Synthesis of γ-valerolactone through coupling of methyl levulinate hydrogenation with aqueous phase reforming of methanol over Pt/CoxAl catalyst
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摘要: 生物质衍生物乙酰丙酸甲酯（ML）加氢制备高值化学品γ-戊内酯（GVL）通常需要在高压氢气中进行，存在成本高和危险性大等问题。本研究采用Pt/CoxAl催化剂，将ML加氢反应与甲醇水液相重整（APRM）相耦合制备GVL，甲醇重整所获得的氢气原位用于ML的加氢反应，避免了外部氢源的使用，并考察了催化剂组成、反应溶液浓度和反应温度等条件对催化反应性能的影响。结果表明，Pt/CoxAl催化剂在该耦合反应体系中具有优异的催化性能，GVL收率高达98.2%，六次循环后性能仍保持稳定。多种表征手段证明，Pt0是ARPM和ML加氢反应的活性中心，Brønsted酸位点则促进ML水解和中间体的内酯化反应，两者之间的协同作用推动了GVL的生成。Pt与CoxAl载体之间存在强相互作用，Co含量适宜时，Pt/CoxAl催化剂具有较高的Pt分散度和丰富的Brønsted酸位点，因而表现出优异的催化性能。这些结果对探索新型高效的生物质衍生物制备燃料和化学品反应过程具有重要的参考价值。Abstract: The synthesis of high-value γ-valerolactone (GVL) from biomass-derived methyl levulinate (ML) conventionally requires a high-pressure hydrogenation process, which incurs significant costs and safety concerns. This study proposes an innovative approach to produce GVL by integrating ML hydrogenation with aqueous phase reforming of methanol (APRM) using Pt/CoxAl catalysts, thereby eliminating the need for an external hydrogen source. The influence of catalyst composition, methanol concentration, and reaction temperature on catalytic performance has been carefully examined. The results suggest that Pt/Co1Al demonstrated exceptional activity, yielding up to 98.2% GVL, and maintaining stable performance over multiple cycles. Characterization results revealed that Pt0 facilitates both APRM and ML hydrogenation, while Brønsted acid sites catalyze the hydrolysis of ML and lactonization of intermediates. The synergy between Pt0 and Brønsted acid sites is essential for GVL formation. The appropriate amount of Co not only enhances Pt dispersion but also increases Brønsted acid sites, thereby boosting catalytic efficiency. This work offers a sustainable and economically feasible strategy for transforming biomass derivatives into valuable fuels and chemicals.
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Key words:
- aqueous phase reforming of methanol /
- methyl levulinate /
- γ-valerolactone /
- Pt /
- hydrogenation
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图 1 CoxAl载体和对应Pt/CoxAl催化剂的XRD谱图
Figure 1 XRD patterns of various CoxAl supports and corresponding Pt/CoxAl catalysts
图 2 Pt/CoxAl催化剂的TEM图像（a）和Pt/Co1Al的Mapping图像（b）
Figure 2 TEM images of various Pt/CoxAl catalysts (a) and mapping images of Pt/Co1Al (b)
图 3 Pt/CoxAl催化剂的H2-TPR （a）、CO2-TPD （b）、NH3-TPD （c）和Py-FTIR谱图 （d）
Figure 3 H2-TPR profiles (a), CO2-TPD profiles (b), NH3-TPD profiles (c), and Py-FTIR spectra (d) of various Pt/CoxAl catalysts
图 4 Pt/CoxAl催化剂的CO原位DRIFTS吸附谱图
Figure 4 In-situ DRIFTS spectra of CO adsorption over various Pt/CoxAl catalysts
图 5 Pt/CoxAl催化剂的Al 2p/Pt 4f （a）、Co 2p （b）及O 1s （c） XPS谱图
Figure 5 XPS spectra of various Pt/CoxAl catalysts in the region of Al 2p/Pt 4f (a), Co 2p (b) and O 1s (c)
图 6 不同Pt/CoxAl催化剂上APRM耦合ML加氢的（a）反应性能，（b）H2产量，及不同浓度甲醇溶液中，Pt/Co0.5Al催化剂（c）反应性能，（d）H2产量
Figure 6 (a) Catalytic performance and (b) H2 production over various Pt/CoxA catalysts for coupling of ML hydrogenation with APRM; (c) catalytic performance and (d) H2 production on the Pt/Co0.5Al catalyst for ML hydrogenation coupled with APRM with different methanol concentrations
图 7 Pt/Co1Al催化剂上反应时间和温度对反应性能（a）、（c）及H2产量（b）、（d）的影响
Figure 7 Effect of reaction time and temperature on the yield of GVL (a), (c) and H2 production (b), (d) for the ML hydrogenation coupled with APRM over the Pt/Co1Al catalyst
图 8 Pt/Co1Al催化剂上ML原位加氢DRIFTS光谱谱图（a）和吸收带强度随温度的演变（b）
Figure 8 In-situ DRIFTS spectra of ML hydrogenation (a) and evolution of bands intensity with temperature (b) on Pt/Co1Al
图 9 Pt/Co1Al催化剂循环使用性能
Figure 9 Recyclability of the Pt/Co1Al catalyst for the ML hydrogenation coupled with APRM
表 1 Pt/CoxAl催化剂的载体粒径、Pt负载量及Co/Al物质的量比
Table 1 Particle size of the CoxAl supports and Pt loading and Co/Al molar ratio of the Pt/CoxAl catalysts
Sample Pt/% Co/Al
by ICPCo/Al
by XPSSupport particle size
before loading Pt/nmSupport particle size
after loading Pt/nmPt/Al2O3 0.95 − − − − Pt/Co0.25Al 0.95 0.24 0.19 11.6 10.6 Pt/Co0.5Al 0.95 0.51 0.24 17.1 15.8 Pt/Co0.75Al 0.96 0.73 0.37 20.6 17.2 Pt/Co1Al 0.93 0.96 0.51 31.1 23.0 
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表 2 Pt/CoxAl催化剂的酸碱性质
Table 2 Acidity/basicity of various Pt/CoxAl catalysts
Sample Basicity by CO2-TPD/
(μmol·g−1)Acidity by NH3-TPD/
(μmol·g−1)Acidity by Py-FTIR/(μmol·g−1) Brønsted Lewis Pt/Al2O3 1838 849 3.68 239.9 Pt/Co0.25Al 1481 570 4.49 159.4 Pt/Co0.5Al 1469 534 5.86 108.1 Pt/Co0.75Al 754 532 7.72 100.3 Pt/Co1Al 659 412 9.94 73.5
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表 3 Pt分散度、CO原位吸附DRIFTS实验及XPS测得的表面Pt相对含量
Table 3 Pt dispersion and relative Pt content determined by CO in-situ DRIFTS and XPS
Sample Pt dispersion/% Peak area of CO adsorption nPt/nPtCoAl/% Pt/Al2O3 42.7 4.1 0.28 Pt/Co0.25Al 31.8 3.2 0.40 Pt/Co0.5Al 37.9 11.6 0.72 Pt/Co0.75Al 49.9 17.9 1.44 Pt/Co1Al 66.8 27.0 1.78
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