麦草浆无元素氯漂白的研究
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摘要
随着环保意识的增强和环境法规的严格控制,造纸工业逐渐从传统的CEH漂白向低/无污染的ECF或TCF漂白方向发展。ECF漂白浆比TCF漂白浆强度好,生产成本低,环境效应二者没有明显差别,因此,以ClO2漂白为基础的无元素氯(ECF)漂白技术日益受到重视,逐渐成为解决漂白废水污染、提高纸浆质量的有效途径之一。我国木材资源匮乏,麦草资源丰富,相当长的一段时期内,麦草仍是我国造纸工业主要的纤维原料。为此国内外科研人员对造纸工业合理利用纤维资源、改进制浆漂白技术、降低环境污染等进行了广泛、深入地研究,并取得了一定的成果。麦草浆CEH漂白废水污染严重、成浆质量不甚理想,因此研究麦草浆的ECF漂白技术更具有现实意义。
本论文对NaOH-AQ麦草浆的ECF漂白工艺条件及作用机理进行了研究。主要对麦草浆ClO2漂白工艺条件和提高效率的措施、ECF漂白及其与CEH漂白结果的比较、木聚糖酶在麦草浆ECF漂白中的应用、己烯糖醛酸对麦草浆ECF漂白的影响及相应漂白机理进行研究。分析了酸处理和木聚糖酶处理前后麦草浆己烯糖醛酸含量的变化,利用扫描电镜、纤维测定仪研究了不同ECF漂白浆料的纤维形态变化,并利用红外光谱分析推断不同漂白过程中木素和糖类功能基及结构的变化规律,了解其反应机理。实验结果表明:
在ClO2漂白过程中,添加五氧化二钒(V2O5)、杂多酸(HPA)都能一定程度上提高纸浆白度,从而提高ClO2的漂白效率。其最佳条件分别为:V2O5用量0.014%,温度70℃,时间120min,初始pH值1.0;HPA用量0.5%～0.6%时,催化效果最为理想,纸浆白度分别提高11.8%ISO和3.5%ISO。
己烯糖醛酸容易与ClO2漂白剂发生反应,影响ClO2漂白效果,酸预处理能够使己烯糖醛酸含量从原来的11.8mmol/g降为6.4mmol/g,白度增加0.7%ISO,提高ClO2的漂白效率。
麦草浆经过不同的ECF漂白流程处理后,漂白浆料的白度都达到了80%ISO以上,其中DXP、DQP、DAP三种漂白流程,浆料白度已经超过83%ISO,物理强度比CEH处理浆好得多。
ODQP漂白流程中,氧漂(O)的最佳漂白条件为:用碱量0.2%,氧压0.6MPa、最高温度110℃、时间60min、浆浓10%,硫酸镁用量0.5%。
二氧化氯(D)段工艺条件:ClO2用量0.8%,温度70℃,时间150min,初始pH值4.0。
螯合处理(Q)段中EDTA用量以0.2%为宜。
过氧化氢(P)段,最佳MgS04加入量(以Mg2+计)为0.04、Na2SiO3用量为3%～4%,纸浆的白度、粘度和返黄值等几乎达到了最好的效果。
ODQP漂白浆的白度与对应的CEH漂白浆相比,白度高,白度稳定性和粘度要好,漂白废水的CODcr、BOD5、SS和AOX量均比CEH漂白废水低得多。
木聚糖酶预处理可以提高ECF的漂白效果,其最佳用量为6U·g-1、pH值6.0、时间60min、浆浓8%。
酸水解处理可以提高ECF的漂白效果,工艺条件为:pH值3～4,温度80℃,时间60min。
With the intensified consciousness of envioronment protection and the require of the environment protection law, the paper industy moves on gradually, from the tradional CEH processes to the low or no pollution ways-ECF or TCF bleaching. There are more and more attention paied to ECF bleaching which based on chlorine dioxide bleaching, due to its good strength and low cost, compared to TCF bleaching. Therefore ECF bleaching has been becoming a way to reduce pollution and improve the pulp quality. In our country, we have a lot of wheat straw material, but little wood, so in a long run, wheat straw will still be main material in the field of paper industry. Many researchers have made an extensive and deep study on how to use the cellulose material properly to improve the technique of bleaching and reduce the pollution and they have acquired certain achievement. The pollution of waste water of CEH bleaching is serious and the quality of bleached pulp is not good, so the study on ECF bleaching of wheat straw pulp is feasible in our country.
In this thesis, the technical processes and mechanism about ECF bleaching of NaOH-AQ wheat pulp were studied. The technical conditions and methods of improving efficiency of chlorine dioxide single bleaching were determined. The optimal treatment conditions with xylanase and acid pretreatment on ECF bleaching were investigated. The effect of HuA for ECF bleaching of wheat straw pulp was studied. And the mechanism kinds of bleaching conditions was studied too. Furthermore, the change of pulp morphological structure was analyzed by SEM (scanning electron microscopy). It also studied the degradation of lignin and the change function group of wheat straw pulp after D and ECF bleaching with UV, FTIR. And the main conclusions are as the follows.
Adding V2O5 or HPA to the process of chlorine dioxide bleaching could improve the pulp brightness, and the bleaching efficiency was advanced. The optimum conditions were: dosage of V2O5 0.014%, temperature 70oC, time of reaction 120min, initial pH value 1.0 and the dosage of HPA is 0.5%-0.6%.
Acid pretreatment could reduce the content of HuA of wheat straw pulp from 11.8mmol/g to 6.4mmol/g, increase brightness about 0.7%ISO, improve the efficiency of chlorine dioxide. Through different processes of ECF bleaching, the brightness of pulp could reach 80%ISO, and the pulp property was better than that by CEH, what’s more, brightness of pulp had excessed 83%ISO by DXP, DQP, DAP bleaching processes, and the pulp property was also better than CEH pulp.
Oxygen bleaching had a significant influence during ODQP bleaching of wheat straw pulp and the best conditions were: dosage of alkali 0.2%, pressure of oxygen 0.6MPa, temperature 110oC, time 60min, pulp consistency 10%, dosage of MgSO4 0.5%.
The content of the Cu2+, Mg2+, Ca2+, and Mn2+ in wheat straw was high, and they were difficult to remove, so we had to input more EDTA during chelated process. When the dosage of EDTA was 0.1%~0.2% in Q step, the brigtness and conglutination of pulp was higher, and the content of Cu2+ and Mn2+ fell.
The input of MgSO4 during P bleaching process could improve the conglutination of the pulp, and the best dosage was 0.04%(calculate by Mg2+).
Inputing Na2SiO3 during P bleaching process could improve the conglutination, brightness, and the stabilization of brightness. When the dosage of Na2SiO3 was 3~4%, the brightness, conglutination and the degree of colour reversion almost got the best situation.
Compared the brightness of bleaching pulp by ODQP with CEH bleaching, the former pulp had higher brightness, better stabilization of brightness and conglutination, the CODcr、BOD5、SS and AOX of the white waste water were much lower.
The pretreatment with xylanase could improve the bleaching effect, and the best dosage was 6U·g-1, degree of pH was 6.0, time was 60min, and consistency of pulp was 8%.
The content of HuA in different material pulp is different. It is about 10mmol/kg in wheat straw pulp, and it’s about 15-20mmol/kg in soft-wood, and it’s about 60-70mmo1/kg in hard-wood.
We can use acid pretreament to reduce the content of HuA in pulp, and the best condition is: pH value 3~4, temperature 80oC,and time 60min.
Removing the HuA could improve the brightness and brightness stability. With the increasing of remotion, the brightness also increased, and the degree of return yellow reduced. The degree brightness was increased about 2%ISO, and the degree of return yellow fell about 0.1 units.
本论文对NaOH-AQ麦草浆的ECF漂白工艺条件及作用机理进行了研究。主要对麦草浆ClO2漂白工艺条件和提高效率的措施、ECF漂白及其与CEH漂白结果的比较、木聚糖酶在麦草浆ECF漂白中的应用、己烯糖醛酸对麦草浆ECF漂白的影响及相应漂白机理进行研究。分析了酸处理和木聚糖酶处理前后麦草浆己烯糖醛酸含量的变化,利用扫描电镜、纤维测定仪研究了不同ECF漂白浆料的纤维形态变化,并利用红外光谱分析推断不同漂白过程中木素和糖类功能基及结构的变化规律,了解其反应机理。实验结果表明:
在ClO2漂白过程中,添加五氧化二钒(V2O5)、杂多酸(HPA)都能一定程度上提高纸浆白度,从而提高ClO2的漂白效率。其最佳条件分别为:V2O5用量0.014%,温度70℃,时间120min,初始pH值1.0;HPA用量0.5%～0.6%时,催化效果最为理想,纸浆白度分别提高11.8%ISO和3.5%ISO。
己烯糖醛酸容易与ClO2漂白剂发生反应,影响ClO2漂白效果,酸预处理能够使己烯糖醛酸含量从原来的11.8mmol/g降为6.4mmol/g,白度增加0.7%ISO,提高ClO2的漂白效率。
麦草浆经过不同的ECF漂白流程处理后,漂白浆料的白度都达到了80%ISO以上,其中DXP、DQP、DAP三种漂白流程,浆料白度已经超过83%ISO,物理强度比CEH处理浆好得多。
ODQP漂白流程中,氧漂(O)的最佳漂白条件为:用碱量0.2%,氧压0.6MPa、最高温度110℃、时间60min、浆浓10%,硫酸镁用量0.5%。
二氧化氯(D)段工艺条件:ClO2用量0.8%,温度70℃,时间150min,初始pH值4.0。
螯合处理(Q)段中EDTA用量以0.2%为宜。
过氧化氢(P)段,最佳MgS04加入量(以Mg2+计)为0.04、Na2SiO3用量为3%～4%,纸浆的白度、粘度和返黄值等几乎达到了最好的效果。
ODQP漂白浆的白度与对应的CEH漂白浆相比,白度高,白度稳定性和粘度要好,漂白废水的CODcr、BOD5、SS和AOX量均比CEH漂白废水低得多。
木聚糖酶预处理可以提高ECF的漂白效果,其最佳用量为6U·g-1、pH值6.0、时间60min、浆浓8%。
酸水解处理可以提高ECF的漂白效果,工艺条件为:pH值3～4,温度80℃,时间60min。
With the intensified consciousness of envioronment protection and the require of the environment protection law, the paper industy moves on gradually, from the tradional CEH processes to the low or no pollution ways-ECF or TCF bleaching. There are more and more attention paied to ECF bleaching which based on chlorine dioxide bleaching, due to its good strength and low cost, compared to TCF bleaching. Therefore ECF bleaching has been becoming a way to reduce pollution and improve the pulp quality. In our country, we have a lot of wheat straw material, but little wood, so in a long run, wheat straw will still be main material in the field of paper industry. Many researchers have made an extensive and deep study on how to use the cellulose material properly to improve the technique of bleaching and reduce the pollution and they have acquired certain achievement. The pollution of waste water of CEH bleaching is serious and the quality of bleached pulp is not good, so the study on ECF bleaching of wheat straw pulp is feasible in our country.
In this thesis, the technical processes and mechanism about ECF bleaching of NaOH-AQ wheat pulp were studied. The technical conditions and methods of improving efficiency of chlorine dioxide single bleaching were determined. The optimal treatment conditions with xylanase and acid pretreatment on ECF bleaching were investigated. The effect of HuA for ECF bleaching of wheat straw pulp was studied. And the mechanism kinds of bleaching conditions was studied too. Furthermore, the change of pulp morphological structure was analyzed by SEM (scanning electron microscopy). It also studied the degradation of lignin and the change function group of wheat straw pulp after D and ECF bleaching with UV, FTIR. And the main conclusions are as the follows.
Adding V2O5 or HPA to the process of chlorine dioxide bleaching could improve the pulp brightness, and the bleaching efficiency was advanced. The optimum conditions were: dosage of V2O5 0.014%, temperature 70oC, time of reaction 120min, initial pH value 1.0 and the dosage of HPA is 0.5%-0.6%.
Acid pretreatment could reduce the content of HuA of wheat straw pulp from 11.8mmol/g to 6.4mmol/g, increase brightness about 0.7%ISO, improve the efficiency of chlorine dioxide. Through different processes of ECF bleaching, the brightness of pulp could reach 80%ISO, and the pulp property was better than that by CEH, what’s more, brightness of pulp had excessed 83%ISO by DXP, DQP, DAP bleaching processes, and the pulp property was also better than CEH pulp.
Oxygen bleaching had a significant influence during ODQP bleaching of wheat straw pulp and the best conditions were: dosage of alkali 0.2%, pressure of oxygen 0.6MPa, temperature 110oC, time 60min, pulp consistency 10%, dosage of MgSO4 0.5%.
The content of the Cu2+, Mg2+, Ca2+, and Mn2+ in wheat straw was high, and they were difficult to remove, so we had to input more EDTA during chelated process. When the dosage of EDTA was 0.1%~0.2% in Q step, the brigtness and conglutination of pulp was higher, and the content of Cu2+ and Mn2+ fell.
The input of MgSO4 during P bleaching process could improve the conglutination of the pulp, and the best dosage was 0.04%(calculate by Mg2+).
Inputing Na2SiO3 during P bleaching process could improve the conglutination, brightness, and the stabilization of brightness. When the dosage of Na2SiO3 was 3~4%, the brightness, conglutination and the degree of colour reversion almost got the best situation.
Compared the brightness of bleaching pulp by ODQP with CEH bleaching, the former pulp had higher brightness, better stabilization of brightness and conglutination, the CODcr、BOD5、SS and AOX of the white waste water were much lower.
The pretreatment with xylanase could improve the bleaching effect, and the best dosage was 6U·g-1, degree of pH was 6.0, time was 60min, and consistency of pulp was 8%.
The content of HuA in different material pulp is different. It is about 10mmol/kg in wheat straw pulp, and it’s about 15-20mmol/kg in soft-wood, and it’s about 60-70mmo1/kg in hard-wood.
We can use acid pretreament to reduce the content of HuA in pulp, and the best condition is: pH value 3~4, temperature 80oC,and time 60min.
Removing the HuA could improve the brightness and brightness stability. With the increasing of remotion, the brightness also increased, and the degree of return yellow reduced. The degree brightness was increased about 2%ISO, and the degree of return yellow fell about 0.1 units.
引文
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