High Temperature Hydrogen Attack Resistance Using Autoclave Testing of Scoop SamplesSM

Tim Munsterman Technology Director Engineering. Antonio Seijas Mechanical Engineering Consultant Dana G. Williams, P.E. Materials & Corrosion Specialist Marathon Petroleum Co, LLC Ashland, Kentucky USA

Lloyds Register Capstone, Inc. Houston, Texas USA

Presented by: Dr John Fuad Edwards Haed of Integrity Services Lloyds Register Kuala Lumpur

Introduction Industry Dilemma Scoop SamplerSM Autoclave Testing Real Time Monitoring Data Interpretation Conclusions

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Introduction
1976 Guard Reactor in a Distillate Hydrotreater Unit A302-B C-Mn- Mo Steel Operating 110C (230oF) above CS Curve High Potential for HTHA based on API 581 Risk Based Inspection No damage found so far, however, limited prior inspections Scoop Sample Removal for Toughness Testing and HTHA Testing

API 941 High Temperature Hydrogen Attack curves.

C Mo Curve

Test Conditions

100 Hr Curve

Carbon Steel Curve

4H + FeCCH4 + Fe
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(atomic hydrogen reacting with iron carbides)

Industry Dilemma: How to tell Good from Bad C Mo Steel?

Microstructure analysis not reliable for HTHA resistance. Current HTHA models incorporate range of HTHA Susceptibility, Probability or Carbon Activity There is no method to measure Carbon Activity Actual HTHA Resistance Is Not Known LR Capstone Approach is Straightforward: Perform a Test Using Vessel Material to Determine Properties Similar Concept to Accelerated Creep Testing Elevated Temperatures and Pressures using H2 Remove Samples From Vessel LR Capstones Scoop SamplerSM Various Plates / Locations

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Scoop SamplerSM
Removes a spherical shaped samples low stress concentration Attach tool using magnets Uses a spherical cold cut saw blade no sparks Local thin area calculations performed prior to avoid repair welding Toughness can only be measured destructively Quantitative HTHA Resistance Over 500 Scoop Samples Removed

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Scoop Sample Locations Guard Reactor

Scoop Sample 2 Scoop Sample 9 Scoop Sample 10 HTHA Testing Impact Testing Scoop Sample 3 Scoop Samples 11 and 12 Scoop Sample 7 Scoop Sample 8

Performed both: MPT Assessment

(Minimum Pressurization Temperature)

Top Head

Scoop Sample 1

Upper Course Scoop Sample 4 Scoop Samples 5 and 6 Lower Course Bottom Head

HTHA Assessment
Samples removed from each shell course and head (bottom head was not accessible at time of testing) Weld metal and HAZs included. Nozzles can be sampled.

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Scoop Samples Removed from Guard Reactor

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High Temperature Hydrogen Autoclaves

97 bara H2 538C

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Full Immersion Coupon for Real Time Incipient Damage Monitoring

0.25 diameter x 0.375 long

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Immersion Coupon Microstructure After Testing Displacement Monitoring of Coupon HTHA Swelling
Hydrogen reacts with carbon to form methane. Methane trapped sub surface Intergranular methane bubbles (voids) and cracking Coupon swells with damage. Incipient damage when rate is nonlinear

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Carbon Steel Reference Coupon

Displacement data is continuously monitored during HTHA testing Change in rate indicates incipient threshold Test duration based on time to incipient damage

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C Mo Coupon from Scoop Sample 11 (Upper Course)

Displacement data showed growth during entire HTHA test Change in rate indicated incipient threshold Similar to a shift from second to third stage creep

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C Mo Coupon from Scoop Sample 9 (Top Head)

Displacement data indicated continuous growth during HTHA testing Change in rate indicated incipient threshold Jump in displacement likely due to blister formation

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C Mo Coupon from Scoop Sample 6 (Lower Course) Single Side Exposure - 830 Hours
Surface Exposed to H2 Large blister at center of coupon Many smaller blisters Cross sectioned this coupon for depth of damage

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C Mo Coupon from Scoop Sample 6 (Lower Course) Single Side Exposure - 830 Hours
One side exposure coupon Cross section view for depth of damage 39.5% through-wall damage High Resistance to HTHA

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Carbon Steel Ref. Coupon Single Side Exposure - 181 Hours

Cross section view for depth of damage 75% Through Wall HTHA Damage Incipient Damage Occurred in 10 Hours.

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Scoop Sample 5 C Mo Coupon Single Side Exposure - 181 Hours

Cross section view for depth of damage 7.4% Through Wall HTHA Damage Incipient Damage Occurred in 151 Hours.

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Data Interpretation
API 941 Incipient Damage Curves Better Approach: The Pw parameter Amount of time to incipient damage First developed by Shewmon Refined by Japan Pressure Vessel Research Council (JPVRC) Included in the Technical Basis for 941 Report, Appendix F

Pw= - 3 ln(PH2)-ln(t)+190000/(8.3145 T)
Where: PH2 = hydrogen partial pressure in MPa, t = time in hours, T= temperature in K

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HTHA Test Results with Pw Calculations

Hours to Incipient Damage API 941 App. A-1 Critical Pw 20 yr No Attack Pw Calculated Projected Years to Increase in Risk

Test Samples

T, C

P, bara

Carbon Steel (516-70) Sample Scoop Sample# 11 (Upper Course) Scoop Sample# 5 (Lower Course) Sample# 9 (Top Head) Scoop Sample# 6 (Lower Course) C Mo Current Op. Conditions

545 544 538 538 538 402

97 97 97 97 97 34

10 110 151 159 232 17.75 16.43 16.33 16.28 15.90

---110

30

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Conclusions
Reactor has similar or better resistance than good C Mo steel Reactor is suitable for this service Reactor will move to a medium potential for HTHA damage after 30 years of operation. It is recommended to perform HTHA inspections based on risk based guidelines given in API 581 or similar.

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Conclusions
The upper course and top head displayed lower HTHA resistance Recommended more thorough inspections of these plates and fewer locations on the lower course Typical RBI assessment for a C Mo vessel operating 110C (230 F) above the carbon steel curve: High likelihood after just 250 hours of exposure (based on API 581, Appendix I, Table I-3).
o

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For more information: Tim Munsterman Phone 1-281-649-2212 Mobile 1-281-414-2136 Fax 1-281-493-5161 Engineering Services Lloyds Register Capstone, Inc. 1505 Highway 6 South Suite 100 Houston, TX 77077 Tim.Munsterman@lr.org
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