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박건유,하백현,이영섭 한국화학공학회 1985 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.23 No.2
Sodium Y zeolite 와 benzene, toluene, ethylbenzene, xylenes과 같은 芳香族 炭化水素가 이루는 吸着系에 대한 吸着特性을 溫度範圍 140∼280℃에서 Gas chromatography를 使用하여 硏究하였다. 또한 cyclohexane, n-pentane 그리고 n-pentene에 대해서도 調査, 比較하였다. Benzene 誘導體에 대한 吸着은 吸着量에 따른 吸着熱이 增加하는 것으로 보아 NaY에서 均一한 吸着系를 갖고 있는 것으로 判斷되며 吸着量과 吸着熱은 알킬기의 置換程度에 따라 增加하였고 이온화 포텐셜이 增加할수록 初期吸着熱은 減少함을 보였다. 이 吸着系에 細孔의 充塡槪念을 導入한 Dubinin-Astarkhov式을 適用시켜 본 結果 n-pentane과 cyclohexane系가 比較的 잘 適用되었으며 n-pentene과 benzene 誘導體는 상당한 偏差를 보여주었다. 또 Sodium Y와 같이 細孔이 큰 構造를 갖고 있는 zeolite에서는 吸着分子크기의 영향보다는 π電子와 알킬기의 영향이 더 큼을 確認하였다. The adsorptive characteristics of sodium Y zeolite for simple aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, xylenes were investigated by means of gas chromatography at 140 to 280℃. For comparison, the adsorptive characteristics made from the isotherm curves, previously published, for cyclohexane, n-pentane and n-pentene on NaY zeolite were also checked. Sodium Y zeolite seems to form a homogeneous system for aromatic compounds. The amount adsorbed and the adsorption heat for benzene derivatives increase with the extent of alkyl substitution. A linear relationship was confirmed between the decrease in the ionization potential of aromatic hydrocarbons and the increase in the initial heat of adsorption. The Dubinin-Astarkhov's equation based on the Polanyi's theory was also applied on the adsorption system. The Dubinin-Astarkhov's equation was fitted well for cyclohexane and n-pentane but not for benzene derivatives and n-pentene. It was found that the adsorption with regard to the large pore zeolite such as sodium Y was preferably affected by the electrons and the extent of alkyl substitution rather than the kinetic diameter of adsorbate.
연구논문초록(’81-’90) : 플루오르산과 규풀루오르산에 의한 재질의 부식에 관한 연구
박건유,권영수,김면섭,국명호 한국부식학회 1991 Corrosion Science and Technology Vol.20 No.1
The corrosion properties of 304 Stainless steel, Cupro-nickel, NiCrMo alloy in hydrofluoric acid and silicofluoric acid has been studied. The corrosion resistance of NiCrMo alloy and Cupro-nickel in hydrofluoric acid or mixed acid of hydrofluoric and sulfuric acid is excellent. Because of lower corrosion resistance of 304 Stainless steel, it would not be used for these corrosion resistant materials. The corrosion activation energy of 304 Stainless steel, Cupro-nickel and NiCrMo alloy in 40% HF solution are 42.7, 58.9 and 89.7kJ/㏖, respectively, by these values, it is assumed that the corrosion ratedeterminingstep is the chemical reaction on surface of metals. In the plastics, Teflon andpolychlorotetrafluoroethylene are most excellent for corrosion resistance in hydrofluoric acid.
R23 의 열분해 반응에 의한 핵사플루오로프로필렌의 제조
박건유,권영수,안병성,문동주,정문조 한국공업화학회 2000 응용화학 Vol.4 No.1
Hexafluoropropylene(C₃F_6, HFP) was synthesized from the pyrolysis of trifluoromethane(CHF₃, R23). Product distributions were estimated by the computer simulation for the pyrolysis of R23 using the kinetic constants for individual reaction mechanisms proposed by other researchers. Based on the computer simulation, the pyrolysis of R23 was investigated in the reaction conditions such as reaction temperature 700-1000℃, contact time 0.01-14 sec and molar ratio R23/tetrafluoroethylene (CF₂=CF₂, TFE) 0.2-2.5. We found that the recycling of unreacted R23 and TFE in the product is to be useful to obtain a high yield of HFP and to stabilize the reaction temperature.
박건유,박태기,정문조 한국화학공학회 1983 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.21 No.5
상용공장에서 사용되는 관형반응기를 사용하여 CHClF₂의 열분해 반응에 대한 반응속도론적 연구를 하였다. CHClF₂는 열분해 반응에 의하여 C₂F₄와 HCl을 생성하며 C₂F₄는 polytetrafluoroethylene의 단량체로서 사용되고 있다. 반응이 층류구간에서 진행되므로 반응기 내부에 온도 및 속도의 구배가 존재하며 반경방향의 온도구배를 측정한 결과 2차 곡선과 잘 일치함을 알 수 있었다. 각 반응조건하에서 얻어진 전환율과 온도 및 속도구배를 사용하고 확산 및 가역반응을 고려하여 활성화 에너지와 Arrhenius상수를 계산하였으며 계산과정에서 computer 를 사용하였다. 계산 결과 γ_A = k₁[CHClF₂] - k₂[CF₂:] [HCl] (k₁= A_(1e)^(-E₁/RT), k₂= A_(2e)^(-E₂/RT) 로 표시되는 반응속도식에서 E₁= 48,951 ㎈/mole A₁= 0.3358 × 10^(15)/sec E₂= 5,117 ㎈/mole A₂= 0.1452 × 10^(14)㎤/mole·sec 의 값을 얻을 수 있었다. Kinetic study has been made on the pyrolysis of CHClF₂ using a tubular reactor of a commercial plant scale under the commercial plant conditions. CHClF₂ is decoposed to HCl and C₂F₄, which is used as a monomer of polytetrafluoroethylene. The pyrolysis proceeds in the laminar flow range, so temperature and velocity gradient exist in the reactor. The activation energies and Arrhenius constants were calculated by computer. Temperature gradient, velocity gradient, diffusion and reversibility of the reactions were considered in the calculation. The parameters were found to be E₁= 48,951 ㎈/mole, A₁= 0.3358 × 10^(15)/sec E₂= 5,117 ㎈/mole, A₂= 0.1452 × 10^(14)㎤/mole·sec in the following overall rate equation, where k₁= A₁Exp(-E₁/RT), k₂= A₂Exp(-E₂/RT)· γ_A = k₁[CHClF₂] - k₂[CF₂:] [HCl]