Handheld X-ray Fluorescence for PMI Residual Elements

Handheld X-ray Fluorescence for PMI & Residual Elements in HF Alkylation Units Don Mears Oil & Gas Industry Consultant NACE San Antonio, Texas March 16, 2010 TEG 119 X Meeting

Presenter – Don Mears • President of Analytical Training Consultants (ATC) • 30+ years of Oil and 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 2

Agenda • • • Thermo Fisher Scientific – The World Leader in Serving Science Speaker Profile Thermo Scientific Niton XRF Analyzer Evolution & History How X-Ray Fluorescence (XRF) works XRF Analysis Capabilities in Oil & Gas Industry XRF X-Ray Tube and Detector Improvements Why PMI According to API RP 578 HF Alkylation Field Test report on Residual Elements ( Cr, Ni, Cu ) Low Si ( < 0. 10% ) Field Test in Carbon Steel Components in Refinery Units • PMI Solutions • Questions Special Thanks to the Borger, Texas Refinery 3

Thermo Fisher Scientific – An Important Mission Enabling our customers to make the world… Healthier Cleaner Safer The world leader in serving science 4

Unmatched Global Capabilities Leading provider of analytical instruments, equipment, reagents and consumables, software and services for research, analysis, discovery and diagnostics. • 2009 revenues: More than $10 billion • 35, 000 employees in 40 countries • Serving 350, 000 customers in 150 countries Serving science in new and compelling ways 5

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Our Refining Products and Service Offerings • • • • 7 Sulfur online process analyzer Toxic vapor analyzer Low-maintenance ultrasonic flow meter Non-contacting coker interface sensor Crude and tower level sensors Lab Information Management Systems (LIMS) Sulfur speciation and total sulfur in fuels Ultra-fast GC for simulated oil distillation X-ray fluorescence (XRF) analyzer for sulfur in fuels Inductively coupled plasma (ICP) analyzer for elemental analysis in biofuels Handheld XRF analyzer for positive material identification (PMI) World-class service offerings Many more….

Brief History of Portable XRF • Earliest XRF alloy analyzers • • 9 Large and bulky, >20 Lbs Two-piece devices Battery lasted only few hours Single element-sequential First generation alloy analyzer, the TN 9200, Several minutes testing per sample 1960 s Primarily high alloy Temperature and environmental conditions affect performance and reliability

Evolution • Since late 1960 s, XRF has evolved through 7 generations; each generation has added new capabilities • • Smaller Faster Better performance Easier to use • Today, nearly alloys can be tested with these powerful tools 10

How XRF Works 11

Latest Developments in Handheld XRF: GOLDD Technology • One-piece, 3 to 4 lbs • Handheld, miniaturized • 25 element simultaneous • 30 elements total • • Variable excitation conditions Hundreds of alloys Ultra high speed Lab-quality performance • Field hardened Handheld Thermo Scientific Niton XRF analyzer being used to inspect piping system 12

Thermo Scientific Niton XRF Analyzers - Product Lineup Niton® XL 2 Value Leader Niton XL 3 GOLDD™ Performance Leader Niton XL 3 Feature Leader 13

New GOLDD Technology • Geometrically Optimized • Improved system geometry to reduce the path length from sample to detector • Allows ~2 X more x-rays to reach the detector with ½ the power • Large-area Drift Detector • 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 14

X-Ray Tube and New Light Element Analysis in Air • New miniaturized 50 k. V x-ray tube, Silver or Gold anode, excitation source that provides higher sensitivity for heavy elements • New ability to test for Mg, Al, Si, P & S without He purge or vacuum 15

Complete System Optimization • Synergy of complete system approach including • • SDD detector 50 k. V tube Optimized geometry, and… On-the-fly parameter optimization … • Produces overall 10 X performance gain with ½ the tube power 16

GOLDD: Quantum Advancements with XL 3 Analyzers • 2 W, 50 k. V X-ray tube, SDD GOLDD • Improved sensitivity, speed, accuracy, precision, stability and confidence • New ability to analyze residual elements • New ability to determine light elements Significantly lower LOD’s for critical elements 17

3 -Sigma LODs: Ti, Fe, and Cu Alloys; All Units %wt TIME Element Sb Sn Pd Mo Nb Zr Bi Pb Se W Zn Cu Ni Co Fe Mn Cr V Ti P S Si Al 18 60 s per filter Ti Base Wt. % 0. 005 0. 002 0. 015 0. 008 0. 012 0. 008 0. 015 0. 017 0. 015 0. 060 N/A 0. 025 N/A 0. 070 0. 375 60 s per filter Fe Base Wt. % 0. 006 0. 008 0. 006 0. 002 0. 009 0. 002 0. 015 0. 009 0. 020 0. 080 NA 0. 020 0. 003 0. 030 0. 050 0. 075 0. 500 60 s per filter Cu Base Wt. % 0. 008 0. 015 0. 010 0. 002 0. 003 0. 002 0. 015 0. 030 N/A 0. 011 0. 005 0. 007 0. 005 0. 003 0. 040 0. 060 0. 080 0. 700

Thermo Scientific Niton XRF Analyzers in Downstream Process Handheld XRF Analyzers 19

Handheld XRF PMI Applications • Existing piping systems • Pipe fittings, valves & flanges • Welds & welding consumables • Longitudinal pipe and weld fittings • Weld overlays or cladding • Low Si in H & S Service • Components from distributors • Forgings • Instruments • Bolting • Expansion joints and bellows • HF Alky- Residual Elements 20

Refining Piping Systems Failure: The Challenge • “ 41% of the 170 largest losses in the hydro-carbon process industry resulted from failures of piping systems…” Source: Marsh and Mc. Lennen (property protection and risk consultants) 21

Guidelines and Application Procedures for API-RP 578 Using XRF and OES Technologies In response to increasing industry safety demands, Analytical Training Consultants has produced the API Certification PMI Training Course 22

Introduction In today's risk-based QC environment, the need for positive material identification (PMI) has grown dramatically in refinery and petrochemical plant operations, requiring 100% alloy material verification for designated critical components. • Purpose of the Course • To certify and re-certify (every 3 years) API 570 inspectors and designated key personnel in understanding and applying API RP 578 in the proper Use and Application of procedures for utilizing XRF and OES technologies for PMI. • 2 one-day sessions • • 23 Classroom instruction on API RP 578 guidelines Hands-on PMI field testing procedures. Understanding of API RP 578 Guidelines Application of proper XRF and OES PMI testing procedures

Inspection Program for HF ALKY Field Tests-API RP-571 • Priority for API 578 2 nd Edition: 24

Inspection Program for HF ALKY All Refineries-API RP-571 • Priority for API 578 2 nd Edition: • Residual Elements in Carbon Steels in Hydrofluoric Acid Alkylation Units: Note: Carbon Steels in HF Acid service have been reported to suffer increased corrosion rates based on the Residual Elements (RE) in steels. • In general, it has been reported that steels with a high RE content are likely to suffer enhanced corrosion attack. Operators should review the potential impact of this in HF service. • A guideline is that for base metal of C> 0. 18% wt% and Cu + Ni + Cr, 0. 15% wt % is optimum. These values are critical as the type and optimum concentrations to be measured will directly affect the analytical methods operations need to adopt. • API RP 571—Pages 12, 38 25

Inspection Program for HF Alky Units – All Refineries Priority for API RP 578 2 nd Edition • Residual Elements in Carbon Steels in Hydrofluoric Acid Alkylation Units • Steels with a high RE content are likely to suffer enhanced corrosion attack. • Optimal RE content guidelines: C> 0. 18 wt% And Cu + Ni + Cr < 0. 20 wt % • Sample preparation is very important: • Al Oxide disc used with a right angle grinder (<10 sec) • approx. 0. 004” removed Cu Cr RE Sum 0. 050 26 Ni 0. 078 0. 084 0. 212

PMI Testing of CS Pipe Interactive-”Live Demonstration” • . . DesktopNDTr 6. 5. lnk 27

Conoco Phillips Crude Unit Test Shot Results Low Si as Discussed in API RP-939 C 28

Inspection Program for Low Si – All Refineries Priority for API RP 578 2 nd Edition • Process Units Susceptible to Sulfidation: • Carbon Steels with low silicon (0. 10%) content can corrode at an accelerated rate • Assets at risk from this type of degradation should apply PMI control to determine Silicon levels. • See API 571 and API RP 939 -C 29

High Temperature Sulfidic Corrosion - API RP 939 -C Low Si-33%, PMI-18%, Specification Break-17% 30

High Temperature Sulfidic Corrosion-API RP-939 -C Field Test • Distillate HDS Unit • From Distillate Furnace to Distillate Reactor • The 9 chrome piping circuit consists of approximately 400’ of 6”, 8” and 10” piping that runs from the Furnace to the Reactor. • In 2003 during a PMI and UT inspection of all chrome circuits in the unit a small section of 10” 5 CR pipe approximately 9” in length was found in the 9 CR circuit. Thickness measurements of the 5 CR showed severe thinning; approximate wall thickness remaining was. 04”. • The 5 CR section was cut out and a visual inspection confirmed that the 5 CR section had heavy thinning while the 9 CR side of the weld was still relatively full thickness. The line operates at about 710 degrees with Sulfur and Hydrogen in the stream. Thin ” 0. 04 5 cr 31

High Temperature Sulfidic Corrosion-API RP-939 -C & HF RE Levels High in Warehouse Test Conoco. Phillips Borger, Texas Jim-SN-36965 Shots on 8 -26 -09 Index Time Duration Line Component Pipe Alloy 1 Cr Cu Ni Sum Si 37 9. 64 A 17 F Elbow 8" Fe/CS : 0. 00 0. 03 0. 05 < LOD 0. 08 38 8/26/2009 16: 49 40. 2 A 17 F Elbow 8" Iron/CS : 0. 22 0. 03 0. 06 < LOD 0. 09 0. 24 39 8/26/2009 16: 52 22. 51 A 17 F Elbow 8" No Match : *4. 06 0. 05 0. 16 < LOD 0. 21 0. 59 40 8/26/2009 16: 59 40. 9 A 17 F Flange 8" Iron/CS : 0. 24 0. 06 0. 04 < LOD 0. 1 0. 22 41 8/26/2009 17: 04 21. 15 A 17 E Elbow 2" No Match : *4. 12 0. 06 < LOD 0. 06 2. 37 42 8/26/2009 17: 05 23. 63 A 17 E Elbow 2" Iron/CS : 0. 24 0. 04 < LOD 0. 04 0. 39 43 8/26/2009 17: 10 14. 4 A 17 G O-let 3/4" No Match : *4. 27 0. 11 < LOD 0. 28 1. 38 44 8/26/2009 17: 11 26. 92 A 17 G O-let 3/4" TS-O 6 : *3. 99 0. 17 0. 13 < LOD 0. 3 1. 31 45 8/26/2009 17: 13 29. 06 A 17 G O-let 3/4" No Match : *4. 07 0. 13 < LOD 0. 3 0. 25 46 8/26/2009 17: 20 29. 18 A 17 G O-let 3/4" No Match : *5. 22 0. 05 0. 1 0. 09 0. 24 0. 82 47 8/26/2009 17: 21 15. 97 A 17 G O-let 3/4" Iron/CS : 0. 30 0. 04 0. 09 < LOD 0. 13 0. 37 48 8/26/2009 17: 27 60 A 02 F Flange 4" Iron/CS : *2. 66 8/26/2009 17: 30 40. 08 A 02 F Flange 8" 0. 23 0. 17 0. 06 < LOD Flange with Low Si-0. 09 % 0. 09 49 Iron/CS : 1. 42 0. 11 0. 24 < LOD 0. 35 0. 18 50 8/26/2009 17: 33 36. 8 A 02 F Elbow 6 Iron/CS : 0. 21 0. 05 < LOD 0. 05 0. 23 51 32 8/26/2009 16: 48 8/26/2009 17: 38 28. 44 A 02 F Elbow 6 Iron/CS : *2. 30 0. 19 0. 06 < LOD 0. 25 0. 16

Summary of Don’s Test Shots- HF-RE’s Both in Warehouse and Field Shots: 10 out of 33 Test Shots: 33% RE’s Higher than 0. 20% 33 XL 3 -S #36909 Residuals OK Residuals High

Summery of Jim’s Test Shots in Both HF-RE’s & Crude Unit Low Si • RE’s 33% Higher than 0. 2% -(16 out of 44 shots) XL 3 -S #36965 • Low Si – Only ~3% Lower than 0. 10%- (1 out of 37 shots) XL 3 -S #36965 Si OK Si Low 34

Field Test with Six Samples Compared to Material Certifications from Independent Laboratory 35

Thermo Scientific Niton XRF Analyzer PMI Solutions Button Reader Hotfoot Extension Pole Buttons Button mounted on plate PMI-15 Certest Wireless Bar Code Reader CMB Manual 36 Wireless Printer GPS

Field Use for Hot Pipes and Difficult Access Extension Pole /Tri-Pod • Variable pole length • Dual electronic triggers • Clip on tri-pod adapter for hands-free analysis of samples on ground or table 37 Niton XL 3 without heat shield: 599 F/315 o C Niton XL 3 with heat shield : 842 F/450 o C

PMI of Welds and Small Spot: Weld. Spot™ and Cam. Shot ™ • Electronic focusing of excitation beam collimation to isolate small parts and narrow weld beads SA`MPLE SAMPLE DET Standard collimation 8 mm dia 38 XX- Y RA Y Y RA RA XX- DET Weld. Spot signal reduced to 3 mm dia • On board CCD camera for verifying and photographing sample area tested

Niton Data Transfer (NDT©) Software • • • 39 Remote viewing and real time download Secure tamper-proof NDT file download Only “Secure” Data Files in Industry Auto-exec to Excel Lab quality data management New software uploads New calibration uploads Empirical calibration capability Multiple user passwords and permissions Multiple custom data fields Powerful FP Quantitative Software

Summary and Conclusions • The new Thermo Scientific Niton GOLDD XRF analyzers provide: • • • Near-lab quality performance in a 3 -4 lb field-hardened package Faster testing Light element detection More sensitive trace and tramp element determination Ability to quantify fractional percent alloying elements • Ultimate benefit is the most rapid and accurate alloy verification • The new generation of handheld XRF alloy analyzers has brought the power and reach of lab XRF spectroscopy to harsh field environments 40

Oil & Gas PMI Market Overview • What are the True PMI needs in your company ? ? ? • Where PMI can and should be used for critical components? Asset Recovery Asset Management 41

Questions • Don Mears, Oil & Gas Consultant • Thermo Scientific Niton Analyzers & Analytical Training Consultants, (ATC) 1719 Burning Tree Kingwood, Texas 77339 Cell Phone: 281 -684 -8881 ATC Office: 281 -358 -1177 Fax: 281 -358 -2177 www. api 578. com 42