台灣處於一個山高坡陡的地勢中，而經山區地帶人為過度開發加上雨水沖蝕山坡地帶，常常造成水庫淤泥的堆積，長年累積大大縮減水庫使用的壽命，而將淤泥資源再利用，甚至再創，就變得十分重要。經前人文獻發現水庫淤泥成分含有氧化矽(SiO2)與氧化鋁(Al2O3)以及它類鹼金、鹼土元素，如鈉、鉀、鈣及鎂，在水熱環境下可和鹼液反應形成沸石礦物。沸石礦物是具有吸附與離子交換的性質，被視為是極佳的淨化材料，加上取得原料淤泥難度不大又助解決水庫阻塞問題，故水庫汙泥很適合做為合成沸石的原料。
本實驗採用的鹼液為NaOH，而實驗過程為分別採用兩種不同溫度的煆燒汙泥(750oC、950oC)、鹼液濃度(5M和9M)、恆溫(60oC、90oC)和持續攪拌(1小時、3小時、6小時)，經過水熱溫度150。C和水熱時間(6hr、12hr和24hr)對沸石合成的影響。
產物相以Zeolite A、sodalite和faujacite相為主，實驗中取4組結晶性較佳的樣品進行BET、氨氮吸附測試與陽離子交換測試，由實驗結果可知4組樣品所測出的比表面積皆大於前人文獻中的數據加上NH4+離子吸附能力皆優於天然沸石礦物，以證明吾人在使實驗中加上的恆溫攪拌過程對於原料結構粉末活性的提升是具效果的。

英文延伸摘要SUMMARY

Taiwan is an island which has many high mountains and precipitous hillsides , due to rain impact erosion and overdeveloping of natural mountain areas, the problem of reservoir sediments in Taiwan precipitate heavily ,it effects Effective duration of the reservoir , so how to recycle of reservoir sediment or even make it to be a now product have become a serious issue. Since sediment contains SiO2、Al2O3 and other flux ions , it can react with alkali solution to form zeolites. Zeolite minerals with adsorption and ion exchange properties, are considered one of the best purification materials, and the other reason is that it’s not that hard to get sediments from reservoirs , the problem with reservoirs clogged can be solved at the mean time .

Sodium hydroxide is used as alkali solution in this experiment , we used calcination temperature of sediment 750 oC and 950 oC、The alkali concentration(5M and 9M)、constant temperature (60 oC、90 oC)and ceaseless mixing (1hour、3hours、6hours) 、 reaction temperature150。C and hydrothermal time(6hr、12hr and 24hr) were discussed on the effect of zoelite synthesis experiment. The results showed that all the numerical values of BET are bigger than references and also NH4+ ion absorption capacity of the five samples are all better than nature zeolite minerals , therefore , it shows that reservoir sediment powders will be broken earlier when you make use of constant temperature mixing in your experiment process.

Key words : reservoir sediments, sodium hydroxide, zeolite, hydrothermal reaction

INTRODUCTION

With the advances in technology of industry，however，behind the advantages，it’s also associated with pollution which is growing threat to human health. Treatments of industrial wastes are more and more important nowadays. In the treatment of waste water and waste gas, it can be adsorbed or isolated to achieve the effect. Zeolite minerals with adsorption and ion exchange properties, are considered one of the best purification materials.

we used calcination temperature of sediment 750 oC and 950 oC、The alkali concentration(5M and 9M)、constant temperature (60 oC、90 oC)and ceaseless mixing (1hour、3hours、6hours)、reaction temperature150。C and hydrothermal time(6hr、12hr and 24hr) were discussed on the effect of zoelite synthesis experiment.

Fly ash can be artificially synthesized zeolite synthesis mechanism Zeolite p experiments to do shows, can be roughly divided into three stages: the temperature at the time of 293-393K, began the first phase: the surface of fly ash particles begin to dissolve, the smooth surface is gradually transformed into a rough surface , the concentration of aluminum ions and silicate ions gradually increased, the concentration of aluminum ions in the first stage will reach the end of the peak at this stage, the concentration of the dissolution rate is based on the base (OH-), the alkalinity of the solution increases the dissolution rate can be effectively improved.

When a temperature of 373K, the second phase starts: In this temperature range, the aluminum due to the formation of colloidal silica, resulting in an aluminum ion concentration dropped dramatically, colloidal aluminum silicate and silica-rich surface on the fly ash particles integrate a sheet surface of the particles of colloidal aluminum start capturing other cations begin to crystallize.

In the beginning of the third stage of 393K: Because aluminum colloidal silica particles have been coated with ash, fly ash can not reach the base, so the system does not increase silicon aluminum ions, whereas the zeolite crystals began in aluminum and fly ash particles in colloidal the interface between the crystalline nucleation, aluminum ions gradually consumed, the reaction of the end of the aluminum ion depleted silicon ion concentration reaches equilibrium system, the end of the system response.

RESULTS AND DISCUSSION

Raw material after calcination treatment, the crystalline phase by heat damage, thereby increasing the chemical reactivity, the raw material of this experiment Shimen Reservoir sludge, by XRD shows that the main composition of mineral phases - Quartz Quartz, muscovite muscovite, albite Albitite and oblique amesite Clinochlore, its reactivity is low, so the raw sludge to from Shimen Reservoir are calcined to look forward to destroy the mud of the mineral phase and increase its chemical activity.

Water provides the energy supplying the heating temperature in the reaction system pressure, thereby to drive the solvents affects the solubility of the zeolite produced in this section for the study target temperature as a parameter, and if you want to compare the temperature of raw materials for the effect of agitation.we found that the stirring temperature will destroy phase to increase the solubility and to make it sufficient to form the other zeolite phases.This section will discuss the impact of stirring time on zeolite synthesis.we also found that in the longer mixing time, the mineral phase decreased significantly, while generating zeolite phase is more obvious.

CONCLUSION

This section should include (1) It was found that sludge powder after calcination, the structure of the phase advance is destroyed, so that the raw material powder is pulverized under high temperatures and damage by more, thus producing more stack of silicon to aluminum ions compared complex phase zeolite mineral. Besides increasing the raw material powder of glass phase and the area, but also improve the reactivity and reaction rate, after calcination of sludge, a lower concentration of sodium hydroxide solution available to the synthesis of zeolite minerals at the same temperature conditions.(2) Si concentration in the base and the aluminum ion concentration is proportional, the higher the concentration of the base is provided, the better the destruction of mineral phases and glass phases.(3) Stir temperatures increase the solubility and would undermine phase, thermostatic stirring time will directly affect the phase formation and destruction, even if the gap is not thermostatic mixing time, changes to the zeolite phase will be affected.(4) We found that during the synthesis of zeolite samples were subjected to a constant temperature bath early damage for increasing the BET is helpful.

參考文獻
1. M. Meftah, W.Oueslati, A. Ben Haj Amara, Synthesis process of zeolite P using a poorly crystallized kaolinite, Physics Procedia 2 (2009) 1081–6.
2. 劉玉梅，向陽絹雲母礦中葉蠟石水熱合成方沸石之研究，碩士論文，國立成功大學 (2006)
3. 吳雅雯，水熱合成方沸石之離子吸附研究，碩士論文，國立成功大學 (2009)
4. 國際沸石協會資料庫，http://www.iza-structure.org/
5. 劉錡樺，水處理污泥轉換活性碳－沸石複合吸附材料之研究，碩士論文，國立中央大學 (2010)
6. X. Querol, N. Moreno, J.C. Umana, A. Alastuey, E. Hernandez, A. Lopez-Soler, F. Plana, Synthesis of zeolites from coal fly ash: an overview, Int. J. Coal Geo. 50 (2002) 413-23.
7. M.W. Ackley, S.U. Rege, H. Saxena, Application of natural zeolites in the purification and separation of gase, Micropor. Mesopor. Mat. 61 (2003) 25–4
8. 曾旭志，芳香烴及環狀烴在 Silicalite-1 沸石中恆溫吸附之分子模擬，碩士論文，國立成功大學(2007)
9. 王倉修，直鏈狀烷類在 MFI 型沸石中恆溫吸附之分子模擬，碩士論文，國立成功大學 (2005)
10. N. Murayama, H. Yamamoto, J. Shibata, Mechanism of zeolite synthesis from coal fly ash by alki hydrothermal reaction, Int. J. Miner. Process. 64 (2002) 1-17.
11. M. Inada, Y. Eguchi, N. Enomoto, J. Hojo, Synthesis of zeolite coal fly ashes with differentsilica-alumina composition, Fuel 84 (2005) 299-304.
12. Y.S. Yoo, K.H. Cheon, J.I. Lee1, B.S. Kim, W.S. Shin, G.T. Seo, Zeolite Synthesis Using Sewage Sludge by Molten-salt Method, Mater. Sci. Forum, Vol. 569 (2008) pp 329-332
13. T Wajima, M.Hagaa, K. Kuzawa, H. Ishimoto, O. Tamadaa, K. Ito, T. Nishiyama, R. T. Downsd, J. F. Rakovan, Zeolite synthesis from paper sludge ash at low temperature (90 ◦C) with addition of diatomite, J Hazard Mater.B132 (2006) 244–252
14. Q. Liu, A. Navrotsky, Synthesis of nitrate sodalite: an in situ scanning calorimetric study, Geochim.Cosmochim. Acta 71 (2007) 2072-8.
15. 彭國文，“利用台灣東部安山岩製造沸石粉體之研究”，碩士論文，國立成功大學礦冶及材料工程系 (1990)
16. J. Temuujin, K. Okada, K. J.D. MacKenzie, Zeolite formation by hydrothermal treatment of waste solution from selectively leached kaolinite, Mater. Lett. 52 (2002) 91-5.
17. A. Chaisena, K. Rangsriwatananon, Synthesis of sodium zeolites from nature and modified diatomite, Mater. Lett. 59 (2005) 1474-9.
18. M. Alkan, C. Hopa, Z. Yilmaz, H. Güler, The effect of alkali concentration and solid/liquid ratio on the hydrothermal synthesis of zeolite NaA from natural kaolinite, Micropor. Mesopor. Mater. 86 (2005)176-84.
19. A.G. San Cristóbal, R. Castelló, M.A. Martín Luengo, C. Vizcayno, Zeolites prepared from calcined and mechanically modified kaolins: A comparative study, Clay Sci. 49 (2010) 239-46.
20. I. D.R. Mackinnon, G. J. Millar, W. Stolz, Low temperature synthesis of zeolite N from kaolinites and montmorillonites, Clay Sci. 48 (2010) 622-30.
21. M. Kazemimoghadam, T. Mohammadi, Preparation of nano pore hydroxysodalite zeolite membranes using of kaolin clay and chemical sources, Desalination (2011) accepted.
22. M. Mezni, A. Hamzaoui, N. Hamdi, E. Srasra, Synthesis of zeolites from the low-grade Tunisian natural illite by two different methods, Clay Sci. 52 (2011) 209-18.
23. Y. Du, S. Shi, H. Dai, Water-bathing synthesis of high-surface-area zeolite P from diatomite, Particuology 9 (2011) 174-8.
24. K. Byrappa, T. Adschiri, Hydrothermal technology for nanotechnology, Prog Cryst Growth Ch, 53 (2007) 117-166
25. 金相灿,賀凱,戶少勇,胡小貞,李勝男, 4種填充料對氨氮的吸附效果, J Lake Sci, 2008,20(6):755-760
26. 熊小京,葉均磊,王新紅,汪任瀾，天然沸石處理低濃度含氨廢水的實驗研究，廈門大學環境科學研究中心.45(2006),
27. 石朝斌,張道方,許智華，天然沸石與泥炭脫氮除磷實驗研究，上海理工大學環境工程系26(2009)