Catalytic Hydrothermal Liquefaction of Lignin to Produce Aromatics over Perovskite Catalysts
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摘要: 为探究钙钛矿(LaBO3--LaCoO3、LaFeO3、LaNiO3)催化液化木质素的性能，以碱木质素为原料，将GC−MS、FT−IR、元素分析等实验表征手段与DFT计算相结合，考察了时间、温度、催化剂用量和B位阳离子对转化率、生物油收率及生物油化合物分布的影响。结果表明：三种钙钛矿都能促进木质素的裂解生成芳香族化合物。其中，LaCoO3对生物油产率有最大的促进作用，并在其添加量为5wt%、反应温度180 °C、时间60 min时生物油产率达到最大值67.20wt%，其次为LaNiO3和LaFeO3。且LaCoO3催化下单芳香族化合物的相对含量最高达89.59%。机理研究表明：LaBO3晶体表面的氧原子通过与木质素中的氧原子的吸附降低了木质素分子内键的解离能，其中LaCoO3的吸附能最大，并具有疏松多孔的形貌和适中的氧化还原能力，能够有效促进木质素分子内的C−C和CAr−OCH3的断裂，实现大分子解聚和脱甲氧基反应，生成苯酚等高附加值化合物。Abstract: To explore the catalytic performance of three perovskites (LaBO3--LaCoO3, LaFeO3, LaNiO3), the experimental characterization methods (GC−MS, FT−IR, elemental analysis) and DFT calculation were combined for researching liquefaction of lignin. The effects of time, temperature, catalyst dosage and B cation on the conversion rate, bio-oil yield and bio-oil component distribution were investigated. The results showed that all the three catalysts could promoted the liquefaction of lignin to produce aromatic compounds. Among them, LaCoO3 had the greatest promoting on bio-oil yield, and the highest bio-oil yield of 67.20wt% was obtained at 180 °C for 60 min over 5wt% LaCoO3, followed by LaNiO3 and LaFeO3. The relative content of mono-aromatic compounds reached 89.59% under LaCoO3. Mechanism studies suggested that the adsorption of oxygen atoms on the surface of LaBO3 crystal with lignin reduced the dissociation energy of bonds of lignin. Moreover, LaCoO3 had moderate redox capacity, largest adsorption energy, loose and porous morphology, which could effectively promoted the fracture of C−C and CAr−OCH3 of lignin, so that achieved macromolecular depolymerization and demethoxylation reaction to produce high value-added compounds such as phenol.
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Key words:
- lignin /
- perovskite /
- liquefaction /
- bio-oil /
- DFT
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Figure 2 Effect of catalyst dosage on HTL of lignin and component distribution of bio-oil over LaCoO3
(Reaction condition: 2.000g AL+150ml methanol, temperature: 180 °C, time: 60min)
Figure 3 Effect of reaction temperature on HTL of lignin and component distribution of bio-oil over LaBO3
（a: LaCoO3 b: LaFeO3 c: LaNiO3 Reaction condition: 2.000 g AL + 150ml methanol, time: 60 min, Catalyst dose: 5.0wt%）
Figure 4 Effect of reaction time on HTL of lignin and component distribution of bio-oil over LaCoO3
(Reaction condition: 2.000g AL+150ml methanol, temperature: 180 °C, Catalyst dose: 5.0wt%)
Figure 5 FT-IR spectra analysis of raw lignin and residue produced over non-catalytic and catalytic HTL
（Reaction condition: 2.000 g AL + 150 ml methanol, time: 60 min, Catalyst dose: 5.0wt%）
Figure 6 Adsorption energy and views of adsorption model over LaBO3
a: Calculated energies for molecular adsorption. b: Views of the adsorption model (C: black, H: white, O: red, La: blue, Co: purple, Fe: yellow, Ni: green)
Figure 7 Views of adsorption model and molecular structure before and after adsorption of GGE over LaCoO3
a: Views of the adsorption model. b: Molecular structure before and after adsorption of GGE (C: black, H: white, O: red, La: blue, Co: purple)
Table 1 Elemental analysis of raw lignin and residue produced under non-catalytic and catalytic (LaCoO3, LaFeO3, LaNiO3) HTL (Reaction condition: 2.000 g AL + 150 ml methanol, time: 60 min, temperature: 180 °C, Catalyst dose: 5.0wt%)
Sample C,% H,% N,% O,% Lignin 40.72 4.13 0.51 53.07 Non-catalyst 38.29 3.95 0.50 54.26 LaCoO3 32.25 5.28 0.62 57.62 LaFeO3 33.43 5.57 0.59 56.63 LaNiO3 32.18 5.24 0.67 56.59 
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Table 2 Major oxygen-contained bond length of guaiacol over LaBO3
Catalyst Oxygen-contained bond type Bio-oil yield under optimal conditions（wt%） CAr–OCH3 CArO–CH3 − Bond Lengtha/Å a 1.387 1.433 43.73 LaCoO3 Bond Lengthb/Å b 1.389 1.431 67.20 △c/Å 0.002 −0.002 LaFeO3 Bond Lengthb/Å b 1.393 1.434 56.69 △c/Å 0.006 0.001 LaNiO3 Bond Lengthb/Å b 1.390 1.432 59.74 △c/Å 0.003 −0.001 a: Bond length in molecular alone.
b: Bond lengths of molecular adsorbed by different perovskite catalysts
c: Difference between the bond length in molecular alone and in adsorbed molecular.
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