生物酶预处理对桐木脱色的影响

doi:10.11707/j.1001-7488.LYKX20210565

摘要/Abstract

摘要：

目的: 探讨二代生物复合酶对桐木的漂白效果和影响规律，为桐木脱色和生物学改良及桐木制浆的发展提供理论基础和科学依据。方法: 以兰考泡桐为试验材料，采用纤维素二代生物复合酶CTEC2进行预处理，控制预处理时间（60、75、90和105 min）、温度（30、50和70 ℃）和pH（3、5和7）等因素，分析预处理前后样品色差、化学组分等变化；利用TGA/DSC3型热重同步分析仪探究泡桐木材热降解性能；使用电镜扫描（SEM）观察预处理前后样品纤维微观形态变化；通过X射线衍射测定预处理泡桐木材结晶度，分析不同预处理条件对样品结晶的影响。结果: 1）颜色测定表明，在温度50 ℃、pH为7的条件下， CTEC2预处理105 min泡桐木材漂白脱色效果最好，亮度和白度均有所提高，且随着预处理时间延长，漂白效果更好；2）组分测定表明，在温度50 ℃、pH为7的条件下，CTEC2预处理泡桐木材效果最好，纤维素相对含量增加10.76%、半纤维素含量减少11.13%、酸溶木质素含量减少3.05%、酸不溶木质素含量减少4.22%、抽提物含量减少1.15%；3）从TGA曲线可知，经预处理的泡桐木材最大质量损失速率对应的温度有所增加，热稳定性有所上升；从SEM图像可知，预处理可有效破坏木质纤维素结构；从XRD可知，经预处理的泡桐木材纤维素结晶度有所提高。结论: 纤维素二代生物复合酶CTEC2可使泡桐木材主要化学组分发生变化，降低木质素、半纤维素和抽提物等含量，从而达到漂白脱色效果。泡桐木材漂白预处理的最佳条件为温度50 ℃、pH 7、预处理时间105 min。

关键词: 泡桐, 预处理, 生物酶, 漂白脱色, 热重分析

Abstract:

Objective: This study explored the bleaching effect and influence of the second-generation biological complex enzyme on tung wood, and provided theoretical basis and scientific basis for the decolorization and biological improvement of tung wood and the development of tung wood pulping. Method: Paulownia elongata was used as the experimental material, and the cellulose second-generation enzyme (CTEC2) was used for pretreatment. The changes of color difference index and chemical components of samples before and after pretreatment were analyzed by controlling pretreatment time(60, 75, 90, 105 min), temperature(30, 50, 70 ℃) and pH value(3, 5, 7), The thermal degradation properties of the samples were analyzed by TGA(thermo gravimetric analysis), the changes of microstructure were investigated by SEM(scanning electron microscope), and the changes of crystallinity after pretreatment bleaching were measured by XRD(X-ray diffraction). Result: 1) Color determination: when the pretreatment conditions were pretreatment temperature 50 °C, pH value 7 and pretreatment time 105 min, the bleaching effect of paulownia wood was the best, and the brightness and whiteness were improved, and the bleaching effect will also be improved with the extension of pretreatment time. 2) Component determination showed that CTEC2 had the best pretreatment effect on Paulownia wood at 50 °C and pH 7. The relative content of cellulose increased by 10.76%, hemicellulose content decreased by 11.13%, acid-soluble lignin content decreased by 3.05%, acid-insoluble lignin content decreased by 4.22%, and extract content decreased by 1.15%. 3) From the TGA curve, the temperature corresponding to the maximum mass loss rate of pretreated paulownia wood increased, and the thermal stability increased. It can be seen from the SEM images that the pretreatment can effectively destroy the lignocellulose structure. XRD showed that the crystallinity of pretreated paulownia wood cellulose increased. Conclusion: CTEC2 can change the main chemical components of paulownia wood, reduce the content of lignin, hemicellulose and extract, so as to achieve bleaching and decolorization effect. The optimum conditions for bleaching pretreatment of paulownia wood were temperature 50 °C, pH 7 and pretreatment time 105 min.

Key words: paulownia, pretreatment, cellulose second-generation enzyme(CTEC2), bleaching and decolorization, thermo gravimetric analysis(TGA)

中图分类号:

S781.4

李书磊,张红,李一博,袁洁莹,谢非凡,王寒星,楚杰,余瑞金. 生物酶预处理对桐木脱色的影响[J]. 林业科学, 2023, 59(5): 157-164.

Shulei Li,Hong Zhang,Yibo Li,Jieying Yuan,Feifan Xie,Hanxing Wang,Jie Chu,Ruijin Yu. Analysis of the Effect of Enzyme Pretreatment on the Decolorization of Paulownia[J]. Scientia Silvae Sinicae, 2023, 59(5): 157-164.

图/表 10

表1

图1

图2

图3

图4

图5

图6

图7

表2

表3

参考文献 0

	曹惠敏, 王文斌, 孙伟圣, 等. FeCl₂处理麻栎木材化学变色工艺及变色机理研究 . 林业工程学报, 2020, 5 (1): 75- 80.
	Cao H M, Wang W B, Sun W S, et al. Technology and mechanism of chemical discoloration of oak(Quercus acutissima) using FeCl₂ solution . Journal of Forestry Engineering, 2020, 5 (1): 75- 80.
	常德龙, 李芳东, 胡伟华, 等. 国内外泡桐木材市场分析与我国发展对策. 世界林业研究, 2018, 31 (1): 57- 62.
	Chang D L, Li F D, Hu W H, et al. Analysis on international and national Paulownia wood market and its development strategy in China . World Forestry Research, 2018, 31 (1): 57- 62.
	常德龙, 宋湛谦, 黄文豪, 等. 真菌对泡桐木材化学成分及其结构的影响. 北京林业大学学报, 2006, 28 (3): 145- 149.
	Chang D L, Song Z Q, Huang W H, et al. Impacts of fungi on chemical components and physical structure of Paulownia elongata wood . Journal of Beijing Forestry University, 2006, 28 (3): 145- 149.
	楚　杰, 张军华, 马　莉, 等. XRD与NMR的热处理竹材结晶性能研究. 光谱学与光谱分析, 2017, 37 (1): 256- 261.
	Chu J, Zhang J H, Ma L, et al. Study of crystallinity performance of pretreated bamboo fibers based on X-ray diffraction and NMR. Spectroscopy and Spectral Analysis, 2017, 37 (1): 256- 261.
	冯严严. 生物酶漂白的研究进展. 黑龙江造纸, 2014, 42 (4): 28- 31.
	Feng Y Y. Research progress of biological enzyme bleaching. Heilongjiang Pulp & Paper, 2014, 42 (4): 28- 31.
	李　峰, 王松林, 宋晓明. 生物酶在纸浆漂白过程中的应用. 云南化工, 2018, 45 (8): 164- 166.
	Li F, Wang S L, Song X M. Application of biological enzymes in pulp bleaching process. Yunnan Chemical Technology, 2018, 45 (8): 164- 166.
	刘志佳, 李　黎, 鲍甫成, 等. 不同条件水热处理木材的漂白工艺. 木材工业, 2009, 23 (2): 40- 42.
	Liu Z J, Li L, Bao F C, et al. Bleaching technology of wood after hydrothermal treatment. China Wood Industry, 2009, 23 (2): 40- 42.
	陆弘毅, 丁春香, 翟胜丞, 等. 透明木材的性能及其应用研究进展. 高分子通报, 2021, (7): 13- 26.
	Lu H Y, Ding C X, Zhai S C, et al. Research progress of properties and applications of transparent wood. Polymer Bulletin, 2021, (7): 13- 26.
	卢庆华, 卢　俊, 蔡　禄. 产木聚糖酶菌种的筛选及其在纸浆漂白中的应用. 科学技术与工程, 2013, 13 (5): 1257- 1260,1275.
	Lu Q H, Lu J, Cai L. The sifting of strains that producing xylanas-eand its application in pulp bleaching. Science Technology and Engineering, 2013, 13 (5): 1257- 1260,1275.
	潘梦丽, 王　春, 平清伟, 等. 纸浆绿色漂白技术新进展. 中国造纸, 2015, 34 (11): 52- 58.
	Pan M L, Wang C, Ping Q W, et al. Pregress of green bleaching technology. China Pulp & Paper, 2015, 34 (11): 52- 58.
	邱乾栋, 莫文娟, 马海燕, 等. 泡桐木材白度与相关变色的生理指标. 东北林业大学学报, 2013, 41 (12): 72- 76.
	Qiu Q D, Mo W J, Ma H Y, et al. Whiteness of paulownia wood and physiological indexes correlated with discoloration. Journal of Northeast Forestry University, 2013, 41 (12): 72- 76.
	许开绍, 郭华清. 生物酶漂白技术的研究进展. 西南造纸, 2002, 31 (4): 7- 8,23.
	Xu K S, Guo H Q. Research progress of biological enzyme bleaching technology. Southwest Pulp and Paper, 2002, 31 (4): 7- 8,23.
	张润青, 曹海兵, 步逸凡, 等. 臭氧对非木材纤维漂白和改性作用研究进展. 中国造纸, 2020, 39 (6): 75- 82.
	Zhang R Q, Cao H B, Bu Y F, et al. Review on the study progress of ozone treatment in bleaching and modifications of non-wood fibers. China Pulp & Paper, 2020, 39 (6): 75- 82.
	祖勃荪, 周　勤. 兰考泡桐木材成分的变色行为及其变色过程. 林业科学, 1998, 34 (3): 97- 103.
	Zu B S, Zhou Q. Discoloration of paulownia wood: susceptibility of extractives. Scientia Silvae Sinicae, 1998, 34 (3): 97- 103.
	Patel A K, Singhania R R, Sim S J, et al. Thermostable cellulases: Current status and perspectives. Bioresource Technology, 2019, 279, 385- 392. doi: 10.1016/j.biortech.2019.01.049
	Pathania D, Katwal R, Sharma G, et al. A biopolymer-based hybrid cation exchanger pectin cerium (IV) iodate: Synthesis, characterization, and analytical applications. Desalination and Water Treatment, 2016, 57, 468- 475.
	Segal L, Conrad C, Creely J, et al. An empirical method for estimating the degree of crystallinity of native cellulose using the X-Ray diffractometer. Textile Research Journal, 1959, 29 (10): 786- 794. doi: 10.1177/004051755902901003
	Shi J T, Lu Y, Zhang Y L, et al. Effect of thermal treatment with water, H₂SO₄ and NaOH aqueous solution on color, cell wall and chemical structure of poplar wood . Scientific Reports, 2018, 8 (1): 17735. doi: 10.1038/s41598-018-36086-9
	Wu Y, Wu J M, Yang F, et al. Effect of H₂O₂ bleaching treatment on the properties of finished transparent wood . Polymers, 2019, 11 (5): 776. doi: 10.3390/polym11050776
	Zhang P, Wei Y X, Liu Y, et al. 2018. Heat-induced discoloration of chromophore structures in Eucalyptus lignin. Materials (Basel, Switzerland), 11(9): 1686.

温度 Temperature/℃	pH	时间 Time/min	L^*	a^*	b^*	?E^*
30	3	60	72.03	5.21	21.34	5.48
		75	67.02	6.30	21.76	6.35
		90	67.00	5.64	20.02	4.75
		105	69.38	5.22	20.25	3.95
	5	60	73.43	4.96	21.04	5.92
		75	69.34	5.68	20.25	4.15
		90	71.50	5.23	18.61	3.09
		105	71.02	5.63	21.37	5.30
	7	60	72.13	4.95	19.69	4.11
		75	68.52	4.37	18.48	2.31
		90	70.84	5.77	19.72	3.89
		105	71.79	4.03	17.20	2.19
50	3	60	70.59	4.20	18.30	1.97
		75	71.68	4.96	21.19	5.14
		90	73.40	4.59	19.90	5.03
		105	73.33	4.84	19.99	5.08
	5	60	63.51	6.17	21.65	8.35
		75	69.87	5.42	20.62	4.36
		90	67.69	5.87	20.88	5.19
		105	70.87	5.37	20.41	4.30
	7	60	71.81	4.38	19.20	3.41
		75	73.79	5.24	19.67	5.33
		90	73.68	5.09	19.23	4.96
		105	74.15	4.95	18.19	4.88
70	3	60	68.73	5.89	22.78	6.61
		75	70.31	5.91	22.20	6.04
		90	69.95	6.32	23.76	7.61
		105	70.03	5.62	21.58	5.33
	5	60	71.02	5.16	22.68	6.38
		75	70.17	5.68	22.87	6.58
		90	69.53	6.00	25.08	8.78
		105	66.95	5.60	22.18	6.49
	7	60	74.05	4.68	20.12	6.02
		75	69.10	5.26	19.27	3.13
		90	70.66	5.62	20.87	4.76
		105	72.50	3.83	16.54	2.80

样品Sample	I_am	I₀₀₂	CI（%）
未处理Untreated	1 343.489	1 616.814	16.91
30-3	1 142.007	1 463.095	21.94
30-5	1 062.084	1 436.291	26.05
30-7	1 020.637	1 399.190	27.05
50-3	1 361.831	1 760.143	22.63
50-5	1 004.362	1 427.863	29.66
50-7	982.857	1 453.986	32.40
70-3	1 318.866	1 657.045	20.71
70-5	1 082.314	1 421.057	23.84
70-7	1 074.863	1 434.888	25.09

样品Sample	B	2θ	D	d
未处理Untreated	0.044 935	20.94	3.102	0.470
30-3	0.043 827	21.03	3.181	0.468
30-5	0.043 749	21.08	3.187	0.467
30-7	0.043 528	21.11	3.203	0.466
50-3	0.043 369	21.05	3.214	0.468
50-5	0.044 258	21.07	3.150	0.467
50-7	0.042 675	21.17	3.270	0.465
70-3	0.043 735	21.01	3.176	0.468
70-5	0.043 257	21.06	3.223	0.467
70-7	0.042 687	21.13	3.256	0.466

[1]	胡同欣,杨艺璇,孙龙,高传宇. 兴安落叶松林和白桦林下种植大球盖菇对枯落物层燃烧性的影响[J]. 林业科学, 2022, 58(7): 32-42.
[2]	李顺福,王慧敏,房丽莎,刘震. 短日照诱导白花泡桐顶芽死亡过程相关基因的表达[J]. 林业科学, 2022, 58(2): 148-158.
[3]	李瑞,苗媛媛,钱晓东,林斌,金祥龙,李慕之,刘镇波. 抽提处理对泡桐木材声学振动性能的影响[J]. 林业科学, 2022, 58(2): 171-181.
[4]	张恒,甄雅星,李佳艳,薛江,张秋良. 内蒙古大兴安岭典型乔灌树种及其地表死可燃物热解特性[J]. 林业科学, 2020, 56(7): 104-114.
[5]	李想,陈妮,齐学敏,楚杰,张军华,常德龙,许雅雅. 乙醇钠预处理木质纤维素原料的组分及结构特性[J]. 林业科学, 2020, 56(2): 156-163.
[6]	黄曹兴, 何娟, 赖晨欢, Narron Robert, Chang Houmin, 勇强. 毛竹预处理黑液木质素和酶解木质素的结构与热学性质[J]. 林业科学, 2018, 54(3): 108-116.
[7]	侯俊峰, 鲍永泽, 周永东. 过热蒸汽预处理对50 mm厚杨木锯材常规干燥的影响[J]. 林业科学, 2018, 54(2): 131-136.
[8]	陈倩, 陈京环, 王堃, 蒋建新, 孙润仓. 热水预处理生物质原料及其生物转化研究进展[J]. 林业科学, 2017, 53(9): 97-104.
[9]	曹亚兵, 翟晓巧, 邓敏捷, 赵振利, 范国强. 泡桐丛枝病发生与代谢组变化的关系[J]. 林业科学, 2017, 53(6): 85-93.
[10]	楚杰, 张军华, 马莉, 路海东. 预处理竹材的结晶度分析[J]. 林业科学, 2017, 53(2): 100-109.
[11]	王艳梅, 张龙冲, 马天晓, 刘震, 任雪敏, 耿晓东, 宋良红. 人工调控对泡桐顶芽生长发育的影响[J]. 林业科学, 2016, 52(8): 53-59.
[12]	曹艳春, 曹亚兵, 赵振利, 翟晓巧, 范国强. 泡桐新品种‘南四泡桐1号’[J]. 林业科学, 2016, 52(8): 168-168.
[13]	李志强, 费本华, 江泽慧. 利用石墨化碳脱除竹材稀酸预处理液中的发酵抑制物[J]. 林业科学, 2016, 52(7): 113-120.
[14]	李康琴, 龚斌, 徐海宁, 戴小英, 彭纪南, 朱培林. 泡桐良种‘天桐C22’[J]. 林业科学, 2016, 52(7): 171-171.
[15]	蒋新元, 廖媛媛, 郭忠, 孟安, 黄泽才, 杨素文. 7种果壳的热解特性及与主要组分相关性分析[J]. 林业科学, 2015, 51(12): 79-86.