Hydrogen in Material Selection

Important Points
Is the alloy available inthe size and thickness required? Is it the most economical choice?
Should it be specified as seamless or welded? Is it suitable for the maximum anticipated
operating temperature or will long-term exposure to these temperatures cause its
mechanical properties to deteriorate? Will it require special welding or heat treatment
requirements?
Desirable to employ least different piping materials as it reduces costs and avoids
confusion.
Hydrocarbons are not corrosive at the temperatures at which they are normally processed
but the impurities in them such as chloride salts, organic acids, water and sulfur
compounds or by- products such as NaOH and H2SO4 formed from breakdown of these
impurities are.

Important Points
Hydrogen may be a tracer gas for leak testing because the molecule is so small that it
will find all practical sources of leak. This is also the reason why hydrogen will escape
more easily than other gases. The diffusion coefficient is 4 times that for methane.
Typical carbon steel piping specifications and practices for hydrogen service
o Seamless pipe (ASTM A 53 Grade B , SA 106Gr B or less commonly SA 333 Gr6);
The basic specification for petroleum refinery service will require that valves have
cast steel bodies with stainless steel trim, usually 12% chromium stainless
steel.Standard A 53 Grade B pipe is widely available and low in cost, can be bent hot
and cold, and cut and welded using simple methods and minimal precautions.
o PWHT requirements as a function of thickness (>3/4) per code.
o No threaded connections, bridge weld couples, leave no exposed threads (leave no
stress concentrators)

 For stainless steels with a low level of Ni, there is a risk of metal structuretransformation
which increases the hydrogen susceptibility. Nickel alloys, on the other hand, should
be avoided in hydrogen gas service.
Rapid gas decompression may be detrimental to carbon fibre reinforced plastics
(plastics or elastomers) from gaseous hydrogen.

Low temperature service.

o The fracture toughness of carbon steel and ferritic alloys decreases with decreasing
metal temperature. Thats why Impact Testing.
o Most ferritic steels can be used to a lower temperature provided they are stress
relieved and qualified by impact testing.
o If ASS is in solution treated condition and contain less than 0.10%carbon, can be
used to temperatures down to -325F withoutbeing impact tested. But there is a
temptation to employ it automatically for temperatures under -20Fshud be avoided.
Hydrocarbon-sulfur (Cr-Mo Steels)
o Sulfide corrosion is strongly temperature dependent.
o The sulfidation rate decreases in proportion to the amount of chromium in the steel.
When carbon steel is used in contact with sulfur over 500F it is common to specify
silicon-killed grades such as ASTM A 106 pipe and A 105 fittings. Steels with 0.15%
to 0.30% silicon have been shown to be greatly superior to steels with under 0.1%
silicon in some environments.
The workhorse alloy in petroleum refining is one containing 5Cr and 1/2Mo
allowing it to be used in the important 525F to 675F temperature range.
In applications where corrosion rates are too severe for 5Cr-0.5 Mo steel, either 7Cr0.5 Mo or 9Cr-1Mo alloy steelsmay be used.
Alloy steels with lower chromium contents such as 11/4 Cr 1/2 Mo and 21/4 Cr-lMo
steels are are primarily used either for very high temperature, noncorrosive services
or for service in high temperature, high pressure hydrogen environments.
Alloy steels containing Cr Mo contain carbides more resistant to reduction by
hydrogen.
Cr is not nearly as effective in reducing corrosion as inhydrogen-free atmospheres.
9Cr-1Mo often used for reactor effluent piping.
9Cr steel is not acceptable while 12 Cr SS has an acceptably low corrosion rate,

 But since 12Cr has low stress values in the code and its low toughness becomes
more significant as the thickness of the pipe increases, thus ASS is preferred than
12Cr.
Material for high temperature hydrotreater piping is austenitic stainless steel, usually
the titanium-stabilized type 321 grade.
316SS is widely used to resistnaphthenic acid corrosion.
Failures of piping welds have been rare in comparison to cracking of pressure vessel
welds in wet sulfideenvironmentsdue to symmetry of piping welds whichproduce a
more even residual stress pattern than in pressurevessel welds.
Hydrogen Problems:
High Pressure H2 service is above 100 psia of hydrogen partial pressure.
Hydrogen at high temperature and high pressure can permeate steel, and when the
conditions are severe enough, react with metal carbides in the microstructure.

ASS
Not susceptible to 885 embrittlement
Have excellent ductility and toughness @ long-term service.
Are susceptible to stresscorrosion cracking when exposed to chloride environments.

For stainless steels with a low level of nickel, there is a risk of metal structure
transformation which increases the hydrogen susceptibility.
Rapid gas decompression may be detrimental to carbonfibre reinforced plastics (plastics
or elastomers) from gaseous hydrogen.
Typical carbon steel piping specifications and practices for hydrogen service
o Seamless pipe (SA 106GrB or less commonly SA 333 Gr6); may call for A672
(specific grades) electric-fusion-welded pipe for sizes >16
o PostweldHeat Treatment requirements as a function of thickness (>3/4) per
code.
o No threaded connections, bridge weld couples, leave no exposed threads (leave
no stress concentrators, keep everything beefy)
o Where flanges are required, gasket reliability is a major focus and continues to
evolve:
Typically moving to spiral wound gaskets for lower pressure classes
1500# classes are reviewed case-by-case, temperature one factor, may
need RTJ (confined metal) gaskets
2500# classes are typically RTJ style or proprietary engineered
confined metal gaskets
Potential Problem areas for H2 Plants
1.Hydrogen induced cracking of hard materials
The refining industry has had very few cases of hydrogen related cracking in pure
hydrogen service.
Sour (H2S) service that charges hydrogen into the material from corrosion is much
more a threat; we have industry and company guidelines to avoid these failures
There have been a few cases of very hard materials cracking in essentially pure
hydrogen service (few if any cases in our refineries, we do not need such hard
materials)