XRF Application Solutions for Petrochemistry

XRF Application Solutions for Petrochemistry

Bruker AXS Inc.

Madison, WI, USA

Welcome

Alexander SeyfarthProduct Manager Bruker AXS Inc.Madison, WI, USA

Luke PecardApplications ScientistBruker AXS Inc.Madison, WI, USA

Today’s Topics:Introduction to Elemental AnalysisX-ray Spectrometry Tools•

EDXRF vs WDXRF•

Resolution•

Sensitivity•

Precision

Petrochemical Applications•

ISO and ASTM Norms•

S in mineral oil•

S in diesel•

Additives in lubricants•

Fuel oils

Petrochemical Solutions: S2 RANGER with PETRO-QUANT

3

The World of the Petrochemical Analyst

Can I analyze an oil sample for more elements than I have standards for?

Quantitative and traceable results –are they nuts?

Hmm, measure “the usual,”plus Ni… and Cr…and Si and Na too…by tomorrow?

What’s in this lube oil, gear oil or grease stuff anyway?

Just do the 2622 and the ISO method…so we are sure…

Introduction

Analysis of elemental composition of petrochemicals:

Not only C, H, OBut also the inorganic components such as S, Ni, V, PImportant for price, quality, process control

How can these be analyzed?

Elemental Analysis Using Electromagnetic Radiation: Light

Absorption of light (infrared/visible/ultraviolet) •

AAS -

Atomic Absorption Spectrometry

Emission of light (infrared/visible/ultraviolet) •

ICP-OES -

Optical Emission Spectrometry

Transitions of electrons between outer shells of the atomEnergy of photons = energy of chemical bindingUsable spectra only for “free“ atoms or ionsSample has to be evaporated or atomized…> dissolved/liquid samplesComplex spectra> peak overlaps

Elemental Analysis Using Electromagnetic Radiation: X-rays

Emission of characteristic X-raysTransitions of electrons between inner shells of the atomEnergy of photons > energy of chemical bindingEnergy of characteristic X-rays independent of chemical bindingSolid and liquid samples can be measured directlyNon-destructive to the sampleSimple spectra: fewer overlaps

7

Please use your mouse to answer the question on your screen:

What elemental analysis methods are you currently using? (Check all that apply.)

XRF

ICP

AAS

IR

Karl Fisher

OES

None

Audience

Poll

X-ray Spectrometry (XRS, XRF)

Energy of X-ray photons•

Which element •

Qualitative analysis

Number of X-ray photons at a given energy •

What concentration •

Quantitative analysis

X-raytube

Sample

E, N

EmissionXrays proportional to concentrations

Tools: Energy-Dispersive XRF (EDX or EDXRF)

The detector is used to record both:•

the energy,

E,

and •

the number,

N, of X-ray photons

X-raytube

Sample

Detector

E, N

Tools: Wavelength-Dispersive XRF (WDX or WDXRF)

An analyzer crystal separates the various wavelengths, λ (energies)

The detector records only the number, N, of X-ray photons at a given wavelength (energy)

X-raytube

Sample

DetectorN

λ

EDXRF and WDXRF: What’s the Difference?

Resolution!

EDX

WDX

Tools: Primary Signal EDXRF

EDXRF Simultaneous Analysis of entire excited spectrumDetector limited by•

Resolution•

Total count rateRegion Of Interest (ROI), Intensity from peak area

Element: peak area is only small part of the usable spectra ~1000 cps

Tools: Primary Signal WDXRF

Sequential analysisposition by positionResolution limited only by crystal and collimator adjustable for applicationIntensity from peak height

Element: Detector can measure over 1 million counts per second

Tools: Sensitivity

Sensitivity

= number of detected X-ray photons (“counts“)per concentration (% or ppm) time ( s )

The sensitivity determines

the counting statistical error (precision)

the ability to measure low concentration (detection limit)

Tools: Precision and Counting Statistics

The precision

is limited by the counting statistical error:of the primary signal N:

Δ

c

/ c =

3 * SQRT(N) / N

Example:

Ν = 100

SQRT (N) = 10

3*SQRT(N) / N = 30 %Ν = 1000

SQRT (N) = 30

3*SQRT(N) / N = 10 %Ν = 10 000

SQRT (N) = 100

3*SQRT(N) / N = 3 %Ν = 100 000

SQRT (N) = 300

3*SQRT(N) / N = 1 %Ν = 1000 000

SQRT (N) = 1000

3*SQRT(N) / N = 0.3 %Ν = 10 000 000

SQRT (N) = 3000

3*SQRT(N) / N = 0.1 %

Tools: Conclusion

The analytical tool mustdetect

and distinguish

desired elements –

RESOLUTIONbe

sensitive

for required detection limit -

SENSITIVITYbe powerful

to achieve required precision -

POWERbe

suitable for desired sample throughput –

SPEED

Petrochemical Applications Which tool for the job?

As there are different “jobs,” you need different capabilities

A good way is to look at methods used for compliance check, international norms or similar

Generally speaking, what can you do with EDX?

Why Wait for Sample Prep!

Ease of Use and Versatility of

TXRF Analysis

Hagen Stosnach

Petrochemical Applications

Luke Pecard

Petrochemical Applications Norms

Analytical norms define and govern:scoperangeaccuracyprecision

for a given application and suitable tool.

The aim of norms is to make results comparable

and traceable

as a basis for regulatory compliance.Many norms define the type of “tool”, instrumentation needed!

Petrochemical Applications Norms for Petrochemistry

Various norms regulate the use of a specific analytical technique and tool for petrochemical applications.

WDXRF

is the most sensitive instrument of choice for the precise determination of sulfur in petrochemicals:

ASTM 2622ISO 20884ISO 14596

WDXRF gasolinepetroleum prod.fuels

ultra low detection limits (< 0.2 ppm)highest precision

ASTM 2622:

Sulfur in mineral oilLOD: 0.2 ppm (100s, 3s)Range: 0-1000 ppm 100 sec measurement

Petrochemical Applications ASTM 2622 for WDXRF

Issue 02/2008

GULF COAST 2008/9 workshop

Petrochemical Applications Norms for Petrochemistry

EDXRF performance has increased dramatically due to new detector developments expanding the analytical range.

Let’s see what EDXRF

can do for sulfur…ASTM 2622ISO 20884ISO 14596


ultra low detection limits < 0.2 ppmhighest precision

ASTM 4294-08a EDXRF Petrochemical products

3 ranges 0-1000 mg/kg , 0-0.1 wt % and 0-5 wt%

ISO 8754 EDXRF gasolinedieselmineral oil

< 5000 ppm

high range < 5 %

Petrochemical Applications ISO 8754: Sulfur in mineral oil

S in 0 -

5000 ppm range

ISO 8754Mineral oil

c [S%]:0 –

5000 ppm

LLD:3.1 ppm

Data from:S2 RANGER withPETRO-QUANT


ISO 8754 requires for acceptance the test of the accuracy and reproducibility, running a fresh sample several times on the system. The results must stay within defined limits:

ISO 8754

Test Samplec [S%] level:0.1000 %

21 repetitions:Mean value 0.103 % +/-

0.0005 %


0,04

0,06

0,08

0,1

0,12

0,14

1 6 11 16 21

Rep.

Co

nc.

S [

%]


The maximum deviation must not exceed 0.01 %. TEST PASSED!

ISO 875421 repetitions:Mean value 0.103 % +/-

0.0005 %

Max. dev.:+/-

0.001 %

ΔMax

ISO 8754:0.010 %


0.05

0.06

0.07

0.08

0.09

0.1

0.11

0.12

0.13

0.14

0.15

1 6 11 16 21

Co

nc.

S [

%]

Rep.

Petrochemical Applications Low sulfur by EDXRF

The S2 RANGER with PETRO-QUANT easily achieves the requirements for ISO 8754. Can it be used for lower concentration ranges?

ASTM 2622ISO 20884ISO 14596


ultra low detection limits < 0.2 ppbhighest precision


- < 5000 ppm- < 5 %

ASTM 4294-08a EDXRF Petrochemical products

3 ranges: 0-1000, 0-0.1 % and 0-4 %


-

1000 ppm


ISO 20847Mineral oil

c [S%]:0 –

1000 ppmDev.: 2.2 ppmLLD:2 ppm



ISO 20847 repeatability has to be tested for the low range with a 10 ppm sample. Are these measurements good enough for ISO? Can EDXRF really perform on 10 ppm?

ISO 20847

Test Samplec [S%] level:10 ppm

21 repetitions:Mean value 8.5 ppm +/-

0.9 ppm


0

10

20

30

40

50

1 6 11 16 21

Rep.

Co

nc.

S [

pp

m]


Required maximum deviation must not exceed 8 ppm. The S2 RANGER with PETRO-QUANT has aced the test!

ISO 875421 repetitions:Mean value 8.5 ppm +/-

0.9 ppm

Max. dev.:+/-

1.9 ppm

ΔMax

ISO 20847:8 ppm


0

5

10

15

20

25

1 6 11 16 21

Co

nc.

S [

pp

m]

Rep.

Petrochemical Applications ASTM 4294-08a: Sulfur in Diesel

Reps.

S m

g/kg

ASTM 4294 DIESEL32 reps:Mean value 13 ppm +/-

1 ppm

Max. dev.:+/-

2 ppm

Repeatability ASTM:< 3.9 ppm


Required maximum deviation must not exceed 3.9 ppm at 13 ppm level! (average of duplicates)

Petrochemical Applications Sulfur: Conclusion

Detection limits and repeatability benefit from:

•

Direct excitation•

High power

X-ray source•

Detector with high count rate

capability

The use of the XFlash®

SDD technology in combination with 50 W direct excitation offer the best performance for the ISO methods.

HIGH POWER + XFLASH®

Now let’s look at multielement analysis…

32

Please use your mouse to answer the question on your screen:

What are your applications? (Check all that apply.)

Sulfur

Chlorine

Lube Oil Elements

Fuel Oil Elements

Wear Metals

Other

Audience Poll

Petrochemical Applications Multielemental analysis

Several petrochemical applications, like fuel oils or additives in lubricants, require the simultaneous analysis of several elements.

Which EDXRF can fulfill specific requirements for these applications?

The analytical performance is determined by the spectral resolution

of the system:separation of neighboring lines correct identification of elements

as well as sensitivity!

Petrochemical Applications Additives in lubricants

Additives in lubricants:Mg, P, S, Cl, Ca, Cu, Zn, Ba

Clear separation of neighboring linesP Kβ

from S Kα1Cl Kα1 from Pd Lα1

(source)



Modern XFlash detectors provide the best

spectral resolution

and maintain

it even at high count rates.



The analytical performance for the determination of additives in

unused lubricants by the S2 RANGER with PETRO-QUANT is shown below:

•

Repeatability (21 repetitions)

LUBRICANT-8Mg(%) P(%) S(%) Cl(%) Ca(%) Cu(%) Zn(%) Ba(%)

Calibration Range [%] 0.2 0.15 0.755 0.15 0.505 0.05 0.15 0.2

Detection limits [ppm] 80 5.5 2.8 2.7 4.2 1.2 0.7 23

Precision Test

Average [%] 0.0831 0.1407 0.6514 0.1524 0.0706 0.0202 0.152 0.0784

Abs.Std.Dev. [%] 0.0054 0.001 0.0039 0.0011 0.0005 0.0002 0.002 0.0011

Petrochemical Applications More requirements

The analytical requirements and capabilities are fulfilled…

But in daily routine the application has to be run in a process environment.

This requires easy sample preparation, easy operation and a very

stable instrument!

What can be done to make the operation in daily routine easy?

Petrochemical Applications Fuel oil

One important analytical task in a refinery is the analysis of fuel oil for:

S in the % range V, Fe and Ni at trace level


First StepPreparation of the cup

1.

Put the foil on top of the cup.2.

Center the outer ring and press it down.

DoneHINT!

It’s easy to prepare a liquid cup for the measurement. The paper frame helps efficiently to avoid contamination.


Second StepFill the sample cup

1.

Place the cup on the balance.2.

Fill with approx 7 g of sample.

Done

Everyone can do this!no rocket scienceand no dilution/digestion


Third StepLoad the sample

1.

Place the cup in the chamber.

Done

That was easy!


Fourth StepSelect the application

1. Select the application2. Enter or read ID3. Press “START”

Done


Get Results

Why Wait for Sample Prep!

Ease of Use and Versatility of

TXRF Analysis

Hagen Stosnach

Petrochemical Solutions

Alexander Seyfarth

Petrochemical Solutions S2 RANGER with PETRO-QUANT

So we need:

ResolutionDirect Excitation Power Ease of use Solutions: Ready to Analyze

How about…


XFlash detector

50 W Power

TouchControlTM

All-in-one system

and…


PETRO-QUANT contains Predefined Methods

S according to ISO 8754S according to ISO 20847S according to ASTM 4294Fuel Oil (S, V, Fe, Ni)Additives in lubricant oil (Mg, P, S, Cl, Ca, Cu, Zn, Ba)P, Ca, S, Zn according to ASTM D6481

Sample PreparationDisposable sample cupsFilm BalanceManual


Sets for each norm and matrix, containingreference samples, quality check and drift correction samples

SulfurISO 8754

Gasoline

each set: Diesel

6 reference samples, blank, QCMineral oilHigh range

7 reference samples

ISO 20847

Gasoline

each set:Diesel

8 reference samples, blank, QCMineral oil

Additives

in lubricating oils

23 reference samples, QC

Fuel Oils

12 reference samples, QC


Sets for each norm and matrix, containingreference samples, quality check and drift correction samples:

Sulfur ASTM 4294 (each Gasoline, Mineral Oil, Diesel)0-0.1 %

LOW

7 reference samples, blank, QC0.1-1%

MEDIUM

4 reference samples, blank, QC0-5%

HIGH

5 reference samples, blank, QC

ASTM D6481 S, P, Ca, Zn

in unused lubricating oils

17 reference samples, QC, DC


Receive pre-calibrated unit

Performance check on-site

Ready to analyze

Any Questions?

Please type any questions you may have in the Q&A panel and then

click Submit.

Thank you for attending!

Please take a moment to complete the brief survey on your screen. Your feedback is very

important to us.

Copies of this presentation and related XRF resource materials will be emailed to you.

www.bruker-axs.com

Visit us at:SME & CME: Society for Mining, Metallurgy and Exploration

& National Western Mining Conference

Feb 23-25, Denver, CO

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Feb 16-18, San Francisco, CA

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Frontiers in XRF Seminar –

Northwest:Your free 1-day seminar on the theory, instrumentation,

preparation and application of ED and WDXRF

Apr 25, Seattle, WA

Gulf Coast Petro Seminar: Jun 25, The Woodlands, TX

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SHORT COURSES

http://www.pittcon.org/short/index.html

NEW COURSES!

138

Primer on XRF Spectrometry: Instrumentation Sunday, Mar 8, 2009 -

1/2 day course

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1/2 day course

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1/2 day course

http://www.pittcon.org/short/index.html

55

THEORY TRAINING

XRF Theory and Application training classes

ICDD X-Ray ClinicMay 18-22, 2009 http://www.icdd.com/education/xrf.htm

University of Western Ontario (UWO)One-week XRF Workshops on Sample Prep & Thin FilmJun 1-12, 2009http://www.uwo.ca/earth/news/xrfcourse/

http://www.icdd.com/education/xrf.htm

http://www.uwo.ca/earth/news/xrfcourse/

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XRF Application Solutions for Petrochemistry