This study assessed the analysis method for measuring volatile organic silicon compounds (namely as siloxanes) by usinggas chromatography with flame ionization detector. Calibration standard gas was made in a laboratory by using six volatileorganic silicons as model gas. Two different types of working gas were prepared to evaluate quality control in GC-FIDanalysis. Less than 0.2 RSD% of repeatability of retention time was observed in the analysis of calibration standard gas. Inthe linearity test, the highest coefficient of determination (R2) was found to be 0.997 for L2 among volatile organic siliconcompounds. This study demonstrated that quantification of volatile organic silicon compounds can be performed by usingGC-FID analysis with direct injection mode, and the GC calibration can be covered by the gas-phase standard method.

실록산(Siloxanes)은 규소와 산소(Si-O-Si)로 이루어져 있으며 각 규소마다 다른 작용기가 결합된 유기규소화 합물로서 혐기성 소화조 또는 매립지에 폐기물의 분해과정에서 저분자화된 유기규소화합물이 휘발함으로서 바이오가스나 매립가스의 불순물로 존재한다. 실록산은 분자구조상 고리구조(D)와 선형구조(L)로 구분하고 있으며, 바이오가스나 매립가스에는 hexamethyldisiloxane(L2), octamethylt-risiloxane(L3), decamethyltetrasilo-xane(L4), dodecamethylpentasiloxanae(L5), octa-methylcyclotetrasiloxane(D4), decamethylcyclopentasiloxane(D5), dodecamethylcyclo-hexasiloxane(D6) 등의 다양한 형태로 존재한다. 실록산은 바이오가스와 매립지 내에 미량 존재하지만, 가스터빈, 보일러, 내연기관 등의 연소과정에서 산화되어 이산화규소(SiO₂)로 전환되어 연소설비의 고장 원인이 되고 있다. 바이오가스의 효율적인 자원화를 위하여 반드시 전처리가 필요한 물질로 인식되고 있다. 본 실험에서는 Lincoff and Gossett의 닫힌계내 평형실험법(Equilibrium partition experiment in closed system, EPICS)을 이용하여 액체상, 기체상 실록산의 기액 물질분배계수를 도출하고자 하였다. 액체상 실록산 기액 평형실험은 L-EPICS, 기체상 실록산 기액 평형실험은 G-EPICS 실험이라고 명명한다. L-EPICS 실험방법은 20ml glass vial에 액체상 실록산을 2 mL 주입 후 기액평형을 실험하였고, G-EPICS 실험방법은 240mL bottle 반응기에서 기체상 실록산과 액체(증류수)사이에서의 물질전달을 실험하였다. 두 반응기는 25℃에서 3시간 이상 방치시킨 후 평형에 도달한 가스 농도를 FID가 장착된 가스크로마토그래피(GC, YL6100GC, Younglin Co, Korea)로 분석하였다. L-EPICS 실험결과, 액상 실록산의 기액 물질분배계수는 선형 실록산인 L2, L3와 L4는 197, 20.04, 8.82이고 고리형 실록산 D4와 D5는 12.84, 6.76으로 도출되었다. G-EPICS 실험에서는 L2, L3와 L4는 8.808, 2.278, 1.455이고 D4와 D5는 3.435, 0.770로 확인되었다. 두 가지 방법에 의한 실험결과 선형과 고리형 실록산의 분자량에 따라 기액 물질분배계수가 영향을 받는 것으로 확인하였다. EPA의 ChemFinder Datebase에서 참고한 실록산의 기액 물질분배계수와 본 실험에서 도출된 값과 상관관계 분석 결과, L-EPICS 실험방법과는 0.983, G-EPICS 실험방법과는 0.874의 상관계수를 나타내었다.

Interest in the measurement of siloxane which reduces energy efficiency of biogas, has increased with its market extend. Even though the impinger absorption method takes long sampling time of 2-3 hours and need a complicated equipment, it has been typically used for the sampling method of siloxane. This study was conducted to apply the gas bag sampling method with tedlar bag and aluminium bag for improving the method of siloxane sampling. To compare efficiencies of siloxane sampling, the manufactured gas, landfill gas, and digestion gas were used as sample gases. According to the result, materials of gas bags did not cause measurement error and there was no loss of siloxane by adsorption on the inner surface of gas bag. The result of D4 calibration in the tedlar bag, showed higher than 0.99 in the coefficient of determination. In case of digestion gas, the analysis results of two samples collected by the tedlar bag and the impinger absorption were almost same. The differences of analysis result between landfill gas and digestion gas were considered due to the short sampling time and the absence of gas storage tank.

This study was conducted to improve the analytical method of siloxanes in biogas. Methanol and hexane were tested as absorption solvents of the impinger absorption method, and also the hexane extraction for pretreatment of sample was evaluated. Manufactured gas contained siloxanes of 50 ppm was completely absorbed by the methanol impinger absorption. The absorption efficiency of biogas containing only 2 ppm, however, was maximum 84%. As the condensate on the first impinger increased, the absorption rate of methanol was decreased. The hexane extraction method of the sample was considered to proper the method of moisture removal. The hexane extraction result showed the high recovery factor and the low relative standard deviation. It is suggested that the suitable choice of solvent and pretreatment is required, as the analysis result of siloxane sample may be differentiated depending on the type of biogas or the sampling point.