1. Ariovaldo Bisi Chromatography line leader Export
Enhanced sample throughput Using Hydrogen Carrier and a new microchannel device
Ariovaldo Bisi
Chromatography line leader Export

2. Program Fast analysis with H2 carrier gas
DHA
SimDist
Swafer- the new device for multidimensional GC
Advantages of H2 carrier gas
Hydrogen generator, no need for cylinder, always available
Low viscosity, allows higher carrier gas linear velocity
Speeds up the analysis increasing productivity

3. Refinery Gas Analysis
Refinery gas typically contains widely varying amounts of unsaturated and saturated hydrocarbons, elemental and inorganic gases, and sulfur compounds.
Each RGA may also be used to provide additional information. Examples of additional information of interest are:
liquid sample analysis
full range hydrogen and/or helium analysis with a dedicated TCD channel using N2 carrier gas
heavy hydrocarbon component speciation
Sequential, entry level RGA with single detector and 40 minutes cycle time
Parallel, multi detector RGA for improved cycle time of 15 minutes
Fast, parallel multi detector system with H2 carrier gas and 7.5 minutes cycle time.

4. PerkinElmer-Arnel Model 1117 High-Speed RGA

5. Model 1117 High-Speed RGA Features
Rapid, 7.5-minute analysis time
Hydrogen carrier gas for light gas and hydrocarbon channels
Three channels – dual thermal conductivity detectors and flame ionization detector (TCD/TCD/FID)
Full-range hydrogen detection using separate channel with nitrogen carrier gas
Rugged packed columns – no degradation from H2O, NH3 or other common contaminants
High column capacity, no need for splitters; improved reproducibility
Critical butene-1/isobutylene separation
Plumbed with sulfur-resistant materials to enhance H2S detection
Includes Model 3062 Software, which contains a merge program to combine multichannel data into one report

6. Model 1117 High-Speed RGA Specifications
Detected compounds
He, H2, O2, N2, CO2, CO, H2S, C1 through C5, C5=/C6+ composite peak
Meets:
ASTM D1945
ASTM D1946
ASTM D2597
UOP
UOP 709

7. Model 1117 High-Speed RGA Detection Ranges
Min (%)
Max (%)
Channel A (TCD)
He and H2
0.01
100
Channel B (TCD)
H2S
0.02
All other components
Channel C (FID)
C5=/C6+ composite
0.002 40
0.001

8. Ready Position Gas Sample In Valve 1 Valve 4 Column 1 FID Vent3 4 5 1 2 8 7 6 10 9
Column 1 3 4 2 1 6 5 8 7
FID
Vent
Column 6
Carrier - Hydrogen
Vent
Carrier - Nitrogen
Column 5
Column 2
Auxiliary - Nitrogen
TCD
TCD
Sample Out
Column 4
Column 3 3 4 5 1 2 8 7 6 10 9
Adjustable Restrictor 1 2 6 4 3 5
Vent
Carrier - Hydrogen
Auxiliary - Hydrogen
Hydrocarbon channel (Valve 1)
Light gas channel (Valves 2 & 3)
Hydrogen channel (Valve 4)
Valve 2
Valve 3

9. Hydrogen and Light Gas Channel Comparison
Model 1117
Hydrogen
Carbon Dioxide
Ethylene
Ethane
Acetylene
Oxygen
Nitrogen
Methane
Carbon Monoxide
15 Minutes
Model 1115

10. Isothermal separation
Hydrocarbon Channel
Model 1117
Isothermal separation
Run time=cycle time
Model 1115
C5=/C6+
Methane
Ethane / Ethylene
Propane
Acetylene
Propylene
I-Butane
Propadiene
n-Butane
Butene-1
I-Butylene
t-Butene-2
c-Butene-2
1,3-Butadiene
i-Pentane
n-Pentane
15 Minutes

11. Fast DHA Overview Why? Who? Where? Based on ASTM D-6730
To Optimize Your Refining Process
Who?
Impatient/Cost Conscious Clients & Laboratories
High Throughput Sites
Where?
Refineries
Contract Laboratories
Based on ASTM D-6730
Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas Chromatography
Boiling Point Range up to 225°C
C1 to C13 Hydrocarbon Range

12. Unique Oven Design: Rapid Cooldown / Enhance Cryogen Delivery
Clarus 600 GC The fastest conventional oven

13. Internal Air Flow Paths in the Clarus 600 GC Oven

14. Exhaust Chimney

15. Heating Rates with 2000-Watt Heater

16. The Soft-Cooling Concept
Ballistic Cooling Rate Resumed Once Threshold Temperature is Reached
Ballistic Cooling

17. Extreme Oven Cooldown to Ambient
4 Minute to Ready End Cycle!
Degrees Celsius
Seconds

18. Priming (Pre-loading) the Autosampler on a Clarus 600
Non-Productive Time GC
Inject
Ready
Cool-Down
Cool-Down
Equilibration
PPC Leak Test
Flame Out Test
Chromatography
Pre-Run Events
Chromatography
AutoSampler
Solvent Wash
Sample Wash
Sample Pump
Solvent Wash

19. Helium to Hydrogen Why? Hydrogen is less expensive the Helium
Can be produced on site with generators – Helium requires cylinders.
Hydrogen is more readily available (worldwide considerations)
Environmental concerns
Conservation of natural resources
Speed – with basically no changes to parameters
Less dense – Higher optimal linear velocity
Further improvements in speed with shorter, narrow bore column:
Reduced column capacity
Concentration dependent separation of some products

20. How it works… Clarus 600 GC Oven Detail
Capillary Split/Splitless Injector
Isothermal (250°C)
1:150 Split Ratio
Flame Ionization Detector (FID)
Isothermal (250°C)
Precolumn & Column
The precolumn is a 5% phenyl/95% dimethylpolysiloxane fused silica open tubular 0.25 mm column connected to a primary 100 meter 0.25 mm 0.5 μm 100% methyl silicone 0.25 mm column.
Clarus 600 GC Oven Detail

21. PreVent Set-Up for light fraction
Split Vent
SS Injector
Tuning Column
Detector F
Modified
T-Piece P P
Capillary Column

22. How it works… DHA Overview
..or take less time if heavy fraction is backflushed
A typical DHA run can take up to 160 minutes to fully elute n-C13 and beyond…
DHA Overview

23. How it works… DHA Overview
PerkinElmer has developed a Fast DHA method to reduce this time to 70 minutes, with a full cycle time of 74 minutes. To accomplish this we needed to:
Switch the carrier gas from Helium to Hydrogen
Revise the temperature ramp
Retune the precolumn
Verify critical separations
Priming (Pre-loading) the autosampler with the Clarus 600 GC
Rapid oven cooldown to ambient with enhanced delivery of cryogen with the Clarus 600 GC
DHA Overview

24. Side By Side Comparison
70 Minutes
160+ Minutes

25. Revise the temperature ramp
Degrees Celsius
Minutes

26. Precolumn Optimization…
The Precolumn Effect on Overall Selectivity
m-xylene
benzene
toluene
p-xylene
ethylbenzene
1-methylcyclopentene
2,3,3-trimethylpentane
2,3-dimethylheptane
DHA Overview

27. Critical Separations i-butane/methanol and ethanol/3-methylbutene-1
These separations represent the initial separations influenced by the cryogenically lower starting temperature. It is noted that a lower temperature has little effect on elution times and orders, but higher temperatures would affect the next temperature ramps elution times.
Ethanol peak shape is characteristic of the application…

28. Critical Separations 1-methylnaphthalene/tridecane
The last key separation is the 1-methylnaphthalene/tridecane. Lowering the final temperature rate of 1.5°C/min by increments of 0.1°C/min until the peak is resolved will help resolve this peak if necessary.

29. Fast DHA Recap User Benefits: Shorter Run Time Cost Saving
Additional runs/day or week
Double the number of runs per day (9 runs vs runs)
73 extra runs per week (63 runs versus 136 runs)
3,814 extra runs per year (3,285 runs versus 7,099 runs)
Cost Saving
H2 Generator
Extended Column Lifetime
Reduce Electricity
Facility HVAC Load
A Greener Solution

30. Simulated Distillation
ASTM D 2887, D 3710, D 5307, D 6352, D 7096, D 7196
Extended (high temperature) analysis capability utilizing the programmable on-column inlet, “POC”
Complete system
Includes sampling procedure
GC methods
Customer samples run
Training
Automatic calibration update for all methods
Multiple methods can be linked together for automatic overnight operation 16

31. Standard 2887 Boiling Point Calibration (Packed Column)37

32. FAST 2887 Boiling Point Calibration with Hydrogen

33. Reference Gas Oil

34. Fast SimDist Experimental Conditions
Column
Fused Silica
Dimethyl Polysiloxane Phase
5.0 m x 0.05 mm i.d. x 0.2 µm film thickness
Chromatography Parameters
Hydrogen 40 psi HP
Sample volume 0.3 µL
Fast Injection
Split Ratio
4000:1
Temperature Program
Initial Temp: 40 °C
Ramp1: 60/min to 300 °C
Ramp2: 0.00/min to 0 Hold 2.0 min
Equilibration Time: 0.5 min
Total Run Time: 6.83 min

35. FAST 2887 Reference Gas Oil

36. Swafer: A flow-switching device…
…that works silently in the hearth of the Clarus GC.

37. In Europe
Page 43

38. Swafer Setup Utility
Page 44

39. Model 4080 Benzene and oxigenates in gasoline
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40. Model 4080 Heart Cut Analyzer EN 12177 & EN 13132
Preliminary Column
MTBE
Toluene
Isobutyl-methyl-ketone
Analytical Column
Benzene