ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

Material Selection Guide For Amine Units

Issue Date Author Keywords

: : :

January 25, 2001 R. van den Berg MEA, DEA, MDEA, DIPA Stress Corrosion Cracking H2S removal CO2 removal

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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

1. INTRODUCTION This standard outlines the basic material requirements for piping and equipment in amine units. It gives a generic description. For each individual specific case, a metallurgist shall be contacted to confirm the specific requirements. Amine units are used to remove hydrogen sulfide and/or carbon dioxide from acid gas. Amine solutions are defined as alkanolamine solutions, e.g. mono-ethanol-amine (MEA), diethanol-amine (DEA), methyl-di-ethanol-amine (MDEA) and di-glycol-amine (DGA) solutions.

2. GENERIC DESCRIPTION OF DEGRADATION MECHANISM Alkanol-amine solutions are commonly used for the removal of H2S and/or CO2 from acid gas since the early 1950's. It is recognized that corrosion is not caused by the amine itself, but is caused by the dissolved hydrogen sulfide and carbon dioxide gases, that are the reason for the existence of amine systems. Corrosion is most severe in systems removing only carbon dioxide. Amine degradation products can further increase the corrosiveness. Corrosion is more severe in plants that use MEA than that use DEA, because MEA is more prone to degradation. Use of MDEA and DIPA gives less corrosion, since CO2 reacted with MDEA and DIPA form no degradation products. Corrosion is most severe at locations where acid gases are desorbed or removed from the rich amine solution. Here, temperature and flow turbulence are highest. This includes the regenerator (stripper) reboiler and top part of the regenerator itself. Corrosion can also be a significant problem on the rich-amine side of the lean/rich amine exchangers, in amine solution pumps and in reclaimers. Besides corrosion, environmental stress cracking is another problem for amine units. Four types of cracking mechanisms can be identified for carbon steel components: Sulfide stress cracking (SSC) Hydrogen induced cracking (HIC) Stress oriented hydrogen induced cracking (SOHIC) Alkaline stress corrosion cracking (ASCC)

After some catastrophes, the NACE task group T8-14 conducted a worldwide survey on stress corrosion cracking of existing amine plants. The conclusion was that cracking in MEA, DEA and other amine solutions was reported for all common operating temperatures and that about 50% of the cracking cases occurred at temperatures below 65C (150 F). Cracking is found in, or adjacent to, welds. It occurred in all types of equipment at temperatures as low as ambient. No cracking has been reported for stress-relieved piping and equipment. Other corrosion phenomena, which can occur in amine units are chloride pitting, chloride stress corrosion cracking, and erosion-corrosion.

3. MATERIAL DESIGN BASIS / RULES

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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

The following material design basis / rules shall be considered for material selection of amine units: All carbon steel equipment and piping in amine service shall be stress-relieved, regardless of operating temperature. In case the amine unit removes H2S, all carbon steel equipment and piping in contact with wet H2S, shall fulfill the sour service (NACE MR-01-75) requirements. Copper, aluminum and zinc based alloys shall not be used in amine service, since they are not resistant against amines. As certain amounts of solids (corrosion products) are always carried in the amine (especially the rich foul amine) solutions, flow velocities in carbon steel piping shall be limited to 1.5 m/s (= 5 ft/s) to avoid erosion-corrosion. Use of long-radius bends (5D) and standard long-radius elbows shall be considered for liquid streams. Butt-welded connections are advised, screwed connections and socket-weld connections shall not be applied. To minimize pitting corrosion of carbon steel in amine service, the maximum recommended chloride level, as HCl, or NaCl and HCl in the solvent, is in the range of 250-500 ppm. Austenitic stainless steels are to be applied where the corrosion rate of carbon steel is excessive. These areas include areas of high velocity, turbulence, vapor flashing, twophase flow, and heat transfer surfaces above about 110C (230 F). To minimize the risk of chloride stress corrosion cracking of austenitic stainless steel parts the chloride level in the solvent shall be limited to 1000 ppm. If higher values are anticipated higher alloys like 254SMO (UNS S31254), alloy 28 (UNS N08028) or alloy 825 (UNS N08825) shall be considered. If possible, place the rich solution on the tube side of lean/rich amine exchangers. If possible, avoid flashing of acid gases in lean/rich amine exchangers by locating the pressure letdown valve downstream of the last exchanger. This prevents release of acid gas in the exchangers. Consider to use oversized pressure letdown valves to reduce erosion and corrosion caused by velocity effects. Letdown valves for high-pressure units should be stainless steel. Consider to use a square-pitch tube layout (or remove interior tubes) to reduce vapor blanketing in reboiler bundles. Further, square-pitch tube layout simplifies cleaning. Consider the use of vertical thermosyphon or pumped liquid reboiler design for the regenerator reboiler and amine reclaimer to assure that their tube bundles are fully immersed in process liquid at all times in order to avoid vapor accumulation.

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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

Provide inert-gas blanketing for storage and surge vessels to reduce oxygen degradation of amine solutions.

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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

4. MATERIALS SELECTION SCHEME The table as shown on the next page can be used as a guideline for materials selection in amine service. It must be realized that the corrosiveness depends on the type of amine, amine concentration, acid gas loading, velocities, and degradation products, as heat stable salts. Further, other media (e.g. NH3, HCN, chlorides, acids) present in the process can influence the corrosion mechanisms and thus the materials selection. Depending on the ratio of H2S and CO2 two different cases can be distinguished in amine units: If the hydrogen sulfide content is less than 1 percent by volume of the total acid gas, carbon dioxide is considered to be the primary corrosive species (CO2 case). If the hydrogen sulfide content is more than 1 percent by volume of the total acid gas, hydrogen sulfide is considered to be the primary corrosive species (H2S case). In this case sour service requirements shall also be considered.

If the process stream is a liquid only (e.g. LPG or LNG), a molar ratio of 0.02 H2S/ CO2 in the liquid corresponds to the above gas phase ratio of 0.01.

The listed materials selection is valid for acid gas loadings (mol acid gas per mol amine) less than 0.4 for primary amines such as MEA and 0.8 for secondary amines. Higher loadings will give higher corrosion rates and thus require higher metallurgy or increased corrosion allowances.

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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

Equipment Absorber / Contactor

CO2 case (H2S < 1 vol%) Shell: 180F: 180<T 200F: T > 200F: Trays:

Rich amine flash drum Rich/lean exchanger

CS + 3mm CA CS + 6mm CA CS + 304L clad 12% Cr or SS 304 (at feed inlet) SS 304L or CS + SS 304L clad

H2S case (H2S > 1 vol%) Shell 230F: T > 230F: Trays: CS + 3mm CA

CS + 3mm CA CS + 304L clad 12% Cr or SS 304

Level control valve Piping from rich/ lean exchanger to regenerator Regenerator

Reboiler (note 1) Reclaimer

Regenerator overhead piping Overhead condenser Overhead drum Drum overhead piping Reflux piping Lean amine piping Lean amine cooler Pumps Filters Valves, control valves (note 3) Amine make-up

Shell (lean amine) 285F: CS + 3mm CA Tubes (rich amine) 180F: CS > 180F: SS 304L Channel 180F: CS + 3mm CA Body: SS 304 / 316 Trim: SS + stellite 6 overlay T 200F: Upstream control valve: CS + 3mm CA Downstream control valve: SS 304L T > 200F: SS 304L Shell: CS + 3mm CA CS + SS 304L clad above and including feed inlet tray Trays: SS 304 Amine side: CS + 3mm CA Steam side: CS + 1.5mm CA Tubes (steam temperature): 300F: CS > 300F: SS 316L SS 304L Header: SS 304L Tubes: SS 304L SS 304L or CS + SS 304L clad SS 304L SS 304L CS + 3mm CA Lean amine: CS + 3mm CA Tubes: CS Casing: SS316 or Ni-resist (note 2) Impeller: SS316 or Ni-resist (A439-D2) Casing: CS + 3mm CA Internals: SS 304 / 316 Body: CS Trim: SS + stellite 6 or PTFE CS + 1.5mm CA (note 4)

Shell (lean amine) 285F: CS + 3mm CA Tubes (rich amine) 240F: CS > 240F: SS 304L Channel 240F: CS + 3mm CA Body: SS 304 / 316 Trim: SS + stellite 6 overlay T 230F: Upstream control valve: CS + 3mm CA Downstream control valve: SS 304L T > 230F: SS 304L Shell: CS + 3mm CA

Trays: SS 304 Amine side: CS + 3mm CA Steam side: CS + 1.5mm CA Tubes (steam temperature): 300F: CS > 300F: SS 316L CS + 3mm CA Header: Tubes: CS + 3mm CA CS + 3mm CA CS + 3mm CA CS + 3mm CA Lean amine: CS + 3mm CA Tubes: CS Casing: SS316 or Ni-resist (note 2) Impeller: SS316 or Ni-resist (A439-D2) Casing: CS + 3mm CA Internals: SS 304 / 316 Body: CS Trim: SS + stellite 6 or PTFE CS + 1.5mm CA (note 4) CS + 3mm CA CS

Notes:
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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

1. 2. 3. 4. 5.

For exchangers where vapor evolution occurs, use stainless steel type 316L tubes for the reboiler. For a low CO2 content (< 0.01 CO2/ mol amine) a carbon steel body casing is acceptable for pumps. In case of flashing of more than 3% vol. in the rich amine, valve and piping for 10 feet (3 meters) downstream valve shall be stainless steel. For clean amine make-up piping, and for atmospheric storage tank with maximum temperature below 140 F, stress-relieving can be omitted. Selected materials as shown in this table shall always be confirmed by a metallurgist.

ELASTOMERS For elastomers, used as O-rings and other specialty seals, the following table can be used as general selection criteria, within the maximum temperature indicated:
Natural Rubber
Not recomm.

Butyl (IIR)
65 C 150 F

Nitrile (Buna-N)
Not recomm.

FKM (Viton)
Not recomm.

EPDM
Not recomm.

FEPM (Aflas)
200 C 400 F

PTFE (Teflon)
220 C 425 F

FFKM (Kalrez)
260 C 500 F

FASTENERS For CS bolts and nuts in amine service, heat treated materials in finished condition shall be applied. This means ASTM A193 grade B7M and ASTM A194 2HM or equivalent. In case strength requirements demand that higher strength bolts are required, high strength Monel K-500 (UNS N05500), ASTM A453 grade 660, or alloy 718 (UNS N07718) bolts can be considered.

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ABB Lummus Global STANDARD for Material Selection Guide for Amine Units

References [1] J.P. Richert, A.J. Bagdasarian, C.A. Shargay, Stress Corrosion Cracking of Carbon Steel in Amine systems, Materials Performance, Volume 27, January 1988. API Recommended Practice 945, Avoiding Environmental Cracking in Amine Units, second edition, October 1997. M.S. DuPart, T.R. Bacon and D.J. Edwards, Understanding Corrosion in Alkanolamine Gas Treating Plants, Hydrocarbon Processing, April/May 1993. P.C. Rooney, et al, Effect of Chlorides on Solution Corrosivity of Methyldiethanolamine (MDEA) Solutions, NACE, Corrosion 97, Paper No. 345. ABB Lummus Global Inc., Materials Selection Guide, Amines, August 1994.

[2]

[3]

[4]

[5]

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