麦草甲酸不溶木质素的结构研究

采用FT-IR、GPC、^1HNMR、Py-GC-MS等手段，分析了麦草在甲酸水解体系中不同温度、不同时间条件下反应后其固体残渣中木质素的结构。FT-IR分析发现，纯化木质素有羧基存在，表明麦草木质素分子结构在甲酸作用下发生了明显的氧化。Py-GC-MS和^1HNMR分析显示，甲酸不溶木质素以愈刨木基为主，紫丁香基含量略高于对羟苯基。Py-GC-MS及GPC分析发现，甲酸反应体系中随着温度、时间的增加，木质素分子质量会降低，各种木质素型的酚类物质占总木质素的高温分类产物的比例都呈下降趋势，表明该反应体系既能促进木质素α-芳基醚键、β-芳基醚键断裂，使得木质素很快溶解在溶液中，同时也能促进木质素的缩合，但总的趋势是使木质素的分子质量下降。     

玉米秸秆酶解木质素及麦草甲酸木质素在钙钛矿催化体系下催化活性比较

考察了玉米秸秆高温爆破法制浆酶解木质素(EL)以及麦草甲酸木质素(SL)在LaMn0.8Cu0.2O3催化体系下催化湿法氧化为芳香醛反应中的活性差异。结果表明:该催化剂对麦草甲酸木质素的对羟基苯甲醛、香草醛、紫丁香醛的最大得率分别提高33%、65%、48%,最大得率分别达到0.56%、2.97%、4.91%;而玉米秸秆酶解木质素分别相应提高85%、57%、208%,最大得率分别达到2.90%、5.07%、14.6%。同时发现麦草甲酸木质素无论在无催化反应还是该催化体系下各芳香醛的得率均远低于玉米秸秆酶解木质素,其原因是麦草甲酸木质素发生了严重缩合,而玉米秸秆酶解木质素接近原始木质素,未发生缩合反应。     

苹果渣中纤维素、半纤维素的提取分离

苹果渣不溶性膳食纤维的主要成分为纤维素、半纤维素、木质素.分别采取甲酸、乙酸、硝酸、硫酸、传统次氯酸钠法及超声波辅助法去除木质素,采用碱处理法分离提取纤维素和半纤维素.     

杨木短时水热处理脱除半纤维素和木质素

对木质纤维素进行水热处理,能够使半纤维素和木质素有效分离进而实现高值利用。本研究探索杨木在温度180~200℃、时间5-10 min的连续多次短时水热处理(SHT),结果表明,半纤维素木糖产率与处理温度正相关,在200℃、5 min条件下2次处理达到最高产量,每吨杨木产出42.7千克木糖,溶出率31.3%。短时水热处理过程中木质素同样大量溶出,在200℃、5 min条件下3次处理,木质素溶出产量达101.1千克/吨木材,溶出率37.6%。与长时间水热处理方式相比,SHT能够更快溶出更多的木质素,这可能与SHT木质素缩合程度低有关。     

基于催化水热预处理棉秆木质素分离及其结构表征

探究了不同催化水热体系对棉秆木质素的分离效果的影响。研究结果表明,基于Ni/H_2O和FeS/H_2O催化水热体系分离得到的棉秆木质素组分得率和纯度均较高。二维核磁谱图表明得到的木质素组分主要是以愈疮木基单元(G型)为主的愈疮木基(G型)-紫丁香基(S型)低分子量木质素片段,类似于典型的阔叶木。此外,棉秆木质素结构单元主要以β-O-4′的连接键连接,同时含有少量的β-β′和β-5′连接。     

麦草秸秆微晶纤维素的制备工艺

研究以麦草秸秆为原料制取微晶纤维素的制备工艺。运用添加乙酸的乙醇法低污染制浆技术,溶出麦草秸秆中的木素、半纤维素等杂质,采用全无氯的臭氧及过氧化氢漂白工艺对粗纤维素进行漂白,然后通过盐酸水解和稀碱处理制备得到微晶纤维素。结果表明,试验制取的微晶纤维素符合合成革用微晶纤维素的标准。在提取粗纤维素过程中催化剂乙酸的最佳用量是2%。水解时间对微晶纤维素产品聚合度的影响较大。麦草秸秆制取微晶纤维素的最佳工艺条件为:液比1:15,水解温度70℃,水解时间90min。碱处理的工艺条件为:碱浓5%,温度80℃,处理时间30min。     

草浆废液制备生物质固沙材料及其在植被恢复上的应用(系列报道之二)生物质固沙材料的结构特性

以禾草纤维制浆废液为主要原料，在合适的条件下经羟甲基化和交联等改性反应后合成新型生物质固沙材料。对生物质固沙材料在反应过程中结构特性变化的研究表明，麦草碱木质素与尿素、甲醛发生了相当程度的缩合，交联产物的大分子量组分有较大幅度提高，而半纤维素与脲醛不能发生交联反应。合成固沙材料的交联反应主要发生在木质素的愈创木基和对-羟基苯基结构上，并且愈创木基结构和对-羟基苯基结构发生交联反应的概率基本相同。生物质固沙材料的固沙强度与木质素C5位交联程度呈现良好的线性关系。     

响应曲面试验优化在过氧甲酸中提取甘蔗渣纤维素的工艺研究

为了获取优质的纤维素,以甘蔗渣为原料,通过降解木质素与半纤维素的,达到提取纤维素的目的。以甘蔗渣为原料研究过氧甲酸氧化降解木质素及半纤维素来提取纤维素的工艺条件,通过单因素试验,分别考察过氧甲酸浓度、反应温度、反应时间对甘蔗渣纤维素含量的影响。在此基础上,应用响应面分析过氧甲酸浓度、反应温度、反应时间及三者两两交互作用对响应值的影响,确定了甘蔗渣纤维素提取的最佳工艺参数。结果表明:各因素对纤维素含量影响的显著性表现为即反应时间>反应温度>过氧甲酸浓度,通过响应面法优化的最佳工艺条件为:温度33.48℃、时间19.71 h、过氧酸浓度0.44 M,在此条件下的纤维素提取率为89.0%。     

葵花籽壳木质素的结构分析及抗氧化活性

以葵花籽壳为原料,采用醋酸法提取木质素,并利用凝胶渗透色谱、紫外光谱、傅里叶变换红外光谱、核磁共振氢谱和热重分析对提取的木质素进行结构表征,并对提取木质素的抗氧化活性进行评价。结果表明:醋酸法木质素提取率为70.12%(相对于Klason木质素),纯度达到88.54%,结合少量的碳水化合物(2.92%)。葵花籽壳木质素为GS型木质素,含有较高的愈创木基结构单元(G),结构单元之间的连接键以β-O-4结构为主,重均分子质量(M_w)、数均分子质量(M_n)和多分散度(M_w/M_n)分别为2 977、1 931 D和1.54。葵花籽壳醋酸提取的木质素主要降解温度在200~400℃之间,最大失质量速率为0.32%/℃。抗氧化活性研究表明,木质素清除1,1-二苯基-2-三硝基苯肼自由基指数值为1.54,显著高于商业合成抗氧化剂二丁基羟基甲苯(0.94),具有很好地应用于食品及其他工业做抗氧化剂的前景。     

热水预水解过程杨木及水解液中组分的变化

探究了热水预水解对杨木组分、微观结构的影响及预水解液中降解产物含量变化的规律。结果表明,在保温时间60 min、保温温度155~175℃以及在保温时间0~120 min、保温温度170℃的条件下,随保温温度的升高或时间的延长,杨木热水预水解后的得率、聚戊糖和Klason木素的相对含量整体减少,纤维素的相对含量和结晶度有所增加;杨木热水预水解后的纤维形貌发生变化,出现不规则碎片和孔洞;预水解液中的酸溶木素含量增加,甲酸、乙酸、糠醛和5-羟甲基糠醛的浓度增加,糖含量随保温温度的升高不断增加,但随保温时间的延长呈先增加后减少的趋势。     

Structural Changes of Wheat Straw Lignin during Formic Acid Treatment

The aromatic nature of lignin makes it a potential renewable source of chemicals and other valuable products.Isolation of lignin from lignocellulosic biomass using organic solvents enables the production of high-purity lignin.The use of formic acid in the organosolv pulping and fractionation process has been widely studied.Characterization of lignin is necessary to achieve valueadded applications of lignin.To simplify the isolation of formic acid-treated lignin,herein,milled wheat straw lignin(MWSL) was employed as an archetype for characterization of the structural changes of lignin during formic acid treatment.The results showed that the MWSL was GSH-type(comprising p-hydroxyphenyl(H),guaiacyl(G),and syringyl(S) monolignols) and underwent structural changes during formic acid treatment.Lignin was esterified during the formic acid treatment.The content of alkyl hydroxyl groups in lignin decreased upon formic acid treatment,corresponding to an increase of the number of double bond equivalents(DBE).Lignin units with active reaction sites were liable to slight condensation,which resulted in a moderate increase of the molecular weight.The molecular weight distribution of formic acid-treated MWSL(FMWSL) was wider than that of the MWSL,although the molecular weight of both species did not differ significantly.The β-O-4 linkage in lignin was partially cleaved during formic acid treatment,resulting in the production of new phenolic structures.This improved the solubility of lignin in the cooking liquor and its reactivity for downstream applications.     

油茶壳木质素理化性质及表征

为充分利用油茶壳资源,研究分别采用醋酸法和碱法提取油茶壳木质素,并对其基本成分、理化性质和结构表征进行了分析。结果表明:提取的醋酸木质素（91.87%）纯度略微低于碱木质素（93.37%）;且醋酸木质素中[C]和固定碳含量较高。两种木质素抗氧化力远大于油茶壳粗膳食纤维;与碱木质素相比,醋酸木质素持水力、溶胀力分别增加了59.49%、55.36%,饱和与不饱和脂肪结合力分别增加了5.06%、2.24%,DPPH自由基清除力增加了10.50%,吸湿率降低了28.14%。紫外和红外光谱谱图可知,醋酸木质素和碱木质素主要由愈创木基和紫丁香基组成;醋酸木质素中愈创木基含量更高,碱木质素中紫丁香基含量更高。热重分析可知,醋酸木质素热稳定性高于碱木质素,更适于高温耐热材料的制备。     

Microwave-assisted organic acid extraction of lignin from bamboo: Structure and antioxidant activity investigation

Microwave-assisted extraction in organic acid aqueous solution (formic acid/acetic acid/water, 3/5/2, v/v/v) was applied to isolate lignin from bamboo. Additionally, the structural features of the extracted lignins were thoroughly investigated in terms of C₉ formula, molecular weight distribution, FT-IR, ¹H NMR and HSQC spectroscopy. It was found that with an increase in the severity of microwave-assisted extraction, there was an increase of phenolic hydroxyl content in the lignin. In addition, an increase of the severity resulted in a decrease of the bound carbohydrate content as well as molecular weight of the lignin. Antioxidant activity investigation indicated that the radical scavenging index of the extracted lignins (0.35–1.15) was higher than that of BHT (0.29) but lower than that of BHA (3.85). The results suggested that microwave-assisted organic acid extraction provides a promising way to prepare lignin from bamboo with good antioxidant activity for potential application in the food industry.     

Effect of ozone and sodium hydroxide treatments on some chemical characteristics of cotton straw

Cotton straw (CS) was treated with ozone or sodium hydroxide, and the effect of treatments on the organic acid and monosaccharide composition and on the chromat-ographic characteristics of alkali lignin was studied. The concentrations of formic and acetic acids in the ozonised CS were 3.98 and 1.36 g 100 g^?1 organic matter (OM) respectively. Oxalic acid was not detected. A high content of uronic acids (9.78 g 100 g^?1 OM) was found in CS. The overall decrease in total monosaccharides in the ozonated CS was very small (5%) with the matrix constituents being principally affected. The 8% sodium hydroxide treatment exerted a very limited effect on the composition of CS cell walls. Ozonation increased the content of soluble carbohydrates from 9.2 to 21.8%; this was contributed mainly by the hemicellulose fraction. Alkali lignin was extracted from CS and was fractionated by gel chromatography. The elution pattern of alkali lignin was very similar for the treated and untreated materials. The three peaks coincided at an average mol. wt of 40 000, as judged from the use of dextran standards.     

Characterization of asparagus lignin by HPLC

Lignin is the cell wall component most frequently associated with hardening. Its characterization and quantification are very important to understand the biochemical modifications related to the changes in texture of vegetables such as asparagus (Asparagus officinalis), in which this organoleptic attribute is a very important quality factor. In this study, asparagus lignin from the basal sections of fresh and stored spears was analyzed using 2 methods, the traditional (Klason lignin) and the recently developed derivatization, followed by reductive cleavage (DFRC) method. The latter is a simple and reproducible technique for lignin characterization based on a degradation procedure that produces analyzable monomers and dimers by cleaving alpha- and beta-aryl ethers in lignins. The primary monomers derived from DFRC degradation of lignins are essentially p-coumaryl peracetate, coniferyl peracetate, and sinapyl peracetate. To evaluate the efficiency of the DFRC method, our investigations have been carried on distinct sample types, including wood (data not shown), straw, and asparagus samples. The results have confirmed that lignin composition is affected by plant nature. It has been found that whereas wood samples mostly contain coniferyl units, plant foods, such as straw and asparagus, contain both coniferyl and guaiacyl units.     

杨木自催化乙醇制浆废液中有机酸的分析

针对杨木自催化乙醇法蒸煮废液成分复杂、副产物价值高等特点,对废液中的有机酸进行分析。首先制取杨木自催化乙醇制浆废液,对分离出木素的废液用乙醚萃取,将萃取物用气相色谱-质谱联用检测仪进行定性分析。结果表明,废液中的各成分复杂而且都很微量,主要是一些酸、酯、低分子木素等,约25种,其中乙酸和甲酸含量较高。其次对杨木自催化乙醇法蒸煮废液减压蒸馏至无液体来分离木素,对全部馏分采用容量分析的方法测得总酸含量为0.043 mol/L,同时用气相色谱定量测得乙酸含量为1.864 g/L、甲酸含量为0.665 g/L。     

Synthetic-resin-free wood panel adhesives from mixed low molecular mass lignin and tannin

Mixed interior wood panel tannin adhesive formulations were developed in which lignin is in considerable proportion, 50%, of the wood panel binder and in which no “fortification” with synthetic resins, such as isocyanates and phenol-formaldehyde resins as used in the past, was necessary to obtain results satisfying relevant standards. A low molecular mass lignin obtained industrially by formic acid/acetic acid pulping of wheat straw was used. Environment-friendly, non-toxic polymeric materials of natural origin constitute up to 94% of the total panel binder. The wood panel itself is constituted of 99.5% natural materials, the 0.5% balance being composed of glyoxal, a non-toxic and non-volatile aldehyde, and of hexamine already accepted as a non-formaldehyde-yielding compound when in presence of condensed tannin. Both particleboard and two types of plywood were shown to pass the relevant interior standards with such adhesive formulations. Moreover, the much cheaper non-purified organosolv lignin showed the same level of results as the more expensive purified type.     

Degradation of tert-butyl alcohol in dilute aqueous solution by an O3/UV process

This paper describes the degradation of tert-butyl alcohol (TBA) in dilute aqueous solution by an O3/UV process. The degradation process was investigated experimentally in a semi-batch reactor under various operational conditions, i.e., ozone gas (O3) dosage, UV light intensity, and water quality in terms of varying bicarbonate concentration. TBA was oxidized rapidly in the O3/UV system, and acetone, hydroxy-iso-butyraldehyde, and formaldehyde were identified as primary intermediates, whereas pyruvaldehyde and acetic, formic, pyruvic, and oxalic acids were generated as a result of further oxidation process. A good organic carbon balance was obtained, indicating that most reaction intermediates have been identified and quantified.