Agilent and ASTM. Update on Recent Activities. Page 1

Transcription

1 Agilent and ASTM Update on Recent Activities Page 1

2 ASTM Committees for Refining, Fuels, Petroelum Products ASTM International D2 Petroleum products & lubricants D3 Gas fuels (natural gas) gas fuels D16 Aromatic Hydrocarbons & related chemicals D32 Catalysts properties & performance Global, non-profit, consensus organization Develop test methods, product specifications, practices, terminology, guides and classifications 4 main areas of focus: materials, products, systems and services Over 130 subcommittees cover specific areas - petroleum, chemicals, environmental, safety, etc. 10,000+ standards published each year in 73 volumes 32,000 members in 100+ countries Page 2

3 Agilent Involvement with ASTM Agilent (HP) and ASTM relationship since the 1960s Currently 6 Agilent scientists actively participate in ASTM D2 and D16 Participation includes developing methods, introducing new technology, round robins Some important methods Agilent (HP) helped develop - D4815: oxygenates in gasoline - D5580: aromatics in gasoline - D2887 and D3710 SIMDIS for diesel and gasoline - D7423 trace oxygenates in C2 to C5 hydrocarbons steams Some current methods under development with ASTM: - 2-D Capillary GC method for oxygenated additives in gasoline (D4815 replacement) - Aromatics and methanol in high methanol fuels using heart-cutting 2-D GC - New inlet conditions (MMI) for biodiesel (D6584) - Alternative carrier gases for D5580 (aromatics in gasoline), D4815 (oxygenates in gasoline), D3606 (benzene/toluene in gasoline), D2887 (SIMDIS for middle distillates) Page 3

4 New ASTM Developments for Gas Phase Analyses New methanol/gasoline blends - methanol easily made from new sources of natural gas (fracking technology) - GC method measures up to 85% methanol in gasoline blends 2-D GC method based on Agilent Deans switch application (pub # N) Recycled motor oils - recovering used motor oil saves petroleum resources - must meet specifications for fuel and glycol contamination - New D7593 method uses GC with back flush to measure gasoline and diesel contamination Agilent helped write GC conditions using 7890 Capillary Flow Technology back flush - GC Headspace method proposed to measure ethylene glycol in oil D4291 will remain the primary method to measure ethylene glycol in oil D4291 uses liquid-liquid extraction followed by GC-FID analysis 4

5 New ASTM Developments for Gas Phase Analyses D7845 approved to measure chemical contaminants in marine fuel oil - fuel contaminated with phenols, styrenes, pinenes, alcohols - method developed on Agilent 5977 GC/MS system with CFT back flush - Agilent will participate in 2014 round robin - a new GC-QQQ method under development to measure FAMEs, fatty acids, bis-phenols and glycerides contaminants in marine fuel Gasoline SIMDIS method D3710 using packed columns is withdrawn - D7096 is the new method using capillary columns D7798 approved as new Ultrafast SMDIS method - D2887 equivalent - developed using Agilent LTM column heating technology - Agilent participated in round robin 5

6 Examples of Agilent s Current Work with ASTM Gasoline and Biofuels - Capillary GC version of D3606 under development Improved separation of benzene from ethanol and butanol gasoline blends Uses fluidic switch (Deans switch) with backflush - Investigation of a new capillary D4815 method improved oxygenate separation from olefins - 3-in-1 ASTM Gasoline Solution Using 7890 Large Valve Oven Configures D3606, D5580 and D4815 on a single instrument Diesel Fuels and Biodiesel - D7798 Ultrafast SIMDIS using direct column heating technology Agilent LTM - Improvements to ASTM D6584 Biodiesel method Better performance using Agilent Multimode Inlet Alternative GC carrier gas - Response to helium shortages and price increases - Reviewing current ASTM GC methods for capability with nitrogen or hydrogen SIMDIS and D4815 methods currently under ballot for nitrogen or hydrogen carrier gas use - New Agilent 7890 Helium Conservation Module - New Agilent 7890 Hydrogen Sensor

7 New D3606 Capillary GC Configuration - Improved Separation of Benzene Jim McCurry Agilent Technologies Wilmington, DE USA 7

8 CFT Splitter at Sample Injection Use FID1 signal to determine time toluene elutes from pre-column. This is the backflush time. P = psig S/S Inlet EPC UDFS restrictor 0.58m x 0.1mm 2.9 ml/min 2.7 ml/min FID 1 FID 2 Pre-column: HP1 30m x 0.25mm x 0.50um Analytical column: Innowax 60m x 0.32mm x 1.00um Aux EPC P = psig

9 Toluene Elution Time on Pre-Column Faster & easier back flush set-up with CFT and UDFS restrictor Pre-column Restrictor FID1 i-c 8 toluene ethanol MIBK 4.22 min back flush time benzene min

10 CFT Splitter at Back Flush Time (4.22 min) P = psig S/S Inlet EPC UDFS restrictor 0.58m x 0.1mm -1.2 ml/min 2.0 ml/min FID 1 FID 2 Pre-column: HP1 30m x 0.25mm x 0.50um Analytical column: Innowax 60m x 0.32mm x 1.00um Aux EPC P = psig

11 Flow Modifications to Resolve Toluene/i-Butanol initial Temp Initial hold ramp 1 Temp 2 Hold 2 Until i-buoh elutes ramp 2 Final temp Final hold 75 o C 8min 5 o C/min 80 o C 5min 10 o C/min 95 o C until n-butanol elutes Backflush time (until toluene elutes) 4.23 analytical Flow rate at time 0 analyltical Flow rate 0.1min after BF time Pre-column flow rate at time ml/min 2.0 ml/min 2.7 ml/min

12 Commercial Pump Gasoline Sample ethanol toluene Better separation of ethanol from benzene compared to D3606 packed column configuration MIBK benzene

13 Comparison of Helium and Nitrogen Carrier Gas Operation for ASTM D4815 Jim McCurry Agilent Technologies Wilmington, DE USA

14 D4815 Configuration Primary flow S/S EPC split/splitless inlet TCEP column HP-1 capillary column Secondary flow Aux EPC variable restrictor FID TCD

15 Helium Conservation Module Seamlessly integrated onto 7890 GC hardware and software To Inlet EPCs Purge Built on 5 th generation EPC Fully controlled by Agilent data systems Flow channel inside the bridge block N 2 in He in Purge channel prevents cross contamination of gases Precise pressure control between tank and GC Switch between gases within 15-30min for most detectors Std. Aux EPC

16 Helium Conservation Module Helium Operation Mode 1 ml/min (out) AUX EPC 1 Nitrogen 0 psig AUX EPC 3 Purge 10 psig AUX EPC 2 Helium 80 psig (< 0.2 ml/min) N 2 Bridge Block To GC Inlet EPC Helium ON at 80 psig, Nitrogen OFF

17 Helium Conservation Modules Nitrogen Operation Mode 1.0 ml/min (out) AUX EPC 1 Nitrogen 80 psig AUX EPC 3 Purge Vent 10 psig AUX EPC 2 Helium 0 psig (< 0.2 ml/min) He Bridge Block 24.2 ml/min N 2 Helium OFF, Nitrogen ON at 80 psig To GC Inlet EPC

18 D4815 Helium and Nitrogen Carrier Gas Operating Conditions Helium GC Conditions Nitrogen Col1: TCEP Micropacked 5.0 ml/min (17.8 psi) 5.0 ml/min (16.7 psi) Col2: PDMS Capillary 3.1 ml/min (14.7 psi) 3.1 ml/min (13.8 psi) Split Flow 70 ml/min 70 ml/min TCEP Backflush Time 0.24 min min TCEP Reset Time 0.84 min min Valve Oven Temp 60 o C 60 o C Column Oven Temp 60 o C 60 o C

19 D4815 Helium and Nitrogen Carrier Gas Calibration of Oxygenates Helium Carrier Gas Nitrogen Carrier Gas Compound corr (>= 0.99) slope y-int y-int test (<0.1) corr (>= 0.99) slope y-int y-int test (<0.1) MeOH EtOH i-proh t-buoh n-proh MTBE BuOH DIPE i-buoh ETBE t-amyl-oh n-buoh

20 D4815 Helium and Nitrogen Carrier Gas MTBE in Gasoline MTBE Helium Carrier Gas Nitrogen Carrier Gas Min.

21 D4815 Helium and Nitrogen Carrier Gas Ethanol in Gasoline Helium Carrier Gas Ethanol Nitrogen Carrier Gas Min.

22 D4815 Helium and Nitrogen Carrier Gas Results from 3 Gasoline Samples Gas1 wt% MTBE Gas2 wt% Ethanol Gas3 wt% Ethanol Helium Nitrogen Helium Nitrogen Helium Nitrogen run run Avg r (calc) r (spec)

23 Inlet Comparison of ASTM D6584: COC vs. Temperature Programmed Split Jim McCurry Agilent Technologies February 19,

24 Inlets With Temperature Program Capability Inlet temp programming provides flexibility for injection volume, analysis of thermally labile samples and minimizing inlet discrimination for high molecular Wt components Greater sensitivity through large volume injections Reduce sample preparation steps, resulting in enhanced productivity Solvent venting and Backflush are possible using auxiliary pressure source and CFT device

25 Multimode Inlet (MMI) Extremely flexible Split/splitless Multiple injection COC Simulation Can eliminate needle discrimination Minimal thermal stress on sample Large volume capability

26 Standard Techniques Cold split injection Cold splitless injection (COC simulation) Hot split injection Solvent venting Stationary phase/solvent venting for focusing

27 Multimode Inlet Features Hardware Temperature range of -160C to 450C 15C/sec Septum/Liner Easily Exchangeable Injection Modes: Hot S/SL, Cold S/SL, all in pulsed mode, solvent vent mode, residue removal mode Support for single stroke injections from 0.1 ml to 250 ml EPC Compatible with Packed Liners Compatible with 7890A, 5975C, 7683, CTC Combi PAL Software Ten temperature ramps Solution for solvent vent timing Fully integrated into ChemStation, MSD ChemStation, EZChrom, MassHunter

28 New Multimode Inlet Improvements Turn-top easy liner exchange Standard 11mm septa Air plus CO2, N2 cryogenic cooling No leaks at liner Standard liner dimensions Standard column nut

29 MMI Conditions Used For ASTM D6584 Column: Agilent Select Biodiesel 15 m x 0.32 mm, 0.10 μm (p/n CP9079) Carrier: Helium 5.6 ml/min constant flow Oven: 50 C (hold 1 min), then to 180 C at 15 C/min, then to 230 C at 7 C/min, then to 380 C at 30 C/min (hold 10 min) Injection: MMI Cold-Splitless, Initial temp 88 C for 0.1min, then to 350 C at 250 C/min (hold 1 min) Purge time 1.00min., Purge Flow 9.6ml/min. Detector: FID at 380 C Sampler: Agilent 7693, 1μL volume injection

30 Soy B100 Run With MMI

31 Comparison of Single Lab Precision (r) For MMI and COC Inlet wt% Glycerol wt% Monoglycerides wt% Diglycerides wt% Triglycerides wt% Total Glycerin COC MMI COC MMI COC MMI COC MMI COC MMI Run Run Average r (calc) r (spec) MMI provides same results as COC MMI provides better precision

32 Summary Agilent and ASTM have a long and successful history for developing new solutions for HPI measurements Agilent continues to provide strong support and leadership within ASTM community Agilent works with ASTM members to understand new measurement technologies and incorporate them into the latest methods 32