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

摘要/Abstract

摘要：

在H₂O₂体系下以Keggin型多金属氧酸盐为催化剂，催化降解木质素为酚类化合物, 比较了4种不同氧化性的Keggin型多金属氧酸盐的催化性能。实验结果表明：H₂O₂体系下，H₃PW₁₂O₄₀和H₅PMo₁₀V₂O₄₀对木质素解聚具有良好催化效果，在温度140 ℃，1 mL H₂O₂，1 h的条件下，H₃PW₁₂O₄₀为催化剂时生物油产率54.60%，单酚类化合物总产率可达6.38%；在温度140 ℃，2 mL H₂O₂，1 h的条件下H₅PMo₁₀V₂O₄₀为催化剂时生物油产率60.96%，单酚类化合物总产率可达11.67%。与HPW对比，强氧化性PMo₁₀V₂在H₂O₂体系下，可显著提高单酚类化合物的产率。对反应产物进行了FT-IR，2D-HSQC，GC-MS等一系列表征分析证明该体系在解聚木质素为酚类化合物中具有有效性。

关键词: 木质素, 杂多酸, 氧化降解, 酚类化合物

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

中图分类号:

TQ35

尉宁馨, 段喜鑫, 徐文彪, 时君友. 多酸/H₂O₂体系催化木质素解聚为酚类化合物[J]. 林产化学与工业, 2022, 42(6): 55-63.

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.

图/表 10

表1

表2

表3

表4

表5

图1

图2

图3

图4

表6

参考文献 31

1	NAIK S N , GOUD V V , ROUT P K , et al. Production of first and second generation bio fuels: A comprehensive review[J]. Renewable & Sustainable Energy Reviews, 2010, 14 (2): 578- 597.
2	BEHLING R , VALANGE S , CHATEL G . Heterogeneous catalytic oxidation for lignin valorization into valuable chemicals: What results? what limitations? what trends?[J]. Green Chemistry, 2016, 18, 1839- 1854. doi: 10.1039/C5GC03061G
3	LIN F , LIU C , WANG X , et al. Catalytic oxidation of biorefinery corncob lignin via zirconium(Ⅳ) chloride and sodium hydroxide in acetonitrile/water: A functionality study[J]. Science of The Total Environment, 2019, 675, 203- 212. doi: 10.1016/j.scitotenv.2019.04.224
4	HU J , ZHANG Q , LEE D J . Kraft lignin biorefinery: A proposal[J]. Bioresource Technology, 2018, 247, 1181- 1183. doi: 10.1016/j.biortech.2017.08.169
5	JUNG K A , WOO S B , LIM S-R , et al. Pyrolytic production of phenolic compounds from the lignin residues of bioethanol processes[J]. Chemical Engineering Journal, 2015, 259, 107- 116. doi: 10.1016/j.cej.2014.07.126
6	ZHU D , LIANG N , ZHANG R , et al. Insight into depolymerization mechanism of bacterial laccase for lignin[J]. ACS Sustainable Chemistry & Engineering, 2020, 8 (34): 12920- 12933.
7	KAWAMATA Y, ISHIMARU H, YAMAGUCHI K, et al. Catalytic cracking of lignin model compounds and degraded lignin dissolved in inert solvent over mixed catalyst of iron oxide and MFI zeolite for phenol recovery[J/OL]. Fuel Processing Technology, 2020, 197: 106190[2021-06-08]. https://doi.org/10.1016/j.fuproc.2019.106190.
8	MELRO E , FILIPE A , SOUSA D , et al. Dissolution of kraft lignin in alkaline solutions[J]. International Journal of Biological Macromolecules, 2020, 148, 688- 695. doi: 10.1016/j.ijbiomac.2020.01.153
9	MOUTHIER T , APPELDOORN M M , PEL H , et al. Corn stover lignin is modified differently by acetic acid compared to sulfuric acid[J]. Industrial Crops and Products, 2018, 121, 160- 168. doi: 10.1016/j.indcrop.2018.05.008
10	CHIO C , SAIN M , QIN W . Lignin utilization: A review of lignin depolymerization from various aspects[J]. Renewable and Sustainable Energy Reviews, 2019, 107, 232- 249. doi: 10.1016/j.rser.2019.03.008
11	ABDELAZIZ O Y , MEIER S , PROTHMANN J , et al. Oxidative depolymerisation of lignosulphonate lignin into low-molecular-weight products with Cu-Mn/δ-Al₂O₃[J]. Topics in Catalysis, 2019, 62 (7): 639- 648.
12	DENG W , ZHANG H , WU X , et al. Oxidative conversion of lignin and lignin model compounds catalyzed by CeO₂-supported Pd nanoparticles[J]. Green Chemistry, 2015, 17 (11): 5009- 5018. doi: 10.1039/C5GC01473E
13	SHILPY M , EHSAN M A , ALI T H , et al. Performance of cobalt titanate towards H₂O₂ based catalytic oxidation of lignin model compound[J]. RSC Advances, 2015, 5 (97): 79644- 79653. doi: 10.1039/C5RA14227J
14	GHAREHKHANI S , ZHANG Y , FATEHI P . Lignin-derived platform molecules through TEMPO catalytic oxidation strategies[J]. Progress in Energy and Combustion Science, 2019, 72, 59- 89. doi: 10.1016/j.pecs.2019.01.002
15	OUYANG X , RUAN T , QIU X . Effect of solvent on hydrothermal oxidation depolymerization of lignin for the production of monophenolic compounds[J]. Fuel Processing Technology, 2016, 144, 181- 185. doi: 10.1016/j.fuproc.2015.12.019
16	LIN Z Y , ZHENG X L , LONG J X , et al. Oxidative cleavage of C—O and benzene ring in lignin catalyzed bypolyoxometalate ionic liquids[J]. CIESC Journal, 2020, 71 (12): 5541- 5550.
17	YANG J , JANIK M J , MA D , et al. Location, acid strength, and mobility of the acidic protons in Keggin 12-H₃PW₁₂O₄₀: A combined solid-state NMR spectroscopy and DFT quantum chemical calculation study[J]. Journal of the American Chemical Society, 2005, 127 (51): 18274- 18280. doi: 10.1021/ja055925z
18	DENG W , ZHANG Q , WANG Y . Polyoxometalates as efficient catalysts for transformations of cellulose into platform chemicals[J]. Dalton Transactions, 2012, 41 (33): 9817- 9831. doi: 10.1039/c2dt30637a
19	陈维林, 王恩波. 多酸化学[M]. 北京: 科学出版社, 2013.
	CHEN W L , WANG E B . Polyacid Chemistry[M]. Beijing: Science Press, 2013.
20	HOU Z , OKUHARA T . Condensation of benzene and aqueous formaldehyde to diphenylmethane in a biphasic system consisting of an aqueous phase of heteropolyacid[J]. Journal of Molecular Catalysis A Chemical, 2003, 206 (1/2): 121- 130.
21	LI Y , ZHANG X , LI Z , et al. Full utilization of lignocellulose with ionic liquid polyoxometalates in a one-pot three-step conversion[J]. ChemSusChem, 2019, 12 (22): 4936- 4945. doi: 10.1002/cssc.201902503
22	WANG M , LU J , ZHANG X , et al. Two-step, catalytic C—C bond oxidative cleavage process converts lignin models and extracts to aromatic acids[J]. ACS Catalysis, 2016, 6 (9): 6086- 6090. doi: 10.1021/acscatal.6b02049
23	HU L H , ZHOU Y H , LIU R J , et al. Progress of production of phenolic compounds via oxidative degradtion of lignin[J]. Biomass Chemical Engineering, 2012, 46 (1): 23- 33. doi: 10.3969/j.issn.1673-5854.2012.01.006
24	ⅡYAMA K , LAM T , STONE B A . Phenolic acid bridges between polysaccharides and lignin in wheat internodes[J]. Phytochemistry, 1990, 29 (3): 733- 737. doi: 10.1016/0031-9422(90)80009-6
25	LI Z , CAO J , HUANG K , et al. Alkaline pretreatment and the synergic effect of water and tetralinenhances the liquefaction efficiency of bagasse[J]. Bioresource Technology, 2015, 177, 159- 168. doi: 10.1016/j.biortech.2014.11.043
26	SCHULTZ T P , TEMPLETON M C . Proposed mechanism for the nitrobenzene oxidation of lignin[J]. Holzforschung, 1986, 40 (2): 93- 97. doi: 10.1515/hfsg.1986.40.2.93
27	XU W, LI X, SHI J. Oxidative depolymerization of cellulolytic enzyme lignin over silicotungvanadium polyoxometalates[J/OL]. Polymers, 2019, 11(3): 564[2021-06-08]. https://doi.org/10.3390/polym11030564.
28	WAHYUDIONO , SASAKI M , GOTO M . Recovery of phenolic compounds through the decomposition of lignin in near and supercritical water[J]. Chemical Engineering and Processing: ProcessIntensification, 2008, 47 (9): 1609- 1619.
29	AZARPIRA A , RALPH J , LU F . Catalytic alkaline oxidation of lignin and its model compounds: A pathway to aromatic biochemicals[J]. BioEnergy Research, 2014, 7 (1): 78- 86. doi: 10.1007/s12155-013-9348-x
30	邓嘉雯, 杨海艳, 史正军, 等. 有机-无机溶剂连续抽提巨龙竹木质素及其结构表征[J]. 生物质化学工程, 2016, 50 (3): 1- 7. doi: 10.3969/j.issn.1673-5854.2016.03.001
	DENG J W , YANG H Y , SHI Z J , et al. Characterization of lignin fractions isolated from Dendrocalamus sinicus with organic-inorganic sequential extraction[J]. Biomass Chemical Engineering, 2016, 50 (3): 1- 7. doi: 10.3969/j.issn.1673-5854.2016.03.001
31	KUMAR A, BISWAS B, SAINI K, et al. Effect of hydrogen peroxide on the depolymerization of prot lignin[J/OL]. Industrial Crops and Products, 2020, 150: 112355[2021-06-08]. https://doi.org/10.1016/j.indcrop.2020.112355.

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

多酸/H₂O₂体系催化木质素解聚为酚类化合物

Degradation of Lignin to Phenolic Compounds by Polyacid/H₂O₂ System

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们

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

[1]	徐富成, 李梅, 夏建陵, 许利娜, 丁海阳, 李守海. 去除木质素木材/聚甲基丙烯酸甲酯复合材料制备及性能研究[J]. 林产化学与工业, 2022, 42(6): 17-23.
[2]	罗文琪, 谢益民, 张功侠. 杨木心材白腐菌预处理及生物化机浆制浆性能研究[J]. 林产化学与工业, 2022, 42(6): 91-98.
[3]	傅成龙, 孟霞, 高超, 刘忠明, 王守娟, 孔凡功. 木质素磺酸钠双网络水凝胶的制备及其性能研究[J]. 林产化学与工业, 2022, 42(5): 23-29.
[4]	郑昊, 周景辉, 李尧. 生物质基炭气凝胶的制备及其应用于超级电容器[J]. 林产化学与工业, 2022, 42(5): 76-82.
[5]	徐广六, 赵智辰, 张瑞, 张寒, 朱均均. 酸性水溶助剂对竹屑组分分离的研究[J]. 林产化学与工业, 2022, 42(4): 16-24.
[6]	王颖, 安邦, 徐明聪, 岳金权, 刘守新, 李伟. 水热-硝酸氧化合成发蓝光和绿光木质素基碳点的研究[J]. 林产化学与工业, 2022, 42(4): 33-39.
[7]	赵辉, 徐雁茹, 任浩. 高替代率木质素酚醛树脂在胶合板中的应用性能比较[J]. 林产化学与工业, 2022, 42(4): 75-80.
[8]	朱文祥, 谌凡更, 何甜, 宿宇辉, 刘运思. 磺甲基化乙酸木质素制备农药分散剂及其性能评价[J]. 林产化学与工业, 2022, 42(3): 19-26.
[9]	杜艺飞, 蒲悦, 张力平, 赵强, 宋先亮. 木质素在直接生物质燃料电池中产电性能研究[J]. 林产化学与工业, 2022, 42(3): 75-82.
[10]	郭奇, 许伟, 刘军利. 磷酸法木质素基活性炭的制备及其电化学性能研究[J]. 林产化学与工业, 2022, 42(2): 31-38.
[11]	胡婷婷, 佟淑慧, 卫家祺, 张磊, 赵佳宁. 酶解木质素炭的制备及其电化学性能研究[J]. 林产化学与工业, 2022, 42(2): 47-55.
[12]	叶俊虎, 赵强莉, 武磊, 付圣熠, 马凯超, 熊振龙. 木质素/聚氯乙烯膜的制备及其亲水性研究[J]. 林产化学与工业, 2022, 42(1): 95-100.
[13]	马春慧, 张继芳, 李伟, 罗沙, 刘守新, 李坚. 电化学催化木质素解聚的研究进展[J]. 林产化学与工业, 2022, 42(1): 110-122.
[14]	金凯楠, 左宋林, 桂有才, 申保收. 木质素制备燃料电池阴极电催化炭材料研究(Ⅰ)——改性酶解木质素的热解过程[J]. 林产化学与工业, 2021, 41(6): 1-9.
[15]	金凯楠, 左宋林, 桂有才, 申保收, 王珊珊, 胡欣. 木质素制备燃料电池阴极电催化炭材料研究(Ⅱ)——改性酶解木质素炭的化学结构演变[J]. 林产化学与工业, 2021, 41(6): 10-18.