Influence of pore size on structure and adsorption properties of porous potato starch

doi:10.16085/j.issn.1000-6613.2017.02.037

Abstract

Abstract: In this paper,a new type of porous potato starch was synthesized by microwave-assisted method. During the preparation process,the parameters of the emulsifier were changed so that the starch granules were not evenly dispersed. Different mesh of porous starches were obtained by grinding and sieving. Using Scanning Electron Microscopy(SEM),Specific surface area analyzer(BET)and Fourier Transform Infrared Spectroscopy(FTIR),the detailed analysis was performed on the morphology and structure of potato starch and porous starch. Isothermal adsorption experiment of different mesh of porous starch was conducted with methylene blue solution(MB)and the influence of Gibbs's free energy on adsorption was studied. The results show that the crosslinking reaction occurs not only within the particles but also between the particles due to the uneven dispersion of starch particles. With the increase of mesh number,the surface structure of porous starch was destroyed and the surface roughness was increased;more and more holes were in the starch and pore size increased gradually. The adsorption process of porous starch was in line with the Langmuir Isothermal adsorption equation. With the increase of mesh size,fitting degree and adsorption amount increase gradually. The maximum adsorption amount of porous starch is 188.7 mg/g at the temperature of 298K.

Key words: porous starch, uneven dispersion, adsorption, methylene blue, Gibbs free energy

摘要： 通过微波辅助制备一种新型的多孔马铃薯淀粉。在制备过程中选择合适的乳化剂参数，使淀粉颗粒不均匀分散。研磨过筛之后得到不同目数的多孔淀粉。通过扫描电子显微镜（SEM）、比表面积仪（BET）和傅里叶红外变换光谱（FTIR）对原淀粉和不同目数多孔淀粉的形貌与结构进行表征，以亚甲基蓝为吸附对象，对不同目数的多孔淀粉进行等温吸附实验并探究吉布斯自由能对吸附的影响。实验结果表明，由于淀粉颗粒的不均匀分散，交联反应不仅发生在颗粒内部也发生在颗粒之间。随着目数的增大，淀粉表面结构被破坏，表面粗糙程度增加，孔洞增多，孔径也逐渐增大。多孔淀粉的吸附过程符合Langmuir等温吸附方程，且随着多孔淀粉目数的增大，拟合度逐渐增大，吸附量也逐渐增大。多孔淀粉在温度为298K时最大吸附量为188.679mg/g。

关键词: 多孔淀粉, 不均匀分散, 吸附, 亚甲基蓝, 吉布斯自由能

CLC Number:

O636.1

WANG Jiankun, FAN Xinyu, GUO Jing, LIANG Ka, ZHANG Hao, XIE Pengyuan. Influence of pore size on structure and adsorption properties of porous potato starch[J]. Chemical Industry and Engineering Progree, 2017, 36(02): 665-671.

王建坤, 范新宇, 郭晶, 梁卡, 张昊, 谢鹏远. 孔径对多孔马铃薯淀粉结构及吸附性能的影响[J]. 化工进展, 2017, 36(02): 665-671.

References

[1] 魏秀芝.新型阴离子淀粉微球的制备及其吸附性能研究[D].杨凌:西北农林科技大学,2010. WEI X Z. Preparation and adsorption performance of a novel anionic starch microspheres[D]. Yangling:Northwest A& F University,2010.
[2] 王航,黄立新,高群玉,等.多孔淀粉的研究进展[J].精细化工,2002,19(s1):102-105. WANG H,HUANG L X,GAO Q Y,et al.Recent advances in porous starch[J].Fine Chemicals,2002,19(s1):102-105.
[3] 何小维.淀粉基生物降解材料[M].北京:中国轻工业出版社,2008. HE X W.Starch based biodegradable materials[M].Beijing:Chinese Light Industry Press,2008.
[4] YANG Y,WEI X,SUN P,et al. Preparation,characterization and adsorption performance of a novel anionic starch microsphere[J].Molecules,2010,15(5):2872-2885.
[5] ADEBOWALE K O, LAWAL O S. Functional properties and retrogradation behavior of native and chemically modified starch of mucuna beanmucu-napruriens)[J].J. Sci. Food Agric.,2003,83(2):1541-1546.
[6] ZHAN G P, HUANG K L, ZHANG F W. The study on synthesis of anion starch micro-spheres[J].New Chem. Mater.,2005,33(10):44-46.
[7] KHALIL M I, ABDEL-HALIM M G. Preparation of anionic starch containing carboxyl groups and its utilization as chelating agent[J].Starke,2001,53(3):35-41.
[8] 常贵娟,肖武,李祥村,等.乳液交联法制备多孔淀粉及其吸附性能[J].化工进展,2014,33(5):1290-1295. CHANG G J,XIAO W,LI X C,et al.Preparation and adsorption properties of porous starch prepared by emulsion crosslinking method[J].Chemical Industry and Engineering Progress,2014,33(5):1290-1295.
[9] 高青雨,石家华,王真卫,等.反相乳液聚合动力学[J].胶体与聚合物,2000,18(3):1-4. GAO C Y,SHI J H,WANG Z W,et al.Inverse emulsion polymerization of N,N-dimethylamino ethyl methacrylate in the presence of a function monomer[J].Chinese Journal of Colloid & Polymer,2000,18(3):1-4.
[10] 王建坤,谢鹏远,李凤艳.微波辅助多孔马铃薯淀粉的制备及其最佳工艺参数[J].天津工业大学学报,2015,34(5):18-22. WANG J K,XIE P Y,LI F Y.Synthesis of porous potato starch with microwave and itsoptimum polymerization conditions[J].Journal of Tianjin Polytechnic University,2015,34(5):18-22.
[11] 潘祖仁.高分子化学[M].北京:化学工业出版社,2011:65-77. PAN Z R.Polymer chemistry[M].Beijing:Chemical Industry Press,2011:65-77.
[12] AN J H,DULTZ S. Adsorption of tannic acid on chitosan montmorillonite as afunction of pH and surface charge properties[J].Appl. Clay Sci.,2007,36(5):256-264.
[13] 林梅莹,尚小琴,李淑妍,等.氨基改性淀粉重金属废水处理剂的制备及应用[J].化工进展,2011,30(4):854-856. LIN M Y,SHANG X Q,LI S Y,et al.Preparation and application of amino-modified starch for heavy metal ions water treatment[J].Chemical Industry and Engineering Progress,2011,30(4):854-856.
[14] 张昊,王建坤,王瑞,等.微波辅助制备接枝阳离子淀粉及其理化性能研究[J].功能材料,2013,44(12):1699-1702. ZHANG H,WANG J K,WANG R,et al.Microwave-initiated synthesis and physicochemical characterization of grafted cationic starch[J].Journal of Functional Materials,2013,44(12):1699-1702.
[15] 金谷.表面活性剂化学[M].合肥:中国科学技术大学出版社,2008. JIN G.Surfactant chemistry[M].Hefei:Press of University of Science and Technology of China,2008.
[16] 张德生.浅谈公式ΔG_m^H=-RT ln K^H的重要意义[J].安徽师范大学学报(自然科学版),1997,3(3):97-99. ZHANG D S.The important meaning of ΔG_m^H=-RT ln K^H[J].Journal of Anqing Teachers College(Natural Science),1997,3(3):97-99.
[17] Reddy M,Dunn S.Distribution coefficients for nickel and zinc in soils environmental pollution series B[J].Chemical and Physical,1986,11(4):303-313.
[18] 吴修利,薛冬桦,徐昆,等.淀粉-丙烯酰氧乙基三甲基氯化铵接枝共聚物的制备与表征[J].功能材料,2008,39(6):1008-1010. WU X L,XUE D Y,XU K,et al.Preparation and characterization of graft copolymer of acryloyloxyethyl trimethylammonium chloride and starch[J].Journal of Functional Materials,2008,39(6):1008-1010.
[19] 乔支卫.交联木薯淀粉微球的合成、表征及吸附性能研究[D].南昌:江西师范大学,2011. QIAO Z W.Studies on synthesis,characterization and adsorption performance of crosslinkedcassava starch microspheres[D].Nanchang:Jiangxi Normal University,2011.
[20] 邢宝山,宋春雨,刘晓冰.土壤有机污染物非理想吸附研究的理论与方法[J].土壤与环境,2002,11(2):144-151. XING B S,SONG C Y,LIU X B.Theory and method for the study of nonideal adsorption of organic pollutants in soils[J].Soil and Environmental Sciences,2002,11(2):144-151.