基于稀酸水解法的纤维素糖化技术研究
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摘要
生物质能源具有广阔的市场前景,对解决日益严峻的能源危机具有极其重要的意义。其中,农业废弃物资源化利用备受关注。本文以玉米秸秆及糖厂制糖残渣纤维素为原料,通过稀酸水解法,以还原糖得率为指标,优化反应条件,主要研究结果如下:
针对木质纤维素类生物质水解的主要成分,以医用脱脂棉和定性滤纸为模化物,以高温高压溶弹为反应器,选取各反应条件的梯度水平,以确立纤维素稀酸水解基本条件。以还原糖得率为指标优化反应条件,得出180℃温度下,反应80min、硫酸浓度4%的最优工艺条件,为后续采用玉米秸秆和制糖残渣进行稀酸水解实验提供了参考数据。
基于解决当前农作物秸秆和糖厂制糖残渣废弃物再利用的实际问题,以自行设计反应器为平台,采用正交实验设计,考查了硫酸浓度、原料粉碎度、液固比和金属盐催化剂浓度对玉米秸秆、甘蔗渣、甜菜粕和甜高粱秸水解还原糖得率的影响。正交实验中玉米秸秆、甘蔗渣、甜菜粕和甜高粱秸分别得到60.42%、69.89%、64.88%和70.28%的最高还原糖得率,并得到各自最优工艺条件。实验对金属盐助催化剂进行了重点研究,通过与空白实验对比发现,所采用的金属盐助催化剂Fe2+、Cu2+均使还原糖得率提高。其中,以Fe2+的催化效果最好,Cu2+的催化效果略次于Fe2+。
在综合对比糖类产物定量和定性分析方法的基础上,对玉米秸秆稀酸水解液中葡萄糖和木糖进行了定量。结果表明,水解液中木糖含量远低于葡萄糖;另外,副产物分析结果表明,金属助催化剂对减少甲酸、乙酸、乙酰丙酸、丙酮、糠醛五种副产物含量具有明显作用。未使用金属盐助催化剂的反应所得水解液中的副产物含量基本高于有助催化剂参与反应所得水解液中副产物的含量。
本实验对稀酸糖化水解纤维素进行了系统的理论和实验研究,为促进农作物秸秆和糖厂制糖残渣纤维素的资源化利用打下基础。
The biomass resource is potential at present,as will play an important role in dealing with the severe fuel crisis.The reuse of agricultural offal is payed more attention.The corn straw and residue from the sugar plant were used as material to hydrolyse under the dilute acid,and the reaction condition was optimized by the reducing sugar yield.The main results are as follows.
The pledget and qualitative filter were chosen to represent the main component of lignocellulose,and the vessel that can endure high temperature and pressure was used as reactor.The reaction conditions grads were chosen to ascertain the basic condition of hydrolysis of cellulose under dilute acids.The reducing sugar yield is used to optimize reation conditions.And the best reation conditions are temperature 180℃and sulfur acid concentration 4% in 80minutes,which provided reference for hydrolysis of straw and residue from the sugar plant under dilute acids.
To carry out the reuse of residue from the sugar plant such as corn straw,saccharum officinarum residue,beet residue and sweet sorghum residue,the reactor was designed.Orthogonal experiment was carried out to research the influence of the sulfur acid concentration,granularity,the ratio of liquid and solid and metal salt catalyst.The results of orthogonal experiment indicated that the highest reducing sugar yields of straw,officinarum residue,beet residue and sweet sorghum residue were 60.42%、69.89%、64.88% and 70.28%.The best reaction conditions of the materials were also reckoned.The experiment did an important research on metal salt catalyst,which concluded that the catalyst such as Fe2+ and Cu2+ could raise the reducing sugar yield by the contrast to CK.There was a good effect of Fe2+,which is better than Cu2+.
On the basis of contrast to quantitative and qualitative analyse of sugar offspring,the glucose and xylose were quantitated.The results indicated that the xylose was less than glucose.And the results to analyse the byproducts indicated that the catalyst played an important role on reducing formic acid,acetic acid,levulinic acid,acetone and furfural.The content of byproducts with catalyst in the liquid was more than that without catalyst in the liquid.
A systemic research about saccharification of lignocellulose under dilute acids was carried out,which will benefit the utilization of straw and residue from the sugar plant.
针对木质纤维素类生物质水解的主要成分,以医用脱脂棉和定性滤纸为模化物,以高温高压溶弹为反应器,选取各反应条件的梯度水平,以确立纤维素稀酸水解基本条件。以还原糖得率为指标优化反应条件,得出180℃温度下,反应80min、硫酸浓度4%的最优工艺条件,为后续采用玉米秸秆和制糖残渣进行稀酸水解实验提供了参考数据。
基于解决当前农作物秸秆和糖厂制糖残渣废弃物再利用的实际问题,以自行设计反应器为平台,采用正交实验设计,考查了硫酸浓度、原料粉碎度、液固比和金属盐催化剂浓度对玉米秸秆、甘蔗渣、甜菜粕和甜高粱秸水解还原糖得率的影响。正交实验中玉米秸秆、甘蔗渣、甜菜粕和甜高粱秸分别得到60.42%、69.89%、64.88%和70.28%的最高还原糖得率,并得到各自最优工艺条件。实验对金属盐助催化剂进行了重点研究,通过与空白实验对比发现,所采用的金属盐助催化剂Fe2+、Cu2+均使还原糖得率提高。其中,以Fe2+的催化效果最好,Cu2+的催化效果略次于Fe2+。
在综合对比糖类产物定量和定性分析方法的基础上,对玉米秸秆稀酸水解液中葡萄糖和木糖进行了定量。结果表明,水解液中木糖含量远低于葡萄糖;另外,副产物分析结果表明,金属助催化剂对减少甲酸、乙酸、乙酰丙酸、丙酮、糠醛五种副产物含量具有明显作用。未使用金属盐助催化剂的反应所得水解液中的副产物含量基本高于有助催化剂参与反应所得水解液中副产物的含量。
本实验对稀酸糖化水解纤维素进行了系统的理论和实验研究,为促进农作物秸秆和糖厂制糖残渣纤维素的资源化利用打下基础。
The biomass resource is potential at present,as will play an important role in dealing with the severe fuel crisis.The reuse of agricultural offal is payed more attention.The corn straw and residue from the sugar plant were used as material to hydrolyse under the dilute acid,and the reaction condition was optimized by the reducing sugar yield.The main results are as follows.
The pledget and qualitative filter were chosen to represent the main component of lignocellulose,and the vessel that can endure high temperature and pressure was used as reactor.The reaction conditions grads were chosen to ascertain the basic condition of hydrolysis of cellulose under dilute acids.The reducing sugar yield is used to optimize reation conditions.And the best reation conditions are temperature 180℃and sulfur acid concentration 4% in 80minutes,which provided reference for hydrolysis of straw and residue from the sugar plant under dilute acids.
To carry out the reuse of residue from the sugar plant such as corn straw,saccharum officinarum residue,beet residue and sweet sorghum residue,the reactor was designed.Orthogonal experiment was carried out to research the influence of the sulfur acid concentration,granularity,the ratio of liquid and solid and metal salt catalyst.The results of orthogonal experiment indicated that the highest reducing sugar yields of straw,officinarum residue,beet residue and sweet sorghum residue were 60.42%、69.89%、64.88% and 70.28%.The best reaction conditions of the materials were also reckoned.The experiment did an important research on metal salt catalyst,which concluded that the catalyst such as Fe2+ and Cu2+ could raise the reducing sugar yield by the contrast to CK.There was a good effect of Fe2+,which is better than Cu2+.
On the basis of contrast to quantitative and qualitative analyse of sugar offspring,the glucose and xylose were quantitated.The results indicated that the xylose was less than glucose.And the results to analyse the byproducts indicated that the catalyst played an important role on reducing formic acid,acetic acid,levulinic acid,acetone and furfural.The content of byproducts with catalyst in the liquid was more than that without catalyst in the liquid.
A systemic research about saccharification of lignocellulose under dilute acids was carried out,which will benefit the utilization of straw and residue from the sugar plant.
引文
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3. 郭成勋.甜菜糖厂“三废”处理及综合利用.北京:中国轻工业出版社, 1990,10.
4. 韩鲁佳,闫巧娟,刘向阳,等.中国农作物秸秆资源及其利用现状.农业工程学报, 2002,18(3):87~91.
5. 何北海,林鹿,孙润仓,等.木质纤维素化学水解产生可发酵糖研究.化学进展, 2007,19(7/8):1142~1145.
6. 胡忠鲠.现代化学基础.北京:高等教育出版社, 2000,1.
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