1 / 30

Ion size (cross-section)

Micro-fabricated Differential Mobility Spectrometers for Process Monitoring and Control Raanan A. Miller, Erkinjon G. Nazarov, David Wheeler, Quan Shi, Denise Zazzera Sionex Corporation, Bedford, MA. +. Ion Mobility as Characteristic of Chemicals. Ion charge. Ion size (cross-section).

trevor-camacho
Download Presentation

Ion size (cross-section)

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. Micro-fabricated Differential Mobility Spectrometers for Process Monitoring and ControlRaanan A. Miller, Erkinjon G. Nazarov, David Wheeler, Quan Shi, Denise ZazzeraSionex Corporation, Bedford, MA

  2. + Ion Mobility as Characteristic of Chemicals Ion charge Ion size (cross-section) Ion Mass ION MOBILITY based technologies use VELOCITY of ion movement under effect of electric field for chemical identification

  3. Differential Mobility Spectrometry Operation Principle microDMXTM Chip

  4. Existing Product Platforms SVAC-V SVAC Analyzer 2nd Generation Sensor and Electronics Thermo Fisher: EGIS Defender Varian: CP4900 Gas Chromatograph General Dynamics: JUNO

  5. Competitive Advantages • High sensitivity with specificity: • Detection limits comparable to much larger, expensive commercial instruments • Quantitative output: • Instead of the qualitative outputs produced by many lower • cost chemical sensors being developed today • Ability to detect a very wide range of chemicals • Near real-time detection (msec) • Low cost: • Ability to address high volume opportunities • Ability to use multiple sensors in single control system

  6. microDMx for Security Applications Chemical Warfare Agents DMS Explosives Detection positive mode negative mode. Able to resolve all 14 TSA Explosives Low PPB Detection Limits G. A Eicemen, et. al, Accepted for publication, Analytical Chemistry 2004

  7. microDMx for Process Control Standalone microDMx: • Suitable for monitoring small numbers of compounds or changes in gas composition of reactors requiring tight parameter control • High sensitivity (parts-per-million – parts-per-trillion) • Quantitative • Low cost – allows distributed sensors – better diagnostic accuracy of reactors (for example for NeSSI) GC - microDMx: • Suitable for monitoring complex mixtures of compounds • High sensitivity (parts-per-million – parts-per-trillion) • Quantitative • Low cost compared with MS– allows distributed analyzers – better diagnostic accuracy of reactors (compatible with NeSSI)

  8. Applicability of Standalone microDMx Configuration for Process Control Differential Mobility Spectrometer M±; MH+;(M-H)-;MO2- ; M2±; M(H2O)H+; M (?) Detection by Differential Mobility Spectrometry Atmospheric pressure chemical ionization of analyte molecules. 63Ni, ESI, UV, plasma ion sources Introduction of analyte molecules Process control Analyzer Reactor Adjust parameters of Reactor or alert operator

  9. Benzene Peak Standalone microDMx System for Monitoring Trace Level Compounds in Bulk Gases p-xylene m-xylene microDmx response to a mixture of Acetone and Benzene microDMx response for Xylenes

  10. GC+microDMx for Complex Mixture Analysis GC Separation GC+microDMx Separation D E F G A,B,C FID detector Retention Time Retention Time 5 Components? A B DMS Compensation Voltage C GC Separations are time based 7 Components

  11. Analysis of Multi-functional Mixture Component

  12. 5,25,26,27 29,30 8,32 9,10 6,31 11,12 7 3,28 5 4 20,43 17,39 18,40,41 34 450 50 100 150 200 250 300 350 400 40 60 80 100 120 23 35,36 38 45 22,44 21 14 33 37 19,42 24 16 15 13 GC-FID Analysis of Multi- functional Mixture Temperature Programmed from 30-120 C @ 10 C/min

  13. GC-microDMx Analysis of Multi-functional Mixture 450 400 350 300 250 Time (s) 200 150 100 50 450 Negative Positive 400 24 Iodine Chlorine 23 45 350 Bromine 44 22 21 300 43 20 19 42 42 250 18 41 40 Time (s) 17 39 200 39 38 16 37 37 15 36 36 150 35 35 34 14 33 13 11 12 10 9 100 32 8 7 31 6 30 29 5 4 28 3 27 25 2 26 1 50 0 0 -20 -15 -10 -5 0 5 -35 -30 -25 -20 -15 -10 -5 Compensation Voltage (volts) Compensation Voltage (volts)

  14. microDMx Selectivity for Sulfur Compounds Odorant Peak (MES) Hydrocarbon (Natural gas related) Peak Trace level control of Sulfur Compounds is important in : Odorant Peak (MES) GC with TCD Detector • Hydrocarbon processing industry • Prevent Corrosion of pipes and equipment • Prevent degradation of catalysts • Increase quality of end products • Fuel Cells • Prevent catalyst poisoning • Safety • Requires control of level of odorants added to natural gas • Environmental Concerns • Control sulfur levels emitted into the atmosphere Odorant Peak (MES) GC with DMS Detector (UV ionization)

  15. microDMx Selectivity for Sulfur Compounds TBM TBM TBM MES Hydrocarbons THT THT MES GC-microDMx Chromatogram GC-microDMx Topographic Plot GC retention time + orthogonal DMS spectra => Selective detection of odorants in natural gas

  16. Detection of Methyl Isocyanate in Air 0.4 ppm (v/v) microDMx • Methyl Isocyanate – highly toxic (Bophal, India) • Need to measure low level methyl Isocyanate in air • Technology tried but unsuccessful FID, E-Nose, SAW TCD microDMx Concentration 1 ppm (v/v) of MIC

  17. Detection of Methyl Isocyanate in Air Stability as a function of time Days

  18. GC + microDMx  Sionex microAnalyzer™ + microDMx Chip GC Column microAnalyzer

  19. Sample trap GC column Molecules Molecules Sionex microDMx™ Sensor Ionization Ion Filtering Detection Ions Ions Ions Radioactive Plasma Corona UV Information Interpretation Algorithm Chromatography SW Sionex EXPERT™ MicroAnalyzer System Architecture

  20. Sionex microAnalyzer™ Carrier gas Air External cylinders No Dimensions 8 x 5 x 3 (in) Average power consumption ~20-30 W Warm-up time <15min Weight 1.81kg Column 10m Molecular sieve cartridge (up to 6 month life ) 8” 5” 3”

  21. 2D GC-DMS Chromatogram for BTEX Retention time Compensation voltage Micro trap material Carbopack B 60/80mesh (RF=1187V)

  22. GC - microDMx™ Chromatogram M,P Xylene O Xylene Ethylbenzene Response (arbitrary units) Benzene Toluene Seconds

  23. Ultra Trace Detection of BTEX by Sionex microAnalyzer™ Samples • Relative standard deviation (RSD) for intensity is below 10% on multiple runs. • RSD Retention Times were less than 0.5% over 40 runs of data.

  24. Conclusions • Differential Mobility Spectrometry provides a flexible platform for: • High sensitivity • High reliability • Quantitative • Near real time • Multi-sensor implementation • Can be made NeSSI compliant • Suitable for online / at line applications • Thoughts and ideas for additional applications of Differential Mobility Spectrometry in process control and monitoring would be greatly appreciated

  25. Acknowledgements • Sionex Corporation wishes to thank: • Dr. Jim Luong and Dr. Ronda Gras of Dow Chemical Corporation. • Dr. G.M. Lambertus and Dr. R.D. Sacks of University of Michigan.

  26. - - - Measurement of Differential Mobility Differential Mobility a b B A A ~ 0.6 microsecond

  27. Top Electrode RF field y E t2 Species A max z To Detector t 2 Species B Carrier Gas Flow t1 E min Species C Time Emax Emin 1.8 Species A Mobility K(E) (a. u.) Species B 1.7 Species C 1.6 0 10000 20000 30000 Electric Field Strength (V/cm) Bottom Electrode t 1 microDMx™ Ion Filter Operation

  28. MeOH, H2S, COS, and CH3SH H2S COS MeOH CH3SH Column: PoraBond Temperature 60°C Carrier: He, 150kPa Transport gas Air LDL: <100 ppb

  29. Detection of Epichlorohydrin Epichlorohydrin (EPI) - an extremely versatile chemical intermediate. 76% of the world’s consumption of (EPI) is used to make epoxy resins. Need to measure low levels of epichlorohydrin in air at a concentration below 1 ppm (v/v) microDMx Epichlorohydrin Peak TCD Trace Epichlorohydrin Glycerol TCD Detector 88 ppb (v/v) of Epichlorohydrin in Air

More Related