Agilent Solutions for the Petrochemical and Oleochemical Industries

Transcription

1 e-seminar Series - Agilent Solutions for the Petrochemical and Oleochemical Industries Date: 12 June 2009 Time : 10am Singapore Time For audio, please dial one of the phone numbers listed: International Telephone Number for Singapore: or Toll Free International Telephone Number for Hong Kong: Toll Free International Numbers: Australia New Zealand China Malaysia Indonesia Taiwan India* South Korea India (Backup)* Philippines Thailand* Vietnam * Phone line needs to be IDD enabled. Not accessible from Mobile Phones

2 Measurement of low levels of FAME in Aviation Fuel by GC-MS Development of IP Method PM-DY/09 Tom Lynch and Alex Ttofi BP Technology Centre Pangbourne Presenter: Jim McCurry Agilent Technologies

3 Trace FAME in Jet Increasing quantities of biodiesel and jet are being co-transported in multi-product pipelines (MPP). In MPP transportation trace amounts of FAME can be found in jet parcels following biodiesel parcels due to FAME trail back. Following pipeline trials to establish the amount and profile of FAME trail back into jet and JIG PQ committee work on the effect of various FAMEs (up to 400 ppm) on the specification properties of jet fuel the main engine OEMs gave their verbal and written approval of up to 5ppm FAMEs in jet fuel. The DFG now consider it is necessary to formalize this acceptance of 5ppm FAMEs in jet fuel in the Def Stan 91-91, Issue 6 specification and have issued a draft specification amendment for consideration by the AFC, ExCo and OEMs (engine and airframe).

4 Trace FAME in Jet Following from this proposed amendment there is an urgent need to develop a referee test method with an acceptable precision at the 5 ppm FAME level. Trace FAME in Jet The method will need to be robust Applicable to all FAME types / unknown blends Suffer no interference from common diesel additives Be subjected to a ruggedness trial

5 Methods Considered Primary/Short Term methods requirements Sensitivity ideally less than 1ppm per FAME species Selectivity Secondary method requirements Confirmation measured species are FAME Fast, equipment readily available, minimal sample preparation 2D GC Comprehensive not widely available, too specialised, data analysis can be complex Multi heart-cut potential but worries about FID sensitivity FTIR & NMR Good selectivity but poor sensitivity would require a pre-concentration step. Different FAMES have different absorption coefficients in FTIR. HPLC (modified IP 436) Looks to have potential but modern stationary phases do not give good results potential for phase development Potentially good sensitivity and selectivity but as yet unproven. GC-MS Even most basic quadrupole systems offer high sensitivity and selectivity Mass spectrum can confirm presence of FAME

6 Fatty acids composition of bio diesel feedstocks (vegetable derived) Acid (% wt) Castor Coconut Corn Linseed Olive Palm Peanut Rape Soya Sunflower Jatropha Saturated acids Caproic C6:0 0.8 Caprylic C8:0 5.4 Capric C10:0 8.4 Lauric C12: Myristic C14: Palmitic C16: Stearic C18: Arachidic C20: Behenic C22: Lignoceric C24: Mono-unsaturated acids Palmitoleic C16: Oleic C18: Ricinoleic C18: Erucic C22:1 Bi-unsaturated acids Linoleic C18: Poly-unsaturated acids Linolenic C18:

7 Initial method for first pipeline trial Developed using an RME (rape seed) fuel as supplied. Principle:- Use a polar GC column to get maximum retention of polar FAME and Selected Ion Monitoring (SIM) for selectivity and sensitivity In summary the specifics of the method are Column HP Innowax (Agilent 19091N-213) 30m x 0.32um id x 0.5um film thickness Initial oven temp 170ºC hold 5mins,ramp 6ºC until 248ºC & hold for 5 mins. Total of run 23 mins Inlet at 325ºC, constant flow of 1.2ml/min Splitless injection of 0.2µl neat sample SIM and Scan data collected

8 GC-MS method for RME in Jet Fuel Abundance Main problem is resolving the RME FAME components from the hydrocarbons and aromatics in the kerosene. Cannot do this with conventional boiling point GC column. Use of a polar Innowax column increases the retention of the RME FAME species relative to the kerosene components However, even with the conventional scanning mode GC- MS did not give sufficient sensitivity (top trace) GC-MS used with multiple single ion monitoring (SIM) to achieve a detection limit of circa 0.1ppm (lower trace) Time--> Abundance Time--> ppm, 3ppm, 1ppm, 0.5ppm and 0.1ppm FAME in Kerosene using conventional GC-MS full scan mode ppm, 3ppm, 1ppm, 0.5ppm and 0.1ppm FAME in Kerosene using GC-MS multi SIM mode

9 GC-MS multi-sim for RME in Jet Fuel Calibration 0.1 to 1ppm FAME in kero by GC-MS y = 42548x R 2 = peak area area Linear (area) ppm FAME

10 Pipeline Study Fame content of Gas/Kero line during Jet import. FAME content (ppm) Time (mins) Fame Content Limit of detection

11 Limitations of initial method Set up for one trial with known RME Used only one component (C18:1) No scope to include Other FAME components as required by customers Required the fuel and FAME blanks to reach maximum sensitivity Require greater resolution of FAME species from aromatics This lead to development of our current method

12 Fatty acids composition of bio diesel feedstocks (vegetable derived) Acid (% wt) Castor Coconut Corn Linseed Olive Palm Peanut Rape Soya Sunflower Jatropha Saturated acids Caproic C6:0 0.8 Caprylic C8:0 5.4 Capric C10:0 8.4 Lauric C12: Myristic C14: Palmitic C16: Stearic C18: Arachidic C20: Behenic C22: Lignoceric C24: Mono-unsaturated acids Palmitoleic C16: Oleic C18: Ricinoleic C18: Erucic C22:1 Bi-unsaturated acids Linoleic C18: Poly-unsaturated acids Linolenic C18:

13 Major components of bio diesel feeds Fatty Acids (% wt) Castor Corn Linseed Olive Palm Peanut Rape Soya Sunflower Jatropha Saturated Palmitic C16: Stearic C18: Mono-unsaturated Oleic C18: Ricinoleic C18:1 89 Bi-unsaturated Linoleic C18: Poly-unsaturated Linolenic C18: Total C Total C18 + C16: Data taken from Bailey s Industrial Oil and Fat Products Vol 1, 4 th Ed, Wiley ISBN Total C18 recovers between 80 and 95% of most feeds listed except Palm Total C18 +C16:0 recovers >95% of all feeds listed.

14 Improved method details Instrument Agilent 5973 MS & 6890 GC (diffusion pump) Column- HP INNOWAX (Agilent 19091N-205) 50 m x 200 um id x 0.4 um film. Constant flow 0.6ml/min Splitless Injector temp - 325ºC, MS source: 230ºC & MS Quad 150ºC Neat sample Injection 1 µl, Oven: Initial 150ºC hold 5 mins, Ramp 12ºC / min until 210ºC hold 17min Ramp 3ºC / min until 252ºC hold 2 min Total run time 43 mins Data collection delay 16 mins MS SIM & SCAN data collected simultaneously, SIM ions - see table on next slide Sum of all 6 SIM ion peaks measured for results

15 SIM Ions for FAMEs in Jet Fuel FAME Species C16:0 C17:0 C18:0 C18:1 C18:2 C18:3 Approximate RT (min.) (2 summed isomer peaks) SIM Ions to be used for quantification (m/z) 227, 239, 270, , 253, , 267, , 265, , 263, 264, 294, , 263, 292, 293

16 Standards Standards of C16:0, C17:0 and C18 Fames mg/kg FAME stock standard Individual FAME species dissolved in 99% n-dodecane Eight GC/MS calibration standards prepared in n-dodecane from stock standard 0.5, 1, 2, 3, 5, 10, 20 and 50 mg/kg + n-dodecane blank All standards stored at 0 o C when not in use

17 Mixed FAME STD in Jet: 200ppm Total ion count Total 6 SIM C14:0 C15:0 C16:0 C18:1 C18:2 C18:3 C17:0 C18:0

18 Calibration overlay for C18 components Abundance C18:1 C18:2 5ppm C18: C18:0 2ppm 1ppm 0.5ppm 0.1ppm Time-->

19 Detection limit C18:2 Abundance ppm ppm 1ppm 0.5ppm 0.1ppm Time--> Reference fuel

20 Calibrations: Total C18 C18 methyl esters peak areas summed C18 methyl esters are C18:0, C18:1, C18:2 & C18: Total Area C18 Calibration R 2 = Total Area Conc FAME ppm

21 FAME STD - C18 individual components FAME in Avtur Low Range Calibration Peak Area C16:0 C17:0 C18:0 C18:1 C18:2 C18:3 Linear (C17:0) Linear (C16:0) Linear (C18:2) Linear (C18:1) Linear (C18:3) Linear (C18:0) C17:0 y = x R 2 = C16:0 y = x R 2 = C18:0 y = x R 2 = C18:1 y = x R 2 = C18:2 y = x R 2 = C18:3 y = 53002x R 2 = mg.kg FAME

22 Limit of detection C16:0 Abundance Reference fuel 5ppm 2ppm 1ppm 0.5ppm 0.1ppm Time-->

23 PME calibration Calibration also developed using Palm oil methyl ester based bio fuel (PME) in Jet Fuel PME in Jet Fuel calibration based on Total C16:0 C18 by GC-MS R 2 = Total C16:0 C18 peak area Conc PME (ppm)

24 RME calibration RME calibration Total C16:0 + C18 Peak Area R 2 = Conc RME (ppm)

25 Repeatability Total Individual FAME FAME C18:3 C18:2 C18:1 C18:0 5ppm standard Standard deviation % limits Mean Variance Number ppm standard Standard deviation % limit Variance Mean number

26 Confirmation of FAME present The mass spectrometer adds the possibility to confirm the peaks as FAMES From TIC we can get a spectrum and library match down to circa 20ppm. From pattern of 6 SIM ions we can also get some confirmation of FAME Abundance Abundance Abundance m/z--> Abundance Scan 697 ( min): K03D006.D\datasim.ms (-667) (-) SIM 16: m/z--> Abundance Scan 1961 ( min): K03D006.D\datasim.ms (-1988) (-) SIM 18: Scan 1263 ( min): K03D006.D\datasim.ms (-1233) (-) SIM 17: Scan 1812 ( min): K03D006.D\datasim.ms (-1779) (-) SIM 18: Abundance m/z--> Scan 2134 ( min): K03D006.D\datasim.ms (-2115) (-) SIM 18: Scan 2363 ( min): K03D006.D\datasim.ms (-2347) (-) SIM 18: m/z--> m/z--> m/z-->

27 5 ppm FAMEs in MEROX Jet Fuel Abundance TIC: K03D023.D\datasim.ms TIC: K03D010.D\datasim.ms (*) Blue trace = 5ppm Rape Seed Methyl Esters in MEROX Black trace = MEROX Time--> Abundance TIC: K03D023.D\datasim.ms TIC: K03D018.D\datasim.ms (*) Blue trace = 5ppm Mixed FAME in Merox Black trace = Merox Time-->

28 5 ppm FAMEs in HDT Jet Fuel Abundance TIC: K03D020.D\datasim.ms TIC: K03D007.D\datasim.ms (*) Blue trace = 5ppm Rape Seed Methyl Esters in HDT Black trace = HDT Abundance Time--> TIC: K03D020.D\datasim.ms TIC: K03D013.D\datasim.ms (*) Blue trace = 5ppm Mixed FAME in HDT Black trace = HDT Time-->

29 Benefits of method Meets 5 ppm detection limit for most first generation bio-diesel feeds. Uses readily available off the shelf equipment No sample preparation samples injected neat Under 1 hour per sample Can confirm peaks are FAMES Good linearity of FAME over wide concentration range Can match FAME contamination to possible source Equipment also very useful for other bio-fuel related analysis

30 Limitations and Options for Improvement Limitations Detection Limits can be influenced by base jet fuel Ideally you need the uncontaminated jet fuel to provide a zero baseline Higher detection limits for lower Carbon number FAME s (C12 for coconut not possible) Mineral diesel fuel contamination interferes. Development Options Better stationary phase with better selectivity for FAME over aromatics Heart cut FAMES using microfluidics to achieve better resolution and sensitivity Chemical Ionisation (CI) may offer greater selectivity and sensitivity, will look at in near future.

31 ??????? Thank you for listening Any further questions or comments

32 Next e-seminar Series Tuesday, 16 th June, :00 AM (Singapore Time) Simplifying sample preparation and speeding up the analysis for the characterisation of simulated distillation samples Speaker: Roger Firor, Agilent Technologies