シリカライトの結晶成長に及ぼす溶液組成の影響 <論文>

Effects of Composition of Synthesis Mixture on Silicalite Crystal Growth

菅原 生豊

竹田 清志

佐野 庸治

川上 雄資

岩崎 晃

日本化学会誌 : 化学と工業化学

Journal of the Chemical Society of Japan : chemistry and industrial chemistry

水熱合成条件下でのゼオライト結晶の成長過程を直接観察するために新しいタイプのその場観察装置を開発し,これを用いてシリカライトの結晶成長速度及び結晶形態に及ぼす結晶化温度及び原料溶液組成の影響を詳細に検討した.孤立した特定の結晶の大きさの経時変化の傾きから求めた長さ及び幅方向の成長速度は結晶化時間によらず一定であり,結晶化温度が高いほど大きくなることがわかった.また,結晶形態は結晶化温度に依存し,高温ほど細長くなることがわかった.次に,出発原料溶液組成を以下のように変えて結晶成長速度に及ぼす溶液組成の影響を調べた.
(1) xTPA2O-0.05Na2O-SiO2 - 300H2O ( x = 0.012 ～ 0.1)
(2)0.05TPA2O -yNa2O- SiO2 - 300H2O ( y=0.025 ～ 0.2)
(3)0.05TPA2O -0.05Na2O - zSiO2- 300H2O ( z = 0.5 ～ 2)
(4)0.05TPA2O -0.05Na2O - SiO2 - wH2O ( w= 100 ～ 1000)
得られた結晶の大きさの経時変化から求めた各組成における長さ方向の成長速度Rlおよび幅方向の成長速度Rwから,次の相関式が得られた.
Rl∝ (TPA+)0.389(OH-)0.518(SiO2) -0.196(6H2O) -0.745
Rw∝(TPA+)0.675(OH-)1.05(SiO2) -0.226(H2O) -1.12
Rl/Rw∝ (TPA+)-0.286(OH-) -0.528(SiO2)0.0296( H2O)0.369

To clarify the crystal growth process of zeolite under hydrothermal synthesis condition, a new type apparatus for the in-situ observation was developed. In the present work, the growth behavior of silicalite crystals from clear aqueous solutions was studied using the apparatus. Effects of the crystallization tern perature and the composition of synthesis mixture on the growth rate and the morphology of specified crystal were investigated systematically. The crystal length growth rate (Rl) and width growth rate (Rw) increased significantly with an increase in the temperature. The morphology was also affected by the temperature.
Next, effects of the composition of synthesis mixture on the crystal growth rate and the morphology was investigated using the following synthesis mixtures.
(1) xTPA2O-0.05Na2O-SiO2 - 300H2O ( x = 0.012 - 0.1)
(2)0.05TPA2O -yNa2O- SiO2 - 300H2O ( y=0.025 - 0.2)
(3)0.05TPA2O -0.05Na2O - zSiO2- 300H2O ( z = 0.5 - 2)
(4)0.05TPA2O -0.05Na2O - SiO2 - wH2O ( w= 100 - 1000)
The growth rate and the crystal morphology were affected markedly by changing the composition of synthesis mixture. The following relationships were obtained;
Rl∝ (TPA+)0.389(OH-)0.518(SiO2) -0.196(H2O) -0.745
Rw∝ (TPA+)0.675(OH-)1.05(SiO2) -0.226(H2O) -1.12
Rl/Rw∝ (TPA+)-0.286(OH-) -0.528(SiO2)0.0296( H2O)0.369

化学 [ 430 ]

日本語

日本化学会

Copyright (c) 1995 The Chemical Society of Japan

[ISSN] 0369-4577

[NCID] AN00186595

[DOI] 10.1246/nikkashi.1995.615

[DOI] https://doi.org/10.1246/nikkashi.1995.615