GCによる超微量不純物分析（関口） - jsac.or.jp

1 2016/3/151 SCD 342 2016 3 4 1 1. 2. 3. 2 3 / SCD Page 4 R = ,0001101001000 SCDareaConcentration(mg/kg)SCDL inearitySCD 5 ConcentrationMeanStandardDeviationPercen t RSD0. 1 ,000 tert-butyl disulfideSCD 6 50% 40% 90% 10 GC 2016/3/152 PoraPLOTQ/HP-PLOT Q (PT)H2S, COS H2S <100ppm 100% PDMS, CP-Sil5 CB Sulfur, 1 > df< 5 m H2S MeSH SCD SilicaPLOT, GasProC8 H2S MeSH 50ppb Select Low SulfurH2S, MeSH (< 10 ppb) max185 C) DB-Sulfur SCDH2S, MeSH ( < 10 ppb)

2 SCD 7H2S H2S C3 COS C3 COS C3 Agilent J&W DB-Sulfur SCD GC C24 SCD G3903-63001DB-SulfurSCD 60m, , C/270 CG3903-63002DB-SulfurSCD 40m, , C/290 CG3903-63003DB-SulfurSCD 70m, , C/270 CG3903-63004DB-SulfurSCD 40m, , C/270 C8DB-Sulfur SCD 1 Hydrogen sulfide2 Carbonyl sulfide3 Methanethiol4 Ethanethiol5 Dimethyl sulfide6 Carbon disulfide7 2-Propanethiol8 2-Methyl-2-propanethiol9 1-Propanethiol10 Ethyl methyl sulfide11 Thiophene12 2-Methyl-1-propanethiol13 Diethyl sulfide14 1-Butanethiol15 Methyl disulfide16 2-Methylthiophene17 3-Methylthiophene18 Diethyl disulfide19 5-Methylbenzothiophene20 3-Methylbenzo(b)thiophene21 Diphenylsulfide (IntStd)min51015202530123456789101112131 415161718192021 Thiophene 2-Methyl-1-propanethiol : Agilent J&W DB-Sulfur SCD, 60 m x mm, m (p/nG3903-63001) H2S COS 9DB-SulfurSCD: min5101520253015 V020040060080010001200 Peak : 400ppb sulfur standard : 1uL : 160.

3 1 ( ) 250 C 10DB-Sulfur SCD 5000005500006000006500007000007500008000 0012345H2 SCOSM ethyl MercaptanSCDArea countsMonths Jim Luong, Ronda Gras, Myron Hawrylukof Dow Chemical Canada : 250 C11 Select Low Sulfur 345678 Time [min]Select Low Sulfur -60m* of H2S, COS and Methyl mercaptan with hydrocarbonsH2 SCOSP ropyleneMethyl mercaptanmethaneethaneethyleneAiracetyle nepropaneConditions:Column: Select Low Sulfur, 60m x : 65 C Carrier Gas: Helium, constant flow2 mL/minInjector: 200 CDetector: PFPDFID 122016/3/153 Select Low Sulfur 13 SelectLowSulfur 1420-290ppbv 7890/SCDS electLowSulfur 157890GC/355 SCDH2S:475ppb,COS:471ppb, ~ [min] [15 V]LPG spl5 2mL | AIB2 A, | LP GS-GasPro(30m, )5mL/min constant flowsample loop: 2cc, split: 5:1oven.

4 60(2)-15-260 MethylMercaptanEthyl MercaptanDimethyl SulfideDimethyl DisulfideEthylmethylSulfideDiethyl Disulfide16 DVB/Carboxen/PDMS Carboxen/PDMS PDMS/DVB PolyacrylateH2 SMethylmercaptanCS2dimethylsulfide3-meth ylthio-1-propanol2-methylthio-ethanolDim ethyl sulfoxideSO2 Dimethyltrisulfide3-methylthiopheheEthyl 3-methylthiopropionate2-Methyl-3-thiolan none SPME 17SO2 SO2 - TD-100 PCMMSDSCDGS-GasPro(30m, TICSCDCOSH2 SCS2+SO2 MMDMStBMDMDSEMS3-methylthiophenetert-but ylmethyldisulfidediethylsulfideThiophene ThiopheneC3C42MC4 DMS3-methylthiophene 182016/3/154 + 3 19 Thiophene - 5 5 5 5 0 QC (cc)01002003004005006007008009001000 = * x - ^2 = : , : , : SCD Page 20100cc1,000ccR2= - 4 4 4 4 0 QC (cc)-50050100150200250300350400450500550 600650700750800850 = * x - ^2 = : , : , : 100,200,400,800,1000cc 25 CR2= 100,200,400,800cc -30 CAIB1 - B: #1 (min) min100ccAIB1 - B.)

5 #1 (min) min800cc 21 100cc020406080100120-30-20m10010203040 NormalizedSCDR esponse(-30C=100)TrapTemperature (C)Effect of Trap Temperature onSCD ResponseCOSH2 SMMEM SCD GC DB-Sulfur-SCD Select Low Sulfur subppb 22