NaOH-AQ/O_2两段蒸煮中氧段硅转移特性的模拟研究
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摘要
麦草是中国造纸工业最重要非木材纤维来源。但是硅干扰是麦草制浆中存在的重要问题,硅溶入黑液中,对黑液碱回收系统造成严重的“硅干扰”,严重影响着整个碱回收系统的稳定运行。NaOH-AQ/O2两段蒸煮是非常有前景的环境友好的麦草制浆方法。本论文通过利用在漂白针叶木浆中人为添加二氧化硅并模拟氧碱蒸煮段工艺,探索硅在氧碱蒸煮过程的转移规律和特性,并通过添加助留剂研究在氧脱木素后硅的留着机理,为在工业生产中推广应用NaOH-AQ/O2两段蒸煮这种环境友好的制浆方法发挥作用。
氧碱蒸煮段,浆料除硅的影响因素主要有:pH值、氧压、温度等。本论文主要的研究结果有:(1)氧碱蒸煮体系的碱度对硅转移有重要影响。在氧压、温度等反应条件固定下,随着pH的降低,浆料中硅含量在升高,当pH为5时,浆料中硅含量最高,水相中硅含量最低;(2)氧碱蒸煮体系的氧压对硅转移有影响。在相同pH和温度的条件下,在一定的压力范围内,随着氧压的增加浆中硅含量提高,而水相中的硅含量下降;(3)氧碱蒸煮体系的温度对硅转移有较大的影响,在相同的pH和氧压等条件下,随着氧碱蒸煮的温度提高,浆料中的硅含量在提高,而水相中的硅含量在下降;通过模拟试验,发现浆中硅含量在氧压为pH为5,0.5MPa,温度100℃,得到最高浆中硅含量为1.49%,水相中的硅含量为0.05g/l,此时硅的转移率达到12.4;(4)氧碱蒸煮后,PEO对蒸煮后体系中硅转移产生较大的影响。pH、PEO用量和浆浓对硅转移产生影响,较好的硅在纤维上保留条件是:pH为9,PEO用量为0.06%,浆浓为3.0%,此时浆中的硅含量高达3.8%;(5)经过SEM扫描发现纤维细胞壁表层发生了细纤维化,并且纤维细胞表层的微纤丝和纤维细胞表层吸附有硅颗粒,证明了模拟试验的可行性。
Wheat straw is one of most important non-wood fiber raw materials for China’s papermaking industry. Silicon in the wheat straw black liquor is a key obstacle to the chemical recovery of the black liquor. NaOH-AQ/O2 two-stage cooking process is a potential process for environmental friendly wheat straw pulping. This paper deals with the silicon transferring properties between the fibers and water phase in simulation alkaline O2 cooking by adding given Na2SiO3 to the O2 cooking system. The purpose is to guide the NaOH-AQ/O2 two-stage cooking process toward industrial application.
The main factors that influence the transfer between fibers and water phase during the oxygen-alkali cooking are pH, oxygen pressure, temperature and so on. The main results obtained are following:
1. The pH value has an important influence on silicon transferring between the fibers and water phase in the oxygen-alkali cooking stage. Under the fixed oxygen pressure, temperature and other conditions, the silicon retention on the fibers increase with the decrease of alkalinity in the system.
2. The oxygen pressure has impact on silicon transferring between the fibers and water phase in the oxygen-alkali cooking stage. Under the given pH, temperature and other conditions, the silicon retention on the fibers increased with the increase of oxygen pressure in the system
3. The temperature has an obvious impact on the oxygen-alkali steam boiling stage. Under the fixed pH value, oxygen pressure and other conditions, the silicon retention on fibers increase with the increasing of temperature while the silicon concentration in the water phase decrease.
The simulation test indicated that high silicon content in the fibers was 1.49%, a low silicon concentration was 0.05g/L in the water phase when the oxygen pressure was 0.50 MPa, pH was 5 and the temperature was 100℃.
4. After O2 cooking, the addition of PEO has an important impact on the silicon transfer between the fibers and water phase. The beneficial parameters to the silicon retention on the fibers, up to 3.8% silicon based on the fibers (o. d), were pH, 9; PEO dosage, 0.06%; the pulp concentration, 3.0%.
5. It is observed that there are silicon gels on the fiber surface by SEM and showed that the silicon can be transferred onto fibers from cooking liquor by oxygen-alkali cooking.
氧碱蒸煮段,浆料除硅的影响因素主要有:pH值、氧压、温度等。本论文主要的研究结果有:(1)氧碱蒸煮体系的碱度对硅转移有重要影响。在氧压、温度等反应条件固定下,随着pH的降低,浆料中硅含量在升高,当pH为5时,浆料中硅含量最高,水相中硅含量最低;(2)氧碱蒸煮体系的氧压对硅转移有影响。在相同pH和温度的条件下,在一定的压力范围内,随着氧压的增加浆中硅含量提高,而水相中的硅含量下降;(3)氧碱蒸煮体系的温度对硅转移有较大的影响,在相同的pH和氧压等条件下,随着氧碱蒸煮的温度提高,浆料中的硅含量在提高,而水相中的硅含量在下降;通过模拟试验,发现浆中硅含量在氧压为pH为5,0.5MPa,温度100℃,得到最高浆中硅含量为1.49%,水相中的硅含量为0.05g/l,此时硅的转移率达到12.4;(4)氧碱蒸煮后,PEO对蒸煮后体系中硅转移产生较大的影响。pH、PEO用量和浆浓对硅转移产生影响,较好的硅在纤维上保留条件是:pH为9,PEO用量为0.06%,浆浓为3.0%,此时浆中的硅含量高达3.8%;(5)经过SEM扫描发现纤维细胞壁表层发生了细纤维化,并且纤维细胞表层的微纤丝和纤维细胞表层吸附有硅颗粒,证明了模拟试验的可行性。
Wheat straw is one of most important non-wood fiber raw materials for China’s papermaking industry. Silicon in the wheat straw black liquor is a key obstacle to the chemical recovery of the black liquor. NaOH-AQ/O2 two-stage cooking process is a potential process for environmental friendly wheat straw pulping. This paper deals with the silicon transferring properties between the fibers and water phase in simulation alkaline O2 cooking by adding given Na2SiO3 to the O2 cooking system. The purpose is to guide the NaOH-AQ/O2 two-stage cooking process toward industrial application.
The main factors that influence the transfer between fibers and water phase during the oxygen-alkali cooking are pH, oxygen pressure, temperature and so on. The main results obtained are following:
1. The pH value has an important influence on silicon transferring between the fibers and water phase in the oxygen-alkali cooking stage. Under the fixed oxygen pressure, temperature and other conditions, the silicon retention on the fibers increase with the decrease of alkalinity in the system.
2. The oxygen pressure has impact on silicon transferring between the fibers and water phase in the oxygen-alkali cooking stage. Under the given pH, temperature and other conditions, the silicon retention on the fibers increased with the increase of oxygen pressure in the system
3. The temperature has an obvious impact on the oxygen-alkali steam boiling stage. Under the fixed pH value, oxygen pressure and other conditions, the silicon retention on fibers increase with the increasing of temperature while the silicon concentration in the water phase decrease.
The simulation test indicated that high silicon content in the fibers was 1.49%, a low silicon concentration was 0.05g/L in the water phase when the oxygen pressure was 0.50 MPa, pH was 5 and the temperature was 100℃.
4. After O2 cooking, the addition of PEO has an important impact on the silicon transfer between the fibers and water phase. The beneficial parameters to the silicon retention on the fibers, up to 3.8% silicon based on the fibers (o. d), were pH, 9; PEO dosage, 0.06%; the pulp concentration, 3.0%.
5. It is observed that there are silicon gels on the fiber surface by SEM and showed that the silicon can be transferred onto fibers from cooking liquor by oxygen-alkali cooking.
引文
[1] 周在峰.行业突现拐点,中国造纸迎来世纪变局,直面全球竞争,内资航母须坐主导席位——中国造纸业发展环境及内外资造纸大企业竞争力分析[J].新远见,2007,(11):108~125
[2] 国家林业局.第 6 次全国森林资源清查结果[J].造纸信息,2005,(6)
[3] 李忠正.禾草类纤维制浆特性及进一步发展我国非木材纤维造纸的对策[J].中国造纸, 2006,(2):6～11
[4] 沈文浩,陈小泉,刘焕彬.中国制浆造纸工业的发展现状和趋势[J]. 造纸科学与技术,2006,(6):15～21
[5] 翟华敏,黄军,龙冬松. 环境友好的麦草留硅两段蒸煮技术[J]. 上海造纸,2005(1):10～13
[6] X A Liu,ZZ, Lee. Cellulose Chemistry and Technol[M],1999,(5):305～317
[7] EI-Ebairy M A ,Hackl H J.Nonwood .Plant Fiber Pulping Progress Report[J].TAPPI, 1982,(13).
[8] 安国兴. 麦草浆氧碱漂白[J].中国造纸学报 1996(11):28～35
[9] AHMET TUTU? AND HǖDAVERDI ERO?LU. A practical solution to the silica problem in straw pulping[J], Appita, Journal, Vol 56, No 2, p111~115 (2003)
[10] 卢立正,胡开堂,蔡秋香. 稻麦草环保型制浆方法—两段氧碱制浆[J]. 西南造纸, 2001(3):6～7
[11] 李晓秀,淦洪,徐金利. 非本资源的开发利用是本材资源的重要补充[J]. 森林工程, 2001,17(3):5～6
[12] 张大同,刘学斌,李忠正. 小麦草各部位纤维形态和化学组成的分析[J]. 中国造纸, 1990(4):16～21
[13] 陈平平. 硅在水稻生活中的作用[J]. 生物学通报,1998,33(8):5～7
[14] 苏润洲,刘志明,李坚,艾军. 麦杆表面硅含量分布的研究[J]. 林业科学, 2002,38(6):99～102
[15] 陆庆玮,王一兵.硅酸凝胶生成条件与机理的探讨[J]. 内蒙古工业大学学报,1994,13(3):17～21
[16] 华南理工大学无机化学教研室编. 无机化学(第三版)[M]. 1994,北京:高等教育出版社
[17] P.J.Kleppe.TAPPI,1970,53:35
[18] 李忠正,国内外制浆造纸工业现状和发展趋势(续) [J].中国造纸,1983.2(3):21
[19] 隆言泉.制浆造纸工艺学(上册) [M].中国轻工业出版社,1987:89
[20] C. H. Tay. R. S. Fairchild, and S. E. Imada.TAPPI, 1985,68(8):98
[21] D. W. Cameron, A. Farrington, P. E. Nelson, Appita, 1982,35:307
[22] 劳嘉葆.草浆黑液除硅新技术[J].纸和造纸 2001(5):49～50
[23] 张陶芸. 草浆黑液硅干扰及除硅技术[J]. 纸和造纸,1991(4):45～46
[24] 罗才典. 非木材纤维原料制浆的除硅方法[J]. 纸和造纸,1991,No.4:45～47
[25] 贺连娟,杜兆年. 草浆黑液 CO2法除硅的试验研究[J]. 甘肃科学学报 2003,15(4):59～62
[26] 马福庭,王存谦. 碱性麦草浆黑液除硅生产试验[J]. 中国造纸,1991(5):10～14
[27] 陈金中,余家鸾,陈嘉翔. 草浆黑液新的除硅方法[J]. 中国造纸,1991,10(2)41～48
[28] 王晓丽、张美霞、王晓秋、郭博书. 絮凝—沉淀法处理苇浆造纸黑液预除硅工艺的探讨[J]. 内蒙古石油化工,1999(26):18～19、24
[29] V.J Bohmer., P.O.Enstra, Silica Removal From Soda Non-wood Pulping[J]. Tappi Journal., 67(11) p116 (1984)
[30] 杜兆年、郑春莉. 麦草浆黑液加碱降粘消除硅干扰的实验研究[J]. 甘肃环境研究与监测 2001, 14(3):144～147
[31] 汪萍,程新华. 草浆黑液降低粘度措施[J]. 中国造纸,1998(1)20～30
[32] 刘福平,韩柳. 麦草碱黑液降粘技术的研究[J]. 西北轻工业学院学报,1999,17(2):20～23
[33] 汪苹,张坷,王新棣. 蒸煮同步除硅工艺生产试验及麦草浆碱回收[J]. 中国造纸(4):64～65
[34] 汪苹,张坷. 同步除硅处理对草浆黑液理化性质(粘度、VIE)的影响[J]. 中国造纸, 1995(4):6～9
[35] 汪苹,邹培昌,张坷,崔莉凤,吴强,梁瀛洲. 在碱法制浆过程中同步除硅——中型试验[J]. 中国环境科学.1995,15(6):443～446
[36] R.P.Beatson, Methods in Lignin Chemistry. Springer Verlag, p473-484 (1992)/eds
[37] 陈嘉川,李昭成,杨桂花,苏雨. 麦草 NaOH—AQ 浆氧脱木质素特性的研究[J]. 中国造纸学报, 2002,17(2):15～17
[38] L.junggren.S. Kinetic Aspects of Lignin Reactions in Oxygen Delignification Proceedings, International Pulp Bleaching Conference[J], Quebec City, June 1985,p115～119
[39] 刘文军,文琼菊. 麦草制浆特性及其发展[J]. 湖北造纸,1998(3):13～15
[40] 曹云峰,杨益琴,张晓丽,李忠正. 麦草氧碱两段蒸煮黑液性能的研究[J]. 中国造纸学报,2002,17(l):64～67
[41] Huamin Zhai, Jun Huang, Qintan Chen. Characteristics of Two-stage Cooking of Wheat Straw by NaOH-AQ/O2, Part 1: Effect of Alkali on Desilication in O2 Cooking Stage[C]. 2nd International Symposium on Technologies of Pulping, Papermaking and Biotechnology on Fiber Plants, Nanjing, China, October 13～14, p132-136 (2004)
[42] 翟华敏,黄军,龙冬松. 环境友好的麦草留硅两段蒸煮技术[J]. 上海造纸,2005(1):10～13
[43] 朱勇强. 造纸助剂与湿部化学讲座(二)造纸湿部化学的基本原理[J]. 上海造纸,2003(6):31-34
[44] 胡志斌,谢来苏.PEO 的特性及其在造纸中的应用[J].黑龙江造纸,2002(1):12～15
[2] 国家林业局.第 6 次全国森林资源清查结果[J].造纸信息,2005,(6)
[3] 李忠正.禾草类纤维制浆特性及进一步发展我国非木材纤维造纸的对策[J].中国造纸, 2006,(2):6～11
[4] 沈文浩,陈小泉,刘焕彬.中国制浆造纸工业的发展现状和趋势[J]. 造纸科学与技术,2006,(6):15～21
[5] 翟华敏,黄军,龙冬松. 环境友好的麦草留硅两段蒸煮技术[J]. 上海造纸,2005(1):10～13
[6] X A Liu,ZZ, Lee. Cellulose Chemistry and Technol[M],1999,(5):305～317
[7] EI-Ebairy M A ,Hackl H J.Nonwood .Plant Fiber Pulping Progress Report[J].TAPPI, 1982,(13).
[8] 安国兴. 麦草浆氧碱漂白[J].中国造纸学报 1996(11):28～35
[9] AHMET TUTU? AND HǖDAVERDI ERO?LU. A practical solution to the silica problem in straw pulping[J], Appita, Journal, Vol 56, No 2, p111~115 (2003)
[10] 卢立正,胡开堂,蔡秋香. 稻麦草环保型制浆方法—两段氧碱制浆[J]. 西南造纸, 2001(3):6～7
[11] 李晓秀,淦洪,徐金利. 非本资源的开发利用是本材资源的重要补充[J]. 森林工程, 2001,17(3):5～6
[12] 张大同,刘学斌,李忠正. 小麦草各部位纤维形态和化学组成的分析[J]. 中国造纸, 1990(4):16～21
[13] 陈平平. 硅在水稻生活中的作用[J]. 生物学通报,1998,33(8):5～7
[14] 苏润洲,刘志明,李坚,艾军. 麦杆表面硅含量分布的研究[J]. 林业科学, 2002,38(6):99～102
[15] 陆庆玮,王一兵.硅酸凝胶生成条件与机理的探讨[J]. 内蒙古工业大学学报,1994,13(3):17～21
[16] 华南理工大学无机化学教研室编. 无机化学(第三版)[M]. 1994,北京:高等教育出版社
[17] P.J.Kleppe.TAPPI,1970,53:35
[18] 李忠正,国内外制浆造纸工业现状和发展趋势(续) [J].中国造纸,1983.2(3):21
[19] 隆言泉.制浆造纸工艺学(上册) [M].中国轻工业出版社,1987:89
[20] C. H. Tay. R. S. Fairchild, and S. E. Imada.TAPPI, 1985,68(8):98
[21] D. W. Cameron, A. Farrington, P. E. Nelson, Appita, 1982,35:307
[22] 劳嘉葆.草浆黑液除硅新技术[J].纸和造纸 2001(5):49～50
[23] 张陶芸. 草浆黑液硅干扰及除硅技术[J]. 纸和造纸,1991(4):45～46
[24] 罗才典. 非木材纤维原料制浆的除硅方法[J]. 纸和造纸,1991,No.4:45～47
[25] 贺连娟,杜兆年. 草浆黑液 CO2法除硅的试验研究[J]. 甘肃科学学报 2003,15(4):59～62
[26] 马福庭,王存谦. 碱性麦草浆黑液除硅生产试验[J]. 中国造纸,1991(5):10～14
[27] 陈金中,余家鸾,陈嘉翔. 草浆黑液新的除硅方法[J]. 中国造纸,1991,10(2)41～48
[28] 王晓丽、张美霞、王晓秋、郭博书. 絮凝—沉淀法处理苇浆造纸黑液预除硅工艺的探讨[J]. 内蒙古石油化工,1999(26):18～19、24
[29] V.J Bohmer., P.O.Enstra, Silica Removal From Soda Non-wood Pulping[J]. Tappi Journal., 67(11) p116 (1984)
[30] 杜兆年、郑春莉. 麦草浆黑液加碱降粘消除硅干扰的实验研究[J]. 甘肃环境研究与监测 2001, 14(3):144～147
[31] 汪萍,程新华. 草浆黑液降低粘度措施[J]. 中国造纸,1998(1)20～30
[32] 刘福平,韩柳. 麦草碱黑液降粘技术的研究[J]. 西北轻工业学院学报,1999,17(2):20～23
[33] 汪苹,张坷,王新棣. 蒸煮同步除硅工艺生产试验及麦草浆碱回收[J]. 中国造纸(4):64～65
[34] 汪苹,张坷. 同步除硅处理对草浆黑液理化性质(粘度、VIE)的影响[J]. 中国造纸, 1995(4):6～9
[35] 汪苹,邹培昌,张坷,崔莉凤,吴强,梁瀛洲. 在碱法制浆过程中同步除硅——中型试验[J]. 中国环境科学.1995,15(6):443～446
[36] R.P.Beatson, Methods in Lignin Chemistry. Springer Verlag, p473-484 (1992)/eds
[37] 陈嘉川,李昭成,杨桂花,苏雨. 麦草 NaOH—AQ 浆氧脱木质素特性的研究[J]. 中国造纸学报, 2002,17(2):15～17
[38] L.junggren.S. Kinetic Aspects of Lignin Reactions in Oxygen Delignification Proceedings, International Pulp Bleaching Conference[J], Quebec City, June 1985,p115～119
[39] 刘文军,文琼菊. 麦草制浆特性及其发展[J]. 湖北造纸,1998(3):13～15
[40] 曹云峰,杨益琴,张晓丽,李忠正. 麦草氧碱两段蒸煮黑液性能的研究[J]. 中国造纸学报,2002,17(l):64～67
[41] Huamin Zhai, Jun Huang, Qintan Chen. Characteristics of Two-stage Cooking of Wheat Straw by NaOH-AQ/O2, Part 1: Effect of Alkali on Desilication in O2 Cooking Stage[C]. 2nd International Symposium on Technologies of Pulping, Papermaking and Biotechnology on Fiber Plants, Nanjing, China, October 13～14, p132-136 (2004)
[42] 翟华敏,黄军,龙冬松. 环境友好的麦草留硅两段蒸煮技术[J]. 上海造纸,2005(1):10～13
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