乙醇钠预处理木质纤维素原料的组分及结构特性

doi:10.11707/j.1001-7488.20200218

摘要/Abstract

摘要：

目的: 分析乙醇钠预处理木质纤维素原料的组分及结构特性，为纤维素原料制备生物乙醇燃料的研究提供参考。[方法: 以针叶材松木、杉木和阔叶材水曲柳为研究对象，在121℃下采用乙醇钠（C₂H₅ONa）进行预处理，通过傅里叶变换红外光谱（FTIR）和X射线衍射参数（XRD）等方法分析预处理木质纤维素原料的主要化学组分变化及结构特性。[结果: 预处理后3种原料的纤维素、木聚糖和木质素含量均有不同程度变化，纤维素、木聚糖含量有所增加，木质素含量略微减少，其中，预处理杉木的纤维素含量增加幅度最大，达48.1%，平均增加8.1%，松木次之，水曲柳最低。从除木素效果看，松木预处理后木质素含量相对降低6.1%，处理效果较好。X射线衍射参数（XRD）和傅里叶变换红外光谱（FTIR）反映的LOI（结晶度指数）、HBI（氢键强度指数）变化结果显示，乙醇钠预处理可提高木质纤维素原料的相对结晶度。不同酶剂量和时间点变化的酶水解效率研究结果表明，葡萄糖和木聚糖的水解得率由大到小依次为预处理杉木>预处理松木>预处理水曲柳。[结论: 乙醇钠预处理杉木纤维素含量提高最多，松木次之，水曲柳最低；针叶材的乙醇钠预处理体系处理效果较好；预处理杉木的相对结晶度高于松木和水曲柳；不同酶剂量和时间点变化的酶水解效率研究进一步验证预处理杉木>预处理松木>预处理水曲柳。

关键词: 木质纤维素原料, 预处理, 结晶度, 傅里叶变换红外光谱

Abstract:

Objective: The aim of this paper was to analyze structural characterization and component, thereby to promote the efficient conversion of lignocelluloses biomass to fuel ethanol.[ Method: Pinus, Cunninghamia lanceolata and Fraxinus mandschurica were used as experimental materials, pretreated by sodium ethoxide(C₂H₅ONa)system under the condition of 121℃ and by Fourier transform infrared spectroscopy(FTIR)and X-ray diffraction(XRD)to analyze chemistry components, structure properties and thermal stability.[ Result: The experimental results showed that the contents of cellulose, xylan and lignin all changed, to a different extent, in the three kinds of pretreatment materials, those were, the contents of cellulose and xylan both increased, whereas the lignin content decreased slightly. The cellulose content of the pretreated C.lanceolata showed a largest increment of 48.1%, average increased by 8.1%, and orderly followed by Pinus and F. mandschurica. From the lignin removal effects perspective, the pretreatments effect of Pinus were better, and the lignin content was decreased by 6.1%. From the experimental results, the conclusion could be obtained that softwood in sodium ethoxide pretreatment system reflected a better effect. In addition, the changed X-ray diffraction(XRD), Fourier transform infrared spectra of the reaction of LOI(crystallinity index)and HBI(hydrogen bond strength index)indicated a changed crystal of pretreatment materials, which suggested that pretreatment can increase the relative crystallinity.[ Conclusion: Enzymatic hydrolysis efficiency was studied by different changes of enzyme dosage and time. The experimental result further verified the result of C. lanceolata > Pinus > F. mandschurica, which might provide a theoretical foundation for energy conversion of woody biomass.

Key words: lignocelluloses biomass, pretreatment, crystallinity, FTIR

中图分类号:

S781.4

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.

Xiang Li,Ni Chen,Xuemin Qi,Jie Chu,Junhua Zhang,Delong Chang,Yaya Xu. Composition and Structure Characteristics of Sodium Ethoxide Pretreated Lignocelluloses Biomass[J]. Scientia Silvae Sinicae, 2020, 56(2): 156-163.

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试件编号Specimen number	预处理温度Pretreated temperature/℃	处理介质Sodium ethoxide	预处理时间Pretreated time/h
1	121	—	1
2	121	1.5%乙醇钠
		1.5% sodium ethoxide	1
3	121	1.5%乙醇钠
		1.5% sodium ethoxide	1
对照Control	—	原材料Raw material	—

原料 Materials	纤维素 Cellulose	木聚糖 Xylan	酸不溶木质素 Acid insoluble lignin	酸溶木质素 Acid soluble lignin	抽提物 Extract
松木对照Pinus control	38.8±0.60	20.7±1.30	29.9±0.02	1.3±0.05	8.2
松木+乙醇钠Pinus + sodium ethoxide	42.6±0.27	22.4±0.39	24.3±0.42	1.8±0.42	/
杉木对照C. lanceolata control	42.8±1.00	16.6±0.30	32.4±0.21	1.4±0.07	6.9
杉木+乙醇钠C. lanceolata + sodium ethoxide	48.1±0.62	15.0±0.03	32.0±0.56	2.1±0.61	/
水曲柳对照F. mandschurica control	37.0±1.40	20.6±0.80	27.6±1.21	1.9±0.52	4.8
水曲柳+乙醇钠F. mandschurica + sodium ethoxide	40.4±0.89	21.9±1.70	25.1±0.19	1.5±0.12	/

波数Wavenumber/cm^-1	基团特征峰归属Group characteristic peak assignment
3 421	羟基中的O—H伸缩振动O—H stretching vibration in hydroxyl group
2 922	甲基、亚甲基中的C—H伸缩振动C—H stretching vibration in methyl and methylene group
1 737	非共轭的酮、羰基和脂中的CO伸缩振动(木聚糖)Non conjugated ketones, carbonyl groups and CO stretching vibration
1 636	木质素羰基共轭芳基酮CO伸缩振动Lignin carbonyl conjugated aryl ketones CO stretching vibration
1 598	苯环骨架伸缩振动加上CO伸缩振动Benzene ring stretching vibration and CO stretching vibration
1 506	苯环骨架伸缩振动Benzene ring stretching vibration
1 460	甲基C—H变形(在—CH和—CH₂—中不对称)、木质素与木聚糖中的CH₂形变振动Methyl C—H deformation, CH₂ deformation vibration of lignin and xylan
1 425	苯环骨架结合C—H在平面变形伸缩振动Benzene ring skeleton combined with C—H stretching vibration in plane deformation
1 332	愈疮木基和紫丁香基的缩合,紫丁香基、CH₂弯曲振动Condensation of guaiacol and syringing, syringa and CH₂ bending vibration
1 245	木质素酚醚键C—O—C伸缩振动Stretching vibration of lignin phenol ether bond
1 161	吡喃糖环上的C—O—C伸缩振动、在脂基团中的CO伸缩振动C—O—C stretching vibration on the glycan ring and CO stretching vibration in lipid groups
1 112	紫丁香醛芳香核Syringic aldehyde aromatic nucleus
1 056	在仲醇和脂肪醚中的C—O变形C—O deformation in secondary alcohols and aliphatic ethers

序号Number	样品名称Samples name	2θ/(°)	C_rI(%)	LOI	HBI
1	N1(松木对照样)N1(Pinus control)	21.26	38.71	0.94	1.24
2	乙醇钠处理松木Sodium ethoxide for Pinus	22.48	41.92	1.02	1.09
3	N2(杉木对照样)N2(C. lanceolata control)	21.20	40.63	0.92	1.11
4	乙醇钠处理杉木Sodium ethoxide for C. lanceolata	22.86	48.42	0.98	1.04
5	N3(水曲柳对照样)N3(F. mandschurica control)	22.19	36.50	0.96	1.15
6	乙醇钠处理水曲柳Sodium ethoxide for F. mandschurica	22.28	38.09	1.04	1.11

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