Understanding the Advantages and Limitations of a Comprehensive API-RP 578 Positive Material Identification (PMI) Program Don Mears Oil & Gas Industry Consultant & API/TPCP Certified Training Provider • Downstream Refining Sector • Downstream Petro Chemical Sector • Upstream Offshore & Transportation Sector 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 1
Presenter – Don Me ars API/TPCP -0118 • President of Analytical Training Consultants (ATC) • 30+ years of Oil & Gas industry experience • Heavy involvement in API work groups • Author of the API RP 578 PMI Certification Course • Certified API Training Provider • Oil & Gas Industry Consultant for Thermo Fisher Scientific 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 2
Presentation Outline • Technologies XRF & OES for Refining Solutions • PMI Field Testing Methods (XRF) Old & New Technologies • New Construction – QA/MVP Programs Renewed & Required • Existing Piping Systems (Retroactive PMI ) Programs & Applications • Control of Incoming Materials & Warehouse • Elements of Maintenance Systems for PMI • Recording & Reporting PMI Test Results • Why the USA Implemented OSHA NEP & API 578 PMI • Why the USA implemented OSHA CHEM/NEP & BSEE, PHMSA/NTSB • Conclusion (Questions & Answers) 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 3
Understanding the Advantages and Limitations of a Comprehensive API-RP 578 Positive Material Identification (PMI) Program Downstream Refining Sector Don Mears Oil & Gas Industry Consultant and API/TPCP Certified Training Provider 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 4
PMI Field Testing Methods ( XRF or OES ) Technologies: Two Primary Technologies for Portable Elemental Analysis: • X-ray Fluorescence Spectroscopy (XRF) – Technique of exciting and ejecting atoms’ inner shell electrons with x-ray radiation and analyzing the fluorescent x-rays emitted when the atoms return to a stable state. X-ray energies emitted correspond to the individual elements, while the intensity is a function of quantity • Optical Emission Spectroscopy (OES) – Technique of vaporizing sample surface and analyzing the emitted light spectra. The wavelength of the light corresponds to the elements present, while the intensity is a function of quantity of that element. 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 5
X-Ray Fluorescence (XRF) – A Simple Overview K α x-ray - - - - L α x-ray 1.25% Cr 0.5% Mo 1. X-ray ejects K-shell electron ……… - - - - - K L M-shells - Alloy 2. L-shell electron moves to replace Grade P11 - - ejected K-shell electron, M-shell - electron replaces L-shell, etc… 4. The x-ray energies and fluxes are - interpreted by the analyzer into the corresponding elements, 3. Reduced energy state is given off as a “K α ”, concentrations, and resultant alloy “L α ”, etc. x-rays, the energies of which are read grade by the detector 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 6
PMI Field Testing Methods: How OES Works Emission-Radiated in form of Light!! Excitation- Outer Shell 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 7
PMI Field Testing Methods ( XRF or OES ) Technologies: Pros: Handheld X-ray Fluorescence Spectroscopy • Accurate • Portable – the handheld XRF analyzer weighs approximately 1.3 kg (3 lbs.) and is transported in a belt holster at the user’s side • Reduced sample preparation • Completely nondestructive • Simplicity – XRF technology is much more user-friendly, allowing relatively unskilled operators to participate in the inspection process Cons: • Can measure elements only down to Mg on the periodic table (cannot measure carbon) • Stricter regulation and licensing requirements 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 8
PMI Field Testing Methods ( XRF or OES ) Technologies: Pros: Transportable Optical Emission Spectroscopy • Accurate • Gives visible clue that material has been tested (burn mark) • Can measure more light elements than XRF (such as C) Cons: • Difficulty of transport – OES instruments tend to be large and unwieldy, posing access problems in hard- to-reach locations • Sample preparation – the OES testing requires careful preparation of the sample by grinding off the oxide layer and eliminating any pitting or inclusions in the test area prior to analysis • Damage to the sample – the OES test burns and vaporizes a small amount of the sample material, resulting in a heat-affected zone that in some cases must be re-heat treated • User expertise – OES instrumentation requires a high level of user sophistication to maintain calibration, recognize data anomalies, proper surface preparation, etc. 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 9
XRF Evolution in Performance Since late 1960s, XRF has evolved through 7 generations; each generation has • added new measurement capabilities as indicated by the 3 groups below – Smaller, faster, better performance, and easier to use • Today, nearly all alloys can be tested with these powerful tools. This addresses PMI concerns in the upstream/downstream & transportation Sectors Measures (up to 30 ) Measured (1) element at a Measured (16 to18 ) elements at a time to: time to: elements at a time to: >/= 0.003% chemistry >= 1.00% chemistry in >= 0.10% chemistry in </= 3 to 12 seconds >/= 1 to 2 minutes </= 30 to 60 seconds 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 10
New GOLDD Detector Technology G eometrically O ptimized • – Improved system geometry to reduce the path length from sample to detector – Allows ~2X more x-rays to reach the detector with ½ the power • L arge-area D rift D etector – Light element detection in air (Mg, Al, Si, P, S) – Increased sensitivity for tramp and trace elements in alloys – Doubling of the speed of alloy and metals testing – Enhanced performance for difficult (nearly twin) alloy separations 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 11
How Filters in XRF Automatically Work the Element Range in the Periodic Table “ Light Filter “engaged “ Low Filter “engaged Automatically for : Automatically for : S, P, Si, Al, Mg Ti ,V , Cr “ Main Filter“ engaged Automatically for : All Elements 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 12
XL3t GOLDD + Limits of Detection in PPM (mg/Kg) Time 60s per filter w/out He AI-based Ti-based Fe-based Cu-based Matrix Alloys Alloys Alloys Alloys Sb 20 35 50 70 Sn 15 30 50 70 Pd 15 20 40 55 Ru 15 15 20 20 Mo N/A 15 15 15 Nb N/A 15 15 15 Zr N/A 15 15 15 Bi 15 15 15 30 Pb 15 15 40 35 Se N/A 15 20 20 W 20 75 120 100 Zn 15 20 40 220 Cu 25 40 70 NA Ni 30 75 100 110 Co 30 70 500 110 Fe 50 175 N/A 175 Mn 70 160 160 175 Cr 50 160 35 65 V 20 550 25 40 Ti 20 N/A 30 30 S N/A* N/A N/A* 90 60* N/A NI'A* P N/A* N/A N/A* 110 65* 110 75* Si 400 320* 900 350* 350 175* 350 200'" AI N/A N/A* 4750 1300* 2200 650* 2500 625* Mg 4000 1500" N/A N/A* N/A N/A* N/A N/A* 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 13
New Construction: PMI Cycle Overview – Renewed & Now Required Emphasis Residual elements found in carbon steel (i.e., Cr, Cu, NI, Mo, V, Ti) MTRs normally do not test for these elements and should not be Asset Recovery in the carbon steel ! Asset Management But they are there!!! 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 14
New Construction: Do Not Rely Solely on Supplier MTRs • Experience has shown that you cannot rely on material test reports (MTRs) alone; there can be significant errors. • One customer site survey revealed that as much as 40% of MTRs did not match actual chemistry. They also tend to lose the reports. They get separated from the existing material. API RP-578-(7.2)-States; “MTR’s Should NOT be considered a substitute for • PMI testing” “Trust but verify” – This is what PMI does !!! 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 15
Existing Piping Systems (Retroactive PMI ) Programs: API RP 578 Material Verification Program for Existing Piping Systems • Responsibilities – The owner/user is responsible for determining if a retroactive material verification program is appropriate for each existing piping system, for prioritizing the piping systems to receive retroactive PMI testing, and for determining the extent of PMI testing required. • Prioritizing piping systems for retroactive PMI testing – If owner/user elects to prioritize piping systems for the material verification program or needs to determine whether PMI testing is needed at all, the owner/user should consider the following: • Likelihood of a material mix-up during previous project and maintenance activities. • Consequences of a failure. Some factors to be considered include: flammability, fire potential, toxicity, proximity to other equipment or community, temperature, pressure, mode of failure, and size of release. • Reason for alloy specification (i.e., corrosion resistance or product purity). • Historical data relating to inadvertent material substitution. This may be related to previous experience with material nonconformities in the process unit or within the operating plant. 8/8/2013 API Beijing-Don Mears-ATC-9/13/213 16
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