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Luo Cuimei, Wang Xujie, Mu Jun, Qi Chusheng. Effects of exogenous acid catalysis on the thermal degradation law of wood hemicellulose[J]. Journal of Beijing Forestry University, 2022, 44(4): 147-156. DOI: 10.12171/j.1000-1522.20210426
Citation: Luo Cuimei, Wang Xujie, Mu Jun, Qi Chusheng. Effects of exogenous acid catalysis on the thermal degradation law of wood hemicellulose[J]. Journal of Beijing Forestry University, 2022, 44(4): 147-156. DOI: 10.12171/j.1000-1522.20210426

Effects of exogenous acid catalysis on the thermal degradation law of wood hemicellulose

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  • Received Date: October 25, 2021
  • Revised Date: February 28, 2022
  • Accepted Date: March 01, 2022
  • Available Online: March 03, 2022
  • Published Date: April 24, 2022
  •   Objective  High-temperature heat treatment can partially degrade wood hemicellulose and improve wood dimensional stability. The use of exogenous acid can reduce the thermal degradation temperature of wood hemicellulose, so it is necessary to clarify its thermal degradation law.
      Method  In this study, hemicelluloses from poplar and Chinese fir were separated by alkali method. Thermal degradation of hemicellulose (The two exogenous acids were AlCl3 and H3PO4, and the concentration of each acid was 0.1mol/L and 0.3mol/L, respectively) under different acidic conditions were investigated by Fourier Infrared Spectrometer (FTIR) and thermogravimetric (TG) analysis.
      Result  The FTIR spectra of wood hemicelluloses isolated by alkali method were consistent with the basic characteristic of hemicellulose of softwood and hardwood. After being treated with AlCl3 and H3PO4, the hydroxyl peak showed red shift, and the characteristic absorption peak intensity of hemicellulose decreased significantly compared with the untreated hemicellulose. TG analysis showed that the initial degradation temperature (T5%) of wood hemicellulose ranged from 200 ℃ to 95–150 ℃ after being pretreated by two kinds of exogenous acids, and the main degradation temperature ranged from 200–300 ℃ to 100–150 ℃. At the same concentration, the T5% value of hemicellulose (150 ℃) after AlCl3 treatment was greater than that of H3PO4 (95 ℃). When the concentration of AlCl3 increased, the thermal decomposition rate of hemicellulose accelerated, but it had almost no effect on T5%. When the concentration of H3PO4 increased, the thermal decomposition rate of hemicellulose and T5% both decreased. Compared with untreated poplar wood hemicellulose (199.68 kJ/mol) and Chinese fir hemicellulose (231.12 kJ/mol), the pyrolysis activation energy was significantly reduced after AlCl3 and H3PO4 treatment. When the concentration was 0.3M, the average activation energy of Chinese fir hemicellulose (112.31 kJ/mol) after AlCl3 treatment was lower than that of H3PO4 (125.82 kJ/mol).
      Conclusion  The two exogenous acids used in this study can significantly reduce the degradation temperature of hemicellulose. In general, the catalytic effect of AlCl3 was better than H3PO4, and the Chinese fir hemicellulose was more sensitive to the catalytic effect of H3PO4. Therefore, different exogenous acidic media can be selected as catalysts according to the difference of softwood and hardwood of hemicellulose to accelerate the pyrolysis reaction rate, thereby providing theoretical support for the application of exogenous acid in low-temperature heat treatment of wood.
  • [1]
    Rowell R M. Handbook of wood chemistry and wood composites [M]. Boca Raton: CRC Press, 2005.
    [2]
    Sjöström E. Wood chemistry fundamentals and applications [M]. New York: Academic Press, 1981.
    [3]
    顾百练, 丁涛, 江宁. 木材热处理研究及产业化进展[J]. 林业工程学报, 2019, 4(4): 1−11.

    Gu B L, Ding T, Jiang N. Development of wood heat treatment research and industrialization[J]. Journal of Forestry Engineering, 2019, 4(4): 1−11.
    [4]
    Yang H C, Yan R, Chen H P, et al. Characteristics of hemicellulose, cellulose and lignin pyrolysis[J]. Fuel, 2007, 86: 1781−1788. doi: 10.1016/j.fuel.2006.12.013
    [5]
    齐文玉, 刘偲, 陈金明, 等. 氮气介质环境中热处理樟子松木材主要性能的变化[J]. 西北林学院学报, 2021, 36(5): 161−167.

    Qi W Y, Liu C, Chen J M, et al. Effect of N2 heat treatment on main properties of Pinus sylvestris var. mongolica wood[J]. Journal of Northwest Forestry University, 2021, 36(5): 161−167.
    [6]
    Salca E A, Hiziroglu S. Evaluation of hardness and surface quality of different wood species as function of heat treatment[J]. Materials & Design, 2014, 62: 416−423.
    [7]
    Xue L, Zhao Z J, Zhang Y, et al. Analysis of gas chromatography-mass spectrometry coupled with dynamic headspace sampling on volatile organic compounds of heat-treated poplar at high temperatures[J]. BioResources, 2016, 11(2): 3550−3560.
    [8]
    吴再兴, 陈玉和, 黄成建, 等. 热处理对木材力学性能的影响综述[J]. 世界林业研究, 2019, 32(1): 59−64.

    Wu Z X, Chen Y H, Huang C J, et al. A review of effects of heat treatment on wood mechanical properties[J]. World Forestry Research, 2019, 32(1): 59−64.
    [9]
    孔繁旭, 邹超峰, 王艳伟, 等. 热处理对木材化学组分及物理力学性能的影响[J]. 林业机械与木工设备, 2019, 47(1): 9−16. doi: 10.3969/j.issn.2095-2953.2019.01.002

    Kong F X, Zou C F, Wang Y W, et al. Effect of heat treatment on chemical composition and physico-mechanical properties of wood[J]. Forestry Machinery & Woodworking Equipment, 2019, 47(1): 9−16. doi: 10.3969/j.issn.2095-2953.2019.01.002
    [10]
    王传贵, 江泽慧, 费本华, 等. 化学成分对木材细胞壁纵向弹性模量和硬度的影响[J]. 北京林业大学学报, 2012, 34(3): 107−110.

    Wang C G, Jiang Z H, Fei B H, et al. Effects of chemical components on longitudinal MOE and hardness of wood cell wall[J]. Journal of Beijing Forestry University, 2012, 34(3): 107−110.
    [11]
    李贤军, 付峰, 蔡智勇, 等. 高温热处理对木材吸湿性和尺寸稳定性的影响[J]. 中南林业科技大学学报, 2010, 30(6): 92−96. doi: 10.3969/j.issn.1673-923X.2010.06.017

    Li X J, Fu F, Cai Z Y, et al. The effect of high temperature thermal treatment on moisture absorption and dimension stability of wood[J]. Journal of Central South University of Forestry & Technology, 2010, 30(6): 92−96. doi: 10.3969/j.issn.1673-923X.2010.06.017
    [12]
    蔡绍祥, 王新洲, 李延军. 高温水热处理对马尾松木材尺寸稳定性和材色的影响[J]. 西南林业大学学报, 2019, 39(1): 160−165.

    Cai S X, Wang X Z, Li Y J. The size stability and color change of Pinus massoniana wood by high temperature hydrothermal treatment[J]. Journal of Southwest Forestry University, 2019, 39(1): 160−165.
    [13]
    Hosseinpourpia R, Adamopoulos S, Mai C. Effects of acid pre-treatments on the swelling and vapor sorption of thermally modified Scots pine (Pinus sylvestris L.) wood[J]. BioResources, 2018, 13(1): 331−345.
    [14]
    Himmel S, Mai C. Effects of acetylation and formalization on the dynamic water vapor sorption behavior of wood[J]. Holzforschung, 2015, 69(5): 633−643. doi: 10.1515/hf-2014-0161
    [15]
    Hosseinpourpia R, Adamopoulos S, Holstein N, et al. Dynamic vapour sorption and water-related properties of thermally modified Scots pine (Pinus sylvestris L.) wood pre-treated with proton acid[J]. Polymer Degradation and Stability, 2017, 138: 161−168. doi: 10.1016/j.polymdegradstab.2017.03.009
    [16]
    孙珂, 漆楚生, 汪莉君, 等. 杉木纤维素的热稳定性及热分解动力学参数[J]. 林产工业, 2018, 45(4): 37−42.

    Sun K, Qi C S, Wang L J, et al. Thermal stablity and decopposition kinetics parameters of Chinese fir cellulose[J]. China Forest Products Industry, 2018, 45(4): 37−42.
    [17]
    Qi C S, Hou S Y, Lu J X, et al. Thermal characteristics of birch and its cellulose and hemicelluloses isolated by alkaline solution[J]. Holzforschung, 2020, 74(12): 1099−1112. doi: 10.1515/hf-2019-0285
    [18]
    李赫龙. 作物秸秆木质素和半纤维素的分离纯化及结构表征[D]. 咸阳: 西北农林科技大学, 2016.

    Li H L. Isolation and structure characterization of ligin and hemicellulose from crop straw[D]. Xianyang: Northwest Agriculture and Forestry University of Science and Technology, 2016.
    [19]
    Akerholm M, Salmen L. Interactions between wood polymers studied by dynamic FT-IR spectroscopy[J]. Polymer, 2001(42): 963−969.
    [20]
    储德淼. 基于阻燃/热处理联合改性杨木表面功能层构建与性能研究[D]. 北京: 北京林业大学, 2019.

    Chu D M. Manufacturing and characterizing of the surface functional layer on poplar using combined treatment of fir retardancy and thermal modification[D]. Beijing: Beijing Forestry University, 2019.
    [21]
    Huang X N, Kocaefe D G, Kocaefe Y, et al. Structural analysis of heat-treated birch (Betule papyrifera) surface during artificial weathering[J]. Applied Surface Science, 2013, 264: 117−127. doi: 10.1016/j.apsusc.2012.09.137
    [22]
    Buta J G, Zadrazil F, Galletti G C. FT-IR determination of lignin degradation in wheat straw by white rot fungus Stropharia rugosoannulata with different oxygen concentrations[J]. Journal of Agricultural and Food Chemistry, 1989, 37(5): 1382−1384.
    [23]
    Rabemanolontsoa H, Saka S. Holocellulose determination in biomass[J]. Green Energy and Technology, 2012: 135−140.
    [24]
    Popescu M C, Froidevaux J, Navi P, et al. Structural modifications of Tilia cordata wood during heat treatment investigated by FT-IR and 2D IR correlation spectroscopy[J]. Journal of Molecular Structure, 2013, 1033: 176−186. doi: 10.1016/j.molstruc.2012.08.035
    [25]
    Sugiyama J, Persson J, Chanzy H. Combined infrared and electron diffraction study of the polymorphism of native celluloses[J]. Macromolecules, 1991, 24: 2461−2466. doi: 10.1021/ma00009a050
    [26]
    Li M Y, Cheng S C, Li D, et al. Structural characterization of steam-heat treated Tectona grandis wood analyzed by FT-IR and 2D-IR correlation spectroscopy[J]. Chinese Chemical Letters, 2015, 26(2): 221−225. doi: 10.1016/j.cclet.2014.11.024
    [27]
    Zabihi O, Ahmadi M, Yadav R, et al. Novel Phosphorous-based deep eutectic solvents for the production of recyclable macadamia nutshell-polymer biocomposites with improved mechanical and fire safety performances[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(12): 4463−4476.
    [28]
    Ma Z Q, Chen D Y, Gu J, et al. Determination of pyrolysis characteristics and kinetics of palm kernel shell using TGA-FTIR and model-free integral methods[J]. Energy Conversion and Management, 2015, 89: 251−259. doi: 10.1016/j.enconman.2014.09.074
    [29]
    吕建雄, 江京辉, 黄荣凤, 等. 木材高温热处理技术与应用[M]. 北京: 科学出版社, 2020.

    Lü J X, Jiang J H, Huang R F, et al. Technology and application of wood high temperature heat treatment[M]. Beijing: Science Press, 2020.
    [30]
    梁韬. 基于Py-GC/MS的半纤维素热裂解机理研究[D]. 杭州: 浙江大学, 2013.

    Liang T. Mechanism research of hemicellulose pyrolvsis based on Py-GC/MS[D]. Hangzhou: Zhejiang University, 2013.
    [31]
    Wang J W, Minami E, Kawamoto H. Thermal reactivity of hemicellulose and cellulose in cedar and beech wood cell walls[J]. Journal of Wood Science, 2020, 66(1): 1−10.
    [32]
    Hajj R, Hage R E, Sonnier R, et al. Influence of lignocellulosic substrate and phosphorus flame retardant type on grafting yield and flame retardancy[J]. Reactive and Functional Polymers, 2020, 153: 1−13.
    [33]
    Sonnier R, Otazaghine B, Virett A, et al. Improving the flame retardancy of flax fabrics by radiation grafting of phosphorus compounds[J]. European Polymer Journal, 2015, 68: 313−325. doi: 10.1016/j.eurpolymj.2015.05.005
    [34]
    程士超. 热处理温度对花梨木化学组分及其结构的影响[D]. 北京: 北京林业大学, 2016.

    Cheng S C. Effect of heat treatment temperature on chemical compositions and structure of Pterocarpus macarpus Kurz wood[D]. Beijing: Beijing Forestry University, 2016.
    [35]
    Qi C S, Yadama V, Guo K Q, et al. Thermal stability evaluation of sweet sorghum fiber and degradation simulation during hot pressing of sweet sorghum-thermoplastic composite panels[J]. Industrial Crops and Products, 2015, 69: 335−343. doi: 10.1016/j.indcrop.2015.02.050
    [36]
    Wang S R, Ru B, Lin H Z, et al. Pyrolysis behaviors of four O-acetyl-preserved hemicelluloses isolated from hardwoods and softwoods[J]. Fuel, 2015, 150: 243−251. doi: 10.1016/j.fuel.2015.02.045
    [37]
    Wang S R, Ru B, Zhang L, et al. Structural characterization and pyrolysis behavior of cellulose and hemicellulose isolated from softwood Pinus armandii Franch[J]. Energy & Fuel, 2016, 30(7): 5721−5728.
    [38]
    Lei Z H, Wang S D, Fu H C, et al. Thermal pyrolysis characteristics and kinetics of hemicellulose isolated from Camellia oleifera shell[J]. Bioresource Technology, 2019, 282: 228−235. doi: 10.1016/j.biortech.2019.02.131

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