具有较高表面活性的木质素磺酸盐的制备
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摘要
以提取自植物秸秆的、采取温和工艺制得的市售木质素为原料,分别采用亚硫酸钠法、亚硫酸钠-硫酸铜法、亚硫酸钠-氯化铁法、亚硫酸钠-甲醛法、亚硫酸钠-甲醛-氯化铁法、硫酸法和发烟硫酸法对木质素进行磺化。采用滴体积法测定了中和后产物溶液的表面张力和与正庚烷的界面张力。通过酸碱滴定、红外光谱和热重分析对原料及磺化产物进行表征。结果表明,所得木质素磺酸钠降低表面张力的能力较强,其中通过亚硫酸钠法、亚硫酸钠-氯化铁法和硫酸法处理得到的产物磺化度较高,中和后产物的水溶液表面张力可低至34~38 m N/m(25℃)。推测原料木质素的结构较均一、自身酸性基团含量高等因素对其磺化产物的表面活性起重要作用。
Lignosulfonates were prepared by sulfonation of lignin product purchased from the market that was obtained from plant stalk with mild technological process; followed by neutralization with sodium hydroxide.Different sulfonation methods were used separately such as Na2SO3 method,Na2SO3-CuSO4 method,Na2SO3-FeCl3 method,Na2SO3-formaldehyde method,Na2SO3-formaldehyde-FeCl3 method,sulfuric acid method and fuming sulfuric acid method. Both surface tension at air / water and interfacial tension at n-heptane / water of the aqueous solutions of lignosulfonate products were measured by drop volume method.Acid-base titration method,infrared spectra and thermal gravity analysis were used to characterize the starting material and the sulfonated products prepared. The results showed that the surface activity of lignosulfonates obtained is relatively high,especially for the products prepared by Na2SO3 method,Na2SO3-FeCl3 method and sulfuric acid method whose surface tension can be as low as 34-38 m N / m( 25 ℃). This work showed that surface activity of the lignosulfonate products may greatly depend on the uniformity as well as content of the acidic groups in the starting lignin material.
Lignosulfonates were prepared by sulfonation of lignin product purchased from the market that was obtained from plant stalk with mild technological process; followed by neutralization with sodium hydroxide.Different sulfonation methods were used separately such as Na2SO3 method,Na2SO3-CuSO4 method,Na2SO3-FeCl3 method,Na2SO3-formaldehyde method,Na2SO3-formaldehyde-FeCl3 method,sulfuric acid method and fuming sulfuric acid method. Both surface tension at air / water and interfacial tension at n-heptane / water of the aqueous solutions of lignosulfonate products were measured by drop volume method.Acid-base titration method,infrared spectra and thermal gravity analysis were used to characterize the starting material and the sulfonated products prepared. The results showed that the surface activity of lignosulfonates obtained is relatively high,especially for the products prepared by Na2SO3 method,Na2SO3-FeCl3 method and sulfuric acid method whose surface tension can be as low as 34-38 m N / m( 25 ℃). This work showed that surface activity of the lignosulfonate products may greatly depend on the uniformity as well as content of the acidic groups in the starting lignin material.
引文
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[28]王万林,王海滨,霍冀川,等.木质素磺酸盐减水剂改性研究进展[J].化工进展,2011,30(5):1039-1044.
[2]赵亚丽,赵丽萍.木质素磺酸钠改性研究[J].四川建材,2012,38(2):24-25.
[3]伍伟青,徐广宇,周宇鹏.改性碱木质素产品作为牺牲剂在三次采油中的应用研究[J].湖南大学学报:自然科学版,2001,28(2):21-26.
[4]邓韶博,曹青,靳利娥,等.木质素磺酸钠的改性及对煤浆分散性研究[J].煤炭转化,2014,37(2):33-36.
[5]宋军旺,王昭晖,赵新法,等.烯丙基磺酸钠/马来酸酐/木质素磺酸钠接枝共聚物的合成及性能评价[J].精细石油化工,2015,32(3):47-51.
[6]宋军旺,郭睿,刘甲斌,等.木质素磺酸钠/衣康酸接枝共聚物的合成以及性能评价[J].应用化工,2015,44(4):659-662.
[7]张黎,张洁,陈刚,等.羟甲基化木质素磺酸盐添加剂对钻井液性能的影响[J].化学研究,2014,25(4):423-427.
[8]曹婉鑫,陈洋,唐瑶,等.改性木质素磺酸盐用作减水剂的研究进展[J].湖南造纸,2015(1):20-23.
[9]杨东杰,李会景,白孟仙,等.不同分子量木质素磺酸钠染料分散剂的结构及性能[J].化工学报,2014,65(10):4138-4144.
[10]周明松,杨东杰,邱学青.不同来源木质素磺酸钠对水煤浆流变特性的影响[J].高校化学工程学报,2007,21(3):386-391.
[11]李琦,雷金选,罗松年,等.关于碱法草浆黑液特性研究的述评[J].中国造纸,1990(6):52-58.
[12]朱瑶,赵振国.界面化学基础[M].北京:化学工业出版社,1996:26-30.
[13]LIDINGO E A,HAGGLUND EKM.Method of producing watersoluble products from black liquor lignin:US,2680113[P].1950-12-19.
[14]何伟,邰瓞生,林耀瑞.麦草碱木素和松木硫酸盐木素磺化反应的比较研究[J].中国造纸,1991(6):10-16.
[15]刘会基,舒余德.木质素磺化的研究[J].化工纵横,2000(12):7-10.
[16]周勇,高德发.碱法造纸废液合成香兰素的研究[J].化学工程师,2000(2):29-30.
[17]穆环珍,黄衍初,杨问波,等.碱法蔗渣制浆黑液木质素磺化反应研究[J].环境化学,2003,22(4):377-379.
[18]王自军.木质素降滤失剂和絮凝剂的合成及性能测试[D].天津:天津大学化工学院,2009.
[19]梁文学,邱学青,欧阳新平,等.麦草碱木质素磺甲基化反应及性能的研究[J].四川大学学报:自然科学版,2007,44(1):129-134.
[20]李雪松.造纸废水处理及资源化利用研究[D].北京:北京化工大学,2008.
[21]赵国玺,朱瑶.表面活性剂作用原理[M].北京:中国轻工业出版社,2003:67-72.
[22]WORSLEY K A,KALININA I,BEJYAROVA E,et al.Functionalization and dissolution of nitric acid treated single-walled carbon nanotubes[J].J Am Chem Soc,2009,131:18153-18158.
[23]朱谱新.高分子表面活性剂在气/液界面上的物理化学性质研究[D].成都:四川大学纺研所,2001.
[24]王凤坤,范晓伟.十二烷基苯磺酸钠水溶液的表面张力测定[J].河南师范大学学报:自然科学版,2008,36(3):66-69.
[25]DONAHUE D J,BARTELL F E.The boundary tension at waterorganic liquid interfaces[J].J Phys Chem,1952,56:480-484.
[26]BI Z,ZHANG Z,XU F,et al.Wettability,oil recovery,and interfacial tension with an SDBS-dodecane-Kaolin system[J].J Colloid Interface Sci,1999,214:368-372.
[27]YIN G,ZHENG Z,WANG H,et al.Preparation of graphene oxide coated polystyrene microspheres by picking emulsion polymerization[J].J Colloid Interface Sci,2013,394:192-198.
[28]王万林,王海滨,霍冀川,等.木质素磺酸盐减水剂改性研究进展[J].化工进展,2011,30(5):1039-1044.