Process and Laboratory Analysisfor Chlorine and Transition Metalsin Crude Oil and Aqueous Matrices

Berry Beumer

Elemental Analysis Solutions using X-Ray Fluorescence

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Sulfur in Fuels

ASTM D7039

ISO 20884

Gas, diesel 4-500ppm

Gas, diesel 5-500ppm

LODDiesel

0.15ppm300s

r (10ppm) 0.6ppm

R (10ppm) 1.1ppm

ASTM D2622

ASTM D7039

ISO 20884

Petroleum3ppm-4.6wt%Gas, diesel4-500ppmGas, diesel 5-500ppm

LODDiesel

0.4ppm300s

r (10ppm) 0.8ppm

R (10ppm) 1.4ppm

ASTM D7039

ISO 20884

Gas, diesel 4-500ppm

Gas, diesel 5-500ppm

LODDiesel

0.4ppm900s

r (10ppm) 0.8ppm

R (10ppm) 1.4ppm

ASTM D7039

ISO 20884

Gas, diesel 4-500ppm

Gas, diesel 5-500ppm

LODDiesel

0.4ppm300s

r (10ppm) 0.8ppm

R (10ppm) 1.4ppm

Silicon in Fuels

ASTM D7757 Gasoline, Ethanol3-100ppm

LODethanol

0.5ppm600s

r (10ppm) 1.0ppm

R (10ppm) 1.8ppm

Phosphorus in Fuels and Water

No ASTM method at this time

LODethanol

0.4 ppm600s

r (10ppm) 1.2ppm

R (10ppm) 2.0ppm

ASTM D7536 0.5-15ppmAromatics

LOD Crude 0.2ppm @300s

r (10ppm) 0.8ppm

R (10ppm) 1.4ppm

Chlorine in Fuels and Water Matrices

Chlorine in Water Repeats

Measurement Number

Measurement Time (s)

CountsMeasured Chlorine (ppm)

Corrected ChlorineA

(ppm)

1 600 739 0.38 0.95

2 600 747 0.40 1.00

3 600 763 0.43 1.08

4 600 728 0.36 0.90

5 600 819 0.54 1.35

6 600 743 0.39 0.98

7 600 748 0.40 1.00

8 600 791 0.49 1.23

9 600 758 0.42 1.05

10 600 780 0.46 1.15

Average 762 0.43 1.07

Std Dev 28 0.06 0.14

%RSD 3.63% 12.92% 12.92%

ACorrection for water samples run on a mineral oil calibration is 2.5*measured result = corrected result.

Chlorine in Water Repeats (cont.)

Measurement Number

Measurement Time (s)

CountsMeasured Chlorine (ppm)

Corrected ChlorineA

(ppm)

1 600 1097 1.09 2.73

2 600 1101 1.10 2.75

3 600 1043 0.98 2.45

4 600 1116 1.13 2.83

5 600 1036 0.97 2.43

6 600 1174 1.24 3.10

7 600 1048 0.99 2.48

8 600 1058 1.01 2.53

9 600 1093 1.08 2.70

10 600 1110 1.12 2.80

Average 1088 1.07 2.68

Std Dev 42 0.08 0.21

%RSD 3.90% 7.90% 7.90%

ACorrection for water samples run on a mineral oil calibration is 2.5*measured result = corrected result.

Single Element On-line Measurements

LOD in hydrocarbon matrixppm in 300 s

– Sulfur 0.6 ppm– Chlorine 0.3 ppm– Phosp 1.2 ppm– Silicon 1.5 ppm– Vanadium 0.05ppm

• Low viscosity process streams and finished product blending

– Diesel– Gasoline

Challenge: On-Line Analysis in Crudes and High Viscosity Process Streams

Dynamic Window Module – Low Viscosity Streams

Transition DataXOS High to Low Cut response

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time

ppm

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10 sec180 secpressure

Film advance

Sulfur in Diesel

On-line Chlorine Detection in Crude and Water

• Corrosion Prevention / Mitigation

– LOD: 0.6 ppm @ 300s – aqueous matrix– LOD: 0.4 ppm @300s – hydrocarbon matrix

• Analysis Time: 10-900s – user adjustable

• Range: 0.4 ppm/wt – 3,000 ppm/wt

• Continuous Measurement

Dynamic Window Module – High Viscosity Streams

• Redesigned DWM:

– Sample Flow Characteristics Optimized for High Viscosity Streams

– Quarter inch sample lines

– Max. Viscosity 160 cSt

– Sample T > cloud point, max 275deg. F

– Filtration: 100um

Analyzer set-up

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Total Chlorine Co

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Date / Time

Cl Transitions & Repeatability 5 min integration time / 15 sec integration time

PPM‐ 15 sec PPM‐ 5 min

Chlorine in crude – (24 hr. run time)

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Total Chlorine Co

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Date / Time

Cl Repeatability  in Desalted Crude Over 72 Hours5 min integration time / 15 sec integration time

Avg = 5.1 ppmw ; Std Dev = 0.21 ppmw

PPM‐ 15 sec PPM‐5 min

Chlorine in Crude

Chlorine in Raw Crude – 12 hr run time

Online Chlorine Analysis in Desalted Crude 5 minute integration time over 10 hours

Chlorine in Raw Crude – 5 hr run time

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0.5 0.55 0.6 0.65 0.7 0.75 0.8

Gulf Coast Crude

FuelPress(psi)

PPMTrend

PPM

5 ppmCl addition (OrganicChloride)

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0.35 0.4 0.45 0.5 0.55 0.6

Gulf Coast Crude #2

PPMTrend

FuelPress(psi)

PPM

Chlorine in Raw Crude – 5 hr run time

Chlorine in Crude – 3 hr run time

Crude Sample Chloride Trend, ppmw

9:36:00 10:04:48 10:33:36 11:02:24 11:31:12 12:00:00 12:28:48 12:57:36 13:26:24time

Online Clora AnalyzerBenchtop Clora

STDEV=1.41

STDEV=0.64

Crude API = 25

Chlorine in Water – 6 hr run time

Aqueous Sample Chloride Trend, ppmw

7:40:48 8:52:48 10:04:48 11:16:48 12:28:48 13:40:48 14:52:48

time

Cl p

pmw

(tre

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Online Clora Analyzer TrendBenchtop Clora

STDEV=1.8 STDEV=1.8STDEV=3.0

Sulfur in Seawater

Clora 6020 AXP Analyzer for Zone 1

Designed for ATEX Zone 1Environment

ATEX Certificate:ITS 08ATEX15799X

Marking:Ɛx II 2 (1) G Ex d ia [ia] px IIC T4

Tamb = -20 ̊C to +40 ̊C

Sample Management System

Sample Inlet Valves (Multiple Inlets for Process, Validation or Multi-Stream)

Pressure Reducing Regulator to Limit Inlet Pressure (< 80 psig or 550 kPa)

Back Pressure Regulator to Regulate Flow; Maintain positive pressure on DWM

Return Valves- One for Analyzer Flow andOne for DWM Purge Flow

Armored Rotameter for Flow Measurement

Sample Conditioning System

Multi-Element Analysis

0.06

0.1 0.1 0.8 40 40 40

0.7 0.4 0.28 0.1 0.06 0.060.14 0.14 0.1

Sn Sb Te I46 47 48 49

LrActinides Cm Bk Cf Es

* 10 minute measurement time in hydrocarbon matrix

Fm MdTh Pa U Np Pu Am No

Yb LuLanthanides

90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ce Pr Nd Pm Sm Eu Gd Tb Dy

Mt

58 59 60 61 62 63 64 65 66 67 68 69 70 71

Ho Er Tm

7 Fr Ra Ac Rf Db Sg Bh Hs

Rn

87 88 89 104 105 106 107 108 109

0.1 0.1

Hg0.08 0.08 0.08 0.10.2

Tl Pb Bi Po AtW Re Os Ir Pt Au6 Cs Ba La Hf Ta1 0.2

Xe

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

Rh Pd Ag Cd In5 Rb Sr Y Zr Nb Mo Tc Ru50 51 52 53 5437 38 39 40 41 42 43 44 45

As Se BrCr Mn Fe Co Ni KrZnCu4 K Ca Sc Ti V Ga Ge1 0.7 0.5 0.7 0.4 0.7

28 29 30 31 32 33 34 35 3619 20 21 22 23 24 25 26 27

11 12 13 14 15 16 17 18

3 Na Mg Al Si P70 15

S Cl Ar9 6

2 Li Be B C N O F Ne

2/17/2012

I VIII1 2

Maxine Base Model1 H He

II III IV V VI VII

Limits of Detection (ppm)*

3 4 5 6 7 8 9 10

Multi Element On-line Detection

• HDXRF Platform – Multi Element AnalysisLOD in ppm – 600 s

– P 25– S 15– Cl 10– K 2– Ca 1.5– V 1.5– Mn 1.5– Fe 1.5– Co 1.0– Ni 0.5– Cu 0.3– Zn 0.3– Hg 0.15– As 0.15– Pb 0.15– Se 0.08

V Fe Ni As Hg Pb

1 4.76 5.05 2.20 0.52 0.52 0.62

2 4.84 5.28 2.25 0.50 0.53 0.66

3 4.89 5.23 2.15 0.53 0.50 0.65

4 4.80 5.18 2.20 0.55 0.49 0.47

5 4.76 5.01 2.17 0.50 0.51 0.63

6 4.75 5.20 2.20 0.59 0.58 0.55

7 5.00 5.04 2.20 0.51 0.46 0.60

8 5.13 5.16 2.20 0.56 0.50 0.59

9 4.57 5.27 2.20 0.56 0.46 0.62

10 4.78 5.20 2.15 0.56 0.47 0.51

average 4.83 5.16 2.19 0.54 0.50 0.59

st dev 0.15 0.10 0.03 0.03 0.04 0.06

%RSD 3.16% 1.87% 1.34% 5.66% 7.26% 10.48%

Maxine Repeatability (ppm) in Mineral Oil

Measurement time 600s

Elements (ppm) in Lube Oil by HD Maxine

Lube Oil #1P S Ca Mn Fe Zn

1 1012 7453 2841 0.65 0.50 1179

2 978 7530 2865 0.66 0.61 1166

3 970 7448 2859 0.67 0.54 1175

4 952 7529 2862 0.64 0.61 1177

5 1095 7482 2865 0.65 0.53 1174

avg 1001 7488 2858 0.65 0.56 1174

SD 56.75 39.65 9.84 0.01 0.05 5.06

Elements (ppm) in Lube Oil by HD Maxine (cont)

Lube Oil #2

P S K Ca Mn Fe Zn

1 492 10451 2731 420 0.22 0.09 271

2 441 10393 2726 410 0.23 0.32 269

3 522 10510 2771 445 0.33 0.27 271

4 451 10589 2759 413 0.33 0.24 271

5 401 10444 2736 422 0.19 0.26 274

avg 461 10477 2745 422 0.26 0.24 271

SD 46.96 74.69 19.57 13.65 0.06 0.09 1.80

Elemental Analysis of WTI Crude by HD Maxine

(ppm) S Cl Ca V Mn Fe Ni Cu Zn

1 3868 694 34.74 4.88 3.78 397 3.96 0.24 0.61

2 4592 508 26.96 5.30 3.10 333 3.31 0.21 0.54

3 3913 493 25.83 5.02 2.49 246 4.00 0.14 0.45

4 4124 734 36.24 5.18 5.09 611 3.80 0.25 0.65

average 4124 607 30.94 5.10 3.62 396 3.77 0.21 0.56

stdev 331.16 124.21 5.31 0.18 1.12 155.78 0.32 0.05 0.09

Conclusion

• On-line and bench-top single element analysis in crude and water is available for Cl, S, P, Si and V at sub ppm detection limits

• Multi element bench-top analysis of critical (transition) elements can be done by HD XRF

• Multi element on-line analysis in crude and process streams available shortly – hope to share field data shortly

Thank you

Berry Beumerbbeumer@xos.com