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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
WDXRF gasolinepetroleum prod.fuels
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
Petrochemical Applications ISO 8754: Sulfur in mineral oil
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 %
Data from:S2 RANGER withPETRO-QUANT
0,04
0,06
0,08
0,1
0,12
0,14
1 6 11 16 21
Rep.
Co
nc.
S [
%]
Petrochemical Applications ISO 8754: Sulfur in mineral oil
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 %
Data from:S2 RANGER withPETRO-QUANT
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
WDXRF gasolinepetroleum prod.fuels
ultra low detection limits < 0.2 ppbhighest precision
ISO 8754 EDXRF gasolinedieselmineral oil
- < 5000 ppm- < 5 %
ASTM 4294-08a EDXRF Petrochemical products
3 ranges: 0-1000, 0-0.1 % and 0-4 %
ISO 20847 EDXRF gasolinedieselmineral oil
-
1000 ppm
Petrochemical Applications ISO 20847: Sulfur in mineral oil
ISO 20847Mineral oil
c [S%]:0 –
1000 ppmDev.: 2.2 ppmLLD:2 ppm
Data from:S2 RANGER withPETRO-QUANT
Petrochemical Applications ISO 20847: Sulfur in mineral oil
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
Data from:S2 RANGER withPETRO-QUANT
0
10
20
30
40
50
1 6 11 16 21
Rep.
Co
nc.
S [
pp
m]
Petrochemical Applications ISO 20847: Sulfur in mineral oil
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
Data from:S2 RANGER withPETRO-QUANT
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
Data from:S2 RANGER withPETRO-QUANT
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)
Data from:S2 RANGER withPETRO-QUANT
Petrochemical Applications Additives in lubricants
Modern XFlash detectors provide the best
spectral resolution
and maintain
it even at high count rates.
Data from:S2 RANGER withPETRO-QUANT
Petrochemical Applications Additives in lubricants
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
Petrochemical Applications Fuel oil
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.
Petrochemical Applications Fuel oil
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
Petrochemical Applications Fuel oil
Third StepLoad the sample
1.
Place the cup in the chamber.
Done
That was easy!
Petrochemical Applications Fuel oil
Fourth StepSelect the application
1. Select the application2. Enter or read ID3. Press “START”
Done
Petrochemical Applications Fuel oil
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…
Petrochemical Solutions S2 RANGER with PETRO-QUANT
XFlash detector
50 W Power
TouchControlTM
All-in-one system
and…
Petrochemical Solutions S2 RANGER with PETRO-QUANT
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
Petrochemical Solutions S2 RANGER with PETRO-QUANT
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
Petrochemical Solutions S2 RANGER with PETRO-QUANT
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
Petrochemical Solutions S2 RANGER with PETRO-QUANT
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.
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Apr 25, Seattle, WA
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