ZSM-5分子筛吸附石蒜碱及加兰他敏的动力学研究

doi:10.3969/j.issn.0253-2417.2018.03.017

摘要/Abstract

摘要： 以ZSM-5分子筛、阳离子交换树脂、大孔吸附树脂作为吸附剂，选择传统药用植物忽地笑中石蒜碱和加兰他敏作为吸附质，研究了分子筛对两种生物碱的吸附及解析效果，并与两种树脂吸附效果进行对比，进一步研究了分子筛对两种生物碱的吸附动力学。研究结果表明：ZSM-5分子筛对石蒜碱及加兰他敏的吸附和解析的综合效果最佳，吸附率均在99.50%以上，解析率分别达到90.35%和84.34%；阳离子交换树脂D-001、HD-8对两种生物碱的吸附率较高，但解析率仅为75%左右；大孔吸附树脂D-101、AB-8对石蒜碱的吸附率较高（均为95%左右），但对加兰他敏吸附效果欠佳，吸附率仅为14.50%和20.56%。静态吸附动力学研究发现：ZSM-5分子筛对石蒜碱及加兰他敏的吸附符合准二级动力学模型，R²值均达到0.999 9，表明化学吸附起主要作用。

关键词: ZSM-5分子筛, 石蒜碱, 加兰他敏, 吸附

Abstract: In order to evaluate the adsorption and purification capability of ZSM-5 molecular sieve on the lycorine and galanthamine, the adsorption and desorption performance of the three adsorbents (including ZSM-5 molecular sieve, cation exchange resin, macroporous resin) on the lycorine and galanthamine from Lycoris aurea were investigated, and then the adsorption kinetics were also studied. The results showed that ZSM-5 had obvious advantages in adsorption and elution of lycorine and galanthamine compared with macroporous resin (AB-8 and D-101) and cation adsorption resin (D-001 and HD-8). Adsorption rates of lycorine and galanthamine on ZSM-5 achieved more than 99.5% and the elution rates achieved 90.35% and 84.84%, respectively. The adsorption rates of D-101 and AB-8 were high, but the elution rates were only about 75%. Adsorption rates of lycorine on D-101 and AB-8 were high, but those of galanthamine were only 14.50% and 20.56%. The result of kinetics study indicated that the adsorption of lycorine and galanthamine on ZSM-5 was in good consistent with the second order kinetics model (R²=0.999 9), and chemisorption occupied the leading role.

Key words: ZSM-5 molecular sieve, lycorine, galanthamine, adsorption

中图分类号:

TQ35

刘云龙, 宋科, 肖卓炳, 郭婕. ZSM-5分子筛吸附石蒜碱及加兰他敏的动力学研究[J]. 林产化学与工业, 2018, 38(3): 122-128.

LIU Yunlong, SONG Ke, XIAO Zhuobing, GUO Jie. Adsorption Kinetics of Lycorine and Galanthamine with Molecular Sieve ZSM-5[J]. Chemistry and Industry of Forest Products, 2018, 38(3): 122-128.

参考文献

[1] 国家中医药管理局《中华本草》编委会. 中华本草:藏药卷[M]. 上海:上海科学技术出版社,2002. State Administration of Traditional Chinese Medicine 《Chinese Materia Medica》 Editorial Committee. Chinese Herbal Medicine:Tibetan Medicine Volume[M]. Shanghai:Shanghai Science and Technology Press,2002.
[2] CAO Z F,YU D,FU S L,et al. Lycorine hydrochloride selectively inhibits human ovarian cancer cell proliferation and tumor neovascularization with very low toxicity[J]. Toxicology Letters,2013,218(2):174-185.
[3] HEINRICH M,TEOH H L. Galanthamine from snowdrop:The development of a modern drug against Alzheimer's disease from local Caucasian knowledge[J]. Journal of Ethnopharmacology,2004,92(2/3):147-162.
[4] 李霞,熊远福,文祝友,等. 大孔吸附树脂纯化石蒜中石蒜碱[J]. 应用化学,2009,26(3):325-328. LI X,XIONG Y F,WEN Z Y,et al. Purification of lycorine from Lycoris Herb by macroporous adsorbent resin[J]. Chinese Journal of Applied Chemistry,2009,26(3):325-328.
[5] 李霞,熊海蓉,黄忠良,等. 大孔吸附树脂纯化石蒜鳞茎中的加兰他敏[J]. 食品科学,2012,33(6):33-36. LI X,XIONG H R,HUANG Z L,et al. Purification of galanthamine from Lycoris radiate bulbs by macroporous resin adsorption[J]. Food Science,2012,33(6):33-36.
[6] 张晓,桑世华,赖晨焕,等. Na₂B₄O₇-Na₂SO₄-NaCl-H₂O四元体系323 K相平衡研究[J]. 化学工程,2009,37(11):44-46. ZHANG X,SANG S H,LAI C H,et al. Phase equilibrium for quaternary system of Na₂B₄O₇-Na₂SO₄-NaCl-H₂O at 323 K[J]. Chemistry Engineering,2009,37(11):44-46.
[7] CUI R Z,SANG S H,HU Y X,et al. Phase equilibria in the ternary systems KBr-K₂B₄O₇-H₂O and KCl-K₂B₄O₇-H₂O at 373 K[J]. Acta Geologica Sinica:English Edition,2013,87(6):1668-1673.
[8] 肖卫强. 氯气在NaX、NaY、MCM-41、MCM-48和丝光沸石分子筛上吸附性能的研究[D]. 太原:太原理工大学硕士学位论文,2010. XIAO W Q. Chlorine adsorption properises of NaX,NaY,MCM-41,MCM-48 and mordenite molecular seives[D]. Taiyuan:Master Degree Thesis of Taiyuan University of Technology,2010.
[9] 郑云武,杨晓琴,王霏,等. 生物质催化裂解制备芳烃化合物的研究进展[J]. 林产化学与工业,2015,35(5):149-158. ZHENG Y W,YANG X Q,WANG F,et al. Reaserch progress of aromatics production from catalytic pyrolysis of biomass[J]. Chemistry and Industry of Forest Products,2015,35(5):149-158.
[10] CHOI M,LEE D H,NA K,et al. High catalytic activity of palladium(Ⅱ)-exchanged mesoporous sodalite and NaA zeolite for bulky aryl coupling reactions:Reusability under aerobic conditions[J]. Angewandte Chemie,2009,48(20):3673-3676.
[11] 曾绍槐. 择形催化[M]. 北京:中国石化出版社,1994:18-23. ZENG S K. Shape-selective Catalysis[M]. Beijing:China Petrochemical Press,1994:18-23.
[12] 张宝香,李永泰. ZSM-5分子筛在炼油工业中的应用[J]. 工业催化,2006,14(8):23-26. ZHANG B X,LI Y T. Application of ZSM-5 zeolites in oil refining[J]. Industrial Catalysis,2006,14(8):23-26.
[13] LE T S,MAO R L V. Preparation of fluorinated-desilicated ZSM-5 zeolites with high surface acidity properties[J]. Microporous & Mesoporous Materials,2000,34(1):93-97.
[14] 王国庆,孙剑平,吴锋,等. 沸石分子筛对甲醛气体吸附性能的研究[J]. 北京理工大学学报,2006,26(7):643-646. WANG G Q,SUN J P,WU F,et al. Adsorption behevior of formaldehyde on zeolites[J]. Journal of Beijing Institute of Technology,2006,26(7):643-646.
[15] 张健,万东锦,朱云云,等. 两种ZSM-5沸石分子筛吸附水中氨氮的研究[J]. 环境科学与技术,2011,34(8):104-108. ZHANG J,WAN D J,ZHU Y Y,et al.Adsorption of NH₄⁺-N from aqueous solution by two kinds of ZSM-5 molecular sieve[J]. Environmental Science & Technology,2011,34(8):104-108.
[16] 赵艺楠,宋科,彭胜,等. 沸石分子筛吸附分离忽地笑中石蒜碱[J]. 天然产物研究与开发,2016,28(2):289-292. ZHAO Y N,SONG K,PENG S,et al. Purification of lycorine from Lycoris aurea using zeolite molecular sieve[J]. Natural Product Research and Development,2016,28(2):289-292.
[17] 吴芳丽,李爱珍,毛慧芳. RP-HPLC测定石蒜中加兰他敏含量[J]. 中国中药杂志,2005,30(7):523-525. WU F L,LI A Z,MAO H F. Determination of galanthamine in bulb of Lycoris radiata by RP-HPLC[J]. China Journal of Chinese Materia Medica,2005,30(7):523-525.
[18] 姜建民,孙乙铭,王志安,等. 不同产地石蒜药材RP-HPLC指纹图谱研究[J]. 中华中医药学刊,2013(8):1804-1807. JIANG J M,SUN YM,WANG Z A,et al. Study on RP-HPLC fingerprint of Lycoris radiata from different areas[J]. Journal of Chinese Medicine,2013(8):1804-1807.
[19] 王鹏,田春莲,刘小攀. 石蒜加兰他敏及石蒜碱的超声波提取工艺[J]. 食品科学,2013,34(20):77-81. WANG P,TIAN C L,LIU X P. Ultrasonic extraction of lycorine and galantham ine from red Spider Lily Bulb[J]. Food Science,2013,34(20):77-81.
[20] HO Y S,NG J C Y,MCKAY G. Kinetics of pollutant sorption by biosorbents:Review[J]. Separation and Purification Methods,2000,29(2):189-232.
[21] 陈莉华,张俊生,朱士龙. 大孔吸附树脂对湘西节节草多糖的吸附特性及机理[J]. 林产化学与工业,2013,33(5):55-60. CHEN L H,ZHANG J S,ZHU S L. Adsorption characteristic and mechanism of mecroporous resin to polysaccharide from Equisetum ramisissimum Desf[J]. Chemistry and Industry of Forest Products,2013,33(5):55-60.
[22] SESEREL W L,JONG G J D. Styrene-divinylbenzene copolymers. Construction of porosity in styrene divinylbenzene matrices[J]. Journal of Applied Polymer Science,1973,17(9):2835-2846.
[23] 韩飞. 新型吸附树脂的设计、制备及其对酚类化合物的吸附性能研究[D]. 青岛:青岛科技大学硕士学位论文,2017. HAN F. Effective removal of phenolic compounds by a newly-synthesized adsorption resin:Design,preparation and adsorption properties[D]. Qingdao:Master Degree Thesis of Qingdao University of Science and Technology,2017.
[24] ZHANG X,LI A M,JIANG Z M,et al. Adsorption of dyes and phenol from water on resin adsorbents:Effect of adsorbate size and pore size distribution[J]. Journal of Hazardous Materials,2006,137(2):1115-1122.
[25] WANG J N,LI A M,LI X,et al. Adsorption of tannic and gallic acids on a new polymeric adsorbent and the effect of Cu(Ⅱ) on their removal[J]. Journal of Hazardous Materials,2009,169(1/2/3):794-800.
[26] HAMEED B H,EI-KHAIARY M I. Kinetics and equilibrium studies of malachite green adsorption on rice straw-derived char[J]. Journal of Hazardous Materials,2008,153(1/2):701-708.