Agilent Technologies, Inc. · NYSE:A
Agilent Technologies — Technical Presentation (January 2014)
47 slides from Agilent Technologies's technical presentation, Jan 7, 2014
Slide 1: Reformulated Fuels and Refinery Gas Analysis using a Large Valve Oven
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Slide 2: Large Valve Oven Analyzers for Refinery Gas Analysis
Large Valve Oven Analyzers for Refinery Gas Analysis Fast and High Capacity Analysis including O2 and H2S January 7, 2014 2
Slide 3: 7890B Large Valve Oven (LVO)
7890B Large Valve Oven (LVO) Isothermal Zone for Valves and Columns • Temperature control: - Independent control of LVO and GC oven zones • Temperature Limit: - Max 330˚C (valve and column dependent) • Valve configurations: - Accommodates 4/6/10/14 port valves including Hastelloy valves • Column Com
Slide 4: Large Valve Oven Features/Benefits
Large Valve Oven Features/Benefits 6 position isothermal valve oven for actuated valves, microgasifiers, needle valves, and columns (including 1/8 in packed columns) with access to valves connections without removing actuators Uses only one 7890B heated zone Current multi-valve configurations
Slide 5: Importance of Refinery Gases and RGA
Importance of Refinery Gases and RGA Process Characterization Quickly and Reliably • Produced from FCC operations and other refinery processes • Typically contains saturated and unsaturated HCs (C1-C5) – H2, O2, N2, CO, and CO2. – C1 - C6 or higher hydrocarbons – Sulfur contaminants, e.g., H2S • Cha
Slide 6: Importance of Refinery Gas Analysis
Importance of Refinery Gas Analysis Analytes of Interest Analyzers typically measure: • Permanent gases • Hydrocarbon content (C1-C5 with C6+ as backflush) • Extended hydrocarbon analysis • Sulfur containing hydrocarbons Two Analyzer Configurations • 1/8 inch Packed Columns • 1/16 inch Micropacked C
Slide 7: LVO Fast RGA with Micropacked Columns
LVO Fast RGA with Micropacked Columns GC/FID/TCD/TCD Micropack System Flow Diagram Micropacked LVO Plumbing UltiMetal tubing used for sample loops, Columns, and tubing on the Permanent Gas channel 4-port for sequence automation LVO Analyzer Training 7 January 7, 2014
Slide 8: Fast RGA with Micropacked Columns – Helium Carrier
Fast RGA with Micropacked Columns – Helium Carrier Selected Method Parameters Split/Splitless inlet: 120 ºC, 100:1 split FID (front): 250 ºC TCD (rear): 260 ºC He carrier Ref. 30 mL/min Makeup 2 mL/min TCD (side): 250 ºC N2 carrier Ref. 45 mL/min Makeup 2 ml/min, neg. polarity Main Oven Program: 60
Slide 9: RGA Plot Column Channel
RGA Plot Column Channel Analytical Performance – Hydrocarbon Channel (FID) Same for Packed and Micropacked Systems LVO Analyzer Training 9 January 7, 2014
Slide 10: Fast RGA with Micropacked Columns
Fast RGA with Micropacked Columns Analytical Performance – Permanent Gas Channel (TCD), LVO at 70 °C 250 uL sample loop 1 2 3 4 5 6 LVO Analyzer Training 10 January 7, 2014
Slide 11: 100 uL Sample Loop on Permanent Gas Channel
100 uL Sample Loop on Permanent Gas Channel More symmetric peak shapes Micropacked system TCD1
Slide 12: Cool Down Ramp Used During Run for Main Oven
Cool Down Ramp Used During Run for Main Oven Will shorten overall cycle time
Slide 13: Fast RGA with Micropacked Columns
Fast RGA with Micropacked Columns Analytical Performance – Oxygen Stability 70 °C 75 °C Stability of Oxygen – Isothermal Oven at 70 °C Stability of Oxygen – Isothermal Oven at 75 °C LVO Analyzer Training 13 January 7, 2014
Slide 14: Fast RGA with Micropacked Columns – Helium Carrier
Fast RGA with Micropacked Columns – Helium Carrier Analytical Performance, % RSD’s Compound Concentration RT Area C6+ 0.06 0.027 0.28 Methane (FID) 4.99 0.006 0.14 Ethane (FID) 4 0.011 0.15 n-butane 0.3 0.045 0.15 t-2-butane 0.3 0.059 0.17 1-butene 0.3 0.059 0.21 n-pentane 0.1 0.038 0.20 Hydrogen 12
Slide 15: Refinery Gas Analysis with Packed Columns
Refinery Gas Analysis with Packed Columns GC/FID/TCD/TCD Column 2 Column 3 Column 1 Std Column LVO Flow Diagram Standard Column LVO Plumbing LVO Analyzer Training 15 January 7, 2014
Slide 16: Refinery Gas Analysis – Helium Carrier
Refinery Gas Analysis – Helium Carrier Selected Method Parameters Split/Splitless inlet: 120 ºC, 100:1 split FID (front): 250 ºC TCD (rear): 260 ºC He carrier Ref. 30 mL/min Makeup 2 mL/min TCD (side): 250 ºC N2 carrier Ref. 45 mL/min Makeup 2 ml/min, neg. polarity Main Oven Program: 60 ºC ( 1 min)
Slide 17: RGA with Packed Columns
RGA with Packed Columns Analytical Performance - LVO at 70 °C Hydrocarbon Channel Permanent Gas Channel Hydrogen Channel LVO Analyzer Training 17 January 7, 2014
Slide 18: RGA with Packed Columns
RGA with Packed Columns Analytical Performance with H2S – TCD Channel, LVO at 70 °C N2 Ethylene O2 CO2 Methane CO H2S LVO Analyzer Training 18 January 7, 2014
Slide 19: RGA with Packed Columns
RGA with Packed Columns Analytical Performance with RGA Checkout Sample, No H2S TCD Channel, N2 LVO at 70 °C CO2 Ethane Methane Ethylene Acetylene O CO 2
Slide 20: RGA with Packed Columns
RGA with Packed Columns Analytical Performance – Oxygen Stability 70 °C Stability of Oxygen – Isothermal Oven at 70 °C LVO Analyzer Training 20 January 7, 2014
Slide 21: RGA with Packed Columns– Helium Carrier
RGA with Packed Columns– Helium Carrier Analytical Performance Compound Concentration RT 65 C RT 70 C Area 65 C Area 70 C C6+ 0.06 0.026 0.022 0.35 0.31 Methane (FID) 4.99 0.009 0.011 0.19 0.12 Ethane (FID) 4 0.02 0.016 0.21 0.15 n-butane 0.3 0.103 0.038 0.23 0.16 t-2-butane 0.3 0.13 0.055 0.22 0.19
Slide 22: Alternate Carrier Gases for RGA
Alternate Carrier Gases for RGA Confidentiality Label February 24, 2014 22
Slide 23: Thermal Conductivities
Thermal Conductivities GAS Thermal Diff. He Diff. N2 Diff H2 Conductivity Hydrogen 471 95 405 Helium 376 310 -95 Methane 89 -287 24 -382 Oxygen 68 -308 2 -403 Nitrogen 66 -310 -405 Carbon monoxide 64 -312 -2 -407 Ethane 58 -318 -7 -413 Ethene 55 -321 -11 -416 Propane 48 -328 -17 -423 Carbon Dioxide
Slide 24: LVO Based RGA with Hydrogen Carrier
LVO Based RGA with Hydrogen Carrier FID Channel Possible hydrogenation of olefins has been reported, although not seen with the test mix C6+
Slide 25: LVO Based RGA with Nitrogen Carrier for FID Channel
LVO Based RGA with Nitrogen Carrier for FID Channel 3.0 mL/min @ constant flow Last hydrocarbon at 5.5 min. Confidentiality Label February 24, 2014 25
Slide 26: LVO Based Fast RGA with Hydrogen Carrier
LVO Based Fast RGA with Hydrogen Carrier Separation with Micropacked columns TCD1: Permanent Gas Channel Run Time less than 7 min. N2 CO2 Ethane Methane Ethylene CO Acetylene O2 LVO Analyzer Training 26 January 7, 2014
Slide 27: LVO Based Micropacked %RSD's
LVO Based Micropacked 60 °C %RSD’s TCD1 Permanent gas channel: Hydrogen Carrier FID Hydrocarbon channel: Nitrogen carrier TCD2 Hydrogen channel: Nitrogen carrier Compound RT Area C6+ 0.028 0.34 Methane (FID) 0.012 0.133 Ethane (FID) 0.014 0.13 n-butane 0.044 0.15 t-2-butane 0.052 0.13 1-butene 0.052
Slide 28: Typical Detection Limits
Typical Detection Limits LVO Based RGA’s High Capacity RGA Analyzer Compounds Limit • Total run time is 16- 18 minutes. Hydrocarbons 0.01 Mol% • Hydrocarbons to C5 (C6+ backflush) Hydrogen Sulfide 500 ppm • Permanent Gases Carbonyl Sulfide 300 ppm • O2 and H2S Hydrogen 0.01 Mol% O2, N2, CO, CO2 0.01
Slide 29: Summary
Summary Two configurations available Packed Columns: 16 to 18 minute run time 1/16” Micropacked: 7 to 9 minute run time Both systems can measure hydrogen sulfide and carbonyl sulfide The Large Valve Oven allows the permanent gas channel to be isothermal Thermally decoupled from the main GC oven Bett
Slide 30: Configuration of ASTM Methods D5580, D3606, and D4815 on a Single GC
Configuration of ASTM Methods D5580, D3606, and D4815 on a Single GC Jim McCurry Agilent Technologies Wilmington, DE USA
Slide 31: Analysis of Oxygenates and Aromatics in Gasoline
Analysis of Oxygenates and Aromatics in Gasoline ASTM D3606 – Benzene and Toluene in Gasoline - official EPA method for benzene (0.1 - 5.0 vol%) and toluene (2 to 20 vol%) in gasoline ASTM Method D4815 – Oxygenated Additives - 14 different ethers and alcohols from 0.1 to 15 wt% - usually only one or
Slide 32: 3-in-1 Gasoline Solution using the New 7890B GC with LVO
3-in-1 Gasoline Solution using the New 7890B GC with Large Valve Oven (LVO) • Larger capacity for valves, packed columns and micro-packed columns • Flexibility for method using complex LVO valve/column configurations • Enables multiple methods to reside on a single GC - reduce instrument costs - run
Slide 33: LVO Specifications
LVO Specifications • Temperature Limit: 330˚C (high temperature valve dependent) • Valves: 6 heated valve positions, 4 needle valve positions • Temperature control: Independent control of Large Valve Oven and GC oven • Valve configurations: 4/6/10/14 port valves including Hastelloy valves • Large co
Slide 34: 3-in-1 Gasoline Solution – LVO Configuration
3-in-1 Gasoline Solution – LVO Configuration Cover Off - Front View Cover Off - Rear View • Valves • Pneumatic Valve Actuators • Variable Restrictor • Variable Restrictor Control • TCEP Pre-column • Heated Column Mandrel 34
Slide 35: 3-in-1 Gasoline Solution – Detailed LVO Configuration
3-in-1 Gasoline Solution – Detailed LVO Configuration TCEP Micro-packed Column on Heated Mandrel Variable Restrictor D3606 6-port Valve D4815 & D5580 10-port Valves 35
Slide 36: GC Configuration for D4815 and D5580
GC Configuration for D4815 and D5580 Similarities between each method - same GC hardware requirements • Inlets, detectors, plumbing and valve configuration - same separation scheme • 2-D separation using polar TCEP micro-packed primary column • 20% TCEP on 80/100 Chromosorb PAW, 22“ x 1/16“ stainles
Slide 37: 3-in-1 Gasoline Solution – Main Column Oven
3-in-1 Gasoline Solution – Main Column Oven D3606 Packed Columns D4815 and D5580 Capillary Columns • PDMS packed pre-column • D4815 HP-1 • Polar packed analytical column (30 m x 0.53 mm x 2.65 µm) • D5580 HP-1 (30 m x 0.53 mm x 5.0 µm 37
Slide 38: 7890 Instrument Conditions for D3606
7890 Instrument Conditions for D3606 carrier gas helium Inlet Purge Packed @ 59.4 psi Inlet temperature 200 Deg C Inlet total flow 23 mL/min Septum purge flow 3 mL/min Column flow 20 mL/min Aux pressure 35.5 psi TCD temperature 250 deg C LVO Temperature 60 deg C LVO temperature remains stable with h
Slide 39: D3606 – Comparison of Manual and WorkBench Sample Prep
D3606 – Comparison of Manual and WorkBench Sample Prep Manual Sample Prep Work Bench Sample Prep • Add 1.0 mL 2-butanol to 25 mL volumetric • Add 0.04 mL 2-butanol to 2 mL vial flask • Add 0.96 mL sample to 2 mL vial • Add sample to 25 mL mark Overlay of 10 Work Bench prepared gasoline samples 2-but
Slide 40: D3606 – Precision and Accuracy for Work Bench Prepared Samples
D3606 – Precision and Accuracy for Work Bench Prepared Samples Commercial Gasoline Sample Volume % D3606 Check Sample run benzene toluene vol%* 1 0.337 5.527 Run Benzene Toluene 2 0.344 5.523 1 0.98 5.00 3 0.344 5.519 2 0.98 4.98 4 0.348 5.524 3 0.97 4.98 5 0.347 5.475 6 0.346 5.483 4 0.98 5.00 7 0.
Slide 41: 7890 Instrument Conditions for D4815 and D5580
7890 Instrument Conditions for D4815 and D5580 D4815 Method D5580 Method carrier gas helium or N2 helium or N2 Inlet Split/Splitless Split/Splitless inlet temperature 200 Deg C 200 Deg C inlet presuure 9 psi (constant P) 25 psi (constant P) TCEP column flow 5 mL/min 10 mL/min split vent flow 70 mL/m
Slide 42: D5580 – Work Bench Prepared Gasoline Sample
D5580 – Work Bench Prepared Gasoline Sample Overlay of 5 replicates run on LVO Configuration toluene Norm. 14000 2-hexanone (IS) 10000 benzene 6000 2000 6 8 10 12 14 16 18 min m,p-xylene Norm. 2-hexanone (IS) 7000 C9 plus aromatics o-xylene 5000 3000 ethylbenzene 1000 12.5 15 17.5 20 22.5 25 27.5 mi
Slide 43: D5580 - Precision for WorkBench Samples
D5580 - Precision for WorkBench Samples Meets ASTM Repeatability (r) Specifications wt% Found in Gasoline Sample 1 benzene toluene ethylbenzene m,p-xylene o-xylene C9 plus Total Run 1 0.96 8.93 2.97 3.00 3.00 6.12 24.98 Run 2 0.96 8.91 2.96 3.00 3.00 6.11 24.94 r (calc) 0.00 0.02 0.01 0.00 0.00 0.01
Slide 44: D4815 – Work Bench Prepared Gasoline Samples
D4815 –Work Bench Prepared Gasoline Samples pA heavy hydrocarbons MTBE 12000 8000 DME (IS) 4000 0 16000 12000 8000 ethanol DME (IS) 4000 0 12000 ethanol 8000 DME (IS) 4000 0 2 4 6 8 10 12 14 16 min 44
Slide 45: D4815 – Comparison of Manual and WorkBench Sample Prep
D4815 – Comparison of Manual and WorkBench Sample Prep Manual Sample Prep Work Bench Sample Prep • Add 0.5 mL DME to 10 mL volumetric flask • Add 0.95 mL sample to an empty 2 mL vial • Record DME weight to 0.1 mg • Record sample weight to 0.01 mg • Add sample to 10 mL mark • Add 0.05 mL DME to sampl
Slide 46: Summary
Summary • New Large Valve Oven for the 7890B GC - greater capacity and flexibility for GC methods using complex valve configurations - allows multiple ASTM gasoline methods to be configured on a single GC • methods can be run sequentially - higher main oven temperature (135 deg C) has no effect on l
Slide 47: Q&A Session
Q&A Session Confidentiality Label February 24, 2014 47
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