Detection of Hydrogen Attack

Background
Hydrogen damage or high temperature hydrogen attack (HTHA) is produced in steel from the seepage of hydrogen that reacts with carbides to form methane gas. This reaction decarburizes the steel, produces micro cracks, and lowers the toughness of steel without necessarily a loss of thickness. Detection of hydrogen attack is important to assure safe operation of pressure vessels and piping susceptible to such damage. Fe 3 C + 2H2 = 3Fe (decarburization) +CH4 (methane) The type of damage caused by hydrogen attack depends on the source. The source of hydrogen in boiler tubes is from a reaction of steam and steel. Hydrogen damage in boiler tubes is, therefore, always associated with ID corrosion. However, in chemical plant the source of the hydrogen is from the flow stream (hydrocarbons) and, therefore, there is no corrosion associated with hydrogen damage.

Figure 1: Hydrogen attack (a) The dark area on the Boiler Tube ID represents hydrogen damage. (b) Hydrogen Attack in the pipe sample removed from a petrochemical plant

PETROCHEMICAL PLANTS
High temperature hydrogen attack (HTHA) in the petrochemical plants is caused when the hydrogen from the stream seeps into carbon and low alloy steels at high temperatures. Hydrogen reacts with the carbides in the steel, decarburizing the steel and forming methane gas bubbles at the grain boundaries with no loss of thickness. The methane gas bubbles grow with time and result in micro cracking. The combination of micro cracking and decaburization reduce the fracture toughness of steels. HTHA is triggered in the components operating at high temperatures and high hydrogen partial pressure. API 941's Nelson curves provide information about the safe operating environment for components operating in hydrogen environments (1). Components operating in the unsafe environments are susceptible to hydrogen attack. The concern is especially true for C-1/2 Mo steels whose curve has been been lowered and now dropped to the same level as that carbon steel (1). Because of this drop, some of the C-1/2 Mo components originally operating in the safe region are now in the unsafe region of the Nelson curves. These components should either be inspected regularly for evidence of HTHA or replaced with a higher grade of steel. Hydrogen Attack can occur both in the base metal and the weld HAZ. The attack in the base metal is wide spread and distributed uniformly. Weld attack is very localized and grows along the HAZ. The susceptibility of attack in the weld HAZ depends on the heat treatment. Post-weld heat treated welds are less susceptible to hydrogen attack compared to the welds that are not heat treated. There have been several cases where the depth of the attack in the HAZ is greater than the depth in the base metal. It is therefore imperative that both the base metal and the weld HAZ be inspected for presence of hydrogen attack. Reference 2 provides guidelines on prioritizing equipment for C-1/2 Mo equipment in hydrogen service. Some of the factors are as follows:

operating conditions (partial pressure of hydrogen and temperature) relative to the operating limits provided in API 941, 1997 edition (3). slow cooled C-1/2 Mo steels have less resistance to hydrogen attack than normalized steels. post-weld heat treated welds are less susceptible to hydrogen attack compared to the welds that are not heat treated.

NDT Technique: Base metal attack as shown in Fig 1 (b) is detected by using a combination of ultrasonic back-scatter and velocity measurements (3,4). Hydrogen attack increases the ultrasonic

backscatter and reduces the ultrasonic velocity in the material. These two measurements are applied to detect hydrogen attack. The ultrasonic backscatter technique was developed by A. S. Birring and was first applied at the Chevron Richmond Refinery in 1989 (3). Details of the UT techniques for HTHA inspection are given in references 3 and 4. Weld HAZ attack is detected using the ultrasonic shear wave technique. Since the cracking caused by hydrogen attack in the weld HAZ is extremely fine, the shear wave inspection is done at a very high sensitivity. Both the base metal and weld HAZ should be inspected for hydrogen attack. Further verification of attack can be done by surface replication.

Field Testing - Petrochemical Plants

NDE Associates, Inc. has performed HTHA inspections for the following clients

Chevron Oil, Richmond Refinery, CA. Conduct follow up inspections after the 1989 fire caused by Hydrogen Attack failure. Irving Oil, St John Refinery, NB, Canada. Huntsman Chemicals, Melbourne, Australia. SK Oil, Korea. Conduct follow up inspections after the failure caused by Hydrogen Attack. Failure date: May 13, 1999. CF (Fertilizers) Industries, Donaldsonville, Louisiana. Conoco Oil Company, Billings Refinery, MT and Denver Refinery, CO.

BOILER TUBES

Hydrogen damage in boiler tubes is caused by a corrosive reaction between steam and steel as follows: Fe + H2O = Fe3O4 + H2 The hydrogen available from the above reaction reacts with carbides to decarburize the steel and forms methane gas at the grain boundaries. Hydrogen damage results in wall loss due to corrosion and a loss of strength in the material attacked by hydrogen. Hydrogen damage occurs in waterwall tubes when the pH level drops below the normal level. The damage usually occurs in areas of high heat flux and flow disturbances. These include circumferential welds, tubes opposite to burners and tube bends. Technique: Inspection for hydrogen damage in boiler tubes is accomplished in a two step procedure (3, 5). The first step is locating areas with ID surface corrosion. This is done with a ultrasonic scanning method that detects areas with ID surface corrosion. The second step is to determine whether the corrosion was a result of hydrogen attack or some other mechanism. Ultrasonic velocity measurements are taken in the material under the corroded area. A loss of ultrasonic velocity is an indication of hydrogen damage. This

velocity loss is measured by a pitch catch method . The loss of ultrasonic velocity is related to hydrogen damage.

Field Testing - Fossil Fired Power Plants

NDE Associates, Inc. personnel have performed boiler tube inspections for the following clients

Houston Lighting and Power Company, Houston, Texas Southern California Edison, Los Angeles, California Public Service of California, Boulder, Colorado Montana Power, Billings, Montana Los Angeles Department of Water and Power, Los Angeles, California

REFERENCES
1. Steels for Hydrogen Service at Elevated Temperatures and Pressure in Petroleum Refineries and Petrochemical Plants, API Recommended Practice 941, Fifth edition, American Petroleum Institute, 1997. 2. Hattori, K. and Aikawa, S., "Scheduling and Planning Inspections of C-0.5Mo Equipment Using the New Hydrogen Attack Tendency Chart", PVP vol 239/MPC-vol 33, Serviceability of Petroleum Process and Power Equipment, ASME, 1992. 3. A. S. Birring, et al. "Method and Means for Detection of Hydrogen Attack by Ultrasonic Wave Velocity Measurements" US Patent, 4,890,496, January 2, 1990 4. A. S. Birring and K. Kawano, " Ultrasonic Detection of Hydrogen Attack in Steels", Corrosion, March, 1989 5. A. S. Birring, et.al. "Detection of Hydrogen Damage", Materials Evaluation, March 1989