Journal of the Korean Industrial and Engineering Chemistry, Vol.2, No.2, 97-107, June, 1991
고중력에서 MFI형 Zeolite 인 Silicalite 결정의 합성 및 성장에 관한 연구
A study on the synthesis and crystal growth of the MFI type zeolite, silicalite under highgravity
초록
실리카가 많이 함유된 제올라이트 즉 silicalite(end member of ZSM-5)를 2.55 Na2O-5.0 TPABr-100 SiO2-2800 H2O 조성으로 180℃에서 7일간 반응시켜 합성하였다. Silicalite 합성을 위한 최초 반웅물들이 담겨진 autoclave들은 반응기간 중 고중력장을 얻기 위하여 특수제작된 열풍식 항온조 내에서 원심분리되었다. 반응은 1, 30 및 50G에서 수행되었다. 30 및 50G의 고중력하에서 합성된 silicalite의 평균 및 최대 결정크기는 동일 조건하의 1G에서 합성된 결정들보다 현저하게 증가되었고, 수율도 4 %에서 55 %정도까지 약 11배가 증가되었다. 1G에서 얻어진 silicalite 결정의 평균크기는 1 일에서 7 일에 걸친 전 반응기간을 통하여 50-70㎛에 불과한 반면, 30 및 50G에서 얻어진 결정의 평균크기는 160-190㎛로 2-3배 증가된 결과가 나타났다. 더욱 특이할만한 현상으로 고중력하에서는 핵심생성과 결정성장이 뚜렷하게 2 단계에 걸쳐 나타남이 관측되었다. 예로써 50G하에서는 단지 2 내지 3 일간의 반응 후에 평균 135㎛ 정도의 silicalite 결정이 생성되는 비교적 빠른 제 1 성장단계(first growing stage)를 보였고, 이어 5일에 이르기까지 평균 200㎛ 정도의 결정이 되는 매우 빠른 제 2 성장단계(second growing stage)가 관찰되었다. 위의 2 단계 결정성장과정에서 얻어진 최대결정 크기는 각각 190 및 300㎛이었다. 고중력이 결정핵 생성, 성장, 수율 및 silicalite 결정의 크기에 미치는 영향들에 관하여 자세히 논의하였다.
Highly-siliceous dealuminated zeolite, silicalite(end member of ZSM-5) was synthesized from a batch composition of 2.55 Na2O-5.0 TPABr -100SiO 2 -2800H20 at 180 ℃ and at times ranging from one to seven days of reaction time. Autoclaves containing the synthesis mixture were centrifuged within the specially-equipped convection oven to provide an elevated gravitational force field like 30 and 50 G. Tests were also conducted at normal gravity. For synthesis performed under elevated gravities, average and maximum crystal sizes were substantially greater than those synthesized under normal gravity and product yields were also found to be affected by elevated gravity ; that is, product yields were substantially enhanced under elevated gravity from 4 % to 55 % with respect to normal gravity. The average crystal sizes of silicalite synthesized at normal gravity were 50 to 70μm over an entire range of reaction time, one to seven days while the average crystal sizes synthsized under elevated gravities, 30 and 50 G, were 160 to 190μm respectively. For the elevated gravity, in particular, two separate nucleations and growths were observed. For examples, at 50 G, large crystals of 200μm were produced through the second growing stage after 5 days of reaction following the rapid first growing stage where fairly large crystals of 135μm were produced only in 2 days of reaction. The maximum crystal sizes obtained through the above two growing stages were 190 and 300μm, respectively. A discussion of how elevated gravity affects nucleation, growth, yield and crystal size of silicalite is presented.
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