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

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (6): 37-49.doi: 10.3969/j.issn.0253-2417.2020.06.006

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

杨倩¹^,², 刘贵锋¹, 金灿¹, 孔振武¹^,*()

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2020-03-19 出版日期:2020-12-28 发布日期:2020-12-29
通讯作者: 孔振武 E-mail:kongzwlhs@163.com
作者简介:孔振武, 研究员, 博士生导师, 主要从事生物基聚合物材料研究; E-mail:kongzwlhs@163.com
杨倩(1994-), 女, 陕西汉中人, 硕士生, 主要从事天然资源化学与利用研究
基金资助:
国家重点研发计划资助项目(2017YFD0601003)

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

Qian YANG¹^,², Guifeng LIU¹, Can JIN¹, Zhenwu KONG¹^,*()

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2020-03-19 Online:2020-12-28 Published:2020-12-29
Contact: Zhenwu KONG E-mail:kongzwlhs@163.com

摘要/Abstract

摘要：

以路易斯酸FeCl₃、CuCl₂和NiCl₂复合Pt/ZrO₂催化碱木质素还原降解制备高酚羟基含量活性低聚物，考察了催化剂组成和用量、反应温度、反应时间、氢气压力等对碱木质素还原降解反应的影响。采用GPC、FT-IR、³¹P NMR、¹³C NMR及2D-HSQC NMR等表征分析了碱木质素及其降解产物，探讨了降解前后碱木质素的化学结构、组成及化学键变化。研究结果表明：与Pt/ZrO₂相比，路易斯酸复合Pt/ZrO₂具有较高的协同催化反应活性，可有效提高降解产物的产率及生成酚类化合物的选择性，Pt/ZrO₂-FeCl₃具有最优催化活性。适宜的催化反应条件为：催化剂Pt/ZrO₂-FeCl₃与碱木质素质量比为1：15、催化剂中FeCl₃与Pt/ZrO₂质量比值为0.2、反应温度300℃、反应时间3 h、氢气压力4 MPa，该条件下碱木质素催化还原降解得到的低聚物数均相对分子质量（M_n）为998，产率为89%，且具有较高的酚羟值（362 mg/g）和较低的固体残渣率（2.70%）。对碱木质素、Pt/ZrO₂催化降解产物（DL1）和Pt/ZrO₂-FeCl₃催化降解产物（DL2）的结构表征表明：在木质素还原降解反应过程中，紫丁香基（S）型结构单元比愈创木基（G）型结构单元更易被破坏，且Pt/ZrO₂-FeCl₃催化剂对碱木质素分子结构中—OCH₃、β-O-4及β-β键断裂表现出较高的选择性。

关键词: 碱木质素, Pt/ZrO₂, 路易斯酸, 协同催化, 还原降解

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

中图分类号:

TQ35

杨倩, 刘贵锋, 金灿, 孔振武. 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[J]. 林产化学与工业, 2020, 40(6): 37-49.

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.

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参考文献 49

1	FIGUEIREDO P , LINTINEN K , HIRVONEN J , et al. Properties and chemical modifications of lignin:Towards lignin-based nanomaterials for biomedical applications[J]. Progress in Materials Science, 2018, 93, 233- 269.
2	LAURICHESSE S , AVÉROUS L . Chemical modification of lignins:Towards biobased polymers[J]. Progress in Polymer Science, 2014, 39 (7): 1266- 1290.
3	ZAKZESKI J , BRUIJNINCX P C A , JONGERIUS A L , et al. The catalytic valorization of lignin for the production of renewable chemicals[J]. Chemical Reviews, 2010, 110 (6): 3552- 3599.
4	SUN D, WANG B, WANG H M, et al.Structural elucidation of tobacco stalk lignin isolated by different integrated processes[J/OL]. Industrial Crops & Products, 2019, 140: 1-9[2020-01-10].https://doi.org/10.1016/j.indcrop.2019.111631.
5	AYESHA K , VAISHAKH N , CARLOS C J , et al. Lignin-based composite materials for photocatalysis and photovoltaics[J]. Topics in Current Chemistry, 2018, 376 (3): 19- 50.
6	CHEN C , JIN D X , OUYANG X P , et al. Effect of structural characteristics on the depolymerization of lignin into phenolic monomers[J]. Fuel, 2018, 223, 366- 372.
7	LIMARTA S O , HA J M , PARK Y K , et al. Efficient depolymerization of lignin in supercritical ethanol by a combination of metal and base catalysts[J]. Journal of Industrial and Engineering Chemistry, 2018, 57, 45- 54.
8	AN L L , SI C L , WANG J H , et al. Enhancing the solubility and antioxidant activity of high-molecular-weight lignin by moderate depolymerization via in situ ethanol/acid catalysis[J]. Industrial Crops & Products, 2019, 128, 177- 185.
9	ZHENG Y L, GUO M, ZHOU Q T, et al.Effect of lignin degradation product sinapyl alcohol on laccase catalysis during lignin degradation[J]. Industrial Crops & Products, 2019, 139: 1-13[2020-01-10].https://doi.org/10.1016/j.indcrop.2019.111544.
10	HAO C , LIU T , ZHANG S , et al. A high lignin content removable and glycol-assisted repairable coating based on dynamic covalent bonds[J]. ChemSusChem, 2019, 12 (5): 1049- 1058.
11	ZHANG S , LIU T , HAO C , et al. Preparation of a lignin-based vitrimer material and its potential use for recoverable adhesive[J]. Green Chemistry, 2018, 20 (13): 2995- 3000.
12	NIU M G , HOU Y C , WU W Z , et al. Degradation of lignin in NaVO₃-H₂SO₄aqueous solution with oxygen[J]. Fuel Processing Technology, 2017, 161, 295- 303.
13	HAKONEN K J , GONZÁLEZ ESCOBEDO J L , MERIÖ-TALVIO H , et al. Ethanol organosolv lignin depolymerization with hydrogen over a Pd/C catalyst[J]. ChemistrySelect, 2018, 3 (6): 1761- 1771.
14	XIN J N , ZHANG P , WOLCOTT M P , et al. Partial depolymerization of enzymolysis lignin via mild hydrogenolysis over Raney Nickel[J]. Bioresource Technology, 2014, 155, 422- 426.
15	HUANG S H , MAHMOOD N , TYMCHYSHYN M , et al. Reductive depolymerization of Kraft lignin for chemicals and fuels using formic acid as an in-situ hydrogen source[J]. Bioresource Technology, 2014, 171, 95- 102.
16	XU C B , FERDOSIAN F . Conversion of lignin into bio-based chemicals and materials:Chapter 3 degradation of lignin by depolymerization[J]. Green Chemistry and Sustainable Technology, 2017, 35, 1- 20.
17	LYU W , SI Z , TIAN Z P , et al. Synergistic effect of EtOAc/H₂O biphasic solvent and Ru/C catalyst for cornstalk hydrolysis residue depolymerization[J]. ACS Sustainable Chemistry & Engineeringer, 2017, 5 (4): 2981- 2993.
18	ZHAI Y , LI C , XU G , et al. Depolymerization of lignin via a nonprecious Ni-Fe alloy catalyst supported on activated carbon[J]. Green Chemistry, 2017, 19 (8): 1895- 1903.
19	ZHANG J , TEO J , CHEN X , et al. A series of NiM(M=Ru, Rh, and Pd) bimetallic catalysts for effective lignin hydrogenolysis in water[J]. ACS Catalysis, 2014, 4 (5): 1574- 1583.
20	YUAN Z S , TYMCHYSHYN M , XU C B . Reductive depolymerization of kraft and organosolv lignin in supercritical acetone for chemicals and materials[J]. ChemCatChem, 2016, 8 (11): 1968- 1976.
21	OUYANG X , HUANG X , HENDRIKS B M S , et al. Coupling organosolv fractionation and reductive depolymerization of woody biomass in a two-step catalytic process[J]. Green Chemistry, 2018, 20 (10): 2308- 2319.
22	HU J , ZHANG S H , XIAO R , et al. Catalytic transfer hydrogenolysis of lignin into monophenols over platinum-rhenium supported on titanium dioxide using isopropanol as in situ hydrogen source[J]. Bioresource Technology, 2019, 279, 228- 233.
23	LI W Z , ZHAO Z K , WANG R . Modulating morphology and textural properties of ZrO₂ for supported Ni catalysts towards dry reforming of methane[J]. International Journal of Hydrogen Energy, 2017, 42 (10): 6598- 6609.
24	ALY K A , KHALIL N M , ALGAMAL Y . Estimation of lattice strain for zirconia nano-particles based on Williamson-Hall analysis[J]. Materials Chemistry and Physics, 2017, 193, 182- 188.
25	ZHANG J W , CAI Y , LU G P , et al. Facile and selective hydrogenolysis of beta-O-4 linkages in lignin catalyzed by Pd-Ni bimetallic nanoparticles supported on ZrO₂[J]. Green Chemistry, 2016, 18 (23): 6229- 9235.
26	ZHANG S M , LIU L , MA Y L . Antioxidant activity of hydrogen reduced alkali lignin prepared using SO₄^2-/ZrO₂ as catalyst[J]. Journal of Functional Materials, 2014, 45 (13): 13071- 13075.
27	SHU R Y , LONG J X , YUAN Z Q , et al. Efficient and product-controlled depolymerization of lignin oriented by metal chloride cooperated with Pd/C[J]. Bioresource Technology, 2015, 179, 84- 90.
28	DEEPA A K , DHEPE P L . Lignin depolymerization into aromatic monomers over solid acid catalysts[J]. ACS Catalysis, 2015, 5 (1): 365- 379.
29	HO Y N, WANG S Y, CHIANG W H, et al.Moderate-temperature catalytic incineration of cooking oil fumes using hydrophobic honeycomb supported Pt/CNT catalyst[J]. Journal of Hazardous Materials, 2019, 379: 1-38[2020-01-20].https://doi.org/10.1016/j.jhazmat.2019.120750.
30	PARK J , OH S H , KIM J Y , et al. Comparison of degradation features of lignin to phenols over Pt catalysts prepared with various forms of carbon supports[J]. RSC Advances, 2016, 6 (21): 16917- 16924.
31	SHU R Y , LONG J X , XU Y , et al. Investigation on the structural effect of lignin during the hydrogenolysis process[J]. Bioresource Technology, 2016, 200, 14- 22.
32	SHU R Y , ZHANG Q , MA L L , et al. Insight into the solvent, temperature and time effects on the hydrogenolysis of hydrolyzed lignin[J]. Bioresource Technology, 2016, 221, 568- 575.
33	CONSTANT S , BASSET C , DUMAS C , et al. Reactive organosolv lignin extraction from wheat straw:influence of Lewis acid catalysts on structural and chemical properties of lignins[J]. Industrial Crops & Products, 2015, 65, 180- 189.
34	YOSHIKAWA T , YAGI T , SHINOHARA S , et al. Production of phenols from lignin via depolymerization and catalytic cracking[J]. Fuel Processing Technology, 2013, 108, 69- 75.
35	YANG X J , FENG M Q , CHOI J S , et al. Depolymerization of corn stover lignin with bulk molybdenum carbide catalysts[J]. Fuel, 2019, 244, 528- 535.
36	SUN Y C , XUE B L . Understanding structural changes in the lignin of Eucalyptus urophylla during pretreatment with an ionic liquid-water mixture[J]. Industrial Crops & Products, 2018, 123, 600- 609.
37	TEJADO A , PEÑA C , LABIDI J , et al. Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis[J]. Bioresource Technology, 2017, 98 (9): 1655- 1663.
38	BRAHIM M , BOUSSETTA N , GRIMI N , et al. Pretreatment optimization from rapeseed straw and lignin characterization[J]. Industrial Crops & Products, 2017, 95, 643- 650.
39	LAGERQUISTA L , PRANOVICHA A , SMEDSA A , et al. Structural characterization of birch lignin isolated from a pressurized hot water extraction and mild alkali pulped biorefinery process[J]. Industrial Crops & Products, 2018, 111, 306- 316.
40	WEN J L , SUN S L , XUE B L , et al. Recent advances in characterization of lignin polymer by solution-state nuclear magnetic resonance (NMR) methodology[J]. Materials, 2013, 6 (1): 359- 391.
41	ZHANG A P , LU F C , SUN R C , et al. Isolation of cellulolytic enzyme lignin from wood preswollen/dissolved in dimethyl sulfoxide/N-methylimidazole[J]. Journal of Agricultural and Food Chemistry, 2010, 58, 3446- 3450.
42	DEL RÍO J C , RENCORET J , PRINSEN P , et al. Structural characterization of wheat straw lignin as revealed by analytical pyrolysis, 2D-NMR, and reductive cleavage methods[J]. Journal of Agricultural and Food Chemistry, 2010, 60, 5922- 5935.
43	BRANDT A , CHEN L , VAN DONGEN B E , et al. Structural changes in lignins isolated using an acidic ionic liquid water mixture[J]. Green Chemistry, 2015, 17 (11): 5019- 5034.
44	SHEN X J , WANG B , HUANG P , et al. Understanding the structural changes and depolymerization of Eucalyptus lignin under mild conditions in aqueous AlCl₃[J]. RSC Advances, 2016, 6 (51): 45315- 45325.
45	BOZELL J J , O'LENICK C J , WARWICK S . Biomass fractionation for the biorefinery:Heteronuclear multiple quantum coherence-nuclear magnetic resonance investigation of lignin isolated from solvent fractionation of switchgrass[J]. Journal of Agricultural and Food Chemistry, 2011, 59 (17): 9232- 9242.
46	HATAKEYAMA H , HATAKEYAMA T . Lignin structure, properties, and applications[J]. Advances in Polymer Science, 2010, 232, 1- 63.
47	LI S , LI W , ZHANG Q , et al. Lignin-first depolymerization of native corn stover with an unsupported MoS₂ catalyst[J]. RSC Advances, 2018, 8 (3): 1361- 1370.
48	DEUSS P J , BARTA K . From models to lignin:Transition metal catalysis for selective bond cleavage reactions[J]. Coordination Chemistry Reviews, 2016, 306, 510- 532.
49	BEHLING R , VALANGE S , CHATAL G . Heterogeneous catalytic oxidation for lignin valorization into valuable chemicals:What results? What limitations? What trends?[J]. Green Chemistry, 2016, 18 (7): 1839- 1854.

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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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

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

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