纳米木质素的热解特性及其反应动力学分析

doi:10.3969/j.issn.0253-2417.2021.06.013

Abstract

Abstract:

DES-lignin was extracted from pine feedstock by using deep eutectic solvents(DES) at treatment temperatures of 100, 130, and 150 ℃, and the resultant DES-lignin samples with nano scale were labeled as L₁₀₀, L₁₃₀, and L₁₅₀, respectively. The yields and elemental compositions of DES-lignin were determined, and the thermal degradation characteristics of nanoscale DES-lignin were studied by fast pyrolysis and thermogravimetric analysis(TGA). The results showed that the yields of L₁₀₀, L₁₃₀ and L₁₅₀ were 33.53%, 81.02% and 82.62%, respectively, along with lower H/C molar ratio. DES treatment temperatures of pine wood had significant effect on the thermal degradation properties of lignin nanoparticles. With the increment of DES treatment temperature, the yields of biochar derived from DES-lignin pyrolysis gradually increased, and biochar obtained by fast pyrolysis at 700 ℃ had great high calorific value(30.97-31.96 MJ/kg) and homogeneous mesoporous. Besides, TG analysis indicated that the intense pyrolysis reaction of DES-lignin took place mainly ranged from the temperature of 200 to 500 ℃, the peak temperatures of the maximum weight loss rate occurred around 265 and 385 ℃, respectively. In addition, non-isothermal Coats-Redfern integration method was used to fit the reaction kinetics of DES-lignin pyrolysis, which demonstrated that DES-lignin pyrolysis was a secondary kinetic reaction in the main reaction temperature zone(200-450 ℃), and the obtained activation energy of L₁₀₀, L₁₃₀ and L₁₅₀ pyrolysis ranged 51.52-52.13 kJ/mol during temperature from 200 to 300 ℃ as well as 32.65-49.25 kJ/mol during temperature from 330 to 450 ℃.

Key words: deep eutectic solvent, lignin nanoparticle, biochar, kinetics

CLC Number:

TQ35

Jie TIAN, Rui LOU, Xiangyu XUE, Hong ZHANG, Shubin WU, Huimin XU. Thermal Degradation Characteristics of Lignin Nanoparticles and Its Reaction Kinetics Analysis[J]. Chemistry and Industry of Forest Products, 2021, 41(6): 97-104.

Figures/Tables 6

Table 1

Fig.1

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Table 2

References 25

1	KANG K , ZHU M Q , SUN G T , et al. Codensification of Eucommia ulmoides Oliver stem with pyrolysis oil and char for solid biofuel: An optimization and characterization study[J]. Applied Energy, 2018, 223, 347- 357. doi: 10.1016/j.apenergy.2018.04.069
2	KAN T , STREZOV V , EVANS T J . Lignocellulosic biomass pyrolysis: A review of product properties and effects of pyrolysis parameters[J]. Renewable and Sustainable Energy Reviews, 2016, 57, 1126- 1140. doi: 10.1016/j.rser.2015.12.185
3	XIAO B , SUN X F , SUN R C . Chemical, structural, and thermal characterizations of alkali-soluble lignins and hemicelluloses, and cellulose from maize stems, rye straw, and rice straw[J]. Polymer Degradation and Stability, 2001, 74 (2): 307- 319. doi: 10.1016/S0141-3910(01)00163-X
4	HAO W M , BJÖRNERBÄCK F , TRUSHKINA Y , et al. High-performance magnetic activated carbon from solid waste from lignin conversion processes: 1.Their use as adsorbents for CO₂[J]. ACS Sustainable Chemistry & Engineering, 2017, 5 (4): 3087- 3095.
5	YANG B S , KANG K Y , JEONG M J . Preparation of lignin-based carbon aerogels as biomaterials for nano-supercapacitor[J]. Journal of the Korean Physical Society, 2017, 71 (8): 478- 482. doi: 10.3938/jkps.71.478
6	WEI R F, XIANG D W, LONG H M, et al. Reduction of iron oxide by lignin: Characteristics, kinetics and superiority[J/OL]. Energy, 2020, 197: 1-10[2020-11-13]. https://doi.org/10.1016/j.energy.2020.117203.
7	LOU R , MA R S , LIN K T , et al. Facile extraction of wheat straw by deep eutectic solvent (DES) to produce lignin nanoparticles[J]. ACS Sustainable Chemistry & Engineering, 2019, 7 (12): 10248- 10256.
8	LI T F, LYU G J, LIU Y, et al. Deep eutectic solvents (DESs) for the isolation of willow lignin (Salix matsudana cv. Zhuliu)[J/OL]. International Journal of Molecular Sciences, 2017, 18(11): 1-11[2020-11-13]. https://doi.org/10.3390/ijms18112266.
9	CHEN Y J , ZHANG L L , YU J , et al. High-purity lignin isolated from poplar wood meal through dissolving treatment with deep eutectic solvents[J]. Royal Society Open Science, 2019, 6 (1): 181- 757.
10	娄瑞, 刘钰, 周寅轩, 等. 低共熔溶剂高效分离纳米木质素及其结构特性研究[J]. 陕西科技大学学报, 2020, 38 (6): 6- 10. doi: 10.3969/j.issn.1000-5811.2020.06.002
	LOU R , LIU Y , ZHOU Y X , et al. Study on the extraction and structural performance of lignin nanoparticles by deep eutectic solvent method[J]. Journal of Shaanxi University of Science & Technology, 2020, 38 (6): 6- 10. doi: 10.3969/j.issn.1000-5811.2020.06.002
11	DAS L , LI M , STEVENS J , et al. Characterization and catalytic transfer hydrogenolysis of deep eutectic solvent extracted sorghum lignin to phenolic compounds[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (8): 10408- 10420.
12	崔兴凯, 赵雪冰, 刘德华. 五种甘蔗渣分离木质素热解特性及动力学[J]. 化工进展, 2017, 36 (8): 2910- 2915.
	CUI X K , ZHAO X B , LIU D H . Pyrolysis characteristics and kinetics of five isolated lignins from sugarcane bagasse[J]. Chemical Industry and Engineering Progress, 2017, 36 (8): 2910- 2915.
13	WANG S R , RU B , LIN H Z , et al. Pyrolysis behaviors of four lignin polymers isolated from the same pine wood[J]. Bioresource Technology, 2015, 182, 120- 127. doi: 10.1016/j.biortech.2015.01.127
14	娄瑞, 武书彬, 赵红霞, 等. 基于不同热分析法的稻草木质素热解反应动力学研究[J]. 中国科技论文在线精品论文, 2017, 10 (9): 1011- 1018.
	LOU R , WU S B , ZHAO H X , et al. Study on pyrolysis kinetics of lignin derived from rice straw by means of several thermosanalysis methods[J]. Chinese Science and Technology Papers Online Boutique Papers, 2017, 10 (9): 1011- 1018.
15	LYU G J , WU Q , LI T F , et al. Thermochemical properties of lignin extracted from willow by deep eutectic solvents (DES)[J]. Cellulose, 2019, 26 (15): 8501- 8511. doi: 10.1007/s10570-019-02489-8
16	COATS A W , REDFERN J P . Kinetic parameters from thermogravimetric data[J]. Nature, 1964, 201 (4): 68- 69.
17	SLUITER A, HAMES B, RUIZ R, et al. Determination of structural carbohydrates and lignin in biomass: Laboratory Analytical Procedure (LAP): NREL/TP-510-42618[G]. Golden: National Renewable Energy Laboratory, 2012-08-03.
18	GUO X J , WANG S R , WANG K G , et al. Influence of extractives on mechanism of biomass pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2010, 38 (1): 42- 46. doi: 10.1016/S1872-5813(10)60019-9
19	张肖肖, 娄瑞, 董继先, 等. 低共熔溶剂应用于松木类木质素分离的研究[J]. 陕西科技大学学报, 2019, 37 (6): 13- 17. doi: 10.3969/j.issn.1000-5811.2019.06.003
	ZHANG X X , LOU R , DONG J X , et al. Study on the separation of lignin from pine biomass based on deep eutectic solvent[J]. Journal of Shaanxi University of Science & Technology, 2019, 37 (6): 13- 17. doi: 10.3969/j.issn.1000-5811.2019.06.003
20	蒋恩臣, 陈爱慧, 秦丽元, 等. 木质素热解制备焦炭的试验研究[J]. 可再生能源, 2015, 33 (7): 1066- 1071.
	JIANG E C , CHEN A H , QIN L Y , et al. Experimental study on char produced from lignin pyrolysis[J]. Renewable Energy Resources, 2015, 33 (7): 1066- 1071.
21	刘洪杰, 邢山川, 张思思, 等. 低共熔溶剂试剂分离提取玉米芯纤维素[J]. 河北科技大学学报, 2017, 38 (6): 548- 554.
	LIU H J , XING S C , ZHANG S S , et al. Study on extraction of cellulose from corn cobs by deep eutectic solvents[J]. Journal of Hebei University of Science and Technology, 2017, 38 (6): 548- 554.
22	LYU G, LI T, JI X, et al, Characterization of lignin extracted from willow by deep eutectic solvent treatments[J/OL]. Polymers, 2018, 10(8): 1-11[2020-11-13]. https://doi.org/10.3390/plym10080869.
23	WANG L , ZHANG R , LI J , et al. Comparative study of the fast pyrolysis behavior of ginkgo, poplar, and wheat straw lignin at different temperatures[J]. Industrial Crops and Products, 2018, 122, 465- 472. doi: 10.1016/j.indcrop.2018.06.038
24	武书彬, 胡元, 娄瑞, 等. 木质纤维生物质及其组分的理化特性与热解规律[M]. 北京: 科学出版社, 2013: 141- 172.
	WU S B , HU Y , LOU R , et al. Physicochemical Properties and Pyrolysis of Lignocellulosic Biomass and Its Components[M]. Beijing: Science Press, 2013: 141- 172.
25	林展飞, 宋兴飞, 刘心志. 黑液木质素焦热解动力学分析[J]. 能源研究与利用, 2019, (5): 38- 53. doi: 10.3969/j.issn.1001-5523.2019.05.017
	LIN Z F , SONG X F , LIU X Z . Pyrolysis kinetics of lignin coke in black liquor[J]. Energy Research & Utilization, 2019, (5): 38- 53. doi: 10.3969/j.issn.1001-5523.2019.05.017

样品sample		C	H	O	N	H/C
DES-木质素 DES-lignin	L₁₀₀	58.31	4.15	34.69	0.41	0.85
	L₁₃₀	58.72	4.58	34.05	0.48	0.94
	L₁₅₀	59.98	5.52	33.56	0.43	1.10
	柳木willow^[15]	60.81	5.50	33.52	0.41	1.09
磨木木质素^[23] milled wood lignin(MWL)	银杏ginkgo	59.34	6.04	33.16	0.81	1.12
	松木pine	59.25	5.98	34.74	0.03	1.21
	杨木poplar	58.73	6.04	34.70	0.10	1.23
酶解/温和酸解木质素^[24] enzymatic/mild acid hydrolysis lignin(EMAL)	麦草wheat straw	63.81	6.12	27.91	0.54	1.15
	棉杆cotton stalk	60.46	5.88	27.24	0.65	1.17
	蔗渣bagasse	57.67	5.78	30.65	0.87	1.20

DES-木质素 DES-lignin	温度/℃ temperature	线性拟合方程 linear fitting equation	R²	E/(kJ·mol^-1)	A/min^-1
L₁₀₀	200~300	Y=-2722.80X-1.00	0.9725	52.13	18.80×10⁴
L₁₀₀	330~450	Y=-2358.95X-1.82	0.9862	49.25	59.00×10³
L₁₃₀	200~300	Y=-3496.39X-0.53	0.9188	51.76	20.14×10⁴
L₁₃₀	330~450	Y=-1765.915X-2.809	0.9859	35.63	28.50×10²
L₁₅₀	200~300	Y=-3062.743X-0.399	0.9662	51.52	14.58×10⁴
L₁₅₀	330~450	Y=-1585.127X-3.174	0.9856	32.65	12.28×10²

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Thermal Degradation Characteristics of Lignin Nanoparticles and Its Reaction Kinetics Analysis

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