多酸/H2O2体系催化木质素解聚为酚类化合物

doi:10.3969/j.issn.0253-2417.2022.06.008

Abstract

Abstract:

The catalytic performance of four keggin-type polyoxometalates with different oxidability to degrade lignin into phenolic compounds in H₂O₂ system was compared. H₃PW₁₂O₄₀ and H₅PMo₁₀V₂O₄₀ catalysts had good effect on the depolymerization of lignin. Under the conditions of 140 ℃, 1 mL H₂O₂, 1 h, the yield of bio-oil could reach 54.60% by using H₃PW₁₂O₄₀ as catalyst, and the total yield of phenolic compounds could reach 6.38%. By using H₅PMo₁₀V₂O₄₀ as catalyst, the yield of bio-oil could reach 60.96% and the total yield of monophenol compounds could reach 11.67% at 140 ℃, 2 mL H₂O₂ and 1 h. Compared with HPW, PMo₁₀V₂ could significantly increase the yield of monophenols in H₂O₂ system due to its strong oxidizing ability. A series of characterizations such as FT-IR, 2D-HSQC, and GC-MS were performed to prove the effectiveness of the system in depolymerizing lignin into phenolic compounds.

Key words: lignin, heteropoly acid, oxidative degradation, phenolic compound

CLC Number:

TQ35

Ningxin WEI, Xixin DUAN, Wenbiao XU, Junyou SHI. Degradation of Lignin to Phenolic Compounds by Polyacid/H₂O₂ System[J]. Chemistry and Industry of Forest Products, 2022, 42(6): 55-63.

Figures/Tables 10

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References 31

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催化剂 catalyst	木质素降解率(w_L)/% lignin conversion rate	生物油产率(w_O)/% bio-oil yield
无催化剂without catalyst	64.00	31.59
H₃PW₁₂O₄₀(HPW)	81.50	54.60
H₃PMo₁₂O₄₀(HPMo)	79.00	47.00
H₄PMo₁₁VO₄₀(PMoV₁)	76.00	53.70
H₅PMo₁₀V₂O₄₀(PMoV₂)	72.85	55.24

催化剂 catalyst	H₂O₂/mL	w_L/%	w_O/%	香草醛/% vanillin	香草乙酮/% acetovanill- one	香草酸/% vanillic acid	丁香醛/% syringal dehyde	乙酰丁香酮/% acetosyring- one	对羟基苯甲醛/% p-hydroxyben- zald ehyde	对羟基苯乙酮/% p-hydroxyphen- yl ketone
	0.5	72.95	42.12	0.29	0.03	0.13	0.09	0.08	0.10	0.07
	1.0	81.52	54.60	0.42	0.08	0.26	0.17	0.17	0.22	0.13
HPW	1.5	83.45	47.35	0.26	0.07	0.29	0.14	0.16	0.23	0.08
	2.0	85.50	35.92	0.25	0.04	0.32	0.10	0.15	0.25	0.10
	2.5	87.80	30.78	0.19	0.02	0.25	0.07	0.14	0.19	0.05
	0.5	69.00	38.68	0.90	0.03	0.40	0.50	0.09	1.00	0.10
	1.0	72.85	55.24	1.02	0.05	0.55	0.63	0.13	1.66	0.26
PMoV₂	1.5	74.34	57.25	1.30	0.08	0.30	0.70	0.15	1.74	0.34
	2.0	77.45	60.96	1.45	0.10	0.20	0.91	0.19	1.80	0.39
	2.5	79.74	58.28	1.40	0.07	0.10	0.89	0.10	1.60	0.30

催化剂 catalyst	时间/min time	w_L/%	w_O/%	香草醛/% vanillin	香草乙酮/% acetovanill- one	香草酸/% vanillic acid	丁香醛/% syringal dehyde	乙酰丁香酮/% acetosyring- one	对羟基苯甲醛/% p-hydroxyben- zald ehyde	对羟基苯乙酮/% p-hydroxyphen- yl ketone
	30	65.00	44.88	0.34	0.04	0.09	0.06	0.09	0.14	0.07
	60	81.52	54.60	0.42	0.05	0.26	0.17	0.17	0.22	0.13
HPW	90	82.56	47.89	0.39	0.06	0.14	0.15	0.11	0.17	0.08
	120	79.80	34.08	0.33	0.03	0.10	0.08	0.09	0.10	0.07
	150	77.40	28.74	0.22	0.04	0.03	0.07	0.07	0.06	0.04
	30	59.92	40.74	0.63	0.05	0.10	0.70	0.10	1.90	0.30
	60	77.45	60.96	1.45	0.10	0.20	0.91	0.19	1.80	0.39
PMoV₂	90	74.44	55.44	1.44	0.09	0.25	0.97	0.18	1.40	0.38
	120	75.41	47.23	1.20	0.07	0.26	1.00	0.17	1.22	0.37
	150	63.44	30.76	1.10	0.06	0.27	0.95	0.16	0.90	0.35

催化剂 catalyst	温度/℃ temp.	w_L/%	w_O/%	香草醛/% vanillin	香草乙酮/% acetovanill- one	香草酸/% vanillic acid	丁香醛/% syringal dehyde	乙酰丁香酮/% acetosyring- one	对羟基苯甲醛/% p-hydroxyben- zald ehyde	对羟基苯乙酮/% p-hydroxyphen- yl ketone
	80	68.41	37.56	0.08	0.01	0.04	0.03	0.03	0.05	0.03
	100	72.36.	40.38	0.10	0.03	0.09	0.05	0.07	0.09	0.04
HPW	120	74.08	44.64	0.19	0.06	0.15	0.09	0.10	0.11	0.09
	140	81.52	54.60	0.42	0.08	0.26	0.17	0.17	0.22	0.13
	160	85.24	31.04	0.30	0.06	0.19	0.12	0.14	0.12	0.10
	80	52.10	30.78	0.40	0.03	0.05	0.30	0.05	1.00	0.10
	100	54.94	37.95	0.70	0.06	0.06	0.40	0.06	1.20	0.20
PMoV₂	120	59.35	45.84	0.90	0.07	0.10	0.60	0.07	1.30	0.23
	140	77.45	60.96	1.45	0.10	0.20	0.91	0.19	1.80	0.39
	160	79.75	37.48	1.30	0.09	0.15	0.70	0.09	1.40	0.30

催化剂 catalyst	用量/g dasage	w_L/%	w_O/%	香草醛/% vanillin	香草乙酮/% acetovanill- one	香草酸/% vanillic acid	丁香醛/% syringal dehyde	乙酰丁香酮/% acetosyring- one	对羟基苯甲醛/% p-hydroxyben- zald ehyde	对羟基苯乙酮/% p-hydroxyphen- yl ketone
无催化剂without catalyst	0	64.00	31.59	0.07	0.02	0.55	0.05	0.07	0.05	0.06
HPW	0.125	80.25	41.52	0.19	0.06	0.35	0.09	0.10	0.18	0.07
	0.250	81.52	54.60	0.42	0.08	0.26	0.17	0.17	0.22	0.13
	0.375	81.36	44.72	0.14	0.07	0.09	0.07	0.05	0.17	0.10
	0.500	82.56	34.56	0.13	0.06	0.17	0.08	0.07	0.10	0.09
PMoV₂	0.125	72.85	35.48	1.20	0.07	0.27	0.50	0.17	1.20	0.27
	0.250	77.45	60.96	1.45	0.10	0.20	0.91	0.19	1.80	0.39
	0.375	75.65	45.39	1.48	0.08	0.18	0.83	0.17	1.60	0.38
	0.500	78.46	30.76	1.50	0.09	0.19	0.78	0.15	1.50	0.37

Degradation of Lignin to Phenolic Compounds by Polyacid/H₂O₂ System

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保留时间/min retention time	化合物 compound	不同催化剂催化木质素降解后产物得率/% product yield of lignin degradation catalyzed by different catalysts
保留时间/min retention time	化合物 compound	HPW	PMoV₂
13.012	对羟基苯甲醛p-hydroxybenzaldehyde	0.22	1.80
13.741	香草醛vanillin	0.42	1.45
14.438	对羟基苯乙酮p-hydroxyphenyl ketone	0.13	0.39
15.890	香草乙酮acetovanillone	0.08	0.10
17.016	香草酸vanillic acid	0.26	0.20
18.260	丁香醛syringaldehyde	0.17	0.91
19.007	乙酰丁香酮acetosyringone	0.17	0.19
21.963	对香豆酸乙酯p-coumaric acid ethyl ester	2.90	3.66

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Degradation of Lignin to Phenolic Compounds by Polyacid/H2O2 System

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Degradation of Lignin to Phenolic Compounds by Polyacid/H₂O₂ System