PO-CON1406E New Applications Using GC BID Detector Pittcon 2014 530-1P Zhuangzhi “Max” Wang, Nicole Lock, Richard Whitney, Clifford M. Taylor Shimadzu Scientific Instruments, Columbia, MD New Applications Using GC BID Detector Introduction The Barrier Ionization Discharge (BID) detector generates a 17.7 eV helium plasma that ionizes almost all compounds except Neon. A newly designed quartz dielectric chamber allows for a lower discharge current and higher operating temperature. The BID is a universal detector with sensitivity greater than 100 times that of a TCD. It is an ideal detector for trace levels of permanent gas, water, volatile fatty acids and light hydrocarbons. Two customized GC applications are presented. Two 6-port valves are used to inject, trap and release permanent gases. A 4-port switching valve was used to direct high concentration sample components to a TCD. Materials and Methods He plasma BID-2010 Plus Principals for Detection A plasma is generated by applying a high voltage to a quartz dielectric chamber, in the presence of helium. Compounds that elute from the GC column are ionized by this He plasma, then captured with collection electrodes and described as peaks. The photon energy of He is extremely high (17.7 electron volt). Therefore it makes possible to detect every compound except Ne (neon) and He which is the plasma gas, with high sensitivity. BID is truly a universal plasma detector. Quartz tube (dielectric substances) Column BID-2010 Plus Cross Section Drawing BID was developed thru collaborative research with Dr. Katsuhisa Kitano, Center of Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, resulting in 3 U.S. patents and 4 patents pending. Plasma Compounds Principle of Ionization Reaction 2 New Applications Using GC BID Detector Structure of BID He Quartz glass tube (Dielectric) Helium plasma Low frequency power supply Plasma generation zone Three electrodes are placed on the quartz tube. High voltage is applied to electrodes, and plasma is generated First purge line High voltage electrode Collection electrode Second purge line Compounds are ionized by plasma, and signal is collected at collection electrode column Peak detection zone Structure of BID Features of BID-2010 Plus BID-2010 Plus of Tracera is a novel universal detector based on dielectric barrier plasma ionization. Tracera makes it possible to conduct many kinds of applications and achieve simple and high sensitive analysis. 1. High Sensitivity Detection Sensitivity over 100x Higher Than TCD, 2x Higher than FID 3. Long-Term Stability Long-Term Stability with New Discharge Design 2. Novel Universal Detector Single Detector Approach for Your Complex Analyses The BID can replace multiple detection schemes Analysis of H2, O2, N2, CH4, CO Analysis of ppm level of CO, CO2 He He carrier Ar carrier TCD Analysis of O2,N2,CH4, CO TCD Analysis of H2 He TCD MTN-1 Impossible to detect FID ppm levels of CO and CO2 are detected Using two TCDs Using a Methanizer and FID BID will detect all of these analytes at low levels 3 New Applications Using GC BID Detector GC-2010Plus BID with Valves Main body of BID-2010 Plus uV BID1 O2 600000 N2 Datafile Name:BID_TogasRep 005.gcd Sample Name:Unknown Sample Sample ID:UNK-0005 500000 0 CARBON MONOXIDE 100000 H2 200000 ACETYLENE,ETHYLENE 300000 ETHANE 400000 CARBON DIOXIDE • Permanent gases are trapped in a MolSieve column, and then released and analyzed by BID. • Light hydrocarbons are analyzed by the BID directly, bypassing the MolSieve column. System I Chromatogram METHANE System I -100000 0.5 Concentration (ppm) 1.0 1.5 2.0 Hydrogen Oxygen 100 2500 2.5 3.0 3.5 4.0 Nitrogen Methane 16900 100 4.5 5.0 5.5 6.0 Carbon Carbon Monoxide Dioxide 100 400 6.5 7.0 7.5 8.0 8.5 min Ethylene Ethane Acetylene 100 100 100 4 New Applications Using GC BID Detector System I Standard Repeatability System I Hydrocarbon Standard 2.0 N-PENTANE 1.5 N-BUTANE 150000 ETHANE uV 175000 BID1 PROPANE Datafile Name:BID_C1-C6Rep 005.gcd Sample Name:Unknown Sample Sample ID:UNK-0005 METHANE N-HEXANE 125000 100000 75000 50000 25000 0 0.5 Concentration (ppm) System I Hydrocarbon Standard Repeatability 1.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 min Methane Ethane Propane N-Butane N-Pentane N-Hexane 100 100 400 100 100 100 System II • Permanent gases are trapped in a MolSieve column, and then released and analyzed by BID. • High concentration sample components are directed to the TCD via a 4 port switching valve. 5 New Applications Using GC BID Detector System II Low Standard- BID System II High Standard - TCD Datafile Name:DDF210-BID-11-8-13-006.gcd Sample Name:HIGH GAS STD Sample ID:DDF210-BID-11-8-13-006 O2 O2 uV 110000 TCD1 N2 uV BID1 100000 CO2 90000 3000000 N2 80000 70000 C2H4/C2H6 60000 30000 CH4 20000 10000 H2 CO 500000 0 0 -10000 2.5 Hydrogen Concentration (ppm) 100 5.0 Oxygen 7.5 10.0 Nitrogen Methane 2500 16900 100 12.5 15.0 Carbon Carbon Monoxide Dioxide 100 400 17.5 Ethylene 100 20.0 22.5 Ethane 100 min Acetylene 100 Concentration (ppm) 2.5 5.0 Hydrogen Oxygen 4990 125310 7.5 CH4 40000 C2H2 1000000 C2H2 50000 1500000 C2H4/C2H6 2000000 CO2 2500000 10.0 Nitrogen Methane 829675 3740 12.5 CO 3500000 Datafile Name:DDF210-TCD only-11-12-13-006.gcd Sample Name:High Gas STD Sample ID:DDF210-TCD only-11-12-13-006 15.0 Carbon Carbon Monoxide Dioxide 5000 20040 17.5 20.0 22.5 min Ethylene Ethane Acetylene 3750 3750 3745 Conclusions • The new Shimadzu GC BID is a universal, sensitive, and rugged detector that can be used in a variety of applications. First Edition: March, 2014 www.shimadzu.com/an/ For Research Use Only. Not for use in diagnostic procedures. The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu. The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice. © Shimadzu Corporation, 2014
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