  不同焙烧温度催化剂的B酸位和L酸位表征结果

    Table  2  Characterization results of B sites and L sites on catalysts with different annealing temperatures

    T(℃)CatalystB acid(µmol·g−1L acid(µmol·g−1B/L
    503Sn1Fe@C4005.4456.470.0964
    3Sn1Fe@C5003.0544.040.0691
    3Sn1Fe@C6002.0469.740.0293
    3Sn1Fe@C7002.1346.160.0461
    3Sn1Fe@C8004.5934.250.134
    2003Sn1Fe@C4004.3116.040.269
    3Sn1Fe@C5001.9518.400.106
    3Sn1Fe@C6001.1931.980.0372
    3Sn1Fe@C7001.2815.590.0818
    3Sn1Fe@C8002.3017.020.135
    2503Sn1Fe@C4000.7311.430.0638
    3Sn1Fe@C5000.836.660.125
    3Sn1Fe@C6000.7011.990.0576
    3Sn1Fe@C7000.814.720.172
    3Sn1Fe@C8001.357.050.191
    The amount of acid sites was determined by quantifying the area of the characteristic diffraction peak. B acid, BrÖnsted acid; L acid, Lewis acid.
    下载: 导出CSV

    表  3  其他催化剂对纤维素转化的影响

    Table  3  The influence of other catalysts on cellulose conversion

    CatalystConv. (%)Yield(C-mol%)
    AcetolLA1-HB3-HBGlyEGEthC6Total CA-L
    Sn@C60056.217.10.16.30007.7017.2
    Fe@C60031.94.37.900000012.1
    Sn@C600+Fe@C60086.717.711.51.30000029.1
    SnO63.423.34.23.80004.0027.5
    SnO224.3001.000007.00
    Reaction condition: 0.2 g cellulose; 0.08 g catalyst; 20 ml deionized water; reaction temperature 240 ℃; reation 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.
    下载: 导出CSV

    表  4  一系列不同催化剂对不同底物转化的影响

    Table  4  The influence of a series of different catalysts on different substrates conversion

    CatalystSubstrateConv. (%)Yield(C-mol%)
    AcetolLA1-HB3-HBGlyEGEthC6Total CA-L
    3Sn-1Fe@C600Glucose10016.93.12.33.3000020.0
    3Sn-1Fe@C600Fructose100126.804.7000018.8
    3Sn-1Fe@C600Glyceraldehyde10021.85.900002.0027.7
    3Sn-1Fe@C6001,3-Dihydroxyacetone100017.10000.10017.1
    3Sn-1Fe@C600Acetol0000000000
    3Sn-1Fe@C600Lactic acid0000000000
    Fe@C600Glucose10013.618.1000.100031.7
    Fe@Ca600Fructose100019.36.213.4000019.3
    Fe@C600Glyceraldehyde10020.521.000000041.5
    Fe@C6001,3-Dihydroxyacetone100021.300000021.3
    Sn@Ca600Glucose1007.24.51.90000011.7
    Sn@Ca600Fructose1007.24.100000011.3
    Sn@Ca600Glyceraldehyde10026.513.400000039.9
    Sn@Ca6001,3-Dihydroxyacetone10049.724.600000074.3
    SnOGlucose1005.60.80000006.4
    SnOFructose1008.11.705.1400009.8
    SnOGlyceraldehyde10015.016.100000031.1
    SnO1,3-Dihydroxyacetone10013.423.300000036.7
    SnO2Glucose100001.600008.60
    Reaction condition: 0.2 g cellulose; 0.08 g catalyst; 20 ml deionized water; reaction temperature 240 ℃; reation time 1 h and 4 Mpa H2. a): 0.2 g cellulose; 0.08 g catalyst; 20 ml deionized water; reaction temperature 240 ℃; reation 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.
    下载: 导出CSV
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  • 收稿日期:  2021-07-23
  • 修回日期:  2021-08-25
  • 网络出版日期:  2021-09-22

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