Rethinking Gas Chromatography
John Crandall, Falcon AnalyticalBrian Rohrback, Infometrix
Enabling delivery of easier, smaller, faster, smarter, and greenergas chromatography hardware and service for upstream, refining,
and distribution in the hydrocarbon industry.
July 22, 2010 Lake Katchess, WA
6/25/2010
Typical Diesel Range Sample Run
6/25/2010
Sample & Standard Overlaid
Summary
We have thrown out 100-year-old design constraints and made maximum use of computer control and interpretation.
The product enables a higher level of quality control: more installations, as much as 100x the throughput for every installation point.This ground-up rethinking of how a chromatograph should function has resulted in a breakthrough, addressing instrument size, ease of use, power consumption, and maintainability.
You can’t control what you don’t measure
Trick is to make all GCs look as much alike as possible.
Interchangeabilitycommon interpretive base
Process Design Considerations
1. Speed of analysis (use to control the process)2. Appropriate detection scheme (flexible
detectors)3. Application coverage (common instrument
platform) 4. Form factor (size, weight, footprint)5. Cost (price, shelter, maintenance, periphery)
The challenge was to design a GC that spans most of the applications in both laboratory and on-line settings.
Cost Considerations
Equipment CostsInstrument, shelter, installation, suppliesCommonality with laboratory devices (data agreement)
Maintenance CostsRobust constructionAutomated data and instrument validation
Peripheral CostsSuppliesEnergy
It is essential to look at the energy requirements: likely the largest hidden cost of analysis.
Speed of Analysis
If we are really going to use GC for control, speed means under 10 minutes for most applications.
Poll of Process Users
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Too slowMarginally slow
OKFast
Indi
ffere
nt
144/day288/day1440/day 96/day
easier, smaller,faster, smarter, and greener
GCs have been neglected
Gas chromatography is ripe for a make-overProcess GCs are largely unchangedLaboratory units are energy hogs
Distinction is in combining speed with analytical competence in a low power, compact unit spanning lab and process.The Green revolution makes compelling the argument for a more-energy balanced approach to GC.Elimination of the discrepancy between lab and process simplifies the management of the process and the release of product.Making full use of the latest, proven technology allows much faster analysis - giving users a level of control that is unmatched.
Form Factor
The smaller the footprint, the better forCheaper and easier deployment… ultimately, We would like the GC to function like a simple sensor.
But… there are trade-offs… given application constraints and the requirements of
Sample introductionCarrier gasValvesDetectors (options)Operational and maintenance flexibility
Form Factor
Because of application constraints & requirements the smaller end of the form scale is restricted to gas analysis via isothermal runs and thermal conductivity detection.
Our approach was to improve detection limits adding FID and FPD and extend the dynamic range to C50+.but still maintaining relatively low weight and small
footprint.
Form Factor
The conventional chromatographs can be configured to do just about any analysis, but you pay a penalty in size, weight and power consumption.
Our technical approach was to eliminate the ovenpositive impact on weight, size and recovery timewhile still maintaining fast, precise temperature
programming.
Flexible
Speed
Power consumption
Portable
Suitable for lab and process
Preset Configurable
Slow Fast
High Low
Fixed Mobile
Process Both
The applications flexibility combined with a more-compact footprint allows the instrument to cover laboratory, process and transportable applications.
Product PositioningSpeed of Analysis (use to control the process)Application Coverage (common instrument platform) Form Factor (size, weight, footprint)Cost (price, maintenance, periphery)
Speed + Applications + Form Factor
High thermal massTemperature stabilitySlow to respond to changeIsothermal methodsColumn switching schemesHeavy & large footprintsKilowatt power requirement
Large unswept (dead) volumesInferior resolutionPeak tailingLonger columnsLong analysis timesHigh consumable rates
Low thermal massTemperature repeatability and reproducibilityQuick responseProgrammed temperature methodsMinimal switching schemesLow power requirement
“Zero” dead volumeHigh resolutionShort columnsFast cycle timesMinimum consumables
Old School New Thinking
Old School vs. New Thinking
14
65 minutes
80 seconds
6/25/2010
Blank Run (demonstrating noise levels and the typical column bleed from the temperature program cycle)
6/25/2010
Restek C5 to C44 Calibration Standard (demonstrating peak shape and resolution across the boiling range.)
6/25/2010
Standard Overlaid the Blank(demonstrating negligible noise and column bleed.)
A GC must still make measurements
SamplingAccepts either gas or liquid phase samplesManageable volumes: 60 nanoliters to ~100 microliters injectedBoiling ranges from permanent gases up to C60Pre-concentration possible (trap or purge & trap techniques)
SeparationsAdequate resolution for the applicationAccepts available column materialMakes use of column specificity characteristicsAdequate column capacity (sample loading)
DetectionUniversal detection required such as TCDHydrocarbon specific such as FIDSulfur specific such as FPDHalogen specific such as ECDCan accept specialty detectors (DID & others)
Diesel-range, 80 seconds
HRVOC Fence Line Analysis
A GC must still make measurements
Data processingProper peak retention time and area determinationChromatographic peak alignmentProper integration of alignment results, response factor and integrationVarious calibration techniques available
StatisticsSystem must perform with acceptable precision and accuracy to yieldRepeatable and reproducible measurements
And the GC should deliverSystem suitability assessments
Is the sample OK?Is the GC OK?Does the sample “pass or fail” the established criteria?
And an acceptable reporting format
Old School vs. New Thinking
Lt Jet Hv Jet Diesel G Oil 800-950 650-1050
240
Situation Analysis
Data processingProper peak retention time and area determinationChromatographic peak alignmentProper integration of alignment results, response factor and integrationVarious calibration techniques available
Kerosene
120 seconds
Ch 1
Ch 2 Ch 2 Aligned
Ch 1 Aligned
LineUp
Raw data file is saved and archived for future reference.
120 seconds
Results Calculations: Envantage SimDist 2000Calibration by boiling point distribution yields ASTM-D2887 results and information about the individual sample.
Single or Dual Channel, FID or TCD -Autosampler, Syringes or Process Valves
FPD in 2011
Single or Dual Channel, FID or TCD -Autosampler, Syringes or Process Valves
Single or Dual Channel, FID or TCD -Autosampler, Syringes or Process Valves
At-Line NeSSI microGC Carts
Methane through Hexane100 Consecutive Runs Overlaid
Typical Crude Oil Overlaid C5 to C44
3 minute run
Isoprenoids
Neat Crude Oil Injections
nC44
Polywax
nC60
Heavy Oil
nC60
24/7 Analytics
And the GC system should deliverSystem suitability assessments
Is the sample OK?Is the GC OK?Does the measurement “pass or fail” the established criteria?
And an acceptable reporting format
Old School: Agilent 6890
For Agilent 6890, fast ramp rates require power >200 volts at >15 Amps(e.g., >3,000 W).
Reference Agilent 6890 Network Gas Chromatograph Data Sheet, January 24, 2007, 5989-3290EN
New Thinking:
Sample processing module power250°C = 40 W
Column module power (1 or 2 columns)35°-350°C @ 5°C/second = 70 W each
Detector module power (1 or 2 detectors, each)150°C = 7 W 250°C = 15 W350°C = 19.5 W
System powerApplication dependent300 W maximumAverage = 225 W
easier, smaller, faster, smarter, and greener
Greener Analysis
Contract analytical services company in CaliforniaEnvironmental, remediation, hazmat18,000 sq. ft. facility, >60 specialized employees19 GC or GC/MS instrumentsAC year-round, capacity ~ 62 tons, accounts for ~ 50% of electrical use = Summer electric use ~ 5,000 kWh/day
“Air conditioning is our biggest maintenance problem.”
Power & maintenance information courtesy of… Mike Brech & David Tsubota of BSK Analytical
What does use of fast GC mean?
Lots of data: 20 results per hour (~500 per day)Lots of interpretation (are the results correct?)Lots of opportunity for errorsDrives the need for automation
analysisdata collectionpreprocessinginterpretationsystem suitability assessmentresultsresult validityfault identificationpass/fail
Means… Chemometrics!
Delivering Smarter
The faster we can process information, the greater the valueThe Falcon hardware speeds the first transition: capturing data 10+ times fasterThe Infometrix role is the second transition: delivering intelligence from that data
Event Data CapturedIntelligence Delivered Action Taken
easier, smaller, faster, smarter,and greener
Faster, Smaller, Easier, Smarter, Greener
6/25/2010
C5 to C60 in 3 minutes
Rethinking Gas ChromatographyTypical Diesel Range Sample RunSample & Standard OverlaidSummaryProcess Design ConsiderationsCost ConsiderationsSpeed of AnalysisGCs have been neglectedForm FactorForm FactorForm FactorProduct PositioningSpeed + Applications + Form FactorOld School vs. New ThinkingBlank Run �(demonstrating noise levels and the typical column bleed from the temperature program cycle)Restek C5 to C44 Calibration Standard (demonstrating peak shape and resolution across the boiling range.) Standard Overlaid the Blank�(demonstrating negligible noise and column bleed.)A GC must still make measurementsA GC must still make measurementsOld School vs. New ThinkingSituation AnalysisSingle or Dual Channel, FID or TCD - Autosampler, Syringes or Process ValvesSingle or Dual Channel, FID or TCD - Autosampler, Syringes or Process ValvesSingle or Dual Channel, FID or TCD - Autosampler, Syringes or Process ValvesAt-Line NeSSI microGC CartsMethane through Hexane�100 Consecutive Runs OverlaidTypical Crude Oil Overlaid C5 to C44IsoprenoidsNeat Crude Oil InjectionsPolywaxHeavy Oil24/7 AnalyticsOld School: Agilent 6890New Thinking: Greener AnalysisWhat does use of fast GC mean?Delivering SmarterFaster, Smaller, Easier, Smarter, Greener
