超声波活化碱木质素及多效碱木质素水处理剂合成与应用研究
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摘要
本论文是国家自然科学基金资助项目“钯/炭-Pb/C催化碱木质素还原反应的研究”(课题编号:30471363)的部分内容。麦草碱木质素是我国造纸工业重要的剩余物,由于麦草碱木质素结构决定了其反应活性比较低,其应用受到较大的限制。本论文以提高麦草碱木质素的反应活性为目标,首次采用超声波法活化麦草碱木质素,研究了超声波处理时间、作用功率和作用液料比等因素对麦草碱木质素总羟基含量的影响,并采用官能团分析、凝胶色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振~1H-NMR等研究手段,探讨了超声波作用于麦草碱木质素的作用机制。根据麦草碱木质素具有多种官能团的结构特点,国内首次合成了麦草碱木质素季胺盐、磺化麦草碱木质素季胺盐、麦草碱木质素膦酸季胺盐和麦草碱木质素膦基盐等四种多效水处理剂,根据其所接官能团结构特点,分别检测其絮凝、分散、络合和阻垢等性能,并阐述了麦草碱木质素季胺盐的絮凝机理和麦草碱木质素膦酸季胺盐的阻垢机理。论文还将麦草碱木质素与超声波处理麦草碱木质素合成的多效水处理剂性能进行比较。结果表明:
超声波可以显著提高碱木质素酚羟基和醇羟基含量。当作用时间为20min,作用功率为200W,液料比为100:1时,碱木质素的醇羟基含量从2.28mmol/g变为8.34mmol/g,酚羟基含量从1.80mmol/g变为2.02mmol/g。均匀设计法研究表明对碱木质素总羟基含量变化的影响因素依次为超声波处理时间,超声波功率,液料比,其中液料比对总羟基含量几乎没有影响。
采用官能团分析、凝胶色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振~1H-NMR等研究手段结果表明,超声波加速了溶液分子与碱木质素分子之间的的摩擦,从而引起C-C键或C-O-C键的裂解,超声波的空化效应所产生的高温高压环境也会导致了苯环上侧链的断裂,这一作用会使碱木质素酚羟基和总羟基含量增加,增加部分的总羟基可能是由羧基部分还原得到,也可能是由甲氧基(-OCH_3)断键,或其它芳基烷基醚断键而产生的。另外,超声波处理麦草碱木质素后数均分子量(M_n)和重均分子量(M_w)分别从1179和10250变为5031和11605,重均分子量(M_w)与数均分子量(M_n)的比值(M_w/M_n)从8.69变为2.31,超声波作用下木质素的C-C键或C-O-O键的裂解和苯环上侧链的断裂有可能产生一定量的自由基,由于声空化效应产生的局部高温高压又会引发这些自由基发生聚合反应,使得碱木质素的分子量增加。超声波处理后麦草碱木质素酚羟基和醇羟基含量提高,反应活性得到提高,木质素发生聚合,分散性得到改善,这对麦草碱木质素的充分利用是有利的。
根据麦草碱木质素具有多种官能团的结构特点,国内首次合成了麦草碱木质素季胺盐、磺化麦草碱木质素季胺盐、麦草碱木质素膦酸季胺盐和麦草碱木质素膦基盐等四种效水处理剂,分别检测其絮凝、分散、络合和阻垢等性能。
对于麦草碱木质素季胺盐,实验表明:木质素季胺盐对酸性黑ATT染料溶液的絮凝效果较好。当处理后木质素季胺盐为1184.5mg/L时,酸性黑ATT染料溶液脱色率为78%。当投加量低于2500mg/L时,超声波处理后木质素季胺盐对酸性黑AFT染料的脱色效果要好于木质素季胺盐。木质素季胺盐中的季铵离子与酸性黑ATT染料中的磺酸
The research is the part of the Study on Pd/C Catalyzing and Deoxidizing Wheat-straw Alkli Lignin and Developing the Hosphono-alkali-lignin Salt,supported by the National Natural Science Foundation of China.Wheat-straw alkli lignin from black liquor is the important by-product in papermaking industry of China. It is less reaction activation centre because of the lignin's structure and its applications are limited.Then the alkali lignin of wheat-straw is processed by the ultrasonic and the activation of the ultrasonic on the alkali lignin is discussed. Three factors, the ultrasonic processing's power, the ultrasonic processing's time and the ratio of liquor to matrial are discussed on the change of the functional group's content of the alkali lignin . The functional group of alkali lignin is measured by the chemical methods ,the molecule weight measured by GPC and the chemical structure analysed by the spectrum of 1~H NMR and FTIR, these indicated that the ultrasonic how to activate the alkali lignin and make it activity.When the ultrasomc processing's time is 20 minutes, the ultrasomc processing's power is 200W, the ratio (0.2N NaOH solution: lignin , w/w ) is 100: 1, the content of phenolic hydroxyl of the alkali lignin is from 1.80mmol/g to 2.02mmol/g, the content of aliphatic hydroxyl of the alkali lignin is from 2.28mmol/g to 8.34mmol/g. The data of the ultrasonic processing under different conditions are analyzed by computer software using Uniformity Design Method. Three factors, the ultrasonic processing's power, the ultrasonic processing's time and the ratio are discussed on the change of the functional group's content of the alkali lignin . As a result, in the three factors, the ultrasonic processing's time is considered to be a primary factor on the change of content of the total hydroxyl . The ultrasonic processing's power is the second factor. The ratio is the third factor and has little effect on the change of content of the total hydroxyl.From the spectrum of 1~H NMR, FTIR, GPC and chemical methods, the increased phenolic hydroxyl and aliphatic hydroxyl is from the -OCH_3 of G-lignin,such as the -OCH_3 ruptured from the G-lignin,or carboxyl deoxidized.The numerical-average molecule weight (M_n) is from 1179 to 5031, the weight-average molecule weight (M_w) is from 5031 to 11605.The value of M_w/M_n is from 8.69 to 2.31.The alkli lignin polymerizated under the ultrasonic process.It is better to use of alkaili lignin after the ultrasonic procees because of the alkli lignin polymerization and the increased content of the total hydroxyl.Four water treatment agents were first synthesized at home basis on that alkali lignin has many functional groups. They were quaternary ammonium salt of alkali lignin, salt of sulfonation-alkali-lignin, quaternary ammonium salt of phosphono-alkali-lignin and hosphono-alkali-lignin salt. Their performance of flocculation, dispersion, chelation and scale inhibition was investigated respectively.It showed that the capability of flocculation of quaternary ammonium salt of alkali lignin
to black acid ATT was good. The decolorization rate of black acid ATT was 78% when the dosage of quaternary ammonium salt of alkali lignin was 1184.5mg/L. when the dosage lower than 2500mg/L the effect of quaternary ammonium salt of alkali lignin by activation of ultrasonic was better than that of not treated. Quaternary ammonium iron reacted with sulfonate groups of black acid ATT and an insoluble substance was produced. After that the purpose of decolorization was achieved. The decolorization rate of acid-red-orange dye and acid red dye increased as the dosage increased. Low pH was favorable to the flocculation, because at low pH the carboxyl was not dissociated and H4 was beside the suspending particles of acid red dye to give a high pH. It was easy to form hydrogen bond and carboxyl offered proton. At the same time quaternary ammonium iron was adsorbed to the surface of suspending particles to neutralize the electric charge. Because particles collided to each other and adsorbed each other the performance of flocculation to acid-red-orange dye and acid red dye was good. The quaternary ammonium salt of alkali lignin had some flocculent effect to kaolin which had better be used at low pH. In addition its quaternary ammonium salt of alkali lignin had some surface activity and could disperse particles of calcium carbonate which induced that it had weak chelation to the solution with calcium and magnesium.Better flocculation effect of quaternary ammonium salt of sulfonation-alkali-lignin to black acid, acid-red-orange dye and acid red dye was achieved. Its combined with amino of dye molecule while the cation combined with sulfonate groups of dye molecule which induced the decrease of hydrophilic groups of dye solution such as sulfonate groups, amino and hydroxyl. The hydrophobic of dye solution increased. The assembles of dye molecule were removed because of the bridge-span. The bleaching efficiency and demand for adsorbent was different for different reactive dyes. It depended on the structure of the molecule. Alumina with a concentration of 500mg/L could produce synergic effect in flocculation effect compared with only agent. The removal rate of COD of monosodium glutamate solution increased with increasing of concentration of quaternary ammonium salt of sulfonation-alkali-lignin. Quaternary ammonium salt of sulfonation-alkali-lignin had some surface activity and could disperse particles of calcium carbonate and kaolin which induced that it had weak chelation to the solution with calcium and magnesium. Though the synthesis of quaternary ammonium salt of sulfonation-alkali-lignin from alkali lignin had not been reported yet, it had favorable flocculation effect, especially to the acid dye waste water.Quaternary ammonium salt of phosphono-alkali-lignin was a multi-effect water treatment agent. It had better effect of scale inhibition to calcium carbonate and calcium sulphate, had some flocculation effect to acid dye solution and had some chelation to calcium and magnesium. For calcium carbonate, the scale prohibition rate was 78.8% when the dosage was 12mg/L. Quaternary ammonium salt of phosphono-alkali-lignin didn't suit high Ca2+ of waste water,it didn't suit iddle and lower Ca2+ of waste water. The scale inhibition rate decreased with decreasing of pH especially when pH>9.0. That was because high pH could result in high concentration of CO32" and high producing rate of CaCO3. Quaternary ammonium salt of
phosphono-alkali-lignin had good dispersion effect to crystal of calcium carbonate. Because of adsorbing to the surface of CaCO3, electrostatic repellent force and dimensional resistance between particles increased and crystals dispersed highly in the solution which could avoid crystalloid to separate out. The effect of scale inhibition and applying condition to CaSO4 was almost the same.The synthesis and research of these water treatment agents by activation of ultrasonic provided a scientific basis for the use of lignin which was still not made full use of and was an abundant, nontoxic, cheap and natural resource. It indicated that a new way of improving the reaction activity of lignin was found.
超声波可以显著提高碱木质素酚羟基和醇羟基含量。当作用时间为20min,作用功率为200W,液料比为100:1时,碱木质素的醇羟基含量从2.28mmol/g变为8.34mmol/g,酚羟基含量从1.80mmol/g变为2.02mmol/g。均匀设计法研究表明对碱木质素总羟基含量变化的影响因素依次为超声波处理时间,超声波功率,液料比,其中液料比对总羟基含量几乎没有影响。
采用官能团分析、凝胶色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振~1H-NMR等研究手段结果表明,超声波加速了溶液分子与碱木质素分子之间的的摩擦,从而引起C-C键或C-O-C键的裂解,超声波的空化效应所产生的高温高压环境也会导致了苯环上侧链的断裂,这一作用会使碱木质素酚羟基和总羟基含量增加,增加部分的总羟基可能是由羧基部分还原得到,也可能是由甲氧基(-OCH_3)断键,或其它芳基烷基醚断键而产生的。另外,超声波处理麦草碱木质素后数均分子量(M_n)和重均分子量(M_w)分别从1179和10250变为5031和11605,重均分子量(M_w)与数均分子量(M_n)的比值(M_w/M_n)从8.69变为2.31,超声波作用下木质素的C-C键或C-O-O键的裂解和苯环上侧链的断裂有可能产生一定量的自由基,由于声空化效应产生的局部高温高压又会引发这些自由基发生聚合反应,使得碱木质素的分子量增加。超声波处理后麦草碱木质素酚羟基和醇羟基含量提高,反应活性得到提高,木质素发生聚合,分散性得到改善,这对麦草碱木质素的充分利用是有利的。
根据麦草碱木质素具有多种官能团的结构特点,国内首次合成了麦草碱木质素季胺盐、磺化麦草碱木质素季胺盐、麦草碱木质素膦酸季胺盐和麦草碱木质素膦基盐等四种效水处理剂,分别检测其絮凝、分散、络合和阻垢等性能。
对于麦草碱木质素季胺盐,实验表明:木质素季胺盐对酸性黑ATT染料溶液的絮凝效果较好。当处理后木质素季胺盐为1184.5mg/L时,酸性黑ATT染料溶液脱色率为78%。当投加量低于2500mg/L时,超声波处理后木质素季胺盐对酸性黑AFT染料的脱色效果要好于木质素季胺盐。木质素季胺盐中的季铵离子与酸性黑ATT染料中的磺酸
The research is the part of the Study on Pd/C Catalyzing and Deoxidizing Wheat-straw Alkli Lignin and Developing the Hosphono-alkali-lignin Salt,supported by the National Natural Science Foundation of China.Wheat-straw alkli lignin from black liquor is the important by-product in papermaking industry of China. It is less reaction activation centre because of the lignin's structure and its applications are limited.Then the alkali lignin of wheat-straw is processed by the ultrasonic and the activation of the ultrasonic on the alkali lignin is discussed. Three factors, the ultrasonic processing's power, the ultrasonic processing's time and the ratio of liquor to matrial are discussed on the change of the functional group's content of the alkali lignin . The functional group of alkali lignin is measured by the chemical methods ,the molecule weight measured by GPC and the chemical structure analysed by the spectrum of 1~H NMR and FTIR, these indicated that the ultrasonic how to activate the alkali lignin and make it activity.When the ultrasomc processing's time is 20 minutes, the ultrasomc processing's power is 200W, the ratio (0.2N NaOH solution: lignin , w/w ) is 100: 1, the content of phenolic hydroxyl of the alkali lignin is from 1.80mmol/g to 2.02mmol/g, the content of aliphatic hydroxyl of the alkali lignin is from 2.28mmol/g to 8.34mmol/g. The data of the ultrasonic processing under different conditions are analyzed by computer software using Uniformity Design Method. Three factors, the ultrasonic processing's power, the ultrasonic processing's time and the ratio are discussed on the change of the functional group's content of the alkali lignin . As a result, in the three factors, the ultrasonic processing's time is considered to be a primary factor on the change of content of the total hydroxyl . The ultrasonic processing's power is the second factor. The ratio is the third factor and has little effect on the change of content of the total hydroxyl.From the spectrum of 1~H NMR, FTIR, GPC and chemical methods, the increased phenolic hydroxyl and aliphatic hydroxyl is from the -OCH_3 of G-lignin,such as the -OCH_3 ruptured from the G-lignin,or carboxyl deoxidized.The numerical-average molecule weight (M_n) is from 1179 to 5031, the weight-average molecule weight (M_w) is from 5031 to 11605.The value of M_w/M_n is from 8.69 to 2.31.The alkli lignin polymerizated under the ultrasonic process.It is better to use of alkaili lignin after the ultrasonic procees because of the alkli lignin polymerization and the increased content of the total hydroxyl.Four water treatment agents were first synthesized at home basis on that alkali lignin has many functional groups. They were quaternary ammonium salt of alkali lignin, salt of sulfonation-alkali-lignin, quaternary ammonium salt of phosphono-alkali-lignin and hosphono-alkali-lignin salt. Their performance of flocculation, dispersion, chelation and scale inhibition was investigated respectively.It showed that the capability of flocculation of quaternary ammonium salt of alkali lignin
to black acid ATT was good. The decolorization rate of black acid ATT was 78% when the dosage of quaternary ammonium salt of alkali lignin was 1184.5mg/L. when the dosage lower than 2500mg/L the effect of quaternary ammonium salt of alkali lignin by activation of ultrasonic was better than that of not treated. Quaternary ammonium iron reacted with sulfonate groups of black acid ATT and an insoluble substance was produced. After that the purpose of decolorization was achieved. The decolorization rate of acid-red-orange dye and acid red dye increased as the dosage increased. Low pH was favorable to the flocculation, because at low pH the carboxyl was not dissociated and H4 was beside the suspending particles of acid red dye to give a high pH. It was easy to form hydrogen bond and carboxyl offered proton. At the same time quaternary ammonium iron was adsorbed to the surface of suspending particles to neutralize the electric charge. Because particles collided to each other and adsorbed each other the performance of flocculation to acid-red-orange dye and acid red dye was good. The quaternary ammonium salt of alkali lignin had some flocculent effect to kaolin which had better be used at low pH. In addition its quaternary ammonium salt of alkali lignin had some surface activity and could disperse particles of calcium carbonate which induced that it had weak chelation to the solution with calcium and magnesium.Better flocculation effect of quaternary ammonium salt of sulfonation-alkali-lignin to black acid, acid-red-orange dye and acid red dye was achieved. Its combined with amino of dye molecule while the cation combined with sulfonate groups of dye molecule which induced the decrease of hydrophilic groups of dye solution such as sulfonate groups, amino and hydroxyl. The hydrophobic of dye solution increased. The assembles of dye molecule were removed because of the bridge-span. The bleaching efficiency and demand for adsorbent was different for different reactive dyes. It depended on the structure of the molecule. Alumina with a concentration of 500mg/L could produce synergic effect in flocculation effect compared with only agent. The removal rate of COD of monosodium glutamate solution increased with increasing of concentration of quaternary ammonium salt of sulfonation-alkali-lignin. Quaternary ammonium salt of sulfonation-alkali-lignin had some surface activity and could disperse particles of calcium carbonate and kaolin which induced that it had weak chelation to the solution with calcium and magnesium. Though the synthesis of quaternary ammonium salt of sulfonation-alkali-lignin from alkali lignin had not been reported yet, it had favorable flocculation effect, especially to the acid dye waste water.Quaternary ammonium salt of phosphono-alkali-lignin was a multi-effect water treatment agent. It had better effect of scale inhibition to calcium carbonate and calcium sulphate, had some flocculation effect to acid dye solution and had some chelation to calcium and magnesium. For calcium carbonate, the scale prohibition rate was 78.8% when the dosage was 12mg/L. Quaternary ammonium salt of phosphono-alkali-lignin didn't suit high Ca2+ of waste water,it didn't suit iddle and lower Ca2+ of waste water. The scale inhibition rate decreased with decreasing of pH especially when pH>9.0. That was because high pH could result in high concentration of CO32" and high producing rate of CaCO3. Quaternary ammonium salt of
phosphono-alkali-lignin had good dispersion effect to crystal of calcium carbonate. Because of adsorbing to the surface of CaCO3, electrostatic repellent force and dimensional resistance between particles increased and crystals dispersed highly in the solution which could avoid crystalloid to separate out. The effect of scale inhibition and applying condition to CaSO4 was almost the same.The synthesis and research of these water treatment agents by activation of ultrasonic provided a scientific basis for the use of lignin which was still not made full use of and was an abundant, nontoxic, cheap and natural resource. It indicated that a new way of improving the reaction activity of lignin was found.
引文
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