Paper # 130-1 Pittsburgh Conference, Orlando, FL; Feb.

28, 2005 (8:30 AM) ; Rm S220C

Determination of Oxygenates & BTX in Beverage Grade CO2
Dr. Jack Driscoll & Jennifer Driscoll PID Analyzers, LLC
copyright 2004-2005 PID Analyzers

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Abstract
Last year, we (1) presented a method for the analysis of BTX at low ppb levels in beverage grade CO2. In this paper, we describe a method for volatile oxgenates and demonstrate that it can be combined with the previous BTX (1) method to perform multifunctional analyte analyses. The photoionization detector (PID) has been improved to provide the sensitivity and ppb detection limits required by the industry. The 301-B now has multiple valve switching capability and multiple autozeros to smooth the baseline when columns are switched in or out. With these changes and system optimizations, we have achieved some complex separations at ppb levels with a minimum of operator time or training required. The following method on the 301-B was developed for the analysis of ppb levels of oxygenates (acetaldehyde, methanol & dimethyl ether) in beverage grade carbon dioxide. The detection limits required were 100 ppb for acetaldehyde and dimethyl ether. The analysis can be automated via a PLC that controls the 301-B (start, calibrate, print report). An optional operating system is Windows XP. If the 301 GC is part of the plant network, the system can be operated from any PC on the network. Of course the system has passwords. The detection limit for this analysis was <100 ppb (acetaldehyde), & <50 ppb (dimethyl ether) for a direct injection with no concentration of the sample. The analysis time for this multicomponent analysis was < 10 minutes. =========================================================================== Driscoll, JN & J. Driscoll, “Detection of ppb Levels of BTX in Beverage Grade CO2”, Paper # 17001100P, Pitt. Conf. on Anal. Chem., Chicago, IL, March 2004

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Presentation Objectives
A new Method has been developed for use with the Model 301-B to analyze both oxygenates and BTX at the same time. This involved the following: •A second column (PLOT) was added to separate acetaldehyde and dimethyl ether from the CO2 and the BTX A 4 port switching valve was used for column selection In addition, a number of improvements have been made in the original 301-B instrumentation
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What are the improvements?
USB based ADC System Touch screen Color VGA display Windows XP Operating System (embedded) with PW Chromatography Software Detectors- PID improved New outputs- Modbus Easier to expand features through USB

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Comparison of uP and PC Based Process GCs Other GCs uP Speed varys 301-B PC Based 500 MHz, 100 MHz Bus

Memory Plug & Play Windows XP (Embedded) Operating Sys Network Capability USB Peripherals

varys No No Special No No

40 Gbyte HD Yes Yes Windows Yes Floppy, USB Disk…

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Model 301-B

mouse

USB Port

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Rear View of Model 301-B

PC

Relays

Fluidics I/O

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GC Signal Schematic
ADC 16 bit Keyboard Display Diagnostics AMP

Detector

PC

DAC to 4-20 mA RS232

Digital I/O Alarms

Digital I/O- valves

Time clock, data calc & storage on hard drive
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301-B GC Fluidics
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Photoionization Detector
Process
R + h ν = R + + ewhere R= molecule hν = a photon with an energy > IP of R R+ = positive ion e- = electron

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PID Characteristics
Linear dynamic range > 5 x107 Detection limit <0.5 ppb benzene Non destructive; other detectors can be run in-series Sensitivity increases as the carbon number increases (carbon counter) For 10.2 eV lamp, responds to carbon aliphatic compounds > C4, all olefins and all aromatics The PID also responds to inorganic compounds such as H2S, NH3, Br2, I2, PH3, AsH3, e.g. any compound with an ionization potential of < 10.6 eV The PID is more sensitive than the FID; >200 x more sensitive for aromatics, 80 times for olefins, & 30 times for alkanes > C6 Non destructive detector; other detectors can be run downstream Concentration sensitive detector
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301-B Process GC
Analytical Column Mode for Specific Detection Six detectors to choose from: Specific to Universal Minimum Maintainance Data Processing of Concentrations X (Div. 1) or Z purge (Div. 2) Outdoor Locations-

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Optimization Parameters for Process GC’s
Pre column- to remove heavies, polar or non column polar species, protect analytical column Inject time- can be varied to remove heavier time species Detector- Selectivity- HNU has 6 detectors to Detector choose from;PID lamp energy can be varied Packed and capillary columns can be mixed Backflushing to remove heavies; foreflushing to remove light compounds, heart cutting to remove a compound during the run
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PID 10.6 eV

On-screen keyboard

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Method

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Calibration

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PID 10.6 eV- 3 ppb

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16 Detector Parameters

PID 10.2 eV

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5 ppb BTX

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Low Level Linearity of Benzene & Ethyl Benzene
25000 20000 Peak Counts 15000 10000 5000 0 0 5 10 15 20 25 ppb Benzene/Ethyl Benzene y = 972.99x - 16.272 2 R = 0.9999 y = 389.31x - 8.112 2 R = 0.9999

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Cal Curve for Oxygenates in CO2 DME (upper)
3000 2500 2000 1500 1000 500 0 0 1000 2000 3000 4000 5000 6000 ppm Acetaldehyde/DME y = 0.4923x + 73.813 R2 = 0.9955

y = 0.1788x + 25.546 R2 = 0.9973

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PID Characteristics
PID Species C1-C4 alkanes C5+ alkanes Alkenes Aromatics Dynamic Range Detection Limits aromatics alkenes alkanes acetaldehyde dimethyl ether < 0.5 ppb <5 ppb < 10 ppb 50-100 ppb 30-50 ppb N Y Y Y 5 x 10exp7

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Summary
The instrument is PC based with considerable expansion capability including LAN, RF modem, USB and additional sensors The system is fully automatic and is controlled by a PLC The reproducibility [coefficient of variation= 100(std. dev./mean)] at 50 ppm benzene is 1.5%; and at 5 ppb- 5% The detection limit for benzene with no preconcentration is < 0.5 ppb; acetaldehyde <50 ppb & DME < 20 ppb BTX and oxygenates can be analyzed & detected wth the same Analyzer
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