Don Mears

Oil & Gas Industry Consultant

NACE San Antonio, Texas

March 16, 2010 TEG 119X Meeting

Handheld X-ray Fluorescence for PMI &Residual Elements in HF Alkylation Units

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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

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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

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Thermo Fisher Scientific – An Important Mission

The world leader in serving science

Enabling our customers to make the world…

Healthier Cleaner Safer

5

Unmatched Global Capabilities

• 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

Leading provider of analytical instruments, equipment, reagents and consumables, software and services for research, analysis, discovery and diagnostics.

6

Thermo Fisher Scientific: Refining Solutions

SOLA FLARE

SOLA IIBlending

SOLA IIFCC Fractionator

SOLA II TRACE

SOLA II TRACESOLA II TRACE

SOLA IIBlending

SOLA II Lab

SOLA IIBlending

Tracker XP

Tracker XP

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Flo-Cal 6000

Sentinel PRO

Sentinel PRO

Sentinel PROPrima PRO

M-PULSe

M-PULSe

M-PULSe

Kril PRO

LevelProDensityPro

LevelProDensityPro

GC-ICP-MS, TS, XRF, ICP

XRF

XRF, ICP

XRF

GC

XRF

GC

GC

XRF

XRF, ICP

GC-ICP-MS, TS, XRF, ICP

LIMS

TVA1000B

GC-ICP-MS, TS, XRF, ICP

A Wide Range of Proven Products and Service Offerings to Help You Improve Product Quality, Process Efficiency, Safety and Environmental Monitoring.

A Wide Range of Proven Products and Service Offerings to Help You Improve Product Quality, Process Efficiency, Safety and Environmental Monitoring.

7

Our Refining Products and Service Offerings

• 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….

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Brief History of Portable XRF

• Earliest XRF alloy analyzers • Large and bulky, >20 Lbs

• Two-piece devices

• Battery lasted only few hours

• Single element-sequential

• Several minutes testing per sample

• Primarily high alloy

• Temperature and environmental conditions affect performance and reliability

First generation alloy analyzer, the TN 9200,

1960s

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• Since late 1960s, XRF has evolved through 7 generations; each generation has added new capabilities

• Smaller

• Faster

• Better performance

• Easier to use

• Today, nearly all alloys can be tested with these powerful tools

Evolution

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How XRF Works

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• 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

Latest Developments in Handheld XRF: GOLDD Technology

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Thermo Scientific Niton XRF Analyzers - Product Lineup

Niton® XL2

Value Leader

Niton XL3 GOLDD™

Performance Leader

Niton XL3

Feature Leader

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New GOLDD Technology

• Geometrically Optimized • 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

• 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

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X-Ray Tube and New Light Element Analysis in Air

• New miniaturized 50kV 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

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Complete System Optimization

• Synergy of complete system approach including

• SDD detector• 50kV tube• Optimized geometry, and…• On-the-fly parameter optimization …

• Produces overall 10X performance gain with ½ the tube power

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GOLDD: Quantum Advancements with XL3 Analyzers

• 2 W, 50 kV 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

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3-Sigma LODs: Ti, Fe, and Cu Alloys; All Units %wtTIME 60s per filter 60s per filter 60s per filter

Element Ti Base Wt. % Fe Base Wt. % Cu Base Wt. % Sb 0.005 0.006 0.008 Sn 0.005 0.008 0.015 Pd 0.005 0.006 0.010 Mo 0.002 0.002 0.002 Nb 0.002 0.002 0.003 Zr 0.002 0.002 0.003 Bi 0.002 0.002 0.003 Pb 0.002 0.009 0.003 Se 0.002 0.002 0.002 W 0.015 0.015 0.015 Zn 0.005 0.005 0.030 Cu 0.008 0.009 N/A Ni 0.012 0.020 0.011 Co 0.008 0.080 0.005 Fe 0.015 NA 0.007 Mn 0.017 0.020 0.007 Cr 0.015 0.003 0.005 V 0.060 0.003 0.003 Ti N/A 0.003 0.003 P 0.025 0.030 0.040 SSi

N/A0.070

0.0500.075

0.0600.080

Al 0.375 0.500 0.700

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Thermo Scientific Niton XRF Analyzers in Downstream Process

Handheld XRF Analyzers

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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

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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 McLennen (property protection and risk consultants)

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In response to increasing industry safety demands, Analytical Training Consultants has produced the API Certification PMI Training Course

Guidelines and Application Procedures for API-RP 578 Using XRF and OES Technologies 

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• 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• 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

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.

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• Priority for API 578 2nd Edition:

Inspection Program for HF ALKY Field Tests-API RP-571

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• Priority for API 578 2nd 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, C> 0.18% wt% and Cu + Ni + Cr, 0.15% wt % is optimum0.15% wt % is optimum. These values are critical as the type and concentrations to be measured will directly affect the analytical methods operations need to adopt.

•  API RP 571—Pages 12,38

Inspection Program for HF ALKY All Refineries-API RP-571

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Priority for API RP 578 2nd 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

Inspection Program for HF Alky Units – All Refineries

Cu Ni Cr RE Sum

0.050 0.078 0.084 0.212

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PMI Testing of CS Pipe Interactive-”Live Demonstration”

• ..\..\..\..\Desktop\NDTr 6.5.lnk

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

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Priority for API RP 578 2nd 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

Inspection Program for Low Si – All Refineries

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High Temperature Sulfidic Corrosion - API RP 939-C

Low Si-33%,PMI-18%,Specification Break-17%Low Si-33%,PMI-18%,Specification Break-17%

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High Temperature Sulfidic Corrosion-API RP-939-CField 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” 5CR pipe approximately 9” in length was found in the 9CR circuit. Thickness Thickness measurements of the 5CR showed severe thinning; approximate wall thickness remaining measurements of the 5CR showed severe thinning; approximate wall thickness remaining was .04”. was .04”.

• The 5CR section was cut out and a visual inspection confirmed that the 5CR section had heavy thinning while the 9CR side of the weld was still relatively full thickness. The line The line operates at about 710 degrees with Sulfur and Hydrogen in the stream.operates at about 710 degrees with Sulfur and Hydrogen in the stream.

5cr 0.04” Thin

5cr 0.04” Thin

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High Temperature Sulfidic Corrosion-API RP-939-C& HF RE Levels High in Warehouse Test

ConocoPhillips Borger, Texas Jim-SN-36965 Shots on 8-26-09Index Time Duration Line Component Pipe Alloy1 Cr Cu Ni Sum Si

37 8/26/2009 16:48 9.64 A17F Elbow 8" Fe/CS : 0.00 0.03 0.05 < LOD 0.08

38 8/26/2009 16:49 40.2 A17F Elbow 8" Iron/CS : 0.22 0.03 0.06 < LOD 0.09 0.24

39 8/26/2009 16:52 22.51 A17F Elbow 8" No Match : *4.06 0.05 0.16 < LOD 0.21 0.59

40 8/26/2009 16:59 40.9 A17F Flange 8" Iron/CS : 0.24 0.06 0.04 < LOD 0.1 0.22

41 8/26/2009 17:04 21.15 A17E Elbow 2" No Match : *4.12 0.06 < LOD < LOD 0.06 2.37

42 8/26/2009 17:05 23.63 A17E Elbow 2" Iron/CS : 0.24 0.04 < LOD < LOD 0.04 0.39

43 8/26/2009 17:10 14.4 A17G O-let 3/4" No Match : *4.27 0.17 0.11 < LOD 0.28 1.38

44 8/26/2009 17:11 26.92 A17G O-let 3/4" TS-O6 : *3.99 0.17 0.13 < LOD 0.3 1.31

45 8/26/2009 17:13 29.06 A17G O-let 3/4" No Match : *4.07 0.17 0.13 < LOD 0.3 0.25

46 8/26/2009 17:20 29.18 A17G 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 A17G O-let 3/4" Iron/CS : 0.30 0.04 0.09 < LOD 0.13 0.37

48 8/26/2009 17:27 60 A02F Flange 4" Iron/CS : *2.66 0.17 0.06 < LOD 0.23 0.09

49 8/26/2009 17:30 40.08 A02F Flange 8" Iron/CS : 1.42 0.11 0.24 < LOD 0.35 0.18

50 8/26/2009 17:33 36.8 A02F Elbow 6 Iron/CS : 0.21 0.05 < LOD < LOD 0.05 0.23

51 8/26/2009 17:38 28.44 A02F Elbow 6 Iron/CS : *2.30 0.19 0.06 < LOD 0.25 0.16

Flange with Low Si-0.09 %Flange with Low Si-0.09 %

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Summary of Don’s Test Shots- HF-RE’s

Both in Warehouse and Field Shots: 10 out of 33 Test Shots:

33%33%RE’s Higher than 0.20%

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Summery of Jim’s Test Shots in Both HF-RE’s & Crude Unit Low Si

• RE’s 33% 33% Higher than 0.2%-(16 out of 44 shots)

• Low Si – Only ~3% Only ~3% Lower than 0.10%- (1 out of 37 shots)

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

Index Date/Time SAMPLETest

Company/Method

Alloy NamesPart

DescriptionCr Ni Cu SUM Fe

5 11/19/2009 2:31 10198 ME Lab/OES Fe/CS : 0.00 Weld Pad 0.02 0.01 0.03 0.06 98.20

6 1/27/2010 14:39 10198 Niton-HHXRF Fe/CS : 0.00 Weld Pad 0.02 < LOD 0.03 0.05 98.62

7 1/27/2010 14:40 10198Stork Services

Lab-OES Fe/CS : 0.00 Weld Pad 0.03 0.01 0.04 0.08 NA

8 1/27/2010 14:40 Average Zn : 0.00 Avg of 5-7 0.02 0.01 0.03 0.06 98.559 11/19/2009 2:24 10197 ME Lab/OES Fe/CS : 0.00 Weld Pad 0.04 0.04 0.13 0.21 98.10

10 1/27/2010 14:43 10197 Niton-HHXRF Fe/CS : 0.00 Weld Pad 0.04 < LOD 0.15 0.19 98.42

11 1/27/2010 14:44 10197Stork Services

Lab-OES Fe/CS : 0.00 Weld Pad 0.05 0.04 0.15 0.24 NA12 1/27/2010 14:44 Average Zn : 0.00 Avg of 9-11 0.03 0.04 0.15 0.22 98.4213 11/18/2009 11:09 s-10178 ME Lab/OES Fe/CS : 0.01 Weld Pad 0.03 0.02 0.08 0.13 97.80

14 1/27/2010 14:47 s-10178 Niton-HHXRF Fe/CS : 0.00 Weld Pad 0.03 < LOD 0.10 0.13 98.21

15 1/27/2010 14:48 s-10178Stork Services

Lab-OES Fe/CS : 0.00 Weld Pad 0.04 0.02 0.10 0.16 NA16 1/27/2010 14:48 Average Zn : 0.00 Avg of 13-15 0.03 0.02 0.09 0.14 98.2417 11/18/2009 11:25 s-10179 ME Lab/OES Fe/CS : 0.00 Weld Pad 0.04 0.02 0.04 0.10 98.20

18 1/27/2010 14:51 s-10179 Niton-HHXRF Fe/CS : 0.00 Weld Pad 0.04 < LOD 0.05 0.09 98.48

19 1/27/2010 14:51 s-10179Stork Services

Lab-OES Fe/CS : 0.00 Weld Pad 0.04 0.02 0.05 0.11 NA20 1/27/2010 14:51 Average Zn : 0.00 Avg of 17-19 0.03 0.02 0.04 0.09 98.51

21 1/4/2007 0:00 s-3476-dTaper-Lok Lab/OES Fe/CS : 0.00 flange 0.08 0.02 0.11 0.21 NA

22 1/27/2010 14:57 s-3476-d Niton-HHXRF Fe/CS : 0.00 flange 0.09 < LOD 0.11 0.20 99.11

23 1/27/2010 14:57 s-3476-dStork Services

Lab-OES Fe/CS : 0.00 flange 0.08 0.04 0.11 0.23 NA24 1/27/2010 14:57 Average s-3476-d Zn : 0.00 Avg of 21-23 0.09 0.03 0.10 0.22 99.11

25 3/12/2007 0:00 t-2714-aTaper-Lok Lab/OES Fe/CS : 0.00 seal-ring 0.08 0.02 0.11 0.21 NA

26 1/27/2010 15:14 t-2714-a Niton-HHXRF Fe/CS : 0.00 seal-ring 0.08 < LOD 0.12 0.20 99.04

27 1/27/2010 15:15 t-2714-aStork Services

Lab-OES Fe/CS : 0.00 seal-ring 0.08 0.04 0.11 0.23 NA28 1/27/2010 15:15 Average t-2714-a Zn : 0.00 Avg of 25-27 0.08 0.03 0.12 0.23 99.07

6 Samples ConocoPhillips Borger, TX- RE's in HF Alky RE's 1-27-10 XRF vs. M. Certification

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Thermo Scientific Niton XRF Analyzer PMI Solutions

Extension Pole

Hotfoot

PMI-15 Certest

Button Reader

Buttons

Wireless Printer

Wireless Bar Code Reader

GPSCMB Manual

Button mounted on plate

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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

Niton XL3 without heat shield: 599 F/315o C

Niton XL3 with heat shield : 842 F/450o C

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PMI of Welds and Small Spot: WeldSpot™ and CamShot ™

• Electronic focusing of excitation beam collimation to isolate small parts and narrow weld beads

• On board CCD camera for verifying and photographing sample area tested

X-X-R

AY

RA

Y

DETDET

WeldSpot signal reduced to 3mm dia

SA`MPLESA`MPLE

DEDETT

X-RA

Y

X-RA

Y

Standard collimation 8 mm dia

SAMPLESAMPLE

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Niton Data Transfer (NDT©) Software

• 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

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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

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Oil & Gas PMI Market Overview

Asset RecoveryAsset Management

• What are the True PMI needs in your company ???

• Where PMI can and should be used for critical components?

42

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.API578.com