Damage Mechanisms Affecting Fixed Equipment in the Refinng Industy 5.83) 5.4.3. Other Mechanisms 5.1.3.4 High Temperature Hydrogen Attack (HTHA) 54.34.41 Description of Damage 2) High temperature hydrogen attack results from exposure to hydrogen at elevated temperatures and pressures. The hydrogen reacts with carbides in steel to form methane (CH,) which cannot diffuse ‘through the steel, The loss of carbide causes an overall loss in strength. b) Methane pressure builds up, forming bubbles or cavities, microfissures and fissures that may combine to form cracks, ¢) Failure can occur when the cracks reduce the load carrying abilty of the pressure containing part SAS12 Affected Materials In order of increasing resistance: carbon steel, C-0.5Mo, Mn-0.5Mo, 1C1-0.5Mo, 1,25C1-0.5Mo, 2.25Cr- Mo, 2.28Cr-1Mo-V, 3Cr-1Mo, C1-0.8Mo and similar steels vith variations in chemistry. 5431.3 Critical Factors a) For a specific material, HTHA Is dependent on temperature, hydrogen partial pressure, time and stress. Service exposure time is cumulative. b)_HTHA Is preceded by @ period of time when no noticeable change In properties Is detectable by normal inspection techniques. ¢) The incubation period Is the time period during which enough damage has occurred to be measured ‘with avaliable Inspection techniques and may vary trom hours at very severe conditions to many years. d) Figure 5-56 contains curves that show a tamperaturelhydrogen partial pressure safe operating envelope for carbon and low alloy steels. Adaitional information on KTHA can be found in API RP. oat. fe) The curves are reasonably conservative for carbon steel up to about 10,000 psi hydrogen partial pressure, 1) 300 Series SS, as well as SCr, Cr and 12 Cr alloys, are not susceptible to HTHA at conditions normally seen in refinery units. S344 Affected Units 8) Hydroprocessing units, such as hydrotreaters (desuifurizers) and hydrocrackers reformers, hydrogen producing units and hydrogen cleanup units, such as pressure swing absorption units, are all susceptible to HTHA, 'b) Boller tubes in very high pressure steam service. 5.3.1.5 Appearance or Morphology of Damage 2) HTHA can be confirmed through the use of specialized techniques including metallographic analysis of damaged areas as described below. b) The hydrogenicarbon reaction can cause surface dacarburization of steel. Ifthe diffusion of carbon to the surface Is limiting, the reaction can result in intemal decarburization, methane formation and cracking (Figures 5-87 to 5-59). ©) Inthe early stages of HTHA, bubbles/cavities can be detected in samples by @ scanning microscope, although it may be diffcult to tel the difference between HTHA cavities and creep cavities. Some: refinery services expose low alloy steels to both HTHA and creep conditions. Early stages of HTHA, can only be confirmed through advanced metallographic analysis of damaged areas.5.84 [API Recommended Practice §71 ) In later stages of damage. decarourization andlor fissures can be seen by examining samples under ‘a microscope and may sometimes be seen by in-situ metallography (Figure 5-60 and 5-51), ) Cracking and fissuring are intergranular and occur adjacent to pearlte (Iron carbide) areas in carbon steels. 1) Some blistering may be visible to the naked eye, due to either molecular hydrogen or methane ‘accumulating in laminations in the steel 543.4.8 —— Prevention/Mitigation 2) Use alloy steels with chromium and molybdenum to increase carbide stabilty thereby minimizing methane formation. Other carbide stabilizing elements include tungsten and vanadium, bb) Normal design practice is to use a 25°F to S0°F (14°C to 28°C) safety factor approach when using the API RP St curves, ©) While the curves have served the industry well, there have been several failures of C-0.5Mo steels in tefinery service under conditions that were previously considered safe, C-0.8Mo carbide stablty under HTHA conditions may be due at least in part to the different carbides formed during tha various heat treatments applied tothe fabricated equipment. 1d) As a result of the problems with the 0.6 Mo alloy steels, Its curve has been removed from the main ‘set of curves and the material is not recommended for new construction in hot hydrogen services. For existing equipment, this concer has prompted an economic review of Inspection cost versus replacement with a more sultable alloy. Inspection is very dificult because problems have occurred, In weld heat affected zones as well as base metal avay from welds. 12) 300 Series SS overlay andlor roll bond clad material is used in hydrogen service where the base ‘metal does not have adequate sulfation resistance, Although It is recognize that properly ‘metallurgically bonded austenitic overtay/ciad wil decrease the hydrogen partial prasure seen by the underiying metal, most refiners make sure the base metal has adequate resistance to HTHA under service conditions, In some cases, refiners take the decrease in partial pressure into account \when evaluating the need for hycrogen outgassing while shutting down heavy wall equipment. 7 Inspection and Monitoring 1a) Damage may occur randomly in welds or veld heat affected zones as well as the base metal, ‘making monitoring and detection of HTHA In susceptible materials extremely difcutt. ) _Uttrasonic techniques using a combination of velocity ratio and AUBT have besn the most successful in finding fissuring and/or serious cracking. HTHA damage can only be found using these techniques if damage has progressed to the point where microvolds would be visiole at a ‘magnification of 1500X or lower, fa sample of the metal was removed for examination. ¢) THA can occur in the base metal at locations remote from welds. In clad vessels, in particular, HTHA damage can occur in base metal at locations where cladding has become disbonded. Bulging Cf the cladding away from the underiying base metal may be a telltale sign that HTHA has occurred. Localized damage Under cladding might be overlooked if inspection methods focus only on the weld ‘seams and nozzles (Reference 4) 4) Invsitu metallography can only detect microfissuring,fissuring and decarburization near the surface. However, most equipment has decarburized surfaces due to the various heat treatments used during fabrication. ) Visual inspection for blisters on the Inside surface may indicate methane formation and potential HTHA. However, HTHA may frequently occur without the formation of surface bisters. ) Other conventional forms of inspection, including WFMT and RT, are severely limited in their ability to detect anything except the advanced stages of damage where cracking has already developed, 9) AET is not a proven method for the detection of damage.‘Damage Mechanisms Affecting Fixed Equipment inthe Refiing Industry 585 5.1.3.4.8 Related Mechanisms A form of HTHA can occur in boiler tubes and Is referred to by the fossil utlity industry as hydrogen damage. 51349 References 1. API RP 941, Steels for Hydrogen Service at Elevated Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants, American Petroleum Institute, Washington, D.C. 2. J. Vitovee. F.H., “The Growth Rate of Fissures During Hydrogen Attack of Steels,” API Division of Refining, Vol. 44 (ll) 1964, pp. 173-188, 3, Materials Property Councii Report FS-26, “Fitness-for Service Evaluation Procedures for Operating Pressure Vessels, Tanks. and Piping in Refinery and Chemical Service.” Draft 5. Materials Properties, ‘Council. NY. 1995, 4. S. Decker et al.. “Safe Operation of a High Temperature Hydrogen Attack Affected DHT Reactor’, Paper #09339, NACE Intemational, Houston, TX, 2008.5.88 [API Recommended Practice S71 Figure 5-56 - Recommended pressure and H2 partial pressure limits per API 941. (Reference 1)Damage Mechanisms Affocting Fixed Equipment inthe Refining industry sar Figure 5-57 ~A pair of 10 inch Carbon-0.5Mo flanged pipe sections (SA335-P1 & SA234.NP1) from ‘hot bypass line ina catalytic reformer that was desighed to remain closed but operated partially ‘or fully open for unknown lengths of time. Thay were in service for ~34 years at temperatures up ‘to 960"F (516°C) and a hydrogen partial pressure of 198 psig (1.37 MPa). ‘A photomicrograph of the outside surface ofa pipe section, shown in the previous figure, exbie normal farite-pearitie stucuure, Mag. 200%"588 [AP| Recommended Practice S71 Figure 5.59 A photomicrograph atthe pipe ID surface exhibiting ofthe pipe shown in the prSvious picture, exniting complete decarburization ofthe oighnal strdcare, Mag. 200K Figure 5-60 ~ A photomicrograph illustrating decarburization and fissuring of C-0.5Mo steel‘Damage Mecnanisms Arecing Hited t-quipmont nthe Kenning Industry 5.61 — High magnification photomicrograph showing linkup of microfiesures to ccontlSuous cracks Note that Gamage s socompanied by sigaficent amount of Gecarburzaion,