PMI in the Petrochemical Plant and Refinery

2009: Niton XL3t GOLDD 7th Generation

Operation of HHXRF

Excitation Source
Atomic Level Process of Fluorescence Production

The Complete System

Primary XRay Beam

Excitation Source

Spectra to P
4

Alloy Sample

Pulses From Detector Detector

3.5

2.5

1.5

DSP

0.5

0 10 10.5 11 11.5 12 12.5 13 13.5 14 14.5 15

Fluorescent X-Rays

Microprocessor (P)

Display

Data Storage

How it works 1
Each individual element produces its own set of characteristic x-rays; the basis for qualitative analysis By counting the number of characteristic x-rays of a given element we can determine its concentration; the basis for quantitative analysis

Results display

Element Range for Alloy Measurement

Not possible with portable XRF, use OES May require GOLDD technology Ideal for routine HHXRF Measured with portable XRF

HHXRF Selected Alloying Element Channels

25/30 elements analyzed in alloys
Note: Analytical capability is not limited to the elements shown; the full analytical range extends from Mg to U

427 alloys in grade library

9

PMI Overview

10

PMI is Mission Critical for Verification

Power Plants

Fast ID With FP Analysis

Automated

Sample Data entry

Refineries Small size Light weight Ergonomic Design

Simple

Producers Fabricators

Point & Shoot Operation

Test 800 F

Test tight

Aerospace

Vibrating Pipes

Corners & & fillet welds

11

Consequences of Using Incorrect Materials Can Range From

To

12

Why do PMI?

Source: Marsh and McLennen (property protection and risk consultants)

13

PMI can Prevent the Largest Losses

41% of the 170 largest losses in the hydrocarbon process industry resulted from failures of piping systems
Second International Symposium on the Mechanical Integrity of Process Piping January 1996, Houston, TX, USA

14

PMI Cycle Overview

15

PMI in Petrochem Industry

analytically speaking

We are facing a seemingly impossible task: analyzing with sufficient accuracy and precision to be able to distinguish one alloy from many thousands of others
(estmates are up to 50,000 alloys grades in use today)
Percent concentration of element

100 90 80 70 60 50 40 30 20 10
Ni

0
NICKEL 200 Monel 500 Mo Inco 625 Mn Inco 750 Inco 825 Cu Haynes 230 RA 333 W Hastelloy B-2 Hastelloy C-276 Co Hastelloy X Nb Stellite 6B Stellite 188 Ti Al

Cr Fe

16

Fortunately, Petrochem Alloys Are Few

17

PMI in Petrochem Industry

analytically speakingcont

We are facing a second seemingly impossible task: Correcting for an awesome variety of samples forms, sizes and shapes

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FP with Normalization
Automatically normalizes for size, shape, curvature and distance (up to ~6 mm)
Mathematical iteration continues until all measured elements add to ~100%

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PMI Tool in Petrochem Industry

Automatically corrects for an intimidating set of environmental and sampling conditions Ambient heat Ambient cold Rain Hot samples Vibrating samples High noise Small samples
Hotfoot Adapter
Temp up to 850oF / 440oC
extension handle keeps hand well away from heat volcano suit protects plastic case Velcro flip cover for ease of viewing

20

Remote Display Option

Wireless data transfer up to 300 ft Remote control of analyzer

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PMI Testing of Welds with WeldSpotTM and CamShotTM

22

Thermo Scientific Niton XL3t XRF Analyzer with GOLDD Technology

Geometrically Optimized Large Area Drift Detector

GOLDD Technology
Thermo Scientific presents the Niton XL3t XRF Analyzer with GOLDD Technology This new analyzer delivers
Light element detection (Mg, Al, Si, P, S) without helium or vacuum purging The lowest limits of detection and the fastest analysis available True lab-quality performance in a handheld instrument
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GOLDD SDD (Silicon Drift Detector)

Similar to Si PIN, but unique electrode array that guides electrons to very low capacitance anode This means that the detector
Has a short rise time, achieving high count rates with minimal pile up Provides better resolution Has lower noise

C2 GND C1 driftfield -V GOLDD with external Field Effect Transistor (FET) Shorter processing, lower cost No partial charge collection under FET No effects on FET from SDD Up to 450,000 counts per second input Anode

UBACK

Homogeneous thin entrance window

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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 LODs for critical elements

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Optimized Excitation
To take advantage of a detector with a higher count rate, more fluorescent x-rays should be produced by the sample That is achieved using a higher voltage x-ray tube
Niton XL3t: 50kV Typical older technology: 40 or 45kV Excitation intensity is 2x more sensitive to increase in high voltage compared to other factors (current, Z of anode material). Increasing the excitation voltage by 25% has a 50% greater effect than increasing the tube current by a similar amount

27

Optimized Geometry
To take advantage of a detector with a higher count rate, you want to collect more of the fluorescent x-rays from the sample For the same size detector, the closer it is to the sample, the more fluorescent x-rays it will detect The Niton XL3t was designed with this optimized geometry

28

Large Area Drift Detector

A large detector will collect more fluorescent x-rays than a small detector The Niton XL3t employs a unique 25 mm2 detector, instead of an off-the-shelf 10 mm2 detector Therefore, the Niton XL3t collects 2.5 times more signal

29

The GOLDD Advantage

This all adds up to the GOLDD Advantage 10X better than conventional Si PIN detectors 2.5X better than analyzers with off-the-shelf SDD detectors

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Twin Alloys and Solutions

Guideline to PMI Alloys that Mix (or May Mix) with XRF based on UNS Spec Ranges
ALLOY/ ELEMENT

Ti

Cr 8 - 10

Mn 1.0*

Fe Bal

Ni

Cu

Cb

Mo 0.9 - 1.1

Other

9Cr(F9) 9Cr+V(F91)

0.2 - 0.5 8 - 10 1.0* Bal 0.9 - 1.1 Long test times on XL3p (30-40s). XL3t with low filter will pick up low V content in seconds 2.0* 2.5* 63 - 70 Bal

M405( R)

M500(K) 0.3 -0.8 1.5* 2.0* 63 - 70 Bal Al 2.3 - 3.15 Long test times on XL3p (30-40s). XLt3 with low filter will separate R/K Monel in seconds. Al determination requires GOLDD Unit SS304 SS304L 18 - 20 18 - 20 2.0* 2.0* Bal 8 - 10.5 8 - 12 ~0.5* C 0.08* C 0.03*

0.15-0.45 17 - 19 SS321 2.0* Bal 9 - 12 304/304L C (OES) / Long test times on XL3p (30-40s). XL3t 304/321 Ti with low filter in seconds / Remove 301 from alloy grade library 15-5 17-4 14 - 15.5 3.5-5.5 2.5-4.5 0.15-0.45

15.5 - 17.5 3-5 3-5 0.15-0.45 Usually unseparable unless Cr, Ni, Cu values at nominal composition 1 - 1.5 0.3 - 0.6 Bal 0.44 - 0.65 0.44 - 0.65 Si 0.5 -1.0 Si 0.1 0.6

F11 F12

0.8 - 1.1 0.3 - 0.6 Bal Long Mtime for Cr / Si determination requires GOLDD Unit 0.8 - 1.1 0.4 - 0.6 Bal

4130 4140

0.15-0.25

C 0.28-0.33 C 0.38-0.43

0.8 - 1.1 0.75-1.0 Bal 0.15-0.25 Not possible with XL3p / Use XL3t with 20s measuring time, or GOLDDD Unit with 5s test time
* Indicates maximum (Mo not specified in 304 but most always present) 31

Thermo Scientific NITON Analyzer Turnkey PMI Kit

Button Reader Hotfoot Extension Pole

CMB Buttons

PMI-15 Certest

Button mounted On plate Wireless Bar Code Reader GPS

EPI Manual

Wireless Printer
32

CMB Buttons: Traceability to Field Components

Computerized Monitoring Buttons ( CMB )-API 570 3rd Edition , Page 30 PMI data are traceable to the point of installation XRF Analyzer data file can tie Report Documentation to the field PI&D drawings

33

PMI of Hot Pipes and Difficult to Access Areas

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 XL3t/p without heat shield: 315o C XL3t with heat shield : 450o C XL3p with heat shield : 540o C

34

API 578
Material Verification Program for New and Existing Alloy Piping Systems May 1999

API RP-578 (section 1)

1. Scope
Guidelines for material QC of ferrous and nonferrous alloys C steel not included Covers owners /users, and indirectly vendors, fabricators, contractors Owner must define roles and responsibilities of each above

36

API Recommended Practice 578 (section 2 and 3)

2. References
API 570 Piping Inspection Code, Publ. 581 RBI, ASME Boiler and Pressure Vessel Code, B31.3 Process Piping, PFI ES22 Color Coding

3. Definitions
See full report for glossary of definitions

37

API Recommended Practice 578 (section 4)

4. Extent of Verification
Owner must establish written program for PMI including up to 100% PMI for higher risk systems

Must provide for review of:

Third party testing Fabrication assembly testing

Cannot substitute mill test report for PMI

38

API Recommended Practice 578 (section 4 cont)

Examples of components covered

Pipes lengths Pipe fittings Flanges Forgings Process valves Pressure containing welds Instruments Weld overlays or cladding Bolting Expansion joints and bellows

39

API Recommended Practice 578 (section 4 cont)

PMI of welding consumables

PMI one electrode per lot Compare markings on balance PMI of weld metal or button is alternative

PMI of longitudinal pipe and weld fittings

Verify base metal and weld metal

PMI of autogenous welds

PMI on base metal only

40

API Recommended Practice 578 (section 4 cont)

PMI of components from distributor
Higher degree of testing due to handling mix-up potential

Existing piping systems

In service but procedures were not in accord with above PMI limited to pressure containing components and attachments Owner determines if retro PMI appropriate and for prioritizing testing Prioritizing considerations

Likelihood of mix based on past verification program Consequences of failure Reason for alloy spec (corrosion, etc) Historical data on past issues with the process unit or plant See API 581 (RBI) for more detailed discussion
41

API Recommended Practice 578 (section 4 cont)

Carbon steel substitutions in LA systems
Greatest number of mixes have been C-steel in place of Cr-Mo steels

SS, Monels, and non-ferrous mix is easier to spot (appearance, weldability) Other Factors
Site specific experience

Past construction and maintenance practices Past PMI procedures - lax vs rigorous
Reason for material specified how critical?

May not be mission critical (SS used for oil purity)

42

API Recommended Practice 578 (section 4 cont)

Component prioritization factors
Some systems have higher likelihood of mix*

Pump and check valve warm-up and bypass lines Small dia. piping & welds (less than 2) Valves and removable devices (discs, spacers, gaskets, etc) Thermowells Bolting Piping as part of packaged system Components without ASTM stamp

* Note: especially in older plants (authors anecdotal experience - data not extracted from API 578)
43

API Recommended Practice 578 (section 4 cont)

Factors in determining extent of PMI
Historical inspection PMI records Number of plant modifications Material control at time of construction or modification Material PMI program quality during construction and fabrication Likelihood of corrosion/degradation Consequence of release

Material Verification Program as element of maintenance systems

Owner must establish written procedures program for repair maintenance activities as well as for receiving and suppliers

44

API Recommended Practice 578 (section 5)

5. Material Verification Program Test Methods
Intended to ID the alloy, not to establish conformance Existing visual stamps and markings not a substitute for PMI

Methods
P-XRF

Principle Interpretation of results

Spectral match or composition percentage Not possible to detect all elements (S, C)

P-OES

Principle Interpretation of results

Spectral match or composition percentage May be able to detect S, C
45

API Recommended Practice 578 (section 5 cont)

Chem lab
Owner approved lab using XRF, OES or wet chemical methods Accuracy higher than needed for PMI May be destructive to sample May be costly and slow

Chemical spot tests

Produces colors to indicate presence of specific elements Slow and subjective

Resistivity testing
Thermoelectric principle, comparative test only Not capable of consistently sorting LA and austenitic SSs

Other
Eddy current, EM, etc., qualitative only; not specific

46

API Recommended Practice 578 (section 5 cont)

Equipment calibration
Accuracy verification: follow mfg s recommendations; or owner must provide procedure

Precision
Repeatability: must be consistent with test objectives; owner must establish acceptance criteria

Personnel qualifications
Operator must be knowledgeable in all aspects of test method and operation Operator qualifications must be approved by owner

Safety issues
PMI method: must include review of any mechanical prep and its effect on sample (integrity) Arcing equipment: will require Hot Work permit (OES) Chemical tests: take appropriate cautions in use of chemicals
47

API Recommended Practice 578 (section 6)

6. Evaluation of PMI Test Results
Methods for material acceptance

Confirm alloying elements against relevant spec (ASTM, ASME, etc) Classify by qualitative sort (ID only) Material out of spec can be accepted if owner (knowledgeable person) evaluates damage mechanisms and confirms performance is OK If material is rejected based on portable or qualitative method a more accurate method can allow acceptance*
Dissimilar metal welds must take into account dilution effect If representative sample of a lot is rejected, extend testing to rest of lot

* Modern P-XRF analyzers rival lab methods

48

API Recommended Practice 578 (section 7)

7. Marking and record keeping
Material ID process

Materials should be IDed by alloy designation (grade) or composition

Acceptable methods
Color coding Low stress stamp Document PMI result and location (drawing)

Color Coding/Marking

Record according to PFI ES22 Marking components Specify

Life of marking legibility If for temporary use, can be semi-permanent paint

49

API Recommended Practice 578 (section 7 cont)

Material certifications (mill reports, CoCs)
Not substitute for PMI

Shop and field test documentation

Individuals performing PMI testing must follow owner approved test procedures

New and existing piping system documentation

Must keep PMI records as long as piping exists in original location

PMI test record information

PMI procedure used Date Instrument ID or serial number Name and company of test person Result of tests Basis and action for resolution Documentation of criteria for prioritizing piping systems for PMI testing
50

API Recommended Practice 578 (section 7 cont)

PMI test procedures
Must include

Techniques Equipment calibration Qualification requirements for PMI test personnel Test methodology Documentation requirements Traceability to field components
All test record info must be traceable to point of installation

51

Why PMI is So Critical to Process Safety Management

It is too Easy to Mix up Alloys with Serious Consequences Without PMI Serious Accidents Will Happen The OHSA (Occupational Health and Safety Administration) Safety Record for Key Industries Handling Highly Hazardous Chemicals is telling:
The Refinery Safety Record is Three Times Worse than the combined Record of the Next Three Vulnerable Industries over the same time period Many of the Serious Incidents have involved Improper or Lack of PMI of Critical Refinery Alloy Components Injuries, Deaths, and Financial Costs have been substantial since 1992: Injuries 250 Deaths 52 Financial Losses Many Tens of Million of Dollars Not Only the PetroChemical Industry, but Many Others are Dependent on Good PMI Utility, DOD, Aerospace, BioTech, Critical System and Subsystem Manufacturing

52

Why do PMI?
Explains How OSHA Instruction-CLP 03-00-004 Nation Emphasis Program (NEP) Applies to The Refining Industry

Source: Marsh and McLennen (property protection and risk consultants)

53

PMI Can Prevent The Largest Losses

Process Safety Management (PSM) 29CFR1910.119 With Proper Material Verification Program and Training

41% of the 170 largest losses in the hydrocarbon process industry resulted from failures of piping systems
Second International Symposium on the Mechanical Integrity of Process Piping January 1996, Houston, TX, USA

Understand & Apply API Recommended Practice 578 Positive Material Identification (PMI) Guidelines

54

Reasons Why

According to OSHAs Data Base:

Since May 1992 (36) Fatality/Catastrophe (FAT/CAT) incidents related to HHC have Occurred Incidents include 52 Employee Deaths and 250 Employee Injuries, 98 of which required Hospitalization The number of Refinery Incidents Surpasses the Combined Total of the Next 3 Highest Industries over the same period, and many are due to Lack of or Faulty PMI
Chemical Manufacturing-12 FAT/CAT Industrial Organic Chemical Manufaturing-12 FAT/CAT Explosives Manufacturing-11 FAT/CAT

55

American Petroleum Institute API

Standard API-570-Piping Inspection Code Standard API-510-Pressure Vessel Inspection Code Standard API-653-Storage Tank Inspection Code Recommended Practice API-RP-578-Material Verification Program-MVP/PMI Recommended Practice API 571-HF ALKY Recommended PracticeAPI 939-C-Sulfidation

RAGAGEP
56

Inspection Program for HF ALKY All Refineries

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, 0.15% 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 571Pages 12,38

57

Inspection Program for Low Si All Refineries

Priority for API PR-5782nd Edition Process Units Susceptible to Sulfidation: Note: Carbon Steels with low silicon (0.10%) content can corrode at an accelerated rate when exposed to hydrogen-free sulfidation conditions. There phenomena are discussed more extensively in API 571 and API RP 939-C. Operators with assets at risk from this type of degradation should consider the risks and the requirements to apply PMI control in order to determine Silicon levels and the extent to which the material may corrode.

58

High Temperature Sulfidic Corrosion-API RP-939-C

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

59

GOLDD Alloy PMI

Stainless Steels for PMI of low Z elements, e.g.,
Si in Zecor alloy at ~6% Al in 13-8Mo at 1%, 17-7 and 301 separation by 1% Al, 303/304 and 410/416 separation by ~0.3% S

HF Alkylation units guideline for base metal of C> 0.18% wt% and Cu + Ni + Cr = 0.15% or less as optimum for minimizing flow accelerated corrosion
LOD for sum is 600 ppm (0.06%) at 10 sec per filter

Process Units Susceptible to Sulfidation: Carbon Steels with low silicon (0.10%) content can corrode at an accelerated rate when exposed to hydrogen-free sulfidation conditions.
Si LOD is 400 ppm (0.04%) in C steels at 15s per filter using He purge

60

GOLDD HF Alkylation, cont.

Al Oxide disc used with a right angle grinder (<10 sec) approx. 0.004 removed
Cu 0.050 Ni 0.078 Cr 0.084 RE Sum 0.212

61