工业木质素分级分离的基础研究
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摘要
在国家“863”计划项目(项目编号:2002AA322050)资助下,针对现有工业木质素因成分复杂、分子量多分散性而导致其熔融加工困难、工业规模化应用价值低的问题,本论文从分子量这一基本物理性质入手,应用现代研究手段,分别采用改进的酸析沉淀法、有机溶剂连续萃取法、逐步沉淀法等分级分离工业木质素,使其分子量分布可控,并对影响各级分应用加工中的纯度、热稳定能力以及热塑性能等关键因素进行测试分析。研究结果如下:
(1)改进的酸析沉淀法分级纯化工业木质素的过程中受酸的种类、碱液浓度、酸析温度、分级pH、离心转速多因素共同作用。通过二次旋转正交组合设计实验获得优化的工艺条件为15%NaOH(W/W),分级温度50-60℃,酸析终点pH值3-5,离心转速3000-4000rpm,可控制级分的分散度在1.6-2.3之间,比原料降低了69.17%-55.68%。IR、UV、TG、DSC等方法对所得级分特性表征,结果表明:与原料相比,被表征的级分中灰分含量最高降幅为59.65%,含糖量最高降幅为53.69%,纯度最高增幅为13.27%。游离羟基、非共轭羰基和酯键中C-O-C的伸缩振动随着分子量增大而增加,酚羟基和芳环上C-H伸缩振动随着分子量增大而减小。高分子量级分紫丁香基结构较少,并且存在较多与羰基相连的苯环。随着分子量的增加,木质素级分最大失重峰往高温区移动,分解温度Tdmax由294.7升高到380.2℃,热稳定性逐渐增强。玻璃化温度最高的级分为206℃,比原料提高了24.8%。改进的酸析沉淀法可用于直接从碱法制浆黑液中分级提取出木质素,同时可避免在传统酸析法中因引入无机酸、SO2、CO2和电解质等化合物而造成的二次污染,为碱法制浆黑液处理工艺改造提供一定的参考依据。
(2)通过进行不同有机溶剂对木质素的溶解能力和溶解特性研究,在此基础上探索有机溶剂连续分级纯化法,对分级效果进行评价,并形成确定的工艺流程。结果表明:有机溶剂对木质素的溶解能力大小依次为二氧六环>丙酮>乙酸乙酯>甲醇>正丁醇。正丁醇对于低分子量级分溶出性较好,分子量<500的低分子量部分占11.29%;乙酸乙酯对于高分子量级分溶出性较好,分子量>10000的高分子量部分占11.91%。采用按极性从小到大的顺序,用溶剂抽提木质素,可以实现对木质素的分级。有机溶剂萃取分级法可以获得纯度>95%,玻璃化温度>150℃,热稳定性良好,可热塑,可降解的系列木质素产品,提高木质素附加经济效益。有机溶剂萃取分级法利用不同有机溶剂对木质素的溶解能力实现分级,工艺流程处理量大、分级速度快、综合成本低,无三废排放,为有机溶
剂制浆造纸企业资源化生产木质素提供一定的参考依据。(3)对木质素/溶剂/沉淀剂的三元沉淀分级体系进行研究,使用丙酮作为溶剂,水作为沉淀剂,对纯化后的工业木质素进行逐步沉淀分级。获得的级分重均分子量Mw逐渐降低,随着重均分子量的增加去除了低分子量尾端,随着重均分子量的降低去除了高分子量尾端,从而有效降低了分散系数,各级分的分散系数在1.1-1.9之间,比分级前降低了63.39%-78.71%,分级回收率R为94.82%。分级使得木质素灰分、多戊糖、水分等杂质含量都有效降低。与原样相比,分级后级分纯度最高增幅为16.67%,Td_(max)最大增幅为22%,玻璃化温度(Tg)最高增幅为29.7%,热稳定性和加工性能加强。
All the works of this research were supported by the Hi-Tech Research and Development Program of China(NO. 2002AA322050). Due to condensation or degradation occurred in isolation process, industrial lignin has the characteristics of low purity, complicated composition and broad molecular weight distribution. Therefore, industrial lignin is is hard to processing and utilization. From the point of molecular weight which is one of the basic physical properties, industrialized classification method of lignin have been studied systematically in this paper. The results are as follows:
(1) Classification process of industrial lignin used the improved acid precipitation method were influenced by the acid type, alkali concentration, temperature, classification pH and rotation speed. Four factors quadratic orthogonal combination experiment demonstrated that the optimal condition of fractionation are 15% sodium hydroxide solution(mass ratio), 50-60℃, pH 3-5 and 3000-4000 rpm centrifuge speed. Molecular weight distribution could be controlled between 1.6-2.3. Characterization of the fractions are as followers: ash and sugar farthest decreased 59.65% and 53.69%, lignin purity farthest increased 13.27%. Free OH, non-conjugated carbonyl and ester bonds in the C-O-C stretching vibration increase with increasing molecular weight, aromatic C-H stretching vibration and phenolic hydroxyl decrease with increasing molecular weight. There are smaller syringyl units and more carbonyl connected to the benzene ring in the high mol.wt fraction. With the increase of molecular weight, maximum weight loss peak of lignin fractions move to the high temperature, decomposition temperature Tdmax increase from the 294.7 to 380.2℃, the thermal stability gradually. The highest glass transition temperature is 206℃and increased by 24.8% than the raw materials. The improved acid precipitation method can be used directly to fractional isolation and purification of lignin from alkaline pulping black liquor. The classification process of lignin by organic acids could avoid secondary pollution which produced by the residues of lignin separation such as inorganic acid, SO2, CO2, electrolytes and other compounds in the traditional separation method. Providing a reference for transformation of alkaline pulping black liquor treatment process.
(2) Organic solvents classification process of lignin has been explored on the basis of the study of different organic solvents’dissolving capacities and characteristics to lignin. Classification results show that: the order of organic solvents on the solubility of lignin is dioxane > acetone > ethyl acetate > methanol > n-butanol. N-butanol is better for low molecular weight party(<500) and 11.29% this part in the fraction. Ethyl acetate is better for high molecular weight party(>10000) and 11.91% this part in the fraction. Lignin can be classified used organic solvents by small to large order of polarity. The lignin fraction obtained through this new process, which purity and glass transition temperature higher than 95% and 150℃, have good thermal and thermoplastic stability. The new process has such advantages as large throughput, fast processing speed, low cost and no waste and could provide a reference for organic solvent pulping papermaking enterprises.
(3) Using acetone as the solvent and water as precipitating agent, purified grade industrial lignin step by step. Fractions obtained by molecular weight Mw decreased, low molecular weight part can be removed with the increase of molecular weight and high molecular weight part can be removed with the decrease of molecular weight. Thus, the dispersion coefficient could be reduced effectively and the molecular weight distribution are between 1.1-1.9. Recovery rate of classification is 94.82%. Classification makes the ash, pentosan, water and other impurities are effectively reduced. The fraction’purity, Tdmax and glass transition temperature are farthest increased 16.67%, 22% and 29.7%. The thermal stability and processing properties of lignin are enhanced. The study could provide theoretical basis for preparation of lignin standard sample and research of lignin macromolecular condensed state.
(1)改进的酸析沉淀法分级纯化工业木质素的过程中受酸的种类、碱液浓度、酸析温度、分级pH、离心转速多因素共同作用。通过二次旋转正交组合设计实验获得优化的工艺条件为15%NaOH(W/W),分级温度50-60℃,酸析终点pH值3-5,离心转速3000-4000rpm,可控制级分的分散度在1.6-2.3之间,比原料降低了69.17%-55.68%。IR、UV、TG、DSC等方法对所得级分特性表征,结果表明:与原料相比,被表征的级分中灰分含量最高降幅为59.65%,含糖量最高降幅为53.69%,纯度最高增幅为13.27%。游离羟基、非共轭羰基和酯键中C-O-C的伸缩振动随着分子量增大而增加,酚羟基和芳环上C-H伸缩振动随着分子量增大而减小。高分子量级分紫丁香基结构较少,并且存在较多与羰基相连的苯环。随着分子量的增加,木质素级分最大失重峰往高温区移动,分解温度Tdmax由294.7升高到380.2℃,热稳定性逐渐增强。玻璃化温度最高的级分为206℃,比原料提高了24.8%。改进的酸析沉淀法可用于直接从碱法制浆黑液中分级提取出木质素,同时可避免在传统酸析法中因引入无机酸、SO2、CO2和电解质等化合物而造成的二次污染,为碱法制浆黑液处理工艺改造提供一定的参考依据。
(2)通过进行不同有机溶剂对木质素的溶解能力和溶解特性研究,在此基础上探索有机溶剂连续分级纯化法,对分级效果进行评价,并形成确定的工艺流程。结果表明:有机溶剂对木质素的溶解能力大小依次为二氧六环>丙酮>乙酸乙酯>甲醇>正丁醇。正丁醇对于低分子量级分溶出性较好,分子量<500的低分子量部分占11.29%;乙酸乙酯对于高分子量级分溶出性较好,分子量>10000的高分子量部分占11.91%。采用按极性从小到大的顺序,用溶剂抽提木质素,可以实现对木质素的分级。有机溶剂萃取分级法可以获得纯度>95%,玻璃化温度>150℃,热稳定性良好,可热塑,可降解的系列木质素产品,提高木质素附加经济效益。有机溶剂萃取分级法利用不同有机溶剂对木质素的溶解能力实现分级,工艺流程处理量大、分级速度快、综合成本低,无三废排放,为有机溶
剂制浆造纸企业资源化生产木质素提供一定的参考依据。(3)对木质素/溶剂/沉淀剂的三元沉淀分级体系进行研究,使用丙酮作为溶剂,水作为沉淀剂,对纯化后的工业木质素进行逐步沉淀分级。获得的级分重均分子量Mw逐渐降低,随着重均分子量的增加去除了低分子量尾端,随着重均分子量的降低去除了高分子量尾端,从而有效降低了分散系数,各级分的分散系数在1.1-1.9之间,比分级前降低了63.39%-78.71%,分级回收率R为94.82%。分级使得木质素灰分、多戊糖、水分等杂质含量都有效降低。与原样相比,分级后级分纯度最高增幅为16.67%,Td_(max)最大增幅为22%,玻璃化温度(Tg)最高增幅为29.7%,热稳定性和加工性能加强。
All the works of this research were supported by the Hi-Tech Research and Development Program of China(NO. 2002AA322050). Due to condensation or degradation occurred in isolation process, industrial lignin has the characteristics of low purity, complicated composition and broad molecular weight distribution. Therefore, industrial lignin is is hard to processing and utilization. From the point of molecular weight which is one of the basic physical properties, industrialized classification method of lignin have been studied systematically in this paper. The results are as follows:
(1) Classification process of industrial lignin used the improved acid precipitation method were influenced by the acid type, alkali concentration, temperature, classification pH and rotation speed. Four factors quadratic orthogonal combination experiment demonstrated that the optimal condition of fractionation are 15% sodium hydroxide solution(mass ratio), 50-60℃, pH 3-5 and 3000-4000 rpm centrifuge speed. Molecular weight distribution could be controlled between 1.6-2.3. Characterization of the fractions are as followers: ash and sugar farthest decreased 59.65% and 53.69%, lignin purity farthest increased 13.27%. Free OH, non-conjugated carbonyl and ester bonds in the C-O-C stretching vibration increase with increasing molecular weight, aromatic C-H stretching vibration and phenolic hydroxyl decrease with increasing molecular weight. There are smaller syringyl units and more carbonyl connected to the benzene ring in the high mol.wt fraction. With the increase of molecular weight, maximum weight loss peak of lignin fractions move to the high temperature, decomposition temperature Tdmax increase from the 294.7 to 380.2℃, the thermal stability gradually. The highest glass transition temperature is 206℃and increased by 24.8% than the raw materials. The improved acid precipitation method can be used directly to fractional isolation and purification of lignin from alkaline pulping black liquor. The classification process of lignin by organic acids could avoid secondary pollution which produced by the residues of lignin separation such as inorganic acid, SO2, CO2, electrolytes and other compounds in the traditional separation method. Providing a reference for transformation of alkaline pulping black liquor treatment process.
(2) Organic solvents classification process of lignin has been explored on the basis of the study of different organic solvents’dissolving capacities and characteristics to lignin. Classification results show that: the order of organic solvents on the solubility of lignin is dioxane > acetone > ethyl acetate > methanol > n-butanol. N-butanol is better for low molecular weight party(<500) and 11.29% this part in the fraction. Ethyl acetate is better for high molecular weight party(>10000) and 11.91% this part in the fraction. Lignin can be classified used organic solvents by small to large order of polarity. The lignin fraction obtained through this new process, which purity and glass transition temperature higher than 95% and 150℃, have good thermal and thermoplastic stability. The new process has such advantages as large throughput, fast processing speed, low cost and no waste and could provide a reference for organic solvent pulping papermaking enterprises.
(3) Using acetone as the solvent and water as precipitating agent, purified grade industrial lignin step by step. Fractions obtained by molecular weight Mw decreased, low molecular weight part can be removed with the increase of molecular weight and high molecular weight part can be removed with the decrease of molecular weight. Thus, the dispersion coefficient could be reduced effectively and the molecular weight distribution are between 1.1-1.9. Recovery rate of classification is 94.82%. Classification makes the ash, pentosan, water and other impurities are effectively reduced. The fraction’purity, Tdmax and glass transition temperature are farthest increased 16.67%, 22% and 29.7%. The thermal stability and processing properties of lignin are enhanced. The study could provide theoretical basis for preparation of lignin standard sample and research of lignin macromolecular condensed state.
引文
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