The document discusses quantifying drag reducing additives (DRA) in jet fuel using rotary evaporation and gel permeation chromatography (GPC) detection. It proposes concentrating the DRA in a jet fuel sample using rotary evaporation, then analyzing it using GPC with an evaporative light scattering detector. Simplifications to the method include using a single GPC column, heptane mobile phase, and refractive index detection. Tests show the method can detect DRA at concentrations as low as 50 parts per billion in jet fuel.

1. Quantification of DRA in jet fuel
Rotary Evaporation with GPC detection
Proposed ASTM Method

2. Overview
- Pipeline Drag Reducing Additive (DRA)
- Optimization of Rotary Evaporation with GPC detection
method

3. DRA chemistry
Example of polymer chemistry
* *
n m
Monomers Poly(alphaolefin)
Linear alpha olefin Drag Reducing Additive
(DRA)
 DRA molecular weights > 25 million Daltons (n and m >200,000)

4. Drag reduction mechanism
DRA mitigates turbulent burst imposing long
DRA range concerted axial motion
Flow
Local flow
direction
100
90
Drag reduction can be thought of as a
reduction in the frictional factor f
% Drag 80
70
reduction 60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90
FLO MXC ppm
high strain regions
DRA > 25 million Da Valves, Pumps, Restrictions Sheared DRA 1 to 3 million Da
(not as effective, reinjection)

5. Fuel pipeline operations
Flow
Jet fuel No inject.
Interface Diesel
(DRA not allowed) Buffer
Potential DRA contamination sources Risk
1.) Use of drag reducers increases interface size Mitigated
Turbulent Flow Laminar Flow
- Flat velocity profile - Faster center velocity
- Low interface volume - Large interface volume
2.) Chemical dispersion No
3.) Pipeline operational mistakes Yes
4.) DRA injector leaks Yes

6. DRA monitoring industry wide
 Verbal reports of DRA contamination in jet fuel
 DRA impacts jet fuel performance (taken from Stan Seto CRC Report 642)
 Diminishing fuel spray angle and atomization capability @ 8.8 - 32 ppm
 A significant loss in engine start capability @ 8.8 and 32 ppm
 The report concluded that DRA was not acceptable for use in aviation fuel
 The actual safe limit has never been identified
 TF is targeted developing methods with a limit of detection of 50 ppb which is
considered low level contamination except for highly active contaminants like
copper

7. Analytical method background

8. Principles of Gel Permeation Chromatography (GPC)
Flow
Jet fuel molecules
DRA polymer
Stationary phase
Mobile phase not shown
Detector (RI, ELSD ...)
Time = 0 1 2 3 and so on…
Area proportional to concentration
Detection
Elution time
Related to molecules size or MW

9. Rotovap Concentrating
with GPC Detection

10. Original proposed method
Sample Prep
Rotovap Pierce Reacti-therm Backfill w/THF
Jet fuel (130oC) Concentrated (120oC) Filter
DRA sample Sample for
(W1 ≈ 400g)
5-8hr
(W2 ≈ 2g) Overnight GPC
Inject 200μl
GPC divert flow from ELSD
GPC column PL type Mixed D
10μ particle size after DRA elutes
ELSD
1 2 3
THF Waste
Data workup Concentration of DRA in jet
fuel = (Determined PPM) x
(W2/W1)
integrated DRA area Determine PPM
 Can detect to 50 ppb
 Sound method but need something simpler for widespread implementation

11. Impact of mobile phase
~2 ppm DRA samples
Can we use heptane instead of
THF in the proposed method?
THF
Original
Proposed
Method
Sample ~200x
conc. (Rotovap)
GPC 5µ PL
column Mixed D
# of
3 Heptane
columns
Mobile THF 
phase Heptane
Detector ELSD
Detection
0.05 ppm
limit
NO, significant loss in ELSD detection sensitivity with heptane

12. Run Time: 25.0 Minutes Channel Name: ELSD Signal
Sample Set Name: 11_29_10 Proc. Chnl. Descr.: ELSD Signal
Baker Hughes GPC setup
0.20
SAM PL E INFO RMAT ION
Can we combine rotovap concentration
FLO_XS
0.00
with Baker Hughes GPC? Sample Name: 37097 Acquired By: weibo
Sample Type: Unknown Date Acquired: 11/29/2010 8:52:50 PM CST
-0.20
Original Vial: 7 Acq. Method Set: GPC _Cpntoller_Method Set
Baker Injection #: 1 Date Processed: 12/1/2010 9:50:50 AM CST
Proposed
Hughes Injection Volume: 200.00 ul Processing Method: flo_quant1
method
LSU
-0.40
Run Time: 25.0 Minutes Channel Name: ELSD Signal
~5x  ~200x Sample Set Name: 11_29_10~ 2.5
Sample ~200x (Dry bath 
ppm DRA sample Signal
Proc. Chnl. Descr.: ELSD
conc. (Rotovap) Rotovap @
EM) -0.60
0.20
GPC 5µ PL 5μ PL
column Mixed D Mixed C
-0.80
FLO_XS
# of 0.00
3 2
columns
Mobile -1.00
THF THF -0.20
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00
phase
Minutes
Detector ELSD ELSD
SampleName 37097; Vial 7; Injection 1; Channel ELSD Signal; Date Acquired 11/29/2010 8:52:50
LSU
Detection -0.40 PM CST
0.05 ppm ~1 ppm
limit
Component Summary Table
No improvement found over original proposed method
-0.60 with respect to detection
Name: FLO_XS sensitivity
SampleName Inj Channel Name RT Area Height Amount Units Vial
1 37097 1 ELSD Signal FLO_XS 10.024 1098 30 7.312 ppm 7
-0.80
Mean 1098 30 7.312

13. Magellan Midstream Partners GPC setup
Can we combine rotovap
concentration with MMP GPC? Original jet fuel sample with 50 ppb DRA
10.7 ppm after concentrating
Original Magellan
proposed Midstream
method Partners
None  ~200x
Sample ~200x
(Rotovap @
conc. (Rotovap)
EM)
GPC 5µ PL 10µ PL
column Mixed D Gel 104 Å
# of
3 1
columns
Mobile
THF Heptane
phase
DRA’s permeating
Detector ELSD RI
Detection
0.05 ppm ~1 ppm Bigger DRA’s excluded
limit
Smaller DRA’s permeate
Yes. Results are very encouraging, GPC
simplified enormously! DRA’s totally excluded

14. Simplifications applied to ASTM draft method
Original Magellan ASTM Draft
proposed Midstream Method
method Partners (Basic GPC)
Sample ~200x none ~200x
conc. (Roto.) (Roto.) Key to getting down to ppb levels
GPC 5µ PL 10µ PL Gel 10µ PL Gel
Column Mixed D <104 Å 104 Å 1) Requires less columns  less run time
2) Better separation  no overnight evap.
# of
columns
3 1 1 3) Sharper peak  RI detections is viable
Mobile
THF Heptane Heptane More acceptable
Phase
Detector ELSD RI RI Common GPC detection
Detection
0.05 ppm ~1 ppm 0.05 ppm
limit Maintained 50 ppb detection limit

15. Ruggedness tests
Sample Prep Calibration GPC
DRA in Jet Fuel by
direct blend of DRA @ 2, 4, 10, 20, 100ppm in jet fuel
Rotovap
Jet fuel (130oC) Concentrated DRA 40000
35000 y = 335.57x
(W1 ≈ 400g) sample R2 = 0.9999
5-8hr 30000
(W2 ≈ 2g) 25000
Area
GPC
20000 Area
104A RI 15000 Linear (Ar
10000
1 5000
0
0 20 40 60 80 100 120
Heptane ppm DRA
Results for 3 Jet fuel samples with 50 ppb DRA Example result (#2)
Sample 1 2 3 S/N > 40
Initial weight sample 399.36 399.45 398.93
Weight of concentrate 1.59 2.26 2.46
ppm from GPC 13.1 10.3 7.1
ppb after correcting for
concentration 52.2 58.3 43.8

16. Limits to quantifying the minimum DRA concentration
0.13
S/N = 13.7
0.09
10x noise
RI
0.05
0.01
Height of high frequency peak to peak noise
-0.03
0 1 2 3 4 5 6
Time (minutess)
 GPC column, 10µm particles with 500Å pore size. Sample analyzed contained 2.9 ppm
DRA in jet fuel (after rotovap concentrating a 50 ppb DRA in jet fuel sample)
 Chromatogram example exhibits a DRA signal that satisfies the >10 S/N. After rotovap
concentrating a 400g sample containing 50 ppb DRA the final weight of the concentrate
should be ~ 7g or less (2.9 ppm or greater concentrate) for this GPC apparatus

17. Tests with different DRA types
0.15
0.13
0.11
0.09
0.07
RI
0.05 50 ppb sheared gel
0.03 50 ppb sheared dispersed
0.01 50 ppb unsheared gel
-0.01
-0.03
0 1 2 3 4 5 6
Time (m inutess)
Description Gel type FLO XS Dispersed type FLO MXC
Sheared/Unsheared sheared unsheared sheared
Wt. of Sample 396.37g/ 396.37g/ 396.54g/ 396.29g/
before/after Rotovaping 6.96g 4.14g 7.74g 5.14g
Concentrated DRA 2.9 ppm 4.9 ppm 1.8 ppm 4.3 ppm
conc.
Calculated conc. DRA 50.9 ppb 51.2 ppb 35.1 ppb 55.8 ppb
of Original Sample
S/N 13.7 15.7 5.5 18.9
 Typical LOQ requires the S/N ratio to be > 10 which is satisfied for sheared DRA (gel and dispersed).
Unsheared exhibits less sensitivity but is above the level of detection (LOD) which typically requires
the S/N ratio to be > 2

18. Tests with different GPC column article pore size
0.49
0.39
0.29
w/ 50Å particle pore size
RI (mv)
0.19 10ppm DRA sheared, gel type in Jet fuel
(calibration sample, no rotovaping)
0.09
-0.01
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Time (min)
Pore size MW range Typical materials PL gel part # Excluded
50Å up to 2000 Jet fuel molecules 1110-6115
100Å up to 4000 1110-6120 DRA &
500Å 500-30,000 1110-6125 Sheared DRA
10^3Å 500-60,000 1110-6130 excluded
10^4Å 10,000-600,000 1110-6140
10^5Å 60,000-2,000,000 Sheared DRA 1110-6150
10^6Å 600,000-10,000,000 Sheared DRA 1110-6160
~25,000,000 DRA
 Results are similar for all pore sizes < 10Å. Tests include 50Å, 500Å and 104Å

19. Calibration samples vs. concentrated samples
0.46
0.36
10.3 ppm after rotovap
50 ppb in Jet fuel
0.26 (S/N 41.6)
RI
10.0 ppm in jet fuel
0.16 calibration sample
(S/N 67.9)
0.06
-0.04
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Time (minutes)
Concentration (ppm) Area Peak height S/N
50ppb Concentrated sample 10.3 3.65 0.345 41.6
Calibration sample 10.0 3.41 0.340 67.9
 RI DRA signal response is similar

20. Does Stadis® 450 cause measurement interference?
0.15
0.13 Both samples
0.11 concentrated on a
0.09
rotovap
0.07
RI
50 ppb sheared gel
0.05
5ppm Stadis 450
0.03
0.01
-0.01
-0.03
0 1 2 3 4 5 6 7
Tim e (m inutess)
 Stadis® 450 MSDS indicates up to 40% trade secret polymer
 No interference observed

21. Conclusion
 Recent efforts were placed on optimizing the DRA quantification method
employing rotary evaporation with GPC detection
 TF was successful in making many improvements making the method more
deployable
 Quantification to 50 ppb appears likely with readily available apparatus and
acceptable solvents
 Method works with both types of DRA; suspension and gel
 Method works with both sheared and unsheared DRA
 Slightly less sensitive for unsheared
 Proposed ASTM draft method has been prepared
Next steps
 Need to progress to a round robin
 GPC hardware is not limited to the basic apparatus described in the method. All
GPC configurations where the DRA peak signal/noise is >10 are acceptable to be
used in the RR

22. Thanks for your data contribution
Nagesh Kommareddi Baker Hughes
Chuck Haber Magellan Midstream partners
Patrick Mollere Intertek
Elisa Redfield Intertek
Thank You

23. Appendix
From PL website
2 3 4 5 6 7
Most mixed columns looks to permeate sheared DRA