石炭灰フライアッシュからのゼオライトのアルカリ水 Title 熱合成と生成物の陽イオン交換特性 Author(s) 村山, 憲弘, 山川, 洋亮, 小川, 和男, 芝田, 隼次 Citation 資源と素材 : 資源 素材学会誌, 116(4): 279-284 Issue Date 2000 URL http://hdl.handle.net/10112/5454 資源 素材学会 (http://www.jstage.jst.go. Rights se/shigentosozai/_vols/-char/ja) Type Journal Article Textversion publisher Kansai University http://kuir.jm.kansai-u.ac.jp/dspace/
(Shigen to Sozai) Vol.116 p. 279 284 (2000) 石炭灰フライアッシュからのゼオライトのアルカリ水熱合成と生成物の陽イオン交換特性 * 1 1 村山憲弘山川洋亮 2 3 小川和男芝田隼次 Alkali Hydrothermal Synthesis of Zeolite from Coal Fly Ash and its Cation Exchange Property by Norihiro MURAYAMA 1, Yousuke YAMAKAWA 1 Kazuo OGAWA 1 and Junji SHIBATA 2 1. R&D Department, Kimura Chemical Plants Co., Ltd., Amagasaki-shi 660-8567 2. Department of Chemical Engineering, Faculty of Engineering, Kansai University, Suita-shi 564-8680 The synthesis of zeolite from coal fly ash by alkali hydrothemal reaction with NaOH was investigated under various conditions and the physical properties of the products were measured in this study. The reaction rate of cation exchange and substitution ratio of calcium ion were examined with some solutions containing calcium ion. Also, some physical properties of calcium type zeolite were measured. Zeolite P which had large cation exchange capacity (about 500 meq / 100 g as CEC) was synthesized from coal fly ash under the particular synthesis condition; reaction temperature of 393 K, reaction time of 5 hrs, NaOH concentration of 1.5 mol / dm 3 and solid-liquid ratio of 200 g / 800 cm 3. The crystal type of synthesized zeolite changed from zeolite P to hydroxysodalite with an increase in concentration of NaOH. The reaction rate was obviously increased when the reaction temperature was over boiling point of water. It was confirmed that the cation exchange reaction of zeolite synthesized in this study could be almost reversible between calcium ion and sodium ion. Optimum condition for zeolite synthesis with high CEC and calcium substitution, and some factors affecting zeolite synthesis and cation exchange reaction were discussed. KEY WORDSCoal Fly Ash, Calcium Ion, Sodium Ion, Zeolite, Alkali Hydrothermal Reaction, Ion Exchange 1 10 20 % 8 700 t 1991 10 ( ) 1) 1999 9 27 12 9 1. () 2. () 3. [ ]FAX 06-6388-8869 ( ) 2) 6) 70 80 wt% 2) Na Ca 2 NH 4 Ca 2 279
2 21 () JIS X (EMAX 3770 ) (S 2400 ) SEM (LA 90 ) (JDX 3530S ) 22 1.5 5.5 mol / dm 3 200 g / 800 cm 3 300 g / 700 cm 3 1200 cm 3 368 413 K 650 rpm X (Cation Exchange Capacity CEC) 2 g 0.5 mol / dm 3 50 cm 3 Na Ca 2 3 Ca 2 80 wt% Ca 2 1.0 mol / dm 3 50 cm 3 NH 4 5 Ca 2 (AA 880 Jarrell Ash ) 100 g CEC 23 22 1.0 2.0 g 0.5 1.0 mol / dm 3 20 cm 3 Na Ca 2 NH 4 Na Ca 2 100 g Na Ca 2 Na Ca 2 Ca 2 (Ca 2 / Na Ca 2 ) a 24 Ca 2 5.0 g 12.5 20 cm 3 ph 3 31 Fig.1SEM photograph of coal fly ash. Table 1Chemical composition of coal fly ash and synthesized zeolites. Fig.2Particle size distributions of coal fly ash, Na and Ca type zeolites. SEM Fig.1 Fig.1 Table 1 70 wt% CEC 18 meq / 100 g Ca 2 Fig.2 15.4 mm (0.1 70 mm ) 32 Fig.2 24.4 mm Fig.3 280
P P Table 1 SEM Fig.4 P (CEC) Fig.5 1.5 mol / dm 3 CEC 500 meq / 100 g 2.5 mol / dm 3 CEC 340 meq / 100 g CEC 5 CEC CEC P P CEC ( 3 4 A) P ( 4 5 A) 7)8) CEC P 33 CEC Fig.6 CEC 200 g / 800 cm 3 5 300 g / 700 cm 3 8 Fig.3X-ray diffraction of coal fly ash and synthesized zeolites. Fig.5Relationship between reaction time and cation exchange capacity at various NaOH concentrations. Fig.4SEM photographs of zeolites synthesized from coal fly ash at the different NaOH concentrations (reaction temperature, time:393k, 5hrs) 281
CEC CEC 300 g / 700 cm 3 Na OH CEC CEC Fig.7 373 K CEC 8) 393 K CEC 393 K CEC Fig.5 7 (NaOH[g] / Fly Ash[g]) Fig.6Effect of ratio of solid and liquid on cation exchange capacity. Fig.7Relationship between reaction time and cation exchange capacity at various reaction temperatures. Fig.8Relationship between amount of NaOH to fly ash and cation exchange capacity. CEC Fig.8 CEC CEC 4)10) Na OH Na OH OH Na 3)4) Na OH 34 Fig.9 120 min Ca 2 Ca 2 Na Fig.10 Ca 2 P 11) Ca 2 282
Fig.11Change in ph of Na and Ca type zeolite slurries at various initial ph. Fig.9Time course of calcium substitution reaction of Na type zeolite by using CaCl 2 solution. Table 2Amount of exchangeable cations, calcium substitution ratio a and ph for various zeolites. Fig.10Behavior of cation exchange reaction on calcium substitution and sodium reverse substitution. Na Ca 2 Ca 2 35 Fig.2 SEM Na Ca 2 ph Fig.11 ph H H OH NH 4 CEC ph Na CEC Ca 2 ph ph Table 2 a ph a CEC(Na + Ca 2 ) 4 Ca 2 Ca 2 1) CEC P 283
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