路易斯酸复合Pt/ZrO2协同催化碱木质素还原降解制备酚类低聚物

doi:10.3969/j.issn.0253-2417.2020.06.006

Abstract

Abstract:

A series of Pt/ZrO₂ and Lewis acid co-catalytic systems, such as Pt/ZrO₂-FeCl₃, Pt/ZrO₂-CuCl₂ and Pt/ZrO₂-NiCl₂, were prepared for selective depolymerization of alkali lignin to generate oligomers with high content of phenolic hydroxyl groups and low content of solid residue. The effects of reaction parameters such as the component and dosage of catalysts, hydrogen pressure, reaction temperature and reaction time on the reductive depolymerization of alkali lignin were investigated. GPC, FT-IR, ³¹P NMR, ¹³C NMR and 2D-HSQC NMR were conducted to reveal the changes of structure and linkage in alkali lignin and its depolymerized products. The results showed that the synergetic catalysis of Pt/ZrO₂ and Lewis acid(FeCl₃, CuCl₂, NiCl₂) exhibited higher catalytic activity and better selectivity for phenolic compounds than Pt/ZrO₂. Pt/ZrO₂-FeCl₃ exhibited the best catalytic activity among Pt/ZrO₂-FeCl₃, Pt/ZrO₂-CuCl₂ and Pt/ZrO₂-NiCl₂. Under the optimal conditions of mass ratio of Pt/ZrO₂-FeCl₃ to lignin 1:15, mass ratio of FeCl₃ to Pt/ZrO₂ 0.2, reaction temperature 300 ℃, reaction time 3 h, hydrogen pressure 4 MPa, the given products with higher content of phenolic hydroxyl groups(362 mg/g) and lower content of solid residue(2.70%) were obtained, as well as, the conversion rate of lignin and the number average molecular mass(M_n) of the product were 89.0% and 998, respectively. Furthermore, the comparative structure characterization of the alkali lignin, Pt/ZrO₂ catalytic depolymerization product(DL1) and Pt/ZrO₂-FeCl₃ catalytic depolymerization product(DL2) demonstrated that S units were more prone to be damaged during the reductive depolymerization of alkali lignin, the cleavage of methoxy groups and intramolecular β-O-4 and β-β linkages were more effective facilitated by Pt/ZrO₂-FeCl₃ than Pt/ZrO₂.

Key words: alkali lignin, Pt/ZrO₂, Lewis acids, synergetic catalysis, reductive depolymerization

CLC Number:

TQ35

Qian YANG, Guifeng LIU, Can JIN, Zhenwu KONG. Synergetic Effects of Pt/ZrO₂ and Lewis Acid on Reductive Depolymerization of Alkali Lignin to Phenolic Oligomers[J]. Chemistry and Industry of Forest Products, 2020, 40(6): 37-49.

Figures/Tables 16

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催化剂catalyst	w_DL/%	w_SR/%	M_n/(g·mol^-1)	w_OH/(mg·g^-1)	w_Ar-OH/(mg·g^-1)
Pd/C	82.9	6.87	1730	351	273
Pt/Al₂O₃	77.6	10.93	1826	347	276
Pt/ZrO₂	82.3	5.07	1284	362	296
Pt/ZrO₂-FeCl₃	89.0	2.70	998	417	362
Pt/ZrO₂-NiCl₂	90.6	6.53	1197	426	361
Pt/ZrO₂-CuCl₂	87.6	6.43	1123	408	351

基团 group	化学位移(δ) chemical shift	不同样品的羟值hydroxyl value of different samples/(mmol·g^-1)
基团 group	化学位移(δ) chemical shift	碱木质素alkali lignin	DL1	DL2
脂肪族羟基aliphatic OH	145.5~150.5	0.48	0.41	0.16
S型结构羟基5-substituted OH	140.0~144.7	2.46	2.83	2.44
G型结构羟基guaiacyl OH	138.2~140.0	0.65	2.10	2.52
H型结构羟基p-hydroxyphenyl OH	137.3~138.2	0.06	0.33	0.60
羧酸羟基carboxylic acid OH	133.6~136.6	0.07	0.07	0.12
酚羟基phenolic OH	137.3~144.7	3.17	5.26	5.56
总羟基total hydroxyl		3.65	5.67	5.72

样品sample	S/%	G/%	H/%	S/G	—OCH₃/%	β-O-4/%	β-β/%	β-5/%	β-1/%
碱木质素alkali lignin	79.2	20.3	0.5	3.89	38.3	79.1	15.1	2.8	3.0
DL1	48.6	50.8	0.6	0.96	24.2	66.5	30.8	0.2	2.5
DL2	32.0	47.0	21.0	0.69	9.2	55.0	40.8	4.2	—

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Synergetic Effects of Pt/ZrO₂ and Lewis Acid on Reductive Depolymerization of Alkali Lignin to Phenolic Oligomers

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Synergetic Effects of Pt/ZrO2 and Lewis Acid on Reductive Depolymerization of Alkali Lignin to Phenolic Oligomers

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Synergetic Effects of Pt/ZrO₂ and Lewis Acid on Reductive Depolymerization of Alkali Lignin to Phenolic Oligomers