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Titanium Hydriding in Refining Equipment

Titanium hydriding occurs when hydrogen diffuses into titanium and reacts to form an embrittling hydride phase, resulting in a complete loss of ductility and fracture toughness. This damage mechanism affects titanium and titanium alloys, and is more likely to occur in specific environments above 165°F and a pH below 3 or above 8, or neutral pH with high H2S content. Hydriding damage has primarily been seen in sulfur recovery unit and amine unit heat exchangers and air coolers operating above 165°F. The damage causes embrittlement but no visible corrosion and can only be detected through metallurgical examination.

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248 views1 page

Titanium Hydriding in Refining Equipment

Titanium hydriding occurs when hydrogen diffuses into titanium and reacts to form an embrittling hydride phase, resulting in a complete loss of ductility and fracture toughness. This damage mechanism affects titanium and titanium alloys, and is more likely to occur in specific environments above 165°F and a pH below 3 or above 8, or neutral pH with high H2S content. Hydriding damage has primarily been seen in sulfur recovery unit and amine unit heat exchangers and air coolers operating above 165°F. The damage causes embrittlement but no visible corrosion and can only be detected through metallurgical examination.

Uploaded by

Mohammad Fouladi
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© © All Rights Reserved
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DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 329

3.66 Titanium Hydriding

3.66.1 Description of Damage

Hydriding of titanium is a metallurgical phenomenon in which hydrogen diffuses into the titanium and reacts to
form an embrittling hydride phase. This can result in a complete loss of ductility and fracture toughness, potentially
enabling a brittle fracture, with no noticeable sign of corrosion or loss in thickness.

3.66.2 Affected Materials

Titanium and titanium alloys.

3.66.3 Critical Factors

a) The critical factors are metal temperature, solution chemistry, and alloy composition.

b) This is a phenomenon that occurs in specific environments at temperatures above 165 °F (75 °C) and at a
pH below 3, pH above 8, or neutral pH with high H2S content.

c) Galvanic contact between titanium and more active materials such as carbon steel and 300 series SS
promotes damage. However, hydriding can occur in the absence of a galvanic couple.

d) Embrittlement occurs over a period of time as hydrogen is absorbed by the component and reacts to form
an embrittling hydride phase. The depth and extent of hydriding will continue to increase until a complete
loss of ductility results.

e) Hydriding has also occurred in some environments as a result of the corrosion of steel that was accidentally
embedded into the surface of the titanium during fabrication.

f) Iron sulfide scale formed from the corrosion of steel in upstream units and equipment can be carried into
titanium equipment and cause hydrogen pickup and resulting hydriding.

g) The solubility of hydrogen in pure titanium and alpha-beta titanium alloys (e.g. Gr. 2. Gr. 7, Gr 12, and Gr.
16) is limited to 50 ppm to 300 ppm. When the hydrogen concentration exceeds this solubility limit, hydride
is formed. Beta alloys are more tolerant of hydrogen, and 2000 ppm can be absorbed without causing
detrimental hydriding. However, beta alloys are not typically used for refinery process equipment.

3.66.4 Affected Units or Equipment

a) Titanium has mainly been used in heat exchangers and air coolers, primarily to take advantage of the
corrosion resistance of titanium tubes in these services. Damage has occurred primarily in SWSs and amine
units in the overhead condensers or air coolers and other heat exchanger tubes, as well as some piping and
other titanium equipment operating above about 165 °F (75 °C). In most cases, cracking has occurred during
maintenance operations, e.g. turnarounds, rather than while the equipment was in service.

b) Hydriding can also occur in hydrogen atmospheres at temperatures > 350 °F (175 °C), especially in the
absence of moisture or oxygen.

c) Cathodic protection potentials less −0.9 v SCE on titanium equipment can promote hydrogen entry and
hydriding.

3.66.5 Appearance or Morphology of Damage

a) Titanium hydriding is a metallurgical change that is not visually apparent and can only be confirmed through
metallurgical examination (Figure 3-66-2 and Figure 3-66-3) or mechanical testing.

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