| 研究生: |
謝旻昌 Hsieh, Min-chang |
|---|---|
| 論文名稱: |
多孔幾丁聚醣薄膜對銅離子的吸附與脫附機制之研究 Study of copper ion adsorption and desorption mechanism upon the porous chitosan film |
| 指導教授: |
廖峻德
Liao, Jiunn-der |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 材料科學及工程學系 Department of Materials Science and Engineering |
| 論文出版年: | 2008 |
| 畢業學年度: | 96 |
| 語文別: | 中文 |
| 論文頁數: | 74 |
| 中文關鍵詞: | 銅離子吸附 、幾丁聚醣薄膜 、胺基 、脫附 |
| 外文關鍵詞: | amide group, desorption, adsorption of copper ion, Chitosan film |
| 相關次數: | 點閱:89 下載:2 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
幾丁聚醣為一種價格便宜且可廣泛的被應用的的天然高分子,胺基可以與重金屬離子形成鍵結而吸附,因此本研究利用冷凍乾燥製程並使用酒精取代氫氧化鈉來將薄膜內的醋酸置換出來。採用掃瞄式電子顯微鏡觀察表面形貌及拉伸試驗機檢測製程時不同階段的機械性質;以三聚磷酸鈉為交聯劑增加對不同化學環境的抵抗能力,並探討在不同pH值或溫度對於吸附和脫附銅離子的影響,利用硝酸進行脫附試驗,使用原子吸收光譜儀檢測銅離子吸附和脫附之間的效率轉換情形;再搭配X光光電子光譜儀及傅立葉轉換紅外光譜儀對化學鍵結變化情形做分析。
實驗結果顯示:使用酒精置換醋酸的幾丁聚醣薄膜可以讓薄膜孔洞直徑約170~240 μm,並在三聚磷酸鈉交聯後平均仍有190 μm。加上交聯劑後的幾丁聚醣薄膜的機械和化學性直接有明顯的變化。從化學分析知,幾丁聚醣對於銅離子的吸附是由於上面的胺基的存在造成,而本製程置備出來的幾丁聚醣薄膜擁有適當的孔洞大小可以讓銅離子輕易的擴散於其中。銅離子以40 oC、pH=5環境下的吸附量最多,吸附量達52.41 mg/g。
由實驗結果推論幾丁聚醣吸附或脫附銅離子的機制如下:(1) 乾燥後由XPS發現大量的Cu-O鍵結和Cu2+訊號,和胺基產生庫倫靜電力相互吸引;(2) 當pH值降低,會造成胺基質子化程度增加而減少用來吸附銅離子的負電荷位置;(3) 脫附則是發生於幾丁聚醣的胺基吸引氫離子或是螯合。然而,幾丁聚醣膜的第一次脫附效率約為75 %,而第二次則為60%。顯示出這樣的環境處理可以使幾丁聚醣於銅離子吸附更為實用。
Chitosan is an inexpensive and a widely available nature polymer; its amine group is usually competent to bind with heavy metal ions. In this study, chitosan films were prepared by freeze-drying procedure, and replaced sodium hydroxide by using alcohol to metathesis acetic acid inner the thin film. Morphologies and mechanical properties of the as-prepared chitosan films in different processing stages were measured by Scanning Electron Microscope and MTS. In addition, the chitosan films were purposely cross-linked with tripolyphosphate to increase the resistance of chemicals in different processing stages, such as the pH values and the temperature for copper ion adsorption/desorption. Desorption rate of copper ions was tested by nitric acid solution and measured by Atomic Adsorption spectrometry. Chemical structures of the tested chitosan films were characterized by Fourier Transform Infrared Spectrometer and X-ray Photoelectron Spectroscopy. The proposed mechanism for copper ion adsorption and desorption was thereafter studied.
Experimental results demonstrated that the pore sizes of the pristine and the cross-linked chitosan films were about 170~240 and 190 μm, respectively. Mechanical and chemical properties of the cross-lined chitosan film were significantly enhanced. From the chemical analyses, the adsorption of copper ions was resulted by the presence of amine group in chitosan and enhanced by the easily-diffusion (or the appropriate porosity) of copper ions in the chitosan matrix. The adsorption capacity was maximized at 52.41 mg/g under 40 oC and the pH value of 5.
The apparent mechanism of the copper ion adsorption/desorption can be proposed as: (1) The bonding of copper-oxygen and copper ion attract amine group each other with electrostatic attraction in the dryied thin film and find copper-oxygen was the mainly bonding from XPS; (2) As decreased the pH value in solution, the protonation of the amine group also increases, leading to the rise of the negatively-charged sites for binding with copper ions; (3) The desorption occurs when the amine group is attacked and chelated by H+. Moreover, the first and second desorption efficiencies were estimated as 75 % and 60 %, which is still promising for the preliminary treatment on the copper ions adsorption.
1.楊肇政,「污染防治」,全威圖書有限公司,6-14,2001。
2.L. Friberg, G. F. Nordberg and B. Vouk, “Handbook on
the technology of metal”, Elsevier, Amsterdam,1979。
3.徐薇如,「幾丁聚醣/藻酸鈣生物高分子對重金屬吸附行為之研
究」,國立交通大學應用化學研究所碩士論文, 2-3,2000。
4.S. V. Madihally and H. W. Matthew, “Porous chitosan
scaffolds for tissue engineering”, Biomaterial, Vol.
20, 1133-1142, 1999。
5.K. L. B. Chang, G. Tsai, J. Lee, W. R. Fu,
“Heterogeneous N-deacetylation of Chitin in Alkaline
solution”, Carbohydrate Research, Vol. 303, 327-332,
1997。
6.陳澄河,「蝦蟹殼傳奇」,科學發展,369期,62-67,2003。
7.M. Mohsen-Niaa, P. Montazeri and H. Modarress, “Removal
of Cu2+ and Ni2+ from wastewater with a chelating agent
and reverse osmosis processes”, Desalination, Vol.217 ,
276–281, 2007。
8.O. Souilah, D, E. Akretche and M. Amara, “Water reuse
of an industrial effluent by means of
electrodeionisation”, Desalination, Vol. 167, 49-54,
2004。
9.B. Biskup and B. Subotic, “Kinetic analysis of the
exchange processes between sodium ions from zeolite A
and cadmium, copper and nickel ions from solutions”,
Separation and Purification Technology, Vol. 37, 17-31,
2004。
10.J. N. Lester, “Heavy metals in wastewater and sludge
treatment process”, CRC Press, Chap. 4, 83-86, 1987。
11.C. Faur-Brasquet, Z. Reddad and K. Kadirvelu,
“Modeling the adsorption of metal ions (Cu+2 , Ni+2 ,
Pb+2) onto ACCs using surface complexation models”,
Applied Surface Science, Vol. 196, 356-365, 2002。
12.Y. H. Li, S. Wang, J. Wei, X. Zhang, C. Xu, Z. Luan, D.
Wu, and B. Wei, “Lead adsorption on carbon
nanotubes”, Chemical Physics Letters, Vol. 357, 263-
266, 2002。
13.E. S. Amany, E. N. Ahmed, K. Azza, A. Ola, “Removal of
toxic chromium from wastewater using green alga Ulva
lactuca and its activated carbon”, Journal of
Hazardous Materials, Vol. 48, 216-228, 2007。
14.A. Kapoor and T. Viraraghavan, “Fungal biosorption —
an alternative treatment option for heavy metal bearing
wastewaters: a review”, Bioresource Technology, Vol.
53, 195-206, 1995。
15.O. Gyliene, R. Rekertas and M. Salkauskas ”Removal of
free and complexed heavy-metal ions by sorbents
produced from fly (Musca domestica) larva shells”,
Water Research, Vol. 36, 4128-4136, 2002。
16.O. A. C. Monteiro Jr and C. Airoldi, “Some
Thermodynamic Data on Copper–Chitin and Copper–
Chitosan Biopolymer Interactions”, Journal of Colloid
and Interface Science, Vol. 212, 212-219, 1999。
17.Y. Kawamura, M. Mitsuhashi, H. Yoshida and H. Tanibe,
“Adsorption of Metal Ions on Polyaminated Highly Porous
Chitosan Chelating Resin”, Industrial Engineering
Chemical Research, Vol. 32, 386-391, 1993。
18.S. T. Lee, F. L. Mi, Y. J. Shen and S. S. Shyu,
“Equilibrium and kinetic studies of copper(II) ion
uptake by chitosan-tripolyphosphate chelating resin”,
Polymer, Vol. 42, 1879-1892, 2001。
19.X. Z. Shu, K. J. Zhu and W. Song, ”Novel pH-sensitive
citrate cross-linked chitosan film for drug controlled
release”, International Journal of Pharmaceutics, Vol.
212, 19-28,2001。
20.Y. Koyama and A. Taniguchi, “Cross-linking of chitosan
for enhanced cupric ion adsorption”, Journal of
Applied Polymer Science, Vol. 31, 1951-1954, 1986。
21.侯孟新,”多孔幾丁聚醣改質膠體對於不同重金屬離子之吸附研
究”,國立成功大學材料科學及工程學系, 31-46,2006。
22.C. Y. Hsieh, S. P. Tsai, M. H. Ho, D. M. Wang, C. E.
Liu, C. H. Hsieh, H. C. Tseng and H. J. Hsieh, “
Analysis of freeze-gelation and cross-linking processes
for prepare porous chitosan scaffolds”, Carbohydrate
Polymers, Vol. 67, 124-132, 2007。
23.L. Jin and R. Bai, “Mechanisms of lead adsorption on
chitosan/PVA hydrogel beads”, Langmuir, Vol. 18, 9765-
9770, 2002。
24.S. Sun and A. Wang, “Adsorption kinetics of Cu(Ⅱ)
ions using N,O-carboxymethyl- chitosan”, Journal of
Hazardous Materials B, Vol. 131, 103-111, 2006。
25.L. Dambies, C. Guimon, S. Yiacoumi and E. Guibal,
“Characterization of metal ion interactions with
chitosan by photoelectron spectroscopy”, Colloids and
Surfaces A, Vol. 177, 203-214, 2001。
26.M. Rhazi, J. Desbrieres, A. Tolaimate, M. Rinaudo, P.
Vottero and A. Alagui, “Contribution to the study of
the complexation of copper by chitosan and oligomers”,
Polymer, Vol. 43, 1267-1276, 2002。
27.張志仲,”可降解及多孔性之適強度幾丁聚醣薄膜膠體對銅離子
吸附的研究”,國立成功大學材料科學及工程學系, 33-52,
2007。
28.S. R. Shukla and R. S. Pai, “Adsorption of Cu(Ⅱ)、Ni
(Ⅱ)、Zn(Ⅱ) on modified jute fibres”, Bioresource
technology, Vol. 95, 1430-1438, 2005。
29.行政院環保署,2008。
30.N. Chiron, R. Guilet and E. Deydier, “Adsorption of Cu
and Pb onto grafted silica : isotherms and kinetic
models”, Water Research, Vol. 37, 3079-3086, 2003.
31.經濟部工業局工業污染防治技術計畫專案,2003。
32.許漢平,以食鹽為造孔劑製備備吸附能力幾丁聚醣薄膜之應用,
國立聯合大學化學工程學系碩士論文, 3-4,2006。
33.J. Brugnerotto, J. Lizardi, F.M. Goycoolea and M.
Rinaudo,”An infrared investigation in relation with
chitin and chitosan characterization”, polymer, Vol.
42, 3569-3580, 2001。
34.M.A.A. Muzzarelli, C. Jeuniaux, G.W. Gooday, “Chitin
in nature and technology”, Plenum press, 1986。
35.S. Babel, T.A. Kurniawan, “Low-cost adsorbents for
heavy metals uptake from contaminated water: a
review”, Journal of Hazard Material, Vol.97, 219-243,
2003。
36.賴淑琪,「水產廢棄蝦、蟹外殼之高度利用」,食品工業,
Vol. 11, 23,1979。
37.K. M. Rudall, “Chitin and its association with other
molecules” Journal of Polymer Science Part C, Vol .
28, 83-102, 1969。
38.X. Wang, Y. Du and H. Liu, “Preparation,
characterization and antimicrobial activity of chitosan-
Zn complex”, Carbohydrate Polymer, Vol. 56, 21-26,
2004。
39.L. G. Filar and M. G. Wirick, “Bulk and solution
properties of chitosan In: Proceed- ings of the 1st
Int. Conf. on chitin/chitosan” Muzzarelli, R. A. A.
and Pariser, E. R. (Eds): 169, 1978。
40.S. I. Aiba, “Studies on chitosan: 4. Lysozymic
hydrolysis of partially N-acetylated chitosans”,
International Journal of Biological Macromolecules,
Vol. 14, 225-228, 1992。
41.呂卦南,「幾丁質與幾丁鉅堂之製備與鑑定」,康寧學報,
Vol. 8,157-170,2006。
42.X. Z. Shu and K. J. Zhu, “Controlled drug release
properties of ionically cross-linked chitosan beads:
the influence of anion structure”, International
Journal of Pharmaceu- tics, Vol. 233, 217-255, 2002。
43.Z. X. Tang, J. Q. Qian and L. E. Shi,
“Characterizations of immobilized neutral proteinase on
chitosan nano-particles”, Process Biochemistry, Vol.
41, 1193-1197, 2006。
44.H. R. Lin, K. S. Chen, S. C. Chen, C. H. Lee, S. H.
Chiou, T. L. Chang and T. H. Wu, “Attachment of stem
cells on porous chitosan scaffold crosslinked by
Na5P3O10” , Material Science and Engineering C, Vol.
27, pp 280-284, 2007。
45.Q. Yang, F. Dou, B. Liang and Q. Shen, “Studies of
cross-linking reaction on chitosan fiber with
glyoxal”, Carbohydrate Polymers, Vol. 59, pp 205-210,
2005。
46.T. Becker, M. Schlaak, H. Strasdeit, “Adsorption of
nickel(Ⅱ), zinc(Ⅱ) and cadmium (Ⅱ) by new chitosan
derivatives”, Reactive & functional polymer, Vol.44,
289-298, 2000。
47.W. S. Wan Ngah, C. S. Endud, and R. Mayanar, “Removal
of copper (Ⅱ) ions from aqueous onto chitosan and
cross-linked chitosan beads”, Reactive & Functional
Polymers, Vol. 50, pp 181-190, 2002。
48.A. A. Atia, “Studies on the interaction of mecury(Ⅱ)
and uranyl(Ⅱ) with modified chitosan resins”,
Hydrometallurgy, Vol. 80, 13-22, 2005。
49.N. Sankararamakrishnan and R. Sanghi, “Preparation and
characterization of a novel xanthated chitosan”,
Carbohydrate Polymers, Vol. 66, 160-167, 2006。
50.林怡伶,化學修飾雙性幾丁聚醣衍生物及其持水特性研究,國立
交通大學材料科學與工程研究所碩士論文, 25-26,2005。
51.M. Hitoshi, R. Giuseppe, C. Tommasina, Y. Yoshiaki and
U. Hiroshi, “Low-degree oxidized scleroglucan and its
hydrogel”, International Journal of Biological
Macromolecules, Vol. 28, 351-358, 2001。
52.C. K. Kuo and P. X. Ma, “Ionically crosslinked
alginate hydrogels as scaffolds for tissue engineering:
Part 1. Structure, gelation rate and mechanical
properties”, Biomaterials, Vol. 22, 511-521, 2001。
53.J. S. Park, J. W. Park and E. Ruckenstein, “Thermal
and dynamic mechanical analysis of PVA/MC blend
hydrogels”, Polymer, Vol. 42, 4271-4280, 2001。
54.W. E. Hennink, S. J. De Jong, G. W. Bos, T. F. J.
Veldhuis and C. F. van Nostrum, “Biodegradable dextran
hydrogels crosslinked by stereocomplex formation for
the controlled release of pharmaceutical protein”,
International Journal of Pharmaceutics, Vol. 277, 99-
104, 2004。
55.蕭奧,張有義,郭蘭生,膠體及界面化學入門,高立出版,15-
30,1997。
56.E. Guibal,.“Interactions of metal ions with chitosan-
based sorbents: a review”, Separation and
Puriification Technology, Vol. 38, 43-74, 2004。
57.林敬智,「下水污泥灰渣應用於銅離子去除的初步探討」,中央
大學環境工程研究所,9-12,2001。
58.H.A. Elliott and C.P. Huang, “Factors affecting the
adsorption of complexed heavy metals on hydrous
Al2O3”, Water science and technology, Vol.17, 1017-
1028, 1984。
59.A.K. Bhattacharya and C. Venkobachar, “Removal of
Cadmium(Ⅱ) by low cost adsorbents”, Journal of
environmental engineering, Vol. 110, 110-112, 1984。
60.C.P. Huang and E.A. Rhoads, “Adsorption of Zn(Ⅱ) onto
hydrous aluminosilicates”, Journal of colloid and
interface science, Vol. 131, 289-306, 1989。
61.J. Ayala, F. Blanco, P. Garcia, P. Rodriguze and J.
Sancho, ”Asturian fly ash as a heavy metal removal
material”, Fuel, Vol.77, 1147-1154, 1998。
62.V. K. Gupta and I. Ali, ”Utilization of bagasse fly
ash (A sugar industry waste) for the removal of copper
and zinc from wastewater”, Separation and purification
technology, Vol. 18, 131-140, 2000。
63.N. H. Turner, “X-ray photoelectron and auger electron
spectroscopy”, Applied Spectroscopy Reviews, Vol. 35,
203-254, 2000。
64.儀器總覽9,環境及安全衛生檢測儀器, 行政院國家科學委員會
精密儀器發展中心出版,pp 67-69,1999。
65.邱承美,陶金華,「儀器分析原理」,科文出版社出版,1994。
66.F. Garbassi, M. Morra, and E. Occhiello, “Polymer
surfaces from physics to technology”, John Wiley &
Sons Ltd, 1994。
67.顏棋鑫,「幾丁聚醣顆粒吸附有害重金屬之探討」,朝陽科技大
學應用化學系碩士論文,pp 13-14,2002。
68.B.Y.M. Bueno, M.L. Torem, F. Molina, L.M.S. de
Mesquita, “Biosorption of lead(Ⅱ), chromiun(Ⅱ) and
copper(Ⅱ) by R. Opacus:Equilibrium and kinetic
studies”, Minerajs engineering, Vol.110, 534-545,
2007。
69.I. Manjubala, S. Scheler, Jorg Bossert, Klaus D. Jandt,
“Mineralisation of chitosan scaffolds with nano-apatite
formation by double diffusion technique”, Acta bio -
material, Vol.2, 75-84, 2006。
70.謝玠揚,「聚麩胺酸及幾丁聚醣複合生醫基材之製程探討、性質
改良及制放應用」,台灣大學化學工程學系博士論文,36-44,
2004。
71.Chunxiu Liu and Renbi Bai, “Preparation of
chitosan/cellulose acetate blend hollow fibers for
adsorptive performance”, Journal of Membrane Science,
Vol. 267, 68-77, 2005.
72.Jiunn-Der Liao, Shu-Ping Lin, and Yi-Te Wu, “Dual
properties of the deacetylated sites in chitosan for
molecular immobilization and biofunctional effects”,
Biomacromolecules, Vol. 6, 392-399, 2005.
73.M. S. Chiou and H. Y. Li, “Adsorption behavior of
reactive dye in aqueous solution on chemical cross-
linked chitosan beads”, Chemosphere, Vol. 50, 1095-
1105, 2003。
74.N. Li, R. Bai, “Copper adsorption on chitosan-
cellulose hydrogel bead:behaviors and mechanisms”,
Separation and purification technology, Vol.42, 237-
247, 2005。
75.Li Jin and Renbi Bai, “Mechanisms of lead adsorption
on Chitosan/PVA hydrogel beads”, Langmuir, Vol. 18,
9765-9770, 2002.
76.M. Rhazi, J. Desbrieres, A. Tolaimate, M. Rinaudo, P.
Vottero, A. Alagui , ”Contribution to the complexation
of copper by chitosan and pligomers”, Polymer, Vol.
43, 1267-1276, 2002.
77.I. F. Amaral, P. L. Granja, and M. A. Barbosa,
“Chemical modification of chitosan by phosphorylation:
an XPS, FT-IR and SEM study”, Journal of Biomaterial
Science Polymer Edition, Vol. 16, 1575-1593, 2005。
78.J. Guzman, I. Saucedo, J. Revilla, R. Navarro, E.
Guibal,” Copper sorption by chitosan in the presence
of citrate ions: influence of metal speciation on
sorption mechanism and uptake capacities”,
International Journal of Biological Macromolecules,
Vol. 33, 57-65, 200.