小麦秸秆加压液化制备乙酰丙酸乙酯

以小麦秸秆为原料,浓硫酸为催化剂,乙醇为溶剂进行液化实验,分析了液化产物的组成,考察了不同条件对目标产物乙酰丙酸乙酯(EL)得率及液化率的影响。结果表明:在浓硫酸用量10%、反应温度190℃、反应时间60 min,液固比为18∶1(g∶g)条件下,小麦秸秆的液化效果较好,液化率为75%,此时EL的得率为18.11%;经红外光谱分析可知秸秆在反应过程中发生降解;液体产物中包含醛、酮、酯、酚、酸类等多种含氧化合物,纤维素降解生成葡萄糖、葡萄糖苷、乙氧基甲基糠醛等中间产物,并最终转化为乙酰丙酸乙酯。     

木粉及其组分的多元醇酸催化热化学液化

分别将木粉、纤维素和木质素在乙二醇中进行热化学液化。研究结果表明木粉中纤维素的非结晶区、木质素和半纤维素首先被液化,而纤维素的结晶区较慢被液化,到液化反应中期基本降解完全,液化产率高于97%。利用在线红外光谱仪跟踪检测了整个液化反应过程,结合GC-MS结果发现:乙二醇在反应过程中脱水生成了二甘醇和三甘醇。在液化反应中,纤维素的糖苷键断裂后生成葡萄糖苷结构,随后葡萄糖苷中的吡喃环也被打开,生成的活性中间体相互反应或与乙二醇反应生成了如3-(2-甲基-[1,3]-二氧戊环-2-基)-丙酸乙酯、乙酰丙酸丁酯等酯类;木质素的苯丙烷结构主要降解为苯酚、2,6-甲氧基苯酚等芳香族衍生物,因此木粉液化产物是聚醚/酯混合多元醇。     

农作物秸秆加压液化制备乙酰丙酸乙酯及其分离初探

分别选取小麦、玉米和水稻等3种农作物的秸秆为原料,乙醇为溶剂,98%浓硫酸为催化剂,在反应压力2.25 MPa,反应温度200℃,催化剂用量5%,反应时间60 min和固液比1∶15(质量比)的条件下,进行加压液化的初步研究,对液化产物进行分析,并分离得到液化产物中的乙酰丙酸乙酯(EL)。结果显示:同等液化条件下,所选原料中小麦秸秆的液化效果最好;FT-IR、TG-DTG和SEM分析表明液化过程中小麦秸秆组分的结构发生改变和降解,液化产物的主要组分为EL,在水相的乙酸乙酯萃取液中EL的GC含量为52.61%;在蒸馏分离的过程中,EL的纯度可达92.71%,回收率达89.93%。     

熔盐裂解液化生物质的研究

为了考察熔盐组成、原料种类和裂解温度等因素对生物质裂解液化的影响,在自行设计的反应器中进行了实验研究。结果表明:纤维素在ZnCl2中液化,生物油得率最高,为35%;在66%(物质的量分数)KCl-CuCl中液化,生物油中水分含量最低,为21%;硝酸盐不适于生物质液化反应,生物油得率为零。以纤维素为原料的生物油得率高于以水稻秸秆为原料的生物油得率,而且生物油中的水分含量较低,说明含纤维素较多的生物质原料更适于裂解液化。热裂解反应受温度影响较大,生物油得率随温度升高呈先升高后降低的趋势,存在一个较优的温度,对纤维素原料而言在530℃左右,水稻秸秆在450℃左右。采用FT-IR和GC-MS对生物油进行初步分析,生物油成分比较复杂,其中呋喃类物质占有较大比例。     

Preparation and Characterization of the Phenolated Wood Using Sulfuric Acid as a Catalyst Ⅱ. FT-IR and GPC Characterization

By means of gel permeation chromatography analysis, the molecular weight of liquefied wood under different reaction conditions was investigated to trace the change in the structural characteristics of the liquefied wood. The insoluble residues were analyzed by Fourier transform infrared to investigate the liquefaction order of three main wood components. The results indicate that both reaction temperature and reaction time could affect the molecular characteristics of the liquefied wood obtained. The molecular weight of liquefied Chinese Fir wood is higher than that of liquefied Poplar wood under most of reaction conditions. During wood liquefaction, lignin is liquefied firstly. Hemicellulose is liquefied in the middle stage and cellulose is the most difficult to be liquefied.     

杉木粉液化与液化产物树脂化的研究

以硫酸为催化剂、苯酚为液化剂采用溶剂热法对杉木粉进行液化,用杉木粉液化产物制备出酚醛树脂;考察了反应温度、反应时间、液比(苯酚-木粉的质量比)和催化剂用量对杉木粉液化效率的影响,并初步探讨了液化产物残渣率对所制酚醛树脂性能的影响。实验结果表明,杉木粉液化的最佳工艺条件是:反应温度160℃,液化时间12 h,液比值3,催化剂用量3%,在此条件下残渣率约为10%。液化产物残渣率的测定表明,升高反应温度、延长反应时间、增加液比和催化剂用量可以降低残渣率,提高液化效率;液比值为0.5~1.5时残渣率随液比增加而显著降低,催化剂用量为0.5%~2%时液化效率的变化明显。红外光谱结果表明,由液化产物所合成的酚醛树脂中羟甲基含量较高。液化产物残渣率低时制备的酚醛树脂残碳率较高。     

Effect of ozone treatment of wood on its liquefaction

The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.Part of this report was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003     

基于微波液化的木质纤维素组分分离和转化——纤维素组分的理化和酶解性质

【目的】将微波加热与甘油利用相结合的综合炼制工艺用于木质纤维素生物质预处理,探索其在燃料乙醇制备中的可行性,为实现经济可行、经济有效的木质纤维素生物质酶解预处理技术和生物燃料生产提供基础信息。【方法】以银腺杨、日本落叶松、刚竹和柳枝稷为试验材料,采用微波液化法对其进行液化处理,将液化产物分为纤维素、半纤维素和木质素组分,并对纤维素纤维组分进行综合表征。【结果】化学分析结果表明,纤维素纤维具有较高的葡聚糖含量;红外光谱显示,木质素和半纤维素的信号逐渐减弱,说明半纤维素和木质素经液化处理后有效脱除;XRD分析结果表明,纤维素纤维结晶度高、表面积大。【结论】相比原木质纤维素生物质,银腺杨、日本落叶松、刚竹和柳枝稷4种原材料纤维素纤维的酶解糖化效率均有不同程度提升(最高酶解转化率可达70%),液化固体产物--纤维素纤维在制备燃料乙醇中具有广阔的潜力和前景。     

Liquefaction and FTIR analysis of two desert shrubs Salix psammophila and Caragana intermedia

1 Introduction Desert shrubs are made up of natural composite mate- rials, composed of cellulose, hemicellulose and lignin. Although there are a large number of hydroxyl groups in them, these are not fully used due to the high crys- tallinity of cellulose and tight interconnection among polymeric components in wood (Cheng et al., 2002). Liquefaction of wood is a new technique in wood in- dustries. It is a novel process which effectively con- verts the chemical composition of wood into macro- …     

Reaction behavior of wood in an ionic liquid, 1-ethylpyridinium bromide

The reactions of Japanese cedar and Japanese beech in a pyridinium-based ionic liquid, 1-ethylpyridinium bromide ([EtPy][Br]) were studied. Japanese beech was more easily liquefied than Japanese cedar. Hemicellulose is liquefied rapidly, lignin more slowly, while cellulose is partially liquefied. X-ray diffraction analyses on the [EtPy][Br]-insoluble residues revealed that the crystalline structure of cellulose is maintained even after treatment. The difference in liquefaction can be explained by chemical structural differences between softwood and hardwood lignins and hemicelluloses.     

沙柳多元醇液化产物流变性能的研究

沙柳木粉在液化剂和催化剂的作用下制成的液化产物可生产制作聚氨酯、环氧树脂、胶黏剂等。研究沙柳液化产物的流变性能,可探索宏观流变性质与液体微观内部反应机理之间的关系,优化设备结构和加工工艺条件,对其高效利用有着重大意义。本试验将沙柳木粉在浓硫酸催化条件下进行多元醇液化,通过改变液化处理条件(反应时间、反应温度和催化剂用量)制备具有不同流变性能的沙柳液化产物。利用旋转型流变仪对所制备的沙柳液化产物进行流变性能测试和分析。沙柳木粉液化条件的单因素试验和正交试验分析结果表明:影响沙柳液化产物黏度的主要因素是反应时间,其次是反应温度和催化剂用量,最佳工艺条件为反应时间70 min、反应温度170℃、催化剂用量5%。在最佳工艺条件下,剪切速率为78.87 s-1时,黏度为0.26 Pa·s。红外光谱(FT-IR)分析得出,液化物中纤维素被大量降解,半纤维素和木质素部分降解,羟基增加,生成更多的反应活性官能团,此条件下液化反应更加充分,流体黏度较大。流变性能测试结果显示:稳态扫描测试时,黏度随剪切速率的增加逐渐减小,表现出剪切变稀的现象;剪切应力随着剪切速率的增加逐渐升高,表现出假塑性流体的性质。通过动态频率扫描曲线变化规律分析,储能模量和损耗模量随着角频率的升高而逐渐增加,复数黏度却随之减小。     

蔗渣在碳酸乙烯酯中的快速液化

研究了蔗渣在碳酸乙烯酯中以硫酸为催化剂的快速液化反应。讨论了温度、液固比及催化剂用量等因素对液化反应的影响。对液化产物进行了表征。结果表明蔗渣在碳酸乙烯酯中反应10～20min,残渣率即可降到3％。液化产物为一聚醚酯多元醇体系,羟值为220．330mg／g,可用来制备环氧树脂粘合剂。     

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

Reaction behavior of wood in an ionic liquid, 1-ethyl-3-methylimidazolium chloride

Reaction of Japanese beech (Fagus crenata) in an ionic liquid, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which can dissolve cellulose, was investigated. Although both lignin and polysaccharides such as cellulose and hemicelluloses can be liquefied at a treatment temperature of around 100°C, the liquefaction of polysaccharides mainly occurs at the beginning of the treatment with [C2mim][Cl]. Cellulose crystallinity in the wood was gradually broken down as the treatment continued. The solubilized polymers were depolymerized to low molecular weight compounds. The results indicate that [C2mim][Cl] is an effective solvent and reagent for the liquefaction of wood components and subsequent depolymerization of them. Part of this report was presented at the 58th Annual Meeting of the Japan Wood Research Society, Tsukuba, April 2008     

超声波-微波对杉木锯屑液化的强化效应研究

以正辛醇为溶剂、浓硫酸为催化剂,探讨了超声波-微波（UW-MW）辅助对杉木锯屑液化的强化作用,考察了工艺参数的影响,并对液化产物进行了表征分析。研究结果表明：超声波-微波具有很好的传质传热强化效应,与传统液化相比,杉木锯屑超声波-微波辅助液化反应时间从60 min缩短至20 min,液化率提高了5.24%。在溶剂与锯屑质量比值6、催化剂H₂SO₄浓度0.6 mol/L时,杉木锯屑液化率达到64.30%;适当添加γ-戊内酯可提高液化率,γ-戊内酯用量40%时液化率达81.17%。液化过程中,少量熔融状物质沉积在残渣（SR）表面,阻碍了原料的进一步液化;纤维素与半纤维素的降解产物主要为小分子糖类等物质,富集在水相产物（WS）中;木质素的降解产物主要由芳香族等物质组成,分布在生物油（BO）产物中。     

思茅松的苯酚液化及树脂化研究

研究了硫酸催化条件下，将恩茅松在苯酚中液化用于制备酚醛树脂的技术工艺，分析了各工艺参数对思茅松液化效率的影响，测定了由液化产物制备的液化木基酚醛树脂的物理化学性质和胶合强度。结论如下：1）．液比、反应温度、时间和木粉目数是影响液化反应效率的重要因素，液化产物的残渣率均随上述工艺参数值的升高而降低。2）．残渣含量对树脂物化性质和胶合强度均有影响，残渣含量降低，树脂粘度减小，聚合时间缩短，游离酚含量降低，胶合强度升高。3）．甲醛／苯酚摩尔比对树脂的物化性质和胶合强度也有影响，甲醛／苯酚摩尔比增加，树脂粘度增加，聚合时间减少，游离酚含量减低，胶合强度升高。     

我国生物质废料液化及产物利用的研究进展

对国内生物质废料液化及液化产物利用的研究进展进行了较全面的概括和评述,指出了在我国进行生物质废料液化研究的重要性,重点讨论了不同液化条件下生物质原料液化过程中的主要影响因素和液化物的利用;分析了一些具有代表性的液化物构成特征;对我国该领域研究的存在问题和产业化发展提出了见解.     

竹材在溶剂中的催化液化技术研究进展

比较分析了不同种类液化介质条件下竹材的催化液化特性,包括液化产率、影响因素和液化产物的应用等。其中最常用的液化溶剂为苯酚和醇类,对竹材均具有很好的催化效果,而其他液化溶剂的催化液化工艺的实际应用技术还有待进一步优化。     

油茶饼粕的苯酚液化及产物的结构表征

为了综合利用油茶饼粕,分析了油茶饼粕的基本组成,采用苯酚为液化剂,硫酸为催化剂,对油茶饼粕进行了液化实验。结果显示油茶饼粕中糖类、粗纤维和粗蛋白质的总质量分数约为75%,能够有效进行液化。研究了反应温度、苯酚与油茶饼粕的质量比(液比)、催化剂的用量及液化时间对液化反应的影响,实验得出较佳的液化工艺条件为:硫酸用量4%,液化时间1.5 h,液化温度140℃,液比值4,此时液化残渣率16.25%。利用傅里叶红外光谱(FT-IR)分析了油茶饼粕及其液化残渣和产物的结构特征,结果显示苯酚与油茶饼粕组分发生了明显酚化反应和醚化反应,形成了更多的活性官能团。油茶饼粕中蛋白质结构遭到破坏,蛋白质也发生了液化反应。     

Rapid wood liquefaction by supercritical phenol

Wood was rapidly liquefied at the supercritical temperature of phenol. Under these conditions, wood was liquefied by over 90% for 0.5 min, and the combined phenol content of the obtained liquefied wood reached about 75%. The effects of various reaction conditions on liquefaction were investigated. With increases in reaction temperature, phenol/wood weight ratio, and the charged mass-to-reactor capacity (w/v) ratio, the amount of methanol-insoluble residue decreased and combined phenol content increased. The range of molecular weights and polydispersity of the products obtained after the time at which sufficient liquefaction was achieved were from 400 to 600 and from 1.5 to 2.5, respectively. Wood showed a marked decomposition to low molecular weight components early in the reaction, and then the molecular weight increased slightly with increasing reaction time. The properties of liquefied wood were investigated and compared with those obtained with conventional liquefaction methods. Combined phenol content was similar to that obtained by other liquefaction methods, except the sulfuric acid–catalyzed method, which resulted in flow properties comparable to those of other liquefaction methods. The flexural strength of moldings prepared using liquefied wood was also comparable to those prepared by other liquefaction methods.