Acid Gas Removal Corrosion Prevention

3700 Acid Gas Removal Plants
Author: B. (Barbara) Cooke
Abstract
Three types of amines are commonly used in acid gas removal plants: monoethanol
amine (MEA), diethanol amine (DEA), and methyl diethanol amine (MDEA). Hot
potassium carbonate systems (Benfield and Catacarb) are primarily used for CO2
removal. This section covers corrosion problems found in CO2 and H2S removal
plants using these processes.
Contents
Page
3710 Introduction
3700-3
3720 Process Description: Amine Treating Plants
3700-3
3730 Corrosion in Amine Treating Plants
3700-6
3731 General or Preferential Corrosion

3732 Stress Corrosion Cracking: Carbon Steel
3733 Stress Corrosion Cracking: Stainless Steels
3734 Influence of Design and Operating Variables
3740 Corrosion Control in Amine Treating Plants
3700-19
3741 Use of Alloy Equipment

3742 Corrosion Inhibitors
3743 Corrosion Monitoring
3750 Process DescriptionHot Potassium Carbonate Plants
3700-24
3760 Corrosion in Hot Potassium Carbonate Plants
3700-26

3764 Influence of Design, Operating Variables
3770 Corrosion Control in Hot Carbonate Treating Plants
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Corrosion Prevention and Metallurgy Manual
3771 Use of Alloys

3772 Use of Corrosion Inhibitors
3780 References
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3710 Introduction
Acid gas removal plants remove carbon dioxide (CO2) or hydrogen sulfide (H2S)
from gas and liquid streams. CO2 removal plants are important parts of hydrogen
manufacturing plants and ammonia plants. H2S removal plants process sour gas
streams from a variety of sources, including producing locations, crude units, catalytic reformers or hydrotreaters, fluid catalytic crackers, and hydrocrackers.
Three types of amines are commonly used in acid gas removal plants. MEA (monoethanol amine) and DEA (diethanol amine) have been used for many years for both
CO2 and H2S removal, while MDEA (methyl diethanol amine) is a relative
newcomer. Also, DIPA (di-isopropanol amine) is used in SCOT tailgas plants at
Port Arthur and Philadelphia. DIPA plants will not be discussed in detail here,
although corrosion problems are similar to those in acid gas removal plants.
For several years, hot potassium carbonate systems (Benfield and Catacarb) have
been used, primarily for CO2 removal. This section reviews these processes and the
variables in design and operation that affect corrosion.
Amine and potassium carbonate plants use chemical solvent processes that depend
on reversible chemical reactions. Other processes use solvents that depend on physical absorption in solution of acid gases. Examples include Shells Sulfinol Process
(Sulfolane, or tetrahydrothiophene dioxide) and Fluors Solvent (propylene
carbonate) and Purisol (NMP or N-methyl-2-pyrrolidone). We use Flour Solvent
and Purisol in hydrogen plants at El Segundo and Pascagoula, but have no plants
using Sulfinol. Neither process will be discussed in this chapter.
All acid gas removal processes share corrosion problems and problem areas:
Corrosion caused by extreme turbulence in which the acid gas flashes (as at
pressure letdown valves and downstream piping, and the regenerator feed
tray/distributor)
Corrosion in regenerator overhead system caused by the presence of wet

acid gas without the alkaline solvent (includes the regenerator shell above the
feed tray)
Corrosion in the hot, lean system (reboiler, hot piping, bottom of regenerator).
The mechanism(s) is not clearly understood but is related to temperature.
These problems will be discussed in more detail later in the section, along with
corrosion problems specific to certain processes.
3720 Process Description: Amine Treating Plants

A flow diagram of a typical amine treating unit is shown in Figure 3700-1. In this
process, acidic gases such as hydrogen sulfide or carbon dioxide react with certain
amines to form compounds that are stable at lower temperatures but may be broken
down by heating. In the case of hydrogen sulfide and DEA, the reaction may be
written as follows:
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Fig. 3700-1 Materials for Amine Gas Treating Plants
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2R2NH + H2S R2NH2SH2NR2

(Eq. 3700-1)
DEA and MEA are the amines most often used. Their advantages include high reactivity and lower solvent cost; their disadvantages are their inability to cope with
COS, CS2, mercaptans, and oxygen-bearing gases, and higher utility costs than the
MDEA and hot potassium carbonate processes. MEA is the most common process
in CO2 removal plants, DEA in H2S removal plants.
MDEA has been tried recently with mixed results: it performs well in H2S or
H2S/CO2 plants, but in CO2-only plants, corrosion control must be carefully
considered.
MDEA and proprietary MDEA blends offer two advantages:
Selectivity. They absorb H2S and reject most CO2. This produces richer feed to
the sulfur plant. The selectivity of the MDEA can be tailored to a specific
process by blending.
Lower cost to regenerate. The lower heat of reaction with H2S and CO2 and
the ability to operate at 50% MDEA concentration greatly reduces the heat to
regenerate MDEA. This results in steam savings in the regenerator.
In an amine treating plant, the sour gas is contacted at high pressures with cool
amine, which absorbs H2S and/or CO2. The purified process gas passes overhead
from the top of the absorber column, while the rich amine solution containing the
H2S and CO2 is removed from the bottom, preheated by a heat exchanger and sent
to the regenerator or stripper column. At the elevated temperatures and reduced
pressures of the regenerator, the acid gases are liberated from the amine and evolved
as the overhead product. The lean amine (more or less free of acid gas components) is withdrawn from the bottom of the column, cooled, and returned to the
absorber column to repeat the cycle. CO2 wastes are sold or vented to atmosphere;
H2S wastes are incinerated or further processed to recover elemental sulfur.
Absorber columns characteristically operate at temperatures from ambient to about
150F and pressures from 100 psi to several thousand psi. Regenerator bottoms
temperatures typically fall between 240F and 280F and pressures normally are a
few psi at most.
Most amine treating plants have a filter system that removes scale, solids, hydrocarbons, and other impurities to minimize erosion and localized corrosion from scale
deposits. The filter system includes both mechanical filtration and in some plants
carbon absorbers. MEA plants also have a reclaimer, but boiling points of other
amines are too high for reclamation to be practical. The MEA reclaimer receives a
slipstream from the regenerator and boils off amine, which is returned to the regenerator. Reclaimer bottoms concentrate degradation products, which are periodically
discarded.
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3730 Corrosion in Amine Treating Plants

The amine treating process has been in use for many years and the inherent corrosion problems are well documented in both published and Company literature.
Despite available knowledge on the subject, corrosion problems are common. Older
plants that have operated trouble-free for a number of years can suddenly become
troublesome following minor operating changes such as introduction of new feeds
(hydrocrackers) or increases in feed rates (loading).
The type and severity of corrosion and the methods of mitigation depend on several
variables. The most important are: the gas being treated, choice of amine (MEA,
DEA, MDEA) as an absorption solution or solvent, operating temperatures, solvent
concentration, acid gas loading, purity or cleanliness of the solvent, feed rates as
percent of design, flow velocities, inhibitors used, and equipment design and
metallurgy.
In general, aqueous amine solutions, being alkaline, are noncorrosive to carbon steel
when not highly loaded with H2S or CO2. For this reason, most equipment in these
plants is carbon steel and suffers little or no attack. Absorber columns and cold
piping are seldom subject to corrosion and are almost always constructed of carbon
steel with a nominal corrosion allowance.
Amine solutions tend to liberate acid gases when heated, creating corrosive conditions. Control of hot amine corrosion requires limiting the regeneration temperatures, the solution concentration, and the level of impurities in the amine solution by
measures such as reclaiming or filtering. Proper selection of materials is also
important.
Figure 3700-1 shows potentially corrosive areas of an amine plant. A portion of
amine plants that characteristically shows serious corrosion is the hot regenerator
bottoms system. Attack may occur in the reboiler, reboiler return line, lower portion
of the column, hot amine piping, and rich/lean amine exchangers. Corrosion is often
not uniform, occurring either as pitting or highly localized attack in turbulent areas.
Figures 3700-2 and 3700-3 show examples of corrosion related to turbulence and
velocity in amine piping.
Although CO2 removal plants often use a corrosion inhibitor, carbonic acid corrosion can occur in the overhead system, particularly in the overhead condenser, if the
inhibitor and the alkaline amine are not carried overhead. Carbonic acid corrosion
takes the form of localized erosion-corrosion. Generally, the remedy for the
condenser tube corrosion is upgrading to T-304 stainless steel. If air coolers are
used, inlet and outlet headers should also be stainless steel. Carbonic acid corrosion
also attacks metal in turbulent sections of piping and the liquid impingement areas
of the reflux drum.
Regenerator overhead corrosion is also a problem in H2S removal plants, which
typically do not use inhibitors. Overhead corrosion has increased with increasing
use of high nitrogen crudes. Cracking or hydrotreating high nitrogen stocks
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Fig. 3700-2 Example 1Corrosion Related to Turbulence and Velocity in Amine Piping
produces cyanide and ammonia, which go overhead in the regenerator, get picked
up in the condensing water, and reflux back to the regenerator. Because the
ammonia and cyanides cannot easily escape from the system, they build up to very
high concentrations. As a result, the regenerator overhead can contain high levels of
ammonium bisulfide (NH4HS) and, often, excess ammonia.
Alkaline sour water corrosion is a problem in plant processing hydrocracker, coker,
or FCC gases. In these plants, experience indicates that stainless steels (Types 304
and 316) corrode at about the same rate as carbon steel. Corrosion control measures
include use of ammonium polysulfide to convert cyanides to harmless thiocyanates,
reflux bleed streams to minimize buildup of NH4HS in reflux loops, velocity limits
(20 fps) in steel piping, and titanium grade 2 condenser tubes. For more information, refer to Sections 3200, 3300, and 3800 of the Corrosion Prevention and Metallurgy Manual, Volume 2.
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Fig. 3700-3 Example 2Corrosion Related to Turbulence and Velocity in Amine Piping
The reflux bleed stream (see Figure 3600-1) allows removal of NH3 and control of
ammonium bisulfide that would otherwise concentrate in the overhead system.
Ideally, NH4HS should be limited to a maximum of 2% to 3%. This is often not
possible, but reducing NH4HS to even 5% to 10% is desirable. The reflux bleed
piping also allows purging of any hydrocarbon trapped in the overhead system.
MDEA Plant Corrosion

Because MDEA can be used at higher concentrations than DEA or MEA, many
plants have converted to MDEA to increase efficiency. Chevron uses MDEA at St.
Helens NH3 Plant, Salt Lakes H2S plant, some H2S/CO2 plants at Port Arthur, and
several natural gas plants. All plants have operated within the limits of 50% (max.)
solution concentration and loadings of 0.45 moles acid gas/mole amine. Suppliers of
MDEA, including Dow and Union Carbide, claim that it is noncorrosive up to
50% solution concentration.
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Company experience and industry surveys indicate that corrosion control is dependent on the acid gas on solution cleanliness [1-3]. In H2S plants, MDEA corrosion is
typically low because the H2S forms a protective sulfide scale on the metal surfaces.
However, some CO2 plants, including St. Helens NH3 plant, Mobils Torrance H2
plant, and an Agrico NH3 plant, have had severe MDEA corrosion. Plants with
MDEA should not use inhibitors intended for MEA because they tend to increase
corrosion.
MDEA is degraded more easily than other amines, and we believe that most corrosion can be avoided by keeping the MDEA free of degradation products. Since
MDEA cannot be reclaimed, this is best done by avoiding oxygen entry and using
carbon absorbers along with mechanical filters to remove impurities. The mechanical filters remove solid contaminants, while the carbon absorbers remove hydrocarbons, which cause foaming.
The carbon absorbers should be changed regularly. Most users rely on Fe measurements to determine when the filters need replacing. Although there is no fixed Fe
concentration to use, Fe typically drops substantially when new filters are installed,
then rises and levels off at a plateau before eventually rising again. Filters should be
changed before this final rise. With proper filtration, MDEA corrosion is typically
no worse than inhibited MEA and is usually not as severe.

Amine Stress Corrosion Cracking
Amine solutions can cause corrosion cracking of nonstress-relieved carbon steel. In
general, MEA can crack steel under milder conditions (e.g. lower temperatures)
than DEA or MDEA. The industry has reported cases of MEA cracking down to
ambient temperatures and DEA cracking down to 140F [4-6]. DEA and MDEA
behave similarly in terms of stress corrosion cracking.
In 1991, amine stress corrosion cracks were found in 150F lean DEA piping in the
El Segundo VGO hydrotreater. Tests showed that the piping had not been stressrelieved or the stress-relief had been inadequate. Although the line temperature was
150F when the piping leaked, temperatures had run as high as 190F during its
17 years of operation [7].
Carbon steel in amine service is most likely to crack in areas of the plant operating
at the highest temperature levels. Stress corrosion can occur both rapidly and extensively at regenerator bottoms temperatures (240280F), but becomes less serious
as the temperature is decreased.
Water-washing prior to shutdown steam-out is essential to prevent stress corrosion
cracking of nonstress-relieved equipment, which operates at low temperatures
during service. A water-wash with distilled water or steam condensate will remove
residual amines, which can crack nonstress-relieved equipment when heated during
steam-out. Residual amines present during steam-outs cracked a nonstress-relieved
MEA absorber column in a Chevron refinery in 1974.
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The most reliable way to avoid stress corrosion cracking is to stress-relieve welds in
amine service. See Figure 3700-4 for a summary of the current stress-relief guidelines. Currently we recommend stress relief of all pressure vessels in MEA service,
regardless of operating temperature. Piping in MEA service should be stressrelieved if it operates above 100F. Even intermittent service lines, like Regenerator
pumpout line to amine storage tank, should be considered.
Fig. 3700-4 Stress Relief Guidelines for Newly Constructed Amine Plants
Stress Relieve?
MEA
DEA and MDEA
Absorber
yes
yes
Regenerator
yes
yes
Pressure Vessels in Main Circulating Loop(1)
yes
yes
Butt Welded Piping Above 100F
yes
yes
Socket and Seal Welds Above 100F
yes
no
Storage Tanks
Shell
Heating Coils
no
yes
no
yes
Notes:
1. External welds often create through-wall stresses sufficient to cause ID SCC. Hence, any external weld should be treated as an
internal one.
2. Operators of existing plants can consult with CRTC Materials and Equipment Engineering to formulate long-term plans on how to
bring their plants up to these new standards.
(1) This includes any absorber overhead K.O. drum
Stress relief guidelines for DEA and MDEA plants can be slightly less restrictive
than those for MEA. Again, all pressure vessels should be stress-relieved regardless
of operating temperature. On piping, butt welds (normally 2 inches and larger)
should be stress-relieved if operating above 100F. Socket and seal welds (normally
1 inches and smaller) do not require stress relief.
Figure 3700-5 gives inspection guidelines for existing plants where original stress
relief was not as extensive. From a technical viewpoint, the Company does not
consider it necessary to inspect DEA and MDEA vessels operating below 150F,
unless more than 50 ppm H2S are present. In that case, refer to inspection guidelines for wet H2S cracking. If equipment was ever in MEA service, it should be
inspected once as an MEA vessel (regardless of its present service), and subsequently according to guidelines for its present service.
When repairing stress-relieved equipment in hot amine service, it is necessary to
stress-relieve repair welds to avoid cracking. A small weld on the outside of a
column or vessel can result in stress corrosion cracking on the inner surface. Cracks
also may start from such apparently unimportant items as an arc strike on a vessel
wall, or fillet welded support shoes on the outside of hot piping. Vessels should be
stress-relieved by ASME Code approved practices (e.g., a full circumferential band
of heat, not localized on one side only).
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Fig. 3700-5 Amine Plant Inspection Guidelines(1)
1. Nonstress-relieved Vessels
Inspection Method
Frequency
MEA
DEA, MDEA
WFMT (3)
WFMT
(2)
T less than 150F

T greater than 150F
(note
(4))
1 every other scheduled

shutdown
1 every scheduled
shutdown
1 every other scheduled

shutdown
WFMT
(note (5))
WFMT
(note 5)
UT (7)
UT
50%/5 years
(note (8))
50%/5 years
2. Stress-relieved Regenerators
Inspection Method
Frequency
3. Nonstress-relieved piping (6)
Inspection Method
Frequency
T Between 100F & 150F
T Greater Than 150F
(1) Some vessels otherwise exempt from the requirements for amine stress corrosion cracking inspection may require special inspection
for wet H2S cracking.
(2) Any evidence of or history of hydrogen blistering in a vessel necessitates inspecting all welds internally, using wet fluorescent magnetic
particle testing (WFMT).
(3) WFMT = wet fluorescent magnetic particle testing
(4) From a technical viewpoint, the CRTC Materials and Equipment Unit does not consider it necessary to inspect DEA and MDEA vessels
operating at less than 150F, unless more than 50 ppm H2S are present. In that case, refer to inspection guidelines for wet H2S cracking.
(5) If not done previously, schedule a one-time internal inspection of the bottom third of the regenerator column. Any future inspections will
be determined by your findings.
(6) Piping 1-1/2 inch and smaller need not be inspected.
(7) UT = shear wave ultrasonic testing
(8) Inspection necessary unless stress corrosion has occurred elsewhere in the plant below 150F.
For general guidelines on equipment inspection and repair, refer to API Recommended Practice 945, Avoiding Environmental Cracking in Amine Units. This
publication also gives a general overview of amine and wet H 2S cracking in amine
plants.
Wet H2S Cracking and Blistering

The term wet H2S cracking refers to hydrogen induced cracking, stress oriented
hydrogen induced cracking, sulfide stress cracking, and hydrogen blistering. All of
these cracking mechanisms can be active where carbon steel is exposed to H2S and
liquid water. A minimum H2S level to 50 ppm is used for inspection purposes, but
some cracks have been found in vessels with less than 50 ppm H2S in water. For
more details and clarification, see Section 450 and Figure 400-39 of the Corrosion
Prevention and Metallurgy Manual, Volume 1.
Sulfide stress cracking (SSC) can occur in carbon steel columns, vessels, heat
exchanger shells, and piping. In 1990, Carter Creek's DEA regenerator had sulfide
cracking in the bottom head and lower shell, following improper application of an
oxidizing corrosion inhibitor. A catastrophic failure in 1984 of a Union Oil amine
absorber from stress oriented hydrogen induced cracking was initiated by SSC of
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hard welds. A maximum hardness of 200 BHN for carbon steel welds is necessary
to avoid SSC. For more information on sulfide cracking, see Section 452 of the
Corrosion Prevention and Metallurgy Manual, Volume 1.
Hydrogen blisters can form in several areas of H2S removal plants. Most blisters
develop in the regenerator overhead system. Cyanides in the overhead system
promote blistering by destroying the protective iron sulfide film on the steel
surfaces. Blistering has also been detected in both the upper and lower sections of
ammonia scrubbers, which are used in amine plants in newer units. In very highly
loaded MEA plants (0.4 moles acid gas/mole amine), hydrogen blisters can form in
the bottom of the absorbers. In these plants, steel blistered in the absence of cyanide
and ammonia.
To control cyanides, ammonium polysulfide is sometimes injected into the overhead system of the cracking unit (i.e. FCC or hydrocracker) upstream of the amine
plant. Most amine plants do not use ammonium polysulfide injection, except as a
temporary measure. Typically, a plant would consider using polysulfide if corrosion
rates were high and a spot FeCl test detected cyanides. (For details on the FeCl test
procedure, consult CRTC Materials and Equipment Engineering). The FeCl test is a
qualitative test for cyanides. The most reliable quantitative test for cyanides is ion
chromatography.
We generally recommend a nominal polysulfide injection rate of five to ten times
the stoichiometric amount needed to react with cyanides in the process. Polysulfide
rates can be optimized by monitoring hydrogen activity using hydrogen probes.
If polysulfide is injected into the regenerator overhead system, use ammonium
polysulfide, rather than sodium polysulfide. Either form of polysulfide will be
refluxed back to the regenerator column and mixed into the circulating amine solution. However, while ammonium polysulfide decomposes in the column, in the case
of sodium polysulfide, the sodium ion stays in the amine and builds up to undesirable high levels. Another advantage of ammonium polysulfides is its faster reactivity with cyanides.

Stainless steels are susceptible to two types of stress corrosion cracking in acid gas
removal plants: chloride cracking and polythionic cracking. Both mechanisms will
crack only austenitic stainless steels (e.g. Type 300 series).
Chloride Cracking
Stainless steel tubes have suffered chloride stress corrosion cracking in amine plant
regenerator reboilers, rich-lean heat exchangers, and MEA relcaimers. Chlorides
can be introduced with produced water or with the caustic, carbonate, or make-up
water added to the system.
Because most commercial grades of both sodium hydroxide and sodium carbonate
contain a significant percentage of sodium chloride, only low-chloride- containing
chemicals should be used in plants with stainless steel equipment. Other chloride
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sources are feed contamination and the water source used for makeup amine
solutions.
Only low-chloride steam condensate should be used for makeup. Acceptable levels
of chloride in amine plants with stainless steel reboilers are not definitely known,
but indications are that levels in the amine solution should not exceed 500 ppm
chloride. This chloride concentration can cause chloride SCC of stainless steel tubes
if U-tube bundles have not been stress-relieved or straight sections fully annealed or
properly stress-relieved after straightening.
Polythionic Cracking
Stainless steels have failed in hydrogen sulfide removal plants through stress corrosion cracking by polythionic acids. (See Section 3400 and Section 400 of the Corrosion Prevention and Metallurgy Manual, Volume 1, for discussions of polythionic
cracking.)
Polythionic cracking is caused by acidic constituents formed from oxidation of iron
sulfide corrosion products. Polythionic acid stress corrosion occurs only in stainless
steel grades that are susceptible to sensitization and therefore subject to intergranular corrosion.
Formation of polythionic acids can occur in amine treating plants only during shutdowns, when the equipment might be allowed to stand in contact with moisture and
oxygen. Iron sulfide scale is first formed from corrosion of carbon steel equipment
and later deposited in the stainless steel piping. During a shutdown, the scale apparently oxidizes enough to form the acidic environment that promotes cracking.
Intergranular stress corrosion cracking of sensitized stainless steel has also occurred
in CO2 removal plants. For this reason, we recommend the following practices for
both H2S and CO2 removal plants. Do not use regular grades of stainless steel such
as Type 304 where welding is required or for U-tubes that require stress relief. Use
only low carbon or stabilized grades (Types 304L, 316L, 321, or 347) in these applications. Review stress relief procedures to assure that they do not sensitize equipment. Use electric resistance stress relief methods for exchanger u-tubes. Soda ash
wash stainless steel equipment that is sensitized.
3734 Influence of Design and Operating Variables

Design and operating variables have a great influence on corrosion in acid gas
removal plants. Changes in operating variables to increase plant throughput tend to
increase corrosion. Considerable information is available, especially for MEA/CO2
plants, on the effect of design and operating variables on corrosion [812]. This
section summarizes the influence of a number of these variables. Most of the principles discussed refer to corrosion of carbon steel in systems using MEA; DEA and
MDEA systems have similar tendencies.
Most company amine plants use alloys in critical equipment such as regenerator
bottoms and reboilers. However, if conditions are severe enough these alloys can
also corrode; therefore, attention to design and operating details is necessary to
minimize corrosion, downtime, and maintenance expenses.
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Primary Operating Variables:

The primary variables are:
Temperature
Solution Strength
Acid Gas Loading
Temperature. Corrosion is a strong function of temperature with increasing temperature increasing corrosion. The highest temperature and, therefore, worst corrosion
is usually found in the regenerator bottoms system.
The high alkalinity of the amine minimizes corrosion until temperatures in excess of
about 250F are reached. Above 250F, carbon steel corrosion is significant and
special alloys and/or inhibitors are required. This corrosion is probably related to
impurities and degradation products in the amine, such as heat stable salt and other
acid compounds.
In MEA reclaimers, tube metal temperatures above 300F325F will result in
amine degradation and corrosion even in stainless steel. Operating and design
conditions must therefore avoid creating hot tube metal surfaces. For more information on reclaimer operating conditions, consult a member of the CRTC Light Hydrocarbon Processing Team.
Solution Strength. Another factor affecting corrosion is amine solution strength,
which is the sum of the free amine concentration and the amine tied up as heat
stable salts. Industry guidelines and company experience indicate that the upper
limit for MEA solution strength is about 20 weight percent MEA in aqueous solution. Above this level serious corrosion is often encountered because high concentrations require increased regeneration temperatures, which tend to degrade the
amine. The upper limits for DEA concentrations are somewhat higher at 25 to
30 weight percent. MDEA can be used up to 50 weight percent.
Acid Gas Loading. Another important solution variable is acid gas loading,
expressed as moles of acid gas per mole amine. Acid gas loading is related to acid
gas feed rate and solution circulation rates that are built into a plant design. Sizing a
plant too small or operating a plant above design limits can lead to serious corrosion. For MEA plants, acid gas (i.e. H2S or CO2) loadings above 0.40 moles acid
gas per mole MEA cause significant corrosion of carbon steel equipment. The
limits for H2S/DEA plants are somewhat higher, at about 0.4 to 0.6 moles H2S per
mole DEA.
These limits are largely dictated by equilibrium considerations (in the H2S/DEA
reaction 0.5 moles H2S per mole DEA is ideal), but ultimately are set by corrosion
considerations. If more H2S or CO2 is dissolved into solution than can react with the
amines, then very corrosive amine compounds form. Even at low loadings, corrosion is a function of the amount of CO2 or H2S dissolved. Figure 3700-6 shows the
effects of CO2 gas loading and temperature on corrosion in an MEA system.
Figure 3700-7 gives optimum and maximum recommended acid gas loadings and
MEA concentrations. New inhibitors may allow operation at higher loadings and
solution concentrations than indicated.
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Fig. 3700-6 Effect of Acid Gas Loading and Temperature on Corrosion. These data were
developed in a pilot plant and are only shown here to illustrate general trends.
The actual corrosion rates may be different for a commercial plant.
Fig. 3700-7 Optimum and Maximum Acid Gas Loadings and MEA Concentrations
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Control of amine solution strengths and acid gas loadings are of prime importance.
Performing routine analyses is good operating practice. If plants have to be operated in excess of design capacity, it is better to operate with slightly higher solution
strengths and moderate loadings, rather than with normal solution strength and high
loadings.
SummaryPrimary Variables. The three primary variables of temperature, solution concentration, and acid gas loading are not independent. If any two are held
constant, corrosion will tend to increase as the third variable increases. The critical
value of the third variable will depend on the magnitude of the other two.
Secondary Operating Variables

The secondary variables are:
Solution cleanliness
Velocity/turbulence
Solution Cleanliness. Contamination or degradation of amine solutions can lead to

serious corrosion and foaming [13]. Operating and corrosion problems usually begin
when the circulating solution gets dirty. For long, trouble-free solution life, it is
necessary to recognize these problems and to know how to prevent them. Contaminants can be degradation products, heat-stable salts, oxygen, dissolved hydrocarbons, liquid hydrocarbons, and solids.
Degradation of amines can occur by several mechanisms. Amines oxidize readily in
the presence of oxygen and form corrosive organic acids. To prevent oxidation, the
amine storage and surge vessels should be gas blanketed to keep air out of the
system. Air leakage into a hot system (pump suctions) causes serious problems.
Organic oxygen scavengers can be injected to reduce corrosion rates, but their use
must be carefully controlled to avoid accumulation in reboilers and heat exchangers.
Organic acids (such as hydrocyanic, formic, acetic, and oxalic) sometimes formed
during the amine plant process or as a result of oxygen contamination can cause
serious heat stable salt problems. Heat stable salts are products of reactions between
these organic acids and the basic amines. For example, HCN will react with H2S to
form thiocyanic acid (HSCN). In turn, the thiocyanic acid will react with an amine
to form heat stable salt amine thiocyanate. The salt is heat stable because the
amine cannot be regenerated by adding heat.
Control of heat stable salts is important because an amine solution becomes more
corrosive as the level of heat stable salts in the solution increases. At high levels of
heat stable salts, overstripping of the amine will further increase corrosion rates
[14]. We believe this occurs because the lean amine does not have enough sulfide to
establish and maintain a protective iron sulfide film on carbon steel surfaces. Union
Carbide recommends limiting heat stable salts to less than 10% of the total mine
concentration (e.g. 2.5 wt.% for a 25 wt.% amine solution). Industry experience
indicates that corrosion is low if a plant limits heat stable salts in the solution to
2.53.0 wt.%.
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Solution degradation can also occur from excessive temperatures or localized overheating. Hot spots in reboilers can decompose the amine to form corrosive
compounds. Gas contaminants like COS or CS2 can also cause degradation of MEA
solutions. These compounds should be removed from gas streams in MEA/CO2
plants (DEA and MDEA are less affected), and regenerator bottoms temperatures
should be kept as low as possible (but above the amine boiling point).
Dissolved or entrained liquid hydrocarbon contamination can lead to fouling, overheating, increased corrosion problems, and foaming. Sludge and suspended solids
are also troublesome. The principal solid impurity is iron sulfide, but magnesium,
calcium, silicate, and other inorganic compounds have been detected. Calcium and
magnesium salts generally result from using raw water as makeup instead of steam
condensate.
Solids in amine solutions contribute to erosion-corrosion, foaming and fouling. The
finely divided iron sulfide may be a corrosion product from the acid gas removal
plant or may enter the absorber with the feed gas stream. As these particles grow
and settle out, they form a black, sticky, and abrasive mass which can cause erosioncorrosion in turbulent flow areas. This sludge also deposits in low-flow areas,
exchanger surfaces, and trays, and can cause severe foaming problems. Under
sludge deposits pitting and preferential attack are common problems.
Solution cleanliness is controlled in DEA and MDEA by filtration and in MEA by
filtration plus reclamation. Good filter systems include mechanical filters, which
remove sludge and solid impurities from the amine solution. Mechanical filters
should receive continuous 100% flow of the solution. The recommended filter size
is 510 microns, and the recommended solids content in the amine solution is
100 ppm. Differential pressure indicators are used to determine when filters are
plugged. For high filtration loads, consider using automatic backwash filters or
3M bag filters.
Because DEA and MDEA cannot be reclaimed, carbon absorption is used to remove
dissolved organic impurities that cause foaming. Carbon absorbers are essential to
control conversion in MDEA plants, since MDEA degrades easily. They are also
desirable in DEA systems, but are not as critical. As a bare minimum, at least 10%
of the solution should pass through the carbon while small plants may filter 100%.
Plants should increase the percentage of flow through the carbon filters as much as
possible. A sock filter is typically placed downstream of the carbon absorbers to
trap carbon fines.
In MEA plants, reclaimers are important in reducing corrosion, foaming, and
fouling. Reclaiming restores the amine usefulness by removing high-boiling and
nonvolatile impurities such as heat-stable salts, suspended solids, and iron products
from the plant solution. It is the most economical and popular method of minimizing contamination of plant MEA solutions. Reclaiming consists of a semicontinuous batch distillation of a 1% to 3% slipstream of the circulating hot, lean MEA
solution. The length of a reclaimer cycle depends on the degree of contamination,
with short cycles required for badly fouled solutions. Problems in Company plants
are sometimes attributable to running a reclaimer too long before dumping. Usually,
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reclaimers are used when degradation levels of the amine solution are over 1%, or
about 10% of the solvent concentration.
Soda ash or caustic soda is added in stoichiometric amounts to the reclaimer to free
the combined MEA and neutralize the heat-stable salts and volatile acids. A lowchloride soda ash, such as natural soda ash, or a rayon or mercury cell grade of
caustic soda should be used to prevent chloride stress corrosion cracking of stainless steel equipment, especially reclaimer tubes (see Section 3733). Some Company
reclaimers have been operated in the past without soda ash or caustic additions. This
practice is not recommended, since solution degradation is enhanced and the amine
tied up with heat-stable salts is not reclaimed.
Both Port Arthur and Pascagoula have used caustic injection as a low cost method
of controlling heat stable salts and corrosion problems. Port Arthur has injected
caustic at several DEA plants including the 841 and 842 Amine Plants and the
1241 FCC Unit. Caustic has also been added in MDEA plants (e.g. #243 and #244
H2S Plants, SCOT Tail Gas Units #1 and #2). In 1992, Pascagoula injected caustic
into lean DEA at the 94 Plant after erosion-corrosion occurred in regenerator
reboilers above 3.5 wt.% heat stable salts. Caustic was injected following a study by
a DEA Task Force [15]. The corrosion rates decreased after adding caustic.
Caustic breaks up heat stable by dissociating the organic acid from the amine and
forming sodium salts. Union Carbide believes that sodium salts are less corrosive
than heat stable salts; however, this is not accepted industry-wide [16]. Another
potential risk of caustic injection is precipitation of sodium salts in equipment operating at relatively low temperatures (<120F). Pascagoula experienced plugging and
high pressure differentials in several absorber columns operating at low temperatures. The plugged columns were taken out of service and water-washed to remove
the sodium salts. Dow and Texaco have reported that caustic can also increase
foaming.
Consult with the CRTC treating expert in the General Processing Unit to determine
the correct procedure for caustic injection. Use the rayon grade of caustic, which has
a low chloride level. The range of caustic concentration and the injection rate will
vary depending on plant conditions, such as the type and concentration of amine
salt. The caustic should be injected as slowly as possible to reduce the risk of
precipitation and plugging. Even at the recommended injection rates, Pascagoula
reported plugging in several absorbers operating at low temperatures (<120F).
Velocity/Turbulence. High flow velocities or turbulence can cause localized
erosion-corrosion in amine acid gas removal plants. For this reason, piping design is
limited to a maximum of 6 fps fluid flow for carbon steel. At points of turbulence in
hot solution piping, long radius bends (if possible) or stainless steel should be used.
Special care is needed at points of solution entry into vessels, reboilers, and
exchangers. Adequate inlet baffles in exchangers are necessary.
Lean amine pumps and rich amine pressure letdown valves often suffer severe
erosion-corrosion. Stainless steel, often hardfaced with Stellite, is usually required
to solve these problems. Pump cavitation is a common problem that leads to accelerated corrosion. Calculation of NPSH requirements should allow for the effect of
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dissolved gases, which is often overlooked. Installing the lean amine pump after the
rich/lean exchanger often solves this cavitation problem.
Longer equipment life can be obtained by selecting the proper point to reduce the
pressure of the amine solution. Desorption of acid gases and dissolved hydrocarbons usually occurs when the pressure of the rich solution is significantly lowered,
and causes excessive corrosion of the control valves and adjacent downstream
piping. The absorber or flashdrum pressure should be maintained through heat
exchangers to minimize flashing of acid gases. Control valves and downstream
piping on the rich solution stream leaving the absorber can be subject to corrosion if
there is a high pressure drop across them. The valves and piping downstream of the
control valves should be stainless steel in all plants. To minimize the length of stainless piping, the control valves should be located close to the flash drum and to the
regenerator. See Figure 3700-1.
3740 Corrosion Control in Amine Treating Plants

3741 Use of Alloy Equipment
Except as discussed below, equipment in amine plants is normally carbon steel.
Refer to Figure 3700-1.
Rich/Lean Exchanger
The hot lean amine side of this exchanger is generally Type 304L stainless steel,
although some gas plants can use carbon steel successfully. The cold rich side is
carbon steel. 70-30 Cu-Ni has been used in H2S-free MEA/CO2 plants where
carbon steel was not adequate. 70-30 Cu-Ni should not be used if oxidative inhibitors (e.g. amine guard) are employed, since they cause pitting. 304L should be used
in these cases.
Absorber Bottom Control Valve and Pressure Letdown Valve to Regenerator

These valves can be subject to acidic erosion-corrosion and so are stellite-hardfaced
Type 304.
Rich Amine Piping from Absorber Bottom Control Valve to Accumulator and
From Pressure Letdown Valve to Regenerator
This piping is also Type 304L to avoid acidic erosion-corrosion.
Regenerator
The regenerator is clad with Type 304L in two areas:
Chevron Corporation
Above the feed tray where acidic corrosion is possible

Below the bottom tray where hot amine corrosion can occur
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Regenerator Overhead Acid Gas Cooler

The tubes in this exchanger are usually Type 304L. If this is an air-cooled
exchanger, 304L is used for the inlet and outlet headers. In H2S removal plants
where cyanide- and ammonia-induced corrosion are possible, titanium tubes have
been used.
Overhead Reflux Return Piping

This piping is T304L to avoid acidic corrosion.
Hot Lean Piping

The following hot lean piping is T304L to avoid hot amine corrosion:
From regenerator to rich/lean exchanger

To reclaimer and return (MEA only)
To reboiler and return
Reclaimer (MEA only)

The tubes in the reclaimer are T304L to avoid hot amine corrosion.
Reboiler
Reboiler tube corrosion can be one of the most serious operating problems encountered in acid gas removal plants, and solutions sometimes involve several variables.
Stress-relieved stainless steel tubes (Types 304L, 321) are usually used in Company
H2S and CO2 removal plants. Monel is often used in MEA/CO2 plants when there
are no sulfur compounds present. Tube corrosion in both stainless steel and Monel
can occur under certain circumstances in all types of plants. Problems are usually
attributable to high localized temperatures and to inadequate stripping in the regenerator. This allows acid gas to be stripped in the reboiler.
Corrosion can occur under baffles when high pressure steam (150 psi or greater) or
hot synthesis gas is used for a heating medium. Poor shellside flow in tube support
baffle crevices creates high tube temperature zones and corrosion of stainless steel.
In MEA/CO2 plants, Monel has proven to be somewhat superior to stainless steel in
resisting this form of high temperature corrosion. However, in plants with H2S,
Monel cannot be used. It is also unsuitable if oxidative inhibitors (e.g., amine guard)
are being used, because these cause pitting of Monel.
Titanium shows promise in severe services where Monel and stainless steel have
had poor corrosion resistance and short service lives (less than 5 years). Company
experience with titanium reboilers is limited to two in H2S plants at El Segundo, in
service since October 1973 and October 1975. In these plants, austenitic stainless
steel suffered intergranular corrosion/cracking and hot spot underbaffle corrosion.
Titanium reboiler tubes are susceptible to hydriding, which makes the tubes brittle
but does not affect their corrosion resistance. Hydrided tubes require careful
handling during shutdowns.
Although often uneconomical in new plants (where stainless steel can be used), the
design alternative to expensive tube materials is to lower the steam pressure in order
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to avoid high skin temperatures and high heat flux rates. Low pressure steam at
50 psi is usually recommended, with inlet temperatures monitored to avoid superheat. Desuperheating is done using condensate injection or inlet restricting orifices
to throttle steam flows. However, when condensate partially floods the reboiler
tubes, the heat load concentrates in the top section of the bundle, which can cause
tube failure.
Mechanical design is an important factor in reboiler corrosion. Regardless of material, the following design considerations should be observed.
The length of U-tubes should be limited to prevent condensate logging and water
hammer. Water hammer can produce severe tube vibration and grooving of the tubes
at support baffles. Reboilers should be designed with a liberal amount of shellside
vapor disengaging space between tubes, and sufficient surface to produce a
simmering action rather than violent boiling.
In existing units where vapor binding is a problem, some tubes can be removed to
form an X or V in the center of the bundle as a path of low resistance for escaping
vapors. A widely spaced square-pitch tube pattern is preferred for easy cleaning and
reduction of the high velocity scrubbing action associated with two-phase flow. The
tube bundle should be elevated about 6 inches from the shell bottom, on a slide. The
bundle should always be kept covered with 6 to 8 inches of liquid to prevent localized drying and overheating, and thus corrosion.
The amine solution should enter the reboiler at several locations to improve the
natural circulation of liquid in the reboiler shell. Several vapor exit locations will
reduce the stagnant pockets of acid gases in the reboiler.
An analysis of solution entering and leaving the reboiler will determine the efficiency of the stripping operation. A high acid gas loading in the reboiler causes tube
corrosion.
New plant designs should consider all of these factors and would benefit from a
thorough analysis of problems in existing plants. If design or operating changes
cannot be made readily, then poor bundle life may be inevitable.
Lean Amine Pump

This pump is usually Type 304, but can be carbon steel if potential cavitation problems are avoided. See Section 3734 on velocity and turbulence effects.
Other General Guidelines for Alloy Equipment

The choice of alloys in acid gas removal plants depends on several variables,
including the nature of the acid gas (H2S or CO2), process used (MEA, DEA,
MDEA), inhibitors used (Dow, Amine guard, etc.), turbulence or flow velocity, and
temperature or nature of corrosion (hot regenerator or cool overhead). Additional
general guidelines on use of alloys follow.
Stainless Steels. Austenitic stainless steels (Type 304 or 304L) are used for critical
equipment in all plants, in both hot areas and overhead condensers. However, some
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H2S/DEA plants do experience serious cyanide-induced corrosion, and here titanium condenser tubes are used.
Type 410 stainless steel (11-13 Cr) often gives poor performance in amine plants;
therefore, Type 304 is used for trays and valve trim when alloy is required.
Stellite hard-facing over Type 304 performs well in pressure letdown valves where
high turbulence causes erosion-corrosion.
To avoid sensitization, only extra-low carbon or stabilized grades of stainless steel
should be used where welding or stress relief is required.
Monel and 70-30 Cu-Ni. Copper and nickel-based alloys (Monel and 70-30 Cu-Ni)
are not suitable in the high temperature areas of H2S removal plants. Brass alloys
are not suitable in any of these plants because of the high alkalinity of the solutions.
Some inhibitors (i.e., Union Carbide amine guard) can cause pitting of Monel in
CO2/MEA systems, so should not be used in plants with Monel reboilers.
Monel has good high temperature resistance to corrosion in sulfur-free MEA/CO2
systems and will outperform stainless steel in reboilers when tube metal temperatures exceed 300F.
70-30 Cu-Ni can be used in sulfur-free MEA/CO2 plants for rich/lean exchangers or
lean MEA coolers when carbon steel is not adequate.
Titanium. Titanium grade 2 tubes (20 ga.) have performed well in H2S/DEA regenerator overhead condensers where cyanide corrosion limited the life of austenitic
stainless steels. Titanium grade 2 tubes are currently used in DEA regenerator overhead condensors at Richmond and El Segundo. Previous titanium bundles in these
condensors hydrided and were replaced after 1219 years.
Titanium tubes have also performed well (since 197375) in MEA and DEA/H2S
reboilers at El Segundo, where austenitic stainless steel suffered intergranular corrosion/cracking and hot spot underbaffle corrosion. A 1990 hydrotest detected no
leaks in the DEA reboiler; however, at least 7% of the bundle had been plugged
previously. Handling may account for some of this damage, since most of the leaks
were in the outer 23 rows of the bundle.
When titanium is chosen for regenerator overhead condensors or amine reboilers,
we recommend grade 2 (commercially pure titanium) tubes with the same material
for the carcass and grade 2 or grade 12 for the tubesheet. Avoiding galvanic couples
reduces the risk of titanium hydriding.
Water-Cooled Exchangers. For water-cooled exchangers, a compromise is
frequently necessary between stock-side and water-side corrosion resistance. For
CO2/MEA plants, this poses no problem, since 70-30 Cu-Ni tubes are resistant to
virtually all types of cooling water as well as to the process fluids. For H2S plants,
the problem is more complicated, especially if sea water or poor quality cooling
water rules out carbon steel.
Stainless steel will pit or crack in brackish cooling water or sea water, but has done
well in lean amine coolers using fresh cooling water. Monel is not adequate for sea
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water cooling, and 7030 bimetallic tubes have had limited success. Titanium has
been used successfully by others in lean amine coolers and has excellent resistance
to sea water. Thin gauge tubes (20 ga) are often cost-competitive with 16 ga
70-30 Cu-Ni.
3742 Corrosion Inhibitors

For many years, H2S removal plants have been inhibited with organic, water-soluble
filming amines (e.g. Kontol K-12 and Betz WS-58). Filming amines prevent sludge
deposits, but their success as inhibitors has been mixed. Betz WS-58 is currently
used at the Carter Creek Gas Plant. Over the past 10 years, the plant has had over
eight years of experience with this inhibitor. To date, hydrogen blistering has not
occurred while injecting WS-58 and coupon corrosion rates have generally been less
than 10 mpy. However, at times, coupons in the rich stream through the rich/lean
exchangers have corroded at rates as high as 26 mpy.
In recent years, DEA plants at Port Arthur and Richmond have had some success
with oxygen scavengers/metal passivators, such as Nalco 5173, which promote
stable sulfide films. Port Arthur's 841 and 842 amine plants, along with the AVU
144 amine plant (now out of service), have successfully used Nalco 5173 to scavenge oxygen, which degraded the amine. A Richmond DEA plant has used 5173
since 1990 to solve an iron sulfide fouling problem. Although pump problems
prevented continuous 5173 injection, the inhibitor appeared to stabilize the formation of heat stable salts when it was injected consistently over a six month period.
Adding the correct dosage continuously into a circulating solvent or overhead
system is critical to a passivating inhibitor's success. If the chemical is underfed, the
inhibitor can accelerate corrosion. Underfeeding Nalco 5173 contributed to sulfide
cracking and corrosion problems at the Carter Creek Gas Plant. After injecting 5173
for about a year, severe sulfide cracking had occurred in the bottom of the DEA
regenerator. Additionally, severe pitting was found in the hottest rich amine
exchanger, and steel coupons in a rich amine line had hydrogen blistered.
For over 30 years, CO2 removal plants (usually MEA) have employed oxidative
inhibitors, such as Union Carbide's Amine Guard. These inhibitors contain metals
(e.g. vanadium, arsenic, antimony), which promote stable oxide films on carbon and
stainless steel. If H2S is present, oxidative inhibitors are not effective because the
formation of a sulfide film will compete with oxide formation. Oxidative inhibitors
tend to increase corrosion of Monel and 70-30 Cu-Ni.
The use of oxidative inhibitors is declining due to restrictions on their disposal. An
alternative to inhibited MEA is MDEA, which can be used at higher concentrations
and does not require inhibition. Oxidative inhibitors should not be used in MDEA
plants because they will increase corrosion.

An inhibitor program will not be successful unless corrosion rates in the system are
continuously monitored. Both retractable corrosion coupons and corrosometer
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probes are used for this purpose. Field experience indicates that in some cases
retractable coupons give more reliable data under both turbulent and laminar flow
conditions. Corrosometers offer the advantage of continuous data collection,
without the need for removing and replacing coupons.
The location of probes or coupons should be chosen with care, particularly if corrosion in the plant is highly localized. New plants should have probe connections
consisting of 1" full port gate valves installed in critical locations, such as reboiler
outlet vapor lines and the rich amine piping between the rich/lean exchanger and the
regenerator.
Probes may not be satisfactory if corrosion occurs by pitting or if the fluid velocities and turbulence at the test are sufficient to cause the probe element to fail by
fatigue. If the best test location is a highly turbulent area such as the reboiler outlet
line, better results will be obtained with retractable corrosion specimens. Retractable specimens are described in Section 500 of the Corrosion Prevention and
Metallurgy Manual.
Coupons normally are removed every 24 weeks for evaluation. Coupon data
should be supplemented with inspection data to confirm the results. Monitoring the
solution's Fe content in CO2 plants, or the filter change frequency in H2S plants, can
also provide valuable information on relative corrosion rates.
3750 Process DescriptionHot Potassium Carbonate Plants

Hot potassium carbonate processes are similar to amine processes, except that they
employ an aqueous solution of K2CO3, and the absorber operates at a higher
temperature, between 230F and 240F. The process cannot be used on gas streams
containing only H2S, so applications are limited to CO2 removal plants. The most
popular carbonate processes are those that contain an activator (promoter) and
inhibitor such as:
Benfield. DEA Activator and Vanadium Inhibitor

Catacarb. Alkanolamine and Borate Activators, Vanadium Inhibitor
The process chemistry is similar in both of these patented processes. All hot potassium carbonate solutions absorb CO2 according to the following reaction:
high pressure
CO2 + H2O + K2CO3 2KHCO3
(Eq. 3700-2)
The flow diagram for a hot carbonate plant, shown in Figure 3700-8, looks very
similar to an amine plant, except rich/lean exchangers are not necessary. Absorbers
operate hot to avoid precipitation of the bicarbonate (KHCO 3) salt. Lines carrying
rich solution are steam traced to maintain temperatures in streams back to the
regenerator.
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Fig. 3700-8 Typical Flow DiagramHot Carbonate Plant
The Benfield process (Union Carbide) requires payment of a process royalty.

Chevron formerly operated a Benfield plant at SACROC. The process may be used
for removal of CO2, H2S, and COS from sour gases at absorber pressures of 150 psi
or greater. It is claimed that the Benfield process provides low utilities costs, high
CO2 removal, low corrosion, and low plant investment.
A properly designed and operated plant can be relatively corrosion-free, but strict
adherence to process details, solution chemistries, etc., is important because poorly
inhibited CO2-rich hot potassium carbonate is very corrosive to carbon steel.
A Benfield plant uses a 2530 weight percent K2CO3 solution with 3 weight percent
DEA as an activator to improve its performance. Vanadium compounds in the solution, such as vanadium pentoxide and potassium meta vanadate, are used to inhibit
corrosion. Inhibitor concentrations are usually about 0.5 weight percent, expressed
as KVO3.
Prepassivation of clean equipment prior to startup is an important part of successful
Benfield plant operation. This is called vanadation and is performed by circulating a
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hot solution of potassium carbonate with about 0.8% of potassium meta vanadate
for 2 to 5 days prior to startup. The minimum time period for vanadation is
48 hours. Temperatures are kept just below boiling (240F) by heat in the reboiler.
This pretreatment coats all equipment with a protective oxide layer (Fe3O4) that
prevents corrosion during operation if temperature, velocities, inhibitor concentrations, and valence states are maintained within design limits. It is not necessary to
revanadate after a shutdown unless repairs have been made or new steel has been
installed. Corrosion problems can occur in areas of high turbulence, but are usually
solved by use of 18-8 stainless steel (Type 304L).
The Catacarb process (Eickmeyer and Associates) also requires payment of a
process royalty and is very similar to the Benfield process. Chevron has a Catacarb
unit at El Segundo (H2 Plant No. 3). The main difference between the Catacarb and
Benfield processes is that the Catacarb process uses an undisclosed activator and
continuous air blowing to maintain the inhibitor in the proper valence state.
As at Benfield plants, vanadium is used in the Catacarb process as an inhibitor. To
be effective, it should be maintained in the +5 valence state. Reducing agents, such
as H2S, can reduce its valence to +4 (vanadium tetroxide, V2O4) or even +3
(vanadium trioxide, V2O3). In these reduced states, vanadium is much less effective
as an inhibitor. The Catacarb process, therefore, uses injection air to keep the vanadium well oxidized (in the +5 valence state) so that it remains effective.
Benfield solutions, evidently because of problems with the DEA activator, do not
use air injection. The vanadium valence state is maintained by use of a chemical
oxidizing agent.
System chemistries are similar for both processes, and prepassivation or vanadation
procedures are important for both.
3760 Corrosion in Hot Potassium Carbonate Plants

Figure 3700-8 shows the potential corrosive areas in a hot potassium carbonate
system. In general, lean carbonate solutions, being alkaline, are not corrosive to
carbon steel and so carbon steel is used for most equipment in these plants.
However, hot carbonate solutions with CO2 are corrosive to carbon steel, which
explains why the proprietary processes all provide inhibitors. A properly designed
and inhibited system should be noncorrosive to carbon steel. However, stainless
steel is still required for reboiler tubes and other critical equipment where turbulence exists, such as pressure letdown valves and piping into the regenerator.
Corrosion inhibition in the Benfield and Catacarb processes depends on an adherent,
high integrity iron oxide layer protecting the carbon steel. The purpose of the vanadium inhibitor is to make the liquid sufficiently oxidizing so that the correct film
(Fe3O4) is formed. Anything that reduces V+5 to V+4 lessens the solution's ability to
passivate steel. For example, bicarbonate and Fe+2 are harmful. Bicarbonate is not
present on initial passivation, but forms after contact with CO2. Solution containing
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Chevron Corporation
bicarbonate can maintain the oxide film, but probably is not oxidizing enough to
reform the film in damaged areas. Once the passive layer is lost it is difficult to
restore. This is especially true in high velocity and turbulent areas.
Any time a repair is made to equipment in a carbonate plant, the steel must be repassivated, regardless of the size of the equipment or its location in the plant. We have
seen severe corrosion in cases where repassivation is not done. At Pascagoula,
corrosion which started at a condensate leak into the absorber eventually became
severe enough to require replacement of large plate sections. Once corrosion starts,
it can be nearly impossible to stop, short of upgrading to Type 304L steel.
The integrity of the protective oxide layer is also endangered by the presence
of H2S. A small amount of H2S is tolerable, but above a few hundred ppm H2S,
the V+5 inhibitor is reduced to V+4 and is ineffective. There is competition between
formation of an oxide scale and formation of a sulfide scale. Neither is stable and
severe corrosion can occur. This, along with mechanical damage of the scale, was
the reason for corrosion on the order of 4000 mpy at SACROC in 1986.
Above several thousand ppm H2S, a sulfide scale is stable and the vanadium inhibitor is not needed. However, the H2S level above which corrosion is acceptable is
not well defined. If H2S levels are expected to be between a few hundred and a few
thousand ppm, an amine process should be used rather than a carbonate one.
Regenerator overhead systems can corrode because the nonvolatile inhibitor does
not protect the overhead. Acidic corrosion can occur in overhead condensers and
turbulent flow areas as a very localized attack in the form of carbonic acid erosioncorrosion. A solution has been to use stainless steel (Type 304) condenser tubes. If
air coolers are used, both tubes and inlet and outlet headers should be stainless steel
because serious corrosion has occurred in carbon steel headers.

Carbonate solutions have caused stress corrosion cracking of carbon steel when the
electrochemical potential of the steel in contact with the solution has been within a
well-defined range [1718]. For example, the regenerator reboiler shell at the North
Snyder gas plant (SACROC) cracked about two-thirds of the way through at a
nonstress-relieved circumferential weld. Also, SCC has occurred behind strip lining
panels in an absorber tower [19]. For this reason, major equipment should always be
stress-relieved in these plants.

As in amine treating plants, austenitic stainless steel reboilers in hot potassium
carbonate plants can be subject to chloride SCC. See Section 3733 for a discussion
of this cracking and potential chloride sources. Again, chlorides should be limited to
a maximum of 500 ppm.
Intergranular corrosion is also possible in hot potassium carbonate plants, and extralow carbon grades of welded or stress-relieved stainless steels are required to avoid
sensitization. See Section 3733.
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3764 Influence of Design, Operating Variables

Corrosion in hot potassium carbonate plants is influenced by process design and
operating variables. The effects of many of these variables are similar in carbonate
plants and amine plants. Alloys used in critical equipment such as regenerator
bottoms and reboilers can corrode if care is not used in defining these variables.
Primary Variables
Temperature. As in amine plants, the worst corrosion is found where temperatures
are highest: regenerator reboilers. The vanadium inhibitor helps protect these areas,
but alloy equipment is still necessary.
Solution Strength. Since hot potassium carbonate processes are licensed, solution
strengths outside of the recommended range, 2530%, are not common. Above this,
corrosion is not necessarily worse, but the solution will crystallize in service and
cause erosion problems and instrument plugging.
Acid Gas Loading: Recommended maximum acid gas loadings for carbonate
plants are set by the Licensor in terms of maximum conversion of carbonate to
bicarbonate in the solution.
Secondary Variables
The secondary variables are:
Solution cleanliness
Velocity/turbulence
Solution Cleanliness. Contamination of carbonate solutions can lead to serious

corrosion. See Section 3734 for a discussion of problems caused by dissolved or
entrained hydrocarbon sludge and suspended solids. As at amine plants, carbon
filtration is a key to solution cleanliness, preventing foaming. It may also reduce
corrosion because the Fe content of the solution will drop with carbon changeout.
Velocity/Turbulence. Hot potassium carbonate solution is more corrosive in areas
of increased velocity and turbulence; therefore, carbon steel velocity is limited to
6 fps here. Also, Union Carbide has recommended the following limits for Benfield
plants: 2, 6.5, and 12 fps for 2, 10, and 26-inch pipe, respectively. Union Carbide
limits vapor phase velocities to 70 fps.
See Section 3734 for information regarding pumps and pressure letdown valves.
The same problems are possible in carbonate plants. Since a substantial portion of
the CO2 flashes when the pressure is reduced (about 1/3), the mechanical design
of the rich solution inlet to the regenerator is extremely important to prevent failures from excess vibration. Vibration can also break the protective oxide film and
result in catastrophic corrosion.
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3770 Corrosion Control in Hot Carbonate Treating Plants

3771 Use of Alloys
Hot potassium carbonate plants (Benfield and Catacarb) are essentially noncorrosive to carbon steel when properly inhibited, but extremely corrosive when not. In
general, the Company refers to the Licensor for materials recommendations. The
following is a list of equipment that usually requires material other than carbon
steel.
Absorber. Below the first tray, T304L cladding is used.
Absorber bottom control valve and pressure letdown valve to regenerator.

These valves are stellite-hard faced T304 to avoid acidic erosion-corrosion.
Piping from absorber bottom control valve to accumulator and from pressure letdown valve to regenerator. This piping is also T304L to avoid acidic
erosion-corrosion.
Regenerator. The top of the regenerator above the feed tray is T304L clad.
Regenerator overhead acid gas cooler. T304L tubes are used in this
exchanger. If this is an air cooler, inlet and outlet headers should also be T304L.
Reboiler. The reboiler tubes are usually T304L. See also the discussion on
effects of reboiler design on corrosion in Section 3741.
Lean carbonate pump. This pump is usually T304, but carbon steel can be
used if potential corrosion problems are avoided. See Section 3734 on velocity
and turbulence effects.
Other General Guidelines

Some other general guidelines on use of alloy equipment in carbonate plants are as
follows:
To avoid sensitization, only extra-low carbon or stabilized grades of stainless

steel should be used where welding or stress relief is required.
Brass alloys are not suitable in these plants, because of the high alkalinity of the
solutions.
For water-cooled exchangers, compromise is frequently necessary to obtain the

best combination of stock-side and water-side corrosion resistance. When fresh
cooling water is used, stainless steel tubes are suitable. If seawater or poor
quality cooling water is used, 70-30 Cu-Ni tubes are an option as long as H2S is
not present. If there is H2S, titanium tubes can be used.
3772 Use of Corrosion Inhibitors

Corrosion inhibitors play a very important part in both the Benfield and Catacarb
processes; poor inhibition can cause serious operating problems and unscheduled
Chevron Corporation
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August 1999
shutdowns. An important operating procedure in these plants is prepassivation, or

vanadation, of clean metal surfaces by circulating a hot carbonate solution
containing 0.8 weight percent of vanadium throughout the plant equipment for
several days.
This pretreatment lays down protective vanadate-iron oxide films which are then
maintained by properly inhibited (0.5 weight percent vanadium) carbonate solutions. Thereafter, the vanadium compounds, to be effective, should be maintained in
a fully oxidized +5 valence state. If reduced to V+4 by sulfur contamination, the
vanadium compounds are less effective as inhibitors and corrosion may result. This
reduction can sometimes be detected as a color change from brown or yellow to
green.
Since corrosion protection in carbonate systems depends on a protective film, accelerated attack can occur at localized breaks in the film. Rapid corrosion can occur
where metal surfaces rub together or in areas of high turbulence.

See Section 3743. Close monitoring of the iron content of carbonate solutions is the
principal method of monitoring corrosion in carbonate plants. Iron contents in
excess of 100 ppm are cause for concern.
3780 References
August 1999
1.
Ploetz, J. P. MDEA Plant Corrosion Coupon Rack,11-15-88, File

75.16.86.01.
2.
Potter, G. L. Survey of Corrosion Experience in MDEA-Based Amine

Systems, November 30, 1990, File 75.16.31.01.
3.
Piehl, R. L. Richmond MDEA Conversion, 9-28-87, File 75.16.31.1;

MDEA Survey, 10-19-88 memo to File 75.16.31.1., MDEA Conversion,
4-28-89, File 75.16.31.02.
4.
Richert, J. P., A. J. Bagdasarian, and C. A. Shargay. Stress Corrosion Cracking

of Carbon Steel in Amine Systems, presented at Corrosion '87, 3-9 to 2-13-87,
San Francisco, paper #187.
5.
Richert, J. P., A. J. Bagdasarian, and C. A. Shargay. Extent of Stress Corrosion Cracking in Amine Plants Revealed by Survey, Oil and Gas Journal,
June 5, 1989, p. 45.
6.
Bagdasarian, A.J., C. A. Shargay, and J. W. Coombs, Stress Corrosion

Cracking of Carbon Steel in DEA and `ADIP' Solutions, Materials Performance, May 1991, pp. 6367.
7.
Klehn, R. Amine Stress Corrosion Cracking of El Segundo P-1600 Discharge

Lean Piping, February 26, 1992, File 75.16.86.
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Chevron Corporation
8.
Ferrell, D. E. Cracked H2S Absorber, C-4001, H2S Plant, Irving Refinery,

Materials Laboratory Report, File No. P-460.14, February 20, 1975.
9.
Ballard, D. How to Operate an Amine Plant, Hydrocarbon Processing,

April 1966.
10. Butwell, K. F. How to Maintain Effective MEA Solutions, Hydrocarbon

Processing, April 1968.
11. Dingman, J. C., D. L. Allen, and T. F. Moore. Minimize Corrosion in MEA
Units, Hydrocarbon Processing, September 1966.
12. Williams, E., and H. P. Leckie. Corrosion and Its Prevention in an MEA Gas
Treating Plant, Materials Protection, July 1968.
13. Pegors, S. R. 5 H2S Foaming Report, Richmond Refinery Memorandum,
June 7, 1989.
14. Wagner, E. J. Pascagoula 1992 Amine Plant High Corrosion Rates,
El Segundo Refinery Memorandum, September 2, 1993.
15. Longworth, A. L. DEA Task Force Recommendation Report, Pascagoula
Refinery Report, August 5, 1992.
16. Keller, A. E., R. M. Kammiller, F. C. Veatch, A. L. Cummings, J. C. Thompsen,
and S. M. Mecum, Heat Stable Salt Removal from Amines by the HSSX
Process Using Ion Exchange, pp. 45. Presented at the Laurence Reid Gas
Conditioning Conference," March 2, 1992.
17. Atkins, K. T. G. Corrosion in CO2 Removal Plant Towers, Ammonia Plant
Safety, a CEP Technical Manual published by AIChE, Volume 16, 1974.
18. Schutt, H. U. Intergranular Wet Hydrogen Sulfide Cracking, Paper #454.
Presented at NACE Corrosion 92 Conference.
19. Kolff, S. W., Technical Department KEMIRA B.V. Corrosion of a CO2
Absorber Tower, Plant/Operation Progress, Vol. 5, No. 2 (April 1986),
pp. 6572. Presented at AIChE 1985 Summer National Meeting, Aug. 25-28,
1985, File 75.16.31.2 (literature).
Suggested Reading
Bienstock, D., and J. H. Field. Corrosion Inhibitors for Hot-Carbonate Systems,
Corrosion, December 1961.
Conners, J. S., and A. J. Miller. Operating Problems Related to Gas Treating,
Oil and Gas Journal, February 2, 1950.
Dingman, J. C. Effect of MEA Variables on Corrosion, Chemical Engr. Prog.,
Safety in Air and Ammonia Plants, Volume 9, 1967.
Goar, B. C. Today's Gas Treating Processes, No. 1 and 2, Oil and Gas Journal,
July 12, 1971 and July 19, 1971.
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August 1999
Hafsten, R. J. Literature SurveyCorrosion in Amine Gas Strippers, API

Subcommittee on Corrosion, May 2, 1957.
Hawkes, E. N., and B. F. Mago. Stop MEA CO2 Unit Corrosion, Hydrocarbon
Processing, August 1971.
Hitchcock, E. A. Modern CO2 Removal, AMPO 74, ICI Operating Symposium,
1974.
Mottley, J. R., and D. R. Fincher. Inhibition of MEA Solutions, Materials
Protection, Vol. 2, No. 8, 26-30, 1963.
Nathan, C. C. Corrosion Inhibitors, NACE Publication, 1973.
Nelson, W. L. Questions on Technology, Oil and Gas Journal, June 20, 1966.
Strelzoff, S. Choosing the Optimum CO2 Removal System, Chemical Engineering, September 15, 1975.
Sudbury, J. D., O. L. Riggs, and J. F. Leterle. LAB Inhibitor Stops DEA
Corrosion, Petroleum Refiner, May 1958.
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Acid Gas Removal Corrosion Prevention

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3700 Acid Gas Removal Plants

Author: B. (Barbara) Cooke

3720 Process Description: Amine Treating Plants

3730 Corrosion in Amine Treating Plants

3731 General or Preferential Corrosion

3741 Use of Alloy Equipment

3760 Corrosion in Hot Potassium Carbonate Plants

3761 General or Preferential Corrosion

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

3771 Use of Alloys

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

Corrosion in regenerator overhead system caused by the presence of wet

3720 Process Description: Amine Treating Plants

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

Fig. 3700-1 Materials for Amine Gas Treating Plants

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

2R2NH + H2S R2NH2SH2NR2

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

3730 Corrosion in Amine Treating Plants

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

MDEA Plant Corrosion

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

3732 Stress Corrosion Cracking: Carbon Steel

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

DEA and MDEA

Pressure Vessels in Main Circulating Loop(1)

Butt Welded Piping Above 100F

Socket and Seal Welds Above 100F

(1) This includes any absorber overhead K.O. drum

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

Fig. 3700-5 Amine Plant Inspection Guidelines(1)

T less than 150F

1 every other scheduled

1 every other scheduled

Wet H2S Cracking and Blistering

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

3733 Stress Corrosion Cracking: Stainless Steels

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

3734 Influence of Design and Operating Variables

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

Primary Operating Variables:

Corrosion Prevention and Metallurgy Manual

3700 Acid Gas Removal Plants

3700 Acid Gas Removal Plants

Corrosion Prevention and Metallurgy Manual

Secondary Operating Variables

Solution Cleanliness. Contamination or degradation of amine solutions can lead to

Corrosion Prevention and Metallurgy Manual