Engineering Development Materials

Intelligent material solutions for catalyst technologies

Principal Engineer Mara Jos Landeira stergrd

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Corrosion in HTASs related technologies

Synthesis gas:
Hydrogen plants and front end of ammonia and methanol plants

Hydrogen attack Stress Corrosion Cracking Hydrogen Sulphide & CO2 Oxidation Carburization Metal Dusting

Corrosion in HTASs related technologies

Ammonia plants As in previous slide and: Nitridation Ammonia induced stress corrosion cracking (carbon steel storage tanks) Methanol plants As in slide about synthesis gas and: Carbonyl corrosion Methanol corrosion WSA-plants Dew point corrosion High temperature sulphidation
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Refinery High temperature H2 corrosion High temperature H2S corrosion Polythionic acid corrosion Ammonium bisulphide Salt corrosion: pitting, crevice, Cl SCC Sulfide stress corrosion Acid corrosion Amine corrosion Naphthenic acid corrosion

Case 1: Tubes and Inlet Tube Sheet Waste Heat Boiler El Segundo Refinery, California.

After about 5 years of operation severe leakage occurred at the inlet tube sheet of the boiler. The inlet tube sheet is thermally protected by a layer of refractory. Moreover, several cracks were found in the tube to tube sheet welds, mainly at the centre portion. Severe corrosion was found at the outside of the tubes in the vicinity of the tube sheet.

6 Tube sheet

Longitudinal

Transversal

7 Tube sheet

Longitudinal

Tubes and Inlet Tube Sheet Waste Heat Boiler El Segundo Refinery, California.

The microstructure of the tubes and the tube sheet is pearlite+ferrite with the exception of specimen 7 which shows spheroidite. This is a strong indication that only specimen 7 has been exposed to temperatures above 650 C This can only be explained if the refractory has been missing.

Case 2: Cracks of Ammonia converter weld, India

A circumferential weld of one ammonia converter in India was found cracked after 6 months of service by through thickness passing cracks in a circumferential segment of ca 1.5 m, through which hydrogen leakage from the reactor was caused. After removal of the external insulation, cracks were found on the external reactor surface, transverse oriented with respect to the circumferential weld and completely contained within the weld metal. 20 distinct cracks on the external reactor surface were detected on the external reactor surface in the segment of the leaking weld. The following inspection of the inner reactor surface showed that the damage was localised and included a weld segment of ca 1.6 meters.
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HTAS S-50 Ammonia Converter

3H2 + N2 2NH3 Iron catalyst Temperature 400 500 C Pressures > 100 bar Recirculation of unconverted synthesis gas

Straight lenght Total Length Internal diameter Wall thickness Shell material Design pressure Design temperature Normal operation pressure Normal H2 partial pressure Normal operation shell temperature Max temp. during catalyst reduction

20250 mm 20250 mm 3000 mm 169 mm (3x42 + 43 mm multiwall) 2.25Cr-1Mo 225 bar 430 C 182 bar 90 bar 370 C 420 C

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Fabrication - Welding issues

Issue
Too low preheat temperature Too high heat input Too low weld rate Too low interpass temperature Too rapid cooling Humid flux Repear welds Too low temperature at PWHT

Risk of
Cold cracking Large grain sizes, reheat cracking Too large weld beads Cold cracking Brittle microstructure Hydrogen uptake Reheat cracking Large residual stresses

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Service Issues
High Temperature Hydrogen Attack Nitriding Low Temperature Hydrogen Attack (at shut downs)

Low Temperature Hydrogen Attack

H adsorption, H absorption, H2 formation Cracks along grain boundaries
H-H H H H H H-H

H-H

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High Temperature Hydrogen Attack (HTHA)

CH4 formation and decarburization

C (from the steel) + 4 H atoms CH4

Cracks parallel to the surface

-H H H H H H-H
CH4

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HTHA Nelson Diagram

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Nitriding
Diffusion controlled process. Parabolic reaction rate Formation of nitrides and methane
Cr23C6 + 11.5N2(g) + 12H2(g) = 23CrN + 6CH4(g) V2C + N2(g) + 2H2(g) = 2VN + CH4(g) N

-N

Nitrided region

N N N CrN, VN

-N

Sound metal

Hardness increase Cracks parallel (perpendicular?) to the surface

2.25Cr 1 Mo

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Nitriding
Depending of the stress level in the welds, nitriding is accelerated by a factor of 3 5

If sufficiently high load and/or residual stresses apply in the axial or tangential direction to the vessel wall, cracks have to be expected propagating slowly across the wall, as crack growth is controlled by diffusion of nitrogen and transformation of carbides to nitrides.

Outer

Inner

Schematic of crack formation in low stress regions (base metal) and high stressed region (e.g. coarse grained welds, welds with insufficient PWHT, etc) 17

Internal reactor surface Internal reactor surface

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Before Stress Relief heat treatment at 690 C for 1.25 h

After Stress Relief heat treatment at 690 C for 1.25 h

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Conclusion

Too elevated hardness values measured in the weld and at the Heat Affected Zone Harndess values considered originated by an erroneous or not performed Post Weld Heat Treatment. Taking into account the service conditions (presence of gaseous hydrogen and atomic hydrogen) it can be stated, that the part of the circumferential weld of high hardness was subjected to Hydrogen embrittlement.

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Thanks for your attention

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