positive metal identification - xrf by alan logan

PMI in the Petrochemical

Plant and RefineryPlant and Refinery

2009: Niton XL3t GOLDD 7th Generation

2

3

Operation of HHXRF

Excitation Source

Atomic Level Process of Fluorescence Production

4

The Complete System

Pulses

From

Detector

Alloy

Sample

Excitation

Source

DSPDetector

Primary X-

Ray Beam

0

0.5

1

1.5

2

2.5

3

3.5

4

Spectra to µP

5

Microprocessor (µP) Display

Data Storage

Fluorescent

X-Rays

10 10.5 11 11.5 12 12.5 13 13.5 14 14.5 15

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

6

for quantitative analysis

Results display

7

Measured with portable XRF

Not possible with portable XRF, use OES

May require GOLDD technology

Ideal for routine HHXRF

Element Range for Alloy Measurement

8

HHXRF Selected Alloying Element Channels

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

9

427 alloys in grade library

PMI Overview

10

PMI Overview

• AutomatedSample

Data entry

• SimplePoint &

•Fast IDWith FPAnalysis

•Small size•Light weight

PowerPowerPlantsPlants

RefineriesRefineries

PMI is Mission Critical for Verification

11

• Test tightCorners &

& fillet welds

Point &Shoot

Operation

• Test 800 ° FVibrating

Pipes

•Light weight•Ergonomic

•Design

AerospaceAerospace

ProducersProducersFabricatorsFabricators

Consequences of Using IncorrectMaterials Can Range From

ToToToToToToToTo

12

Why do PMI?

13

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

PMI can Prevent the Largest Losses

“41% of the 170 largest losses in the

hydrocarbon process industry

resulted from failures of piping

14


systems…”

Second International Symposium on the Mechanical Integrity of Process Piping

January 1996, Houston, TX, USA

PMI Cycle Overview

15

PMI in Petrochem Industry analytically speaking…

5 0

6 0

7 0

8 0

9 0

1 0 0

Pe

rce

nt

co

nc

en

tra

tio

n o

f e

lem

en

t

We are facing a We are facing a

seemingly seemingly

impossible task:impossible task:

analyzing with analyzing with

sufficient sufficient

accuracy and accuracy and

16

NIC

KE

L 2

00

Mo

nel

500

Inco

625

Inco

750

Inco

825

Hay

nes

230

RA

333

Has

tell

oy

B-2

Has

tell

oy

C-2

76

Has

tell

oy

X

Ste

llit

e 6B

Ste

llit

e 18

8

N iC r

F eM o

M nC u

WC o

N bT i

A l

0

1 0

2 0

3 0

4 0

Pe

rce

nt

co

nc

en

tra

tio

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lem

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precision to be precision to be

able to able to

distinguish one distinguish one

alloy from many alloy from many

thousands of thousands of

others others

(estmates are up to (estmates are up to 50,000 alloys grades 50,000 alloys grades in use today)in use today)

Fortunately, Petrochem Alloys Are Few

17

PMI in Petrochem Industry analytically speaking…con’t

We are facing a second We are facing a second seemingly impossible seemingly impossible task:task:

18

Correcting for an Correcting for an awesome variety of awesome variety of samples forms, sizes samples forms, sizes and shapesand shapes

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%

19

PMI Tool in Petrochem Industry

•• Automatically corrects Automatically corrects for an intimidating set of for an intimidating set of environmental and environmental and sampling conditionssampling conditions

•• Ambient heatAmbient heat

•• Ambient coldAmbient cold

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� 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

•• Ambient coldAmbient cold

•• RainRain

•• Hot samplesHot samples

•• Vibrating samplesVibrating samples

•• High noiseHigh noise

•• Small samplesSmall samples

Hotfoot Adapter

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

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Thermo Scientific Niton XL3t XRF Analyzer Analyzer with GOLDD Technology

Geometrically Optimized Large Area Drift

Detector

GOLDD Technology

�Thermo Scientific presents

the Niton XL3t XRF

Analyzer with GOLDDTechnology

�This new analyzer delivers

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• 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

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

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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

GND C1C2

UBACK Homogeneous thin entrance window

-V

drift–field Anode

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

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Significantly lower LOD’s for critical elements

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

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• 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

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

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� 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

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

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off-the-shelf 10 mm detector

� Therefore, the Niton XL3t collects 2.5 times more signal

The GOLDD Advantage

� This all adds up to the GOLDDAdvantage

� 10X better than conventional Si PIN detectors

� 2.5X better than analyzers with

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� 2.5X better than analyzers with off-the-shelf SDD detectors

Twin Alloys and SolutionsGuideline to PMI Alloys that Mix (or May Mix) with XRF based on UNS Spec Ranges

ALLOY/ ELEMENT Ti V Cr Mn Fe Ni Cu Cb Mo Other

9Cr(F9) - 8 - 10 1.0* Bal 0.9 - 1.1

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

M405( R) - 2.0* 2.5* 63 - 70 Bal -

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 18 - 20 2.0* Bal 8 - 10.5 ~0.5* C 0.08*

SS304L 18 - 20 2.0* 8 - 12 C 0.03*

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SS304L 18 - 20 2.0* 8 - 12 C 0.03*

SS321 0.15-0.45 17 - 19 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 14 - 15.5 3.5-5.5 2.5-4.5 0.15-0.45

17-4 15.5 - 17.5 3 - 5 3 - 5 0.15-0.45

Usually unseparable unless Cr, Ni, Cu values at nominal composition

F11 1 - 1.5 0.3 - 0.6 Bal 0.44 - 0.65 Si 0.5 -1.0

F12 0.8 - 1.1 0.3 - 0.6 Bal 0.44 - 0.65 Si 0.1 0.6

Long Mtime for Cr / Si determination requires GOLDD Unit

4130 0.8 - 1.1 0.4 - 0.6 Bal 0.15-0.25 C 0.28-0.33

4140 0.8 - 1.1 0.75-1.0 Bal 0.15-0.25 C 0.38-0.43

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)

Thermo Scientific NITON Analyzer Turnkey PMI Kit

Extension

Pole

Hotfoot

Button Reader

CMB Buttons

32

PMI-15

Certest

Wireless

Printer

Wireless

Bar Code

Reader

GPSEPI

Manual

Button

mounted

On plate

�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

CMB Buttons: Traceability to Field Components

33

PMI of Hot Pipes and Difficult to Access Areas

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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

API 578Material 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 non-

ferrous alloys

36

• C steel not included

• Covers owners /users,

and indirectly vendors,

fabricators, contractors

• Owner must define

roles and responsibilities

of each above

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

37

� 3. Definitions

• See full report for glossary of definitions

� 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:

API Recommended Practice 578 (section 4)

38

• Must provide for review of:

� Third party testing

� Fabrication assembly testing

• Cannot substitute mill test report for PMI

� Examples of components covered

• Pipes lengths

• Pipe fittings

• Flanges

• Forgings

• Process valves

API Recommended Practice 578 (section 4 cont)

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• Process valves

• Pressure containing welds

• Instruments

• Weld overlays or cladding

• Bolting

• Expansion joints and bellows

� 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


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� PMI of longitudinal pipe and weld fittings

• Verify base metal and weld metal

� PMI of autogenous welds

• PMI on base metal only

� 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


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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

� 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


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• 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)

� 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)


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• Thermowells

• Bolting

• Piping as part of packaged system

• Components without ASTM stamp

* Note: especially in older plants (author’s anecdotal experience -- data not extracted from API 578)

� 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


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• 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

� 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


45

• 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

� 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


46

• 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 SS’s

� Other

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

� 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


47

• 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 it’s effect on sample (integrity)

• Arcing equipment: will require Hot Work permit (OES)

• Chemical tests: take appropriate cautions in use of

chemicals

� 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


48

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

� 7. Marking and record keeping

• Material ID process

• Materials should be ID’ed by alloy designation (grade) or composition

� Acceptable methods

• Color coding

• Low stress stamp

• Document PMI result and location (drawing)


49

• 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

� Material certifications (mill reports, CoC’s)

• 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


50

� 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

� PMI test procedures

• Must include

• Techniques

• Equipment calibration

• Qualification requirements for PMI test personnel

• Test methodology


51

• Test methodology

• Documentation requirements

� Traceability to field components

• All test record info must be traceable to point of

installation

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) SafetyRecord 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

52

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

Why do PMI?

� Explains How OSHA Instruction-CLP 03-00-004 Nation Emphasis Program (NEP)

Applies to The Refining Industry

53

�

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

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


systems…”Second International Symposium on the Mechanical Integrity of Process Piping

54

� Understand & Apply API Recommended Practice 578

Positive Material Identification (PMI) Guidelines

Second International Symposium on the Mechanical Integrity of Process Piping

January 1996, Houston, TX, USA

�According to OSHA’s Data Base:

• Since May 1992 (36) Fatality/Catastrophe (36) Fatality/Catastrophe (FAT/CAT) incidents related to HHC have Occurred

• Incidents include 52 Employee Deaths 52 Employee Deaths and 250 Employee Injuries, 98 of which required Hospitalization

Reasons Why

55

Injuries, 98 of which required Hospitalization

• The number of “Refinery” Incidents SurpassesSurpasses the Combined Total of the Next 3 Highest Industries 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

�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

American Petroleum InstituteAPI

56

�Recommended Practice API-RP-578-Material

Verification Program-MVP/PMI

�Recommended Practice –API 571-HF ALKY

�Recommended Practice—API 939-C-Sulfidation

RAGAGEP

� 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,

Inspection Program for HF ALKYAll Refineries

57

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 571—Pages 12,38

� Priority for API PR-578—2nd 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

Inspection Program for Low SiAll Refineries

58

and the requirements to apply PMI control in order to determine Silicon levels and the extent to which the material may corrode.

High Temperature Sulfidic Corrosion-API RP-939-C

59

Low SiLow Si--33%,PMI33%,PMI--18%,Specification Break18%,Specification Break--17%17%

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

60

+ 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

GOLDD HF Alkylation, cont.

Al Oxide disc used with a right angle grinder (<10 sec)

approx. 0.004” removed

Cu Ni Cr RE Sum

0.050 0.078 0.084 0.212

61

positive metal identification - xrf by alan logan

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