人工林木材的苯酚液化及树脂化研究Ⅰ.液比和催化剂对液化反应的影响

在硫酸催化作用下用苯酚对人工林杉木和杨木进行液化,考察液比(苯酚与木粉的质量比)及催化剂用量对液化反应效率和液化产物分子特征的影响,结果表明:随着液比的提高和催化剂用量的增加,液化反应效率提高,液化产物残渣率降低;液化产物的重均分子量及分子量分布随着液比的提高而迅速减小,随着催化剂用量的增加而逐渐增大.     

超临界水中蔗渣的液化反应及其产物的结构表征

以Na2CO3、K2CO3、NaOH为催化剂,在375~400℃的超临界水中进行蔗渣的液化反应。考察了液固比、反应时间、反应温度和催化剂对蔗渣液化的影响。在380℃、液固比18∶1(质量比)、反应时间20 min条件下,NaOH或Na2CO3催化剂用量为1%时,液化残渣率降到10%以下,而在同样条件下,KCO催化剂用量为3%时,液化反应的残渣率降到7%以下。对液化产物进行了表征。GC-MS分析表明,液体产物的主要组成是含环状结构的酮和一些含甲基、羟甲基等官能团的苯酚类化合物,气体产物主要为C1~C4烷烃和CO、CO2、H2等无机气体,且其组成因液化温度而变化。液化残渣经过FT-IR分析和扫描电镜分析,发现其主要由焦炭以及尚未完全分解的木质素组成。     

杨木粉液化产物及其树脂制备工艺

随着石油资源的不断匮乏,速生杨木这种可再生生物质资源逐渐被人们所重视,为制备可以替代传统树脂的新型树脂材料,解决当今能源危机问题,许多国家都在生物质资源利用方面做了研究。以杨木屑为原料,通过液化试验制备液化产物,再通过液化产物制备树脂,研究催化剂和液化剂用量、反应时间以及反应温度对液化产物所制树脂的影响,寻找较优制备条件。结果表明:液化反应在液固比为1.5的70%苯酚用量、聚乙二醇400的复合液化剂,4%浓硫酸催化剂用量,135℃的液化反应温度,120 min的液化反应时间条件下,可制备出效果较好的液化产物,其残渣率为7%,羟值为370 mg/g。通过液化产物制备树脂的较佳条件是:甲醛与液化产物摩尔比1.2,Na OH与液化产物摩尔比0.5,反应温度85℃反应时间120 min。在此条件下制得优质树脂,黏度为4 500~6 500 m Pa·s,固含量70%~80%。     

芭蕉芋渣苯酚液化物制备酚醛发泡材料

以苯酚为液化剂对芭蕉芋渣进行液化,获得的液化产物树脂化后用于制备发泡材料。探讨液固比、温度、催化剂对芭蕉芋渣液化效果的影响,并分析芭蕉芋渣液化物的树脂化制备发泡材料的性能。结果表明,苯酚与芭蕉芋渣的质量比为6以上获得较好的液化效果;温度在120℃时,残渣率较低;用硫酸(98%)作催化剂比磷酸、盐酸的效果好。芭蕉芋渣液化的最佳工艺条件是液固比6,温度120℃,催化剂为硫酸(98%)、用量5%,液化时间是60 min。制备的芭蕉芋渣树脂的游离甲醛含量为1.09%,可在一定意义上取代酚醛树脂,既能减少成本,又有利于保护环境。     

木材液化及其在聚氨酯胶黏剂上的应用研究

通过考察木粉在催化剂存在下的加溶剂液化,确定了木粉液化的最佳工艺条件,即:温度160℃,m(苯酚)∶m(木粉)为5∶1,催化剂用量1.2 mmol/g,反应时间60min,残渣率降至3.5%.并发现随着反应时间的延长,液化物出现再凝聚的残渣.利用液化产物制备了聚氨酯胶黏剂,拉伸剪切强度达5 MPa,达到应用要求,为今后的工业化生产提供了依据.     

竹材苯酚液化及胶黏剂制备工艺

采用单因素试验和正交试验研究了竹材加工剩余物的苯酚液化工艺,并进一步研究了竹材苯酚液化产物-甲醛树脂胶黏剂(BPF)的制备工艺和性能。试验结果表明:竹材苯酚液化过程中,液化温度对液化效果的影响最为显著,其次是液比和液化反应时间,催化剂用量2%~4%范围内对液化效果影响不大。竹材加工剩余物苯酚液化的优选工艺为:液固比值3.5、催化剂用量4%、液化温度145℃、液化时间60 min;在此工艺下竹材液化率为99.1%。胶黏剂制备过程中,竹材苯酚液化物与甲醛溶液(甲醛质量分数为37%)的合理质量比为100∶164.8~199.5,其中以100∶182.1较佳。BPF的固化温度低于普通酚醛树脂胶黏剂(PF),因而可在较低温度下固化良好,在130℃或140℃热压温度条件下,用其制备的胶合板的胶合强度均比较理想,热压温度为140℃时的试验结果更佳。     

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。     

酸催化下苯酚液化木材的制备与表征

在硫酸作用下用苯酚对人工林杨木和杉木进行液化,考察反应时间、反应温度等对液化反应的影响,并对液化产物进行表征分析.结果表明:1)在硫酸催化下,杨木和杉木被苯酚液化的历程相似,但残渣含量稍有不同.酸性催化剂不仅对纤维素和半纤维素起作用,对木质素也起作用.2)反应温度比反应时间对液化效率的影响大,二者均能影响液化产物的分子量和分子量分布.通常杉木液化产物的重均分子量高于杨木.3)液化过程中,木质素和半纤维素首先被液化,最后是纤维素.木材组分的分解、酚化和再缩聚反应主宰整个液化动力学过程及液化产物的结构特征.     

沙柳聚乙二醇/丙三醇液化工艺研究

以聚乙二醇400和丙三醇为液化剂,浓硫酸为催化剂,对沙柳木粉进行液化试验,通过单因素分析和正交试验,探索了不同条件对液化反应的影响,试验结果表明:当液固比为5:1,聚乙二醇400用量为液化剂用量的75%,催化剂用量为液化剂用量的4%,液化时间为110min,液化温度为170℃时,液化残渣率可低至1.32%。沙柳木粉液化产物的羟值随时间的增加从389mg/g降到334mg/g,能满足制备聚氨酯纤维对原料的要求。     

玉米秸秆的催化热化学液化研究

研究了玉米秸秆在多元醇中的液化反应,讨论了不同反应条件的影响,并分析探讨了液化产物的性质及其组成成分随反应时间的变化.实验结果表明:玉米秸秆在聚乙二醇-丙三醇 (质量比80∶ 20) 的液化溶剂中,当催化剂H2 SO4质量分数为3%、液固质量比为10∶ 2,反应温度150℃时液化效率较高,液化反应180min后其残渣率仅为8.1%.在液化反应初期,玉米秸秆中的木质素已完全液化;随着液化反应时间的延长,其液化残渣率逐渐降低,液化产物的羟值在375 ~ 330mg/g间逐渐降低、酸值在13 ~ 27mg/g间逐渐增加;其重均相对分子质量(MW)为1200 ~ 1450.GC-MS分析表明,液化产物中主要含有多元醇的低聚合体,以及多元醇和玉米秸秆降解产物的氧化和酯化反应产生的羧酸及其酯.     

Factors affecting the resinification of liquefied phenolated wood

Wood of Chinese fir and poplar were liquefied in phenol at 150℃ and atmospheric pressure. The liquefied wood were reacted with formaldehyde to synthesize the liquefied wood-based resin. The factors affecting the resinification and the properties of new resin were investigated. The results show that the formaldehyde/liquefied wood molar ratio, reaction temperature, reaction time and sodium hydroxide/liquefied wood molar ratio have important influence on the resin characteristics. With the increase of formaldehyde/liquefied wood molar ratio, the yield of resin increases, and the flee phenol content of resins decreases, showing that the resinification of liquefied wood is more complete at higher formaldehyde/liquefied wood molar ratios. The reaction temperature on the viscosity of the liquefied resin has considerable effect; the viscosity of resin increased with increasing reaction temperature, and the amount of liquefied poplar resin increased more quickly than that of liquefied Chinese fir resin. The resinification time also has obvious influence on the viscosity of resin; the viscosity of liquefied poplar resin is more sensitive to resinification time compared with that of liquefied Chinese fir. The amount of sodium hydroxide can improve the water miscibility of liquefied wood resin. The optimum sodium hydroxide/liquefied wood molar ratio for preparation of liquefied wood-based resins exceeds 0.4.     

在酸催化下不同形态木材液化的研究

对粉状、纤维状和刨花状等形态木材,在不同酸催化下的液化效果进行的研究发现,木材液化率几乎不受木材颗粒粒度的影响,木液比和催化剂的种类是影响液化反应的重要因素,对液化率的影响较大.     

Effects of phosphoric acid on liquefaction of wood in phenol and optimum liquefaction processing parameters

To clarify the influencing factors of liquefaction of wood in phenol using phosphoric acid as a catalyst and get its liquefaction technology, a study on the liquefaction technology of Chinese fir (Cunninghamia lanceolata) and poplar (triploid Populus tomentosa Carr) under different conditions was conducted. The results indicate that the residue rate decreases with the increase of liquefaction temperature, liquefaction time, catalyst content or liquid ratio. It is also found that the optimum condition of liquefaction for poplar is estimated as: the reaction temperature of 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio)of 4.5 and catalyst content of 8%, and 4.2% residue rate could be obtained. Under the processing parameters of temperature 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio) of 4 and catalyst content of 10%, the residue rate of Chinese fir can reach 5.6%.     

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。     

Preparation and Characterization of Phenolated Wood Using Sulfuric Acid as a Catalyst I: Liquefaction Behavior of Plantation Wood

Chinese fir (Cunninghamia lanceolata) and poplar (Populus spp.) wood meal were phenolated in the presence of sulfuric acid used as a catalyst. The effects of reaction time and reaction temperature on the wood liquefaction were investigated. The results showed that the reaction temperature had the greater influence on the residue content than reaction time. Additionally, the liquefaction curve for the Chinese fir and Poplar were similar in general.     

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     

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。     

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。     

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。     

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.