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

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

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.

PerkinElmer-Arnel Model 1117 High-Speed RGA

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

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 539-87 UOP 709

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

Ready Position Gas Sample In Valve 1 Valve 4 Column 1 FID Vent 3 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

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

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

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

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

Internal Air Flow Paths in the Clarus 600 GC Oven

Exhaust Chimney

Heating Rates with 2000-Watt Heater

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

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

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

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

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

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

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

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

Side By Side Comparison 70 Minutes 160+ Minutes

Revise the temperature ramp Degrees Celsius Minutes

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

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…

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.

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. 19.5 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

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

Standard 2887 Boiling Point Calibration (Packed Column) 37

FAST 2887 Boiling Point Calibration with Hydrogen

Reference Gas Oil

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 Carrier @ 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

FAST 2887 Reference Gas Oil

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

In Europe Page 43

Swafer Setup Utility Page 44

Model 4080 Benzene and oxigenates in gasoline ..\..\..\Swafer\Swafer shared drive March25\Swafer Animations\D4 - Heartcutting.wmv

Model 4080 Heart Cut Analyzer EN 12177 & EN 13132 Preliminary Column MTBE Toluene Isobutyl-methyl-ketone Analytical Column Benzene