钙钛矿催化木质素水热液化

娄静; 廖玮婷; 王智玉; 李璐; 李雁; 解新安

doi:10.1016/S1872-5813(22)60004-5

钙钛矿催化木质素水热液化

doi: 10.1016/S1872-5813(22)60004-5

华南农业大学食品学院, 广东广州 510642

基金项目: 国家自然科学基金(21576107)资助

详细信息

通讯作者:
E-mail: xinanxie@scau.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2022-01-04
- 修回日期: 2022-02-12
- 网络出版日期: 2022-05-19
- 刊出日期: 2022-08-26

Hydrothermal liquefaction of lignin to aromatics over the perovskite catalysts

College of Food Science, South China Agricultural University, Guangzhou 510642, China

Funds: The project was supported by the National Natural Science Foundation of China (21576107)

摘要

摘要: 以碱木质素为原料，采用GC-MS、FT-IR、元素分析等实验表征手段并结合DFT计算，对LaBO₃钙钛矿（LaCoO₃、LaFeO₃和LaNiO₃）催化液化木质素的性能进行了研究，考察了反应时间、温度、催化剂用量和B位阳离子对木质素转化率、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，但LaCoO₃木质素液化催化性最好，其次为LaNiO₃和LaFeO₃。LaCoO₃添加量为5%、180 °C下反应60 min时，生物油产率最高达67.20%，单芳香族化合物的相对含量最高达89.59%。LaBO₃晶体表面的氧原子通过吸附木质素中的氧原子降低了木质素分子内键的解离能（LaCoO₃的吸附能最大），同时其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C_Ar−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。
- 木质素 /
- 钙钛矿 /
- 液化 /
- 生物油 /
- DFT计算
Abstract: The catalytic performance of three LaBO₃ perovskites including LaCoO₃, LaFeO₃ and LaNiO₃ in the liquefaction of lignin was investigate through a series of experimental characterization methods such as GC-MS, FT-IR and elemental analysis as well as DFT calculation. The effects of reaction time, temperature, catalyst amount and B cation on the lignin conversion, bio-oil yield and products distribution were considered. The results indicate that all three perovskite catalysts can promote the liquefaction of lignin to produce aromatic compounds; among them, LaCoO₃ shows the highest catalytic performance, following by LaNiO₃ and LaFeO₃. In particular, by using 5% LaCoO₃, the bio-oil yield achieves 67.20% after reaction at 180 °C for 60 min, whilst the relative content of mono-aromatic compounds reaches 89.59%. The adsorption of oxygen atoms on the LaBO₃ crystal surface conduces to the decrease of bond dissociation energy for lignin (LaCoO₃ shows the moderate redox capacity and greatest adsorption energy), whilst the loose and porous morphology can effectively promote the fracture of C−C and C_Ar−OCH₃ of lignin. All these contribute to the macromolecular depolymerization and demethoxylation reaction, producing high value-added compounds such as phenol.
- lignin /
- perovskite /
- liquefaction /
- bio-oil /
- DFT calculation

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FIG. 1768. FIG. 1768.

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图 1 三种钙钛矿催化剂的表征

Figure 1 FT-IR spectra (a), XRD patterns (b) and SEM images (c) of three LaBO₃ perovskites

(a): FT-IR; (b): XRD; (c): SEM

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图 2 催化剂用量对LaCoO₃上木质素HTL和生物油组分分布的影响

Figure 2 Effect of catalyst dosage on the lignin conversion, bio-oil yield, and product distribution for the HTL of lignin over LaCoO₃

Reaction conditions: 2.000 g AL + 150 mL methanol, reaction at 180 ℃ for 60 min

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图 3 反应温度对LaBO₃上木质素的液化及生物油化合物分布的影响

Figure 3 Effect of reaction temperature on the HTL of lignin over three LaBO₃ perovskites

(a): LaCoO₃; (b): LaFeO₃; (c): LaNiO₃ Reaction conditions: 2.000 g AL + 150 mL methanol; reaction time, 60 min; catalyst dose, 5.0%

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图 4 反应时间对LaCoO₃催化木质素液化和生物油组分分布的影响

Figure 4 Effect of reaction time on HTL of lignin over LaCoO₃

Reaction condition: 2.000 g AL + 150 mL methanol, 180 ℃, catalyst dose: 5.0%

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图 5 木质素原料及液化木质素产生残渣的FT-IR谱图

Figure 5 FT-IR spectra of raw lignin and residue produced from lignin HTL over various LaBO₃ perovskite catalysts

Reaction conditions: 2.000 g AL + 150 mL methanol, reaction time, 60 min; catalyst dose, 5.0%

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图 6 模型分子在LaBO₃表面的吸附模型及吸附能

a:吸附能， b:吸附模型 (C:黑色，H:白色，O:红色，La:蓝色，Co:紫色，Fe:黄色，Ni:绿色)

Figure 6 Adsorption energy (a) and views of adsorption model (b) of m-methoxy-phenol on 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)

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图 7 模型分子（GGE）与LaCoO₃表面的吸附模型及吸附前后分子结构

Figure 7 Adsorption energy (a) and views of adsorption model (b) of guaiac-based glycerol ether (GGE) on LaBO₃

(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)

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表 1 木质素原料及液化木质素产生残渣的元素分析

Table 1 Elemental composition (%) of the raw lignin and residue produced under non-catalytic and catalytic HTL

Sample	Ultimate analysis w /%
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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表 2 愈创木酚在LaBO₃上吸附后的主要含氧键长

Table 2 Major oxygen-contained bond length of guaiacol over three LaBO₃ perovskite catalysts

Catalyst		Oxygen-contained bond type		Bio-oil yield under optimal conditions w/%
Catalyst		C_Ar–OCH₃	C_ArO–CH₃	Bio-oil yield under optimal conditions w/%
−	Bond length^a/Å	1.387	1.433	43.73
LaCoO₃	Bond length^b/Å	1.389	1.431	67.20
	△^c/Å	0.002	− 0.002
LaFeO₃	Bond length^b/Å	1.393	1.434	56.69
	△^c/Å	0.006	0.001
LaNiO₃	Bond length^b/Å	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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