API 934F Task Group Procedure to Calculate the

Minimum Pressurization Temperature (MPT) for Heavy

Wall Vessels in High Temperature High Pressure
Hydrogen Service - 2Cr-1Mo

Presentation at API 934F Task Group Meeting,
September 18, 2012, New Orleans, LA
Jim McLaughlin
Consultant
Basis for Calculating the MPT of Heavy Wall Vessels in
High Temperature High Pressure Hydrogen Service
Fast Fracture Considerations
Low energy brittle fracture promoted by temper embrittlement effects
Older reactor vessels (fabricated before circa 1980) without compositional
controls to limit impurity levels, such as P, Sn, Sb and As
Newer reactor vessels (fabricated after circa 1980) with compositional
controls to limit impurity levels, such as P, Sn, Sb and As
Effect of hydrogen on fast fracture new consideration
Slow Stable Crack Growth Considerations
Hydrogen embrittlement controls slow stable crack growth
Recent research at UVa shows that hydrogen embrittlement effects
rapidly disappear at a threshold temperature above which no
embrittlement occurs
Hydrogen embrittlement effects also function of impurity levels
MPT determined by limiting temperature consideration due to fast
fracture and slow stable crack growth considerations
Fast Fracture Considerations - Temper Embrittlement Guidance
Fast fracture addressed in same manner as in Part 3 of API579, paragraph
3.4.3.1, Pressure Vessels, Method A
Need to establish starting temperature for entering Figure 3.7 to establish the
Minimum Allowable Temperature (MAT) as a function of the applied stress ratio
follows same temperature reduction curves as in Section VIII, Divisions 1 and 2 of
the ASME Code.
Use an estimate of the 40 ft-lb transition temperature in the temper embrittled
condition as the starting temperature
Use 250F (121C) for older reactor vessels (fabricated before circa 1980)
without compositional controls to limit impurity levels, such as P, Sn, Sb and As
Use 300F (149C) for older reactor vessels without compositional controls and
made from plate with long seam made with single ESW pass
Use 150F (65C) for newer reactor vessels (fabricated after circa 1980) with
compositional controls to limit impurity levels, such as P, Sn, Sb and As
For reactor vessels with step cool requirements, use the maximum calculated or
allowed temperature after the step cooling heat treatment with a 3.0 multiplier
factor
When is temper embrittlement a consideration?
Suggesting that temper embrittlement be considered only when the maximum
expected operating temperature (normally the end of run temperature) for the
reactor vessel is 700F (371C) or higher
Effect of Hydrogen on Fast Fracture New Consideration
Effect of hydrogen on fast fracture at low temperatures
ArcelorMittal data
Effect of Hydrogen on Fast Fracture New Consideration
Hydrogen has significant effect on fast fracture at low temperatures
summary of ArcelorMittal data on 2Cr-1Mo with a very low FATT of
-80C (-112F)

Effect of Hydrogen on Fast Fracture New Consideration
Test conducted on 2Cr-1Mo with high impurity levels as prepared by Kobe Steel
shows that the effect of hydrogen on fast fracture at higher temperatures decreases
As the temperature approaches 150F (65C), the fracture toughness approaches 100
MPam even when soluble hydrogen levels are 3 ppm, highest expected level in
refining hydroprocessing service.
Conclusion: Effect of hydrogen on fast fracture insignificant above 150F (65C)
Effect of Hydrogen on Fast Fracture New Consideration
Combining results on the effects of hydrogen on fast fracture at low temperature
per the ArcelorMittal testing, with the results of the Kobe tests at higher
temperatures, the following curve can be used to define the shift in the fracture
toughness transition temperature that results from the effect of hydrogen on fast
fracture
Slow Stable Crack Growth Considerations
Hydrogen embrittlement controls slow stable crack growth considerations
Hydrogen embrittlement effects as determined by a slow strain rate rising
load test show that the effects disappear once the temperature reaches a
threshold temperature above which hydrogen embrittlement effects are
insignificant.
Above threshold temperature reactor pressure limited to the full design
pressure
Below threshold temperature reactor pressure limited to 30% of the full design
pressure
Testing performed at UVa and data available from other sources are used
to develop curves for the hydrogen embrittlement threshold temperature
as a function of the bulk hydrogen level in the steel and the concentration
of hydrogen that can accumulate in the plastic zone a head of a crack.
Curves were developed for 2Cr-1Mo steel with high impurity levels and low
impurity levels.

Hydrogen Embrittlement Threshold Temperature
(High Impurity 2Cr-1Mo)
Hydrogen Embrittlement Threshold Temperature
(Low Impurity 2Cr-1Mo)
Suggested Hydrogen Embrittlement Threshold Temperature
Curves for Use in MPT Assessment
Each curve represents a constant ratio of the bulk hydrogen concentration
in the steel versus the concentration at a distance of 470m from the
crack tip.
For the purposes of an assessment 3 different levels of hydrogen
concentration at the crack tip are defined. Each of these levels represent
different stress intensity levels the higher the stress intensity the greater
the hydrogen concentration at the crack tip
Nominal hydrogen concentration (C
470m
/C
bulk
= 1) This is the level that would
be expected with a crack similar to the crack that existed in the compact
tension sample used for testing for hydrogen embrittlement
Conservative hydrogen concentration (C
470m
/C
bulk
= 1.54) This is the level
that would be expected with a crack that has a higher stress intensity than the
crack in the compact test specimen.
Non-conservative hydrogen concentration (C
470m
/C
bulk
= 0.5) This is the level
that would be expected with a crack that has a lower stress intensity than the
crack in the compact test specimen.


Hydrogen Embrittlement Threshold Temperature
(High Impurity 2Cr-1Mo)
Hydrogen Embrittlement Threshold Temperature
(Low Impurity 2Cr-1Mo)
MPT Assessment of Typical Hydroprocessing Reactors
MPT assessment for 2 typical reactor vessels


Fast fracture considerations Both reactors screened base materials
and welding consumables with a step cooling procedure




For this assessment the starting temperature for fast fracture curve after
temper embrittlement effects are accounted for is 75F

MPT Assessment of Typical Hydroprocessing Reactors
Effect of hydrogen on fast fracture


First need to determine the bulk hydrogen level in the
reactor wall
The following assumptions are made for this calculation
Calculation is made at the maximum expected operating
temperature and hydrogen partial pressure using the latest
diffusivity and solubility data from Kobe Steel
Assume that the cladding is cracked so that there is no benefit
from the stainless steel cladding in reducing hydrogen
solubility in the steel
No benefit calculated for outgassing during reactor shutdown
MPT Assessment of Typical Hydroprocessing Reactors
Effect of hydrogen on fast fracture



Reactor 1 Fast Fracture Starting Point Temperature 75F + 31F = 106F
Reactor 2 Fast Fracture Starting Point Temperature 75F + 25F = 100F
MPT Assessment of Typical Hydroprocessing Reactors
Slow Stable Crack Growth Hydrogen Embrittlement Effects



MPT Assessment of Typical Hydroprocessing Reactors
Slow Stable Crack Growth Considerations Control Over Entire
Temperature Range for MPT Assessment



Reactor 1
Reactor 2
Low Impurity 2Cr-1Mo
Does Not
Meet MPT
Guidance
Meets MPT
Guidance
MPT Assessment of Typical Hydroprocessing Reactors
(Old Reactors without Compositional Controls)
MPT assessment for 2 typical reactor vessels


Fast fracture considerations Both reactors were fabricated prior to
1980 and did not have any compositional controls to maintain low impurity
levels
For this assessment the starting temperature for fast fracture curve after
temper embrittlement effects are accounted for is 250F
Since the starting temperature for the fast fracture curve is above 150F,
there will be no additional temperature added to the starting temperature
to account for the effect of hydrogen on fast fracture

MPT Assessment of Typical Hydroprocessing Reactors
Slow Stable Crack Growth Hydrogen Embrittlement Effects



High Impurity 2Cr-1Mo
MPT Assessment of Typical Hydroprocessing Reactors
Fast Fracture Controls at Higher Temperatures and Slow Stable Crack
Growth Controls at Lower Temperatures



High Impurity 2Cr-1Mo
Does Not
Meet MPT
Guidance
Meets MPT
Guidance
Additional Work Needed on MPT Assessment Procedure
Improved understanding of the 3 curves being suggested for the hydrogen
embrittlement threshold temperature as a function of bulk hydrogen levels
What are typical crack sizes/geometries indicated for each of these curves in a
reactor vessel
Ted Anderson will discuss further
Assumptions included in the MPT procedure Are they too conservative?
Assuming that a crack compromises the stainless steel cladding
Using the dissolved hydrogen level at the maximum expected metal
temperature and hydrogen partial pressure level without any reduction provided
for out gassing during shutdown
3 curves being suggested for the hydrogen embrittlement threshold
temperature
Use of rising load test results to define hydrogen embrittlement effects
Need to conduct testing on 2Cr-1Mo-V material
Hydrogen embrittlement effort
Effects of hydrogen on fast fracture