XIX International Gas Convention AVPG 2010, May 24th - 26th Caracas, Venezuela

AMINE CONTAMINATION AND ASSOCIATED PROBLEMS IN

THE GAS TREATING UNITS

Authors
E.R.Baumeister - Senior Technical Service Specialist – Dow Chemical Co.-
R.C. Souza - Senior Oil &Gas Development Specialist – Dow Brasil S/A
Carlos Ihle Rusque - Senior Oil &Gas Development Specialist – Dow Mexico S/A

Summary
Amine contamination and associated problems in the amine gas treating units cannot be completely
avoided or eliminated. They can be cost effectively mitigated using a thorough Amine Management Program.
Economic and performance benefits realized from an amine management program include several improvements
and performance index. Better yields, lower costs, and fewer environmental concerns are some of the additional
advantages of using a comprehensive amine management system to help run the amine gas treating unit.

Abstract
Amine gas treating systems may face problems with solvent degradation for many reasons including
operating conditions that permit inlet contaminants. An important consequence of degradation is the formation of
Heat Stable Amine Salts (HSAS). HSAS is defined as the amount of amine cation required to neutralize acids not
regenerated under normal regenerator conditions. HSAS formation can cause operational problems such as:

• Corrosion and erosion of metal components are accelerated by the precipitation of salts or corrosion end
products.
• Foaming may be caused by changes in the surface and the increased viscosity of the solution.
• Reduced acid gas carrying capacity as the result of less amine present in a usable absorptive state.

The challenge lies in identifying the acceptable operating limits of heat stable salts and preventing the
escalation of these problems, a number of factors must be included in determining those limits; nature of the heat
stable salt species, operating conditions of the amine unit and mechanical design of the amine unit.

Reduction or removal of HSAS requires reclaiming the amine solution by electrodialysis, vacuum
distillation, ion exchange resin treating, dilution through purge and make up or total solvent replacement.

HSAS are formed with acidic components other than H2S and CO2 in the inlet process stream to the amine
absorber. Typical acidic components include acids that form salts of chloride, sulfate, formate, acetate, oxalate,
cyanide, thiocyanide, and thiosulfate. In addition, oxygen absorbed into the amine solution creates amine oxidation
products that include formate, acetate, and glycolate.

The term "heat stable" is a broad term used to describe a number of undesirable salts in an amine solution.
They are undesirable because they cannot be effectively removed in the normal pressure/temperature swing in the
absorption and desorption cycle of gas treating within amines units. In actuality, the stability of these salts depends
on the species of the anion and cation which makes up the salt.

This paper will cover aspects involved with amine contamination and degradation, explaining the reasons
they occur, the different degradation for each amine used for acid gas removal, the consequences in the system and
how to control them with an Amine Management System, based on a low total cost approach to treat HSAS, reduce
contamination, amine losses and minimize corrosion.

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1. Introduction

Amine solvent formulations are used to remove acidic components such as CO2 and H2S from gas streams
to comply with sales gas specifications for end use or to make the gas suitable for liquefaction.

During operation of an amine unit, degradation of the solvent occurs due to reaction with contaminants like
oxygen, sulfur dioxide, and acids or acid precursors in the feed gas. Some of the tertiary amine oxidation products
include secondary amines. These degradation products lead to a number of operational problems in the amine units
if allowed to build up in concentration. Build up over time is related to solvent age, use and handling and will occur
in every amine solvent.

Common Operational Problems include:

1. Increased corrosion rates, particularly at the lean side of the amine unit.
2. Fouling in those parts of the unit where solvent flow velocities are low and the solvent loading of H2S or
CO2 is high, i.e. the trays and the bottom of the contactor and the lean/rich heat exchanger. In “CO2-only” systems,
fouling tends to occur more often in the regenerator overhead. Fouling of the heat exchanger leads to a reduction in
heat transfer and an increased steam use for regeneration. Ultimately, plugging of the heat exchanger may occur,
restricting solvent circulation and treating capacity.
3. Decreased treating capacity of the unit due to lower amount of active amine available for acid gas
removal.
4. Increased foaming tendency of the solvent from higher levels of suspended solids (also requiring a
higher rate of filter change outs).
5. A high flash gas production due to a high carry-under of gas with solvent in the main absorber.
6. Decreased CO2 slip due to the presence of secondary amines.

The overall result is a high activity of the “iron pump” mechanism leading to high corrosion rates and
associated fouling problems. Careful monitoring of the operation of the unit in combination with measuring solvent
composition and solvent properties, combined with good solvent maintenance practices will ensure reliable
operation of the amine unit.

2. Amine Treatment Unit

Amine treatment units are typically employed for the removal of acid components from natural gas.
Depending on the concentration of CO2 and H2S in the gas, the required specification of the treated gas and the
required selectivity of the removal of H2S over CO2 an appropriate alkanolamine formulation are chosen.

Due to an increased environmental awareness and stricter operational disciplines, most of gas treating
plants have reduced solvent losses and the subsequent make up with fresh amine. This has resulted in build up of
amine degradation products becoming an important issue. A solvent quality monitoring service can be used to
measure the amine composition of the solvent and to determine the presence of acid components and heavy amine
degradation products.

Because the amine unit uses an aqueous solution of the amine, absorption of hydrocarbons, mercaptans and
organic sulfur species from gas streams is minimal. MDEA is normally chosen when a high selectivity for H2S
absorption relative to CO2 is of paramount importance. Other amines used in refinery applications are DEA (di-

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ethanolamine), MEA (monoethanolamine), DGA (di-glycolamine), sterically hindered amines and various specialty
amines which are proprietary mixtures of amines and additives to improve selectivity, kinetics and stability.

3. Amine Contaminants and Degradation

3.1. Contaminants
Amine contaminants can be grouped into four distinct categories; (1) heat stable salt anions, (2) injection
chemicals, (3) hydrocarbons and (4) particulates. All of these contaminants categories are typically present in any
given amine system at the same time, although the amount of each one can vary from insignificant to several
percent.

1) Heat Stable Salts:

Acid anions such as formate, acetate, thiosulfate, thiocyanate, and chloride can tie up an amine molecule to
form a salt that is not capable of being regenerated by the addition of heat, and are thus referred to as Heat Stable
Salts. Not only do they tie up the amine and thereby reduce the acid gas carrying capacity, but at higher
concentrations they may also be corrosive. Anions observed in HSAS originated from variety of sources are listed in
table 1.

Table 1. Common sources of the anions of heat stable salts

2) Injection Chemicals:
Corrosion inhibitors from upstream pipeline operations and amine system injections, such as anti-foam
chemicals can concentrate in amine systems. While these chemicals are excellent in controlling other operational
problems, their injection into an amine system over months or years can build up to a substantial percentage of the
amine composition concentration. A large buildup of injection chemicals can eventually lead to fouling and can
cause changes in solution physical properties, such as viscosity and mass transfer.

3) Hydrocarbons:
Heavy hydrocarbons from natural gas streams can condense in the contactor and lubrication oil from
upstream reciprocating compression can build up in amine systems over time. These hydrocarbons can cause
foaming, and at high enough concentrations, can change amine solvent physical properties.

4) Particulates or Suspended Solids:

Typical insoluble particulates include iron sulfides, metals from equipment corrosion, charcoal fines from
amine filters, and catalyst fines from upstream units.

Amine manufacturers and suppliers stress overall solvent quality. When thinking about overall amine
hygiene, it should be kept in mind that any compounds in an amine system that are not either (1) amine or (2) water
are considered contaminants and should be removed when they exceed recommended levels.

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3.2. Degradation

Effect of Heat Stable Salts

Carbon dioxide and hydrogen sulfide are weak enough acids that their reactions with amines are thermally
reversible. Acids which are sufficiently strong so that their reactions with amines are not thermally reversible are
called heat stable salt forming acids. That is, products of their acid-base reactions with amines form heat stable salts.
If heat stable acids enter an amine unit or are generated there by reaction with trace amounts of an oxidizer (oxygen
or SO2), or by thermal degradation of the amine, the heat-stable salts will remain in solution and accumulate.

Heat stable salts have several sources. In refineries, FCCU gases may contain trace amounts of formic and
acetic acids. Traces of oxygen in various refinery gas streams (FCCU, Delayed Coker, Vacuum Unit, Vapor
Recovery System), air leaking into gas gathering systems operating under vacuum, and oxygen in un-blanketed
amine storage tanks and sumps can react with the amine to form low molecular weight carboxylic acids and react
with H2S to form elemental sulfur and thiosulfate. If HCN is present in the feed gas, elemental sulfur in the amine
solution reacts with cyanide to form thiocyanate.

Heat stable salts reduce the acid gas removal capacity of the amine solution because they react irreversibly
with the amine under normal amine unit operating conditions. Additional amine is required to maintain targeted
solution strength levels for acid gas removal. Amine solutions can also be corrosive if they are contaminated with
heat stable salts.

Heat stable salts are corrosive because they facilitate the corrosion reactions and may also act as chelating
agents, dissolving non-sulfide protective films covering the base metal. It is also possible that low levels of some of
the weaker heat stable acids, such as formic acid, are present under regenerator conditions which will react with
exposed carbon steel surfaces that condense water vapor.

Effect of Amine Type on Amine Solution Corrosion

It is well known that the choice of amine affects corrosion. Primary amines like MEA and DGA are more
corrosive than secondary amines like DEA and DIPA. In turn, DIPA and DEA are more corrosive than tertiary
amines like MDEA. Exactly why this is true is not fully understood. Several investigators have shown that all
amines are equally non corrosive when no acid gas is present.

In the presence of H2S and O2 in the gas, a range of reactions may occur leading to the formation of
thiosulfate, sulfur, polysulfides and sulfate.

One of the first markers of oxygen ingress in the solvent, in the presence of H2S, is the formation of
thiosulfate. Part of the thiosulfate will be oxidized further to give sulfate. If oxygen ingress is only periodic or if it
is the result of a single operational event, then this will be evidenced by a sudden increase of the thiosulfate content
of the solvent, followed by a steady decrease to steady state concentration.

Reaction with oxygen

The presence of oxygen in the feed gas to the amine unit may lead to degradation of the amine solvent. In
lab experiments, several mechanisms have been identified, depending on the composition of the gas. Oxygen can
react directly with the amine or alternatively, if H2S is present in the feed, oxygen can react with a sulfur species
first, followed by a subsequent reaction with the amine.

The product distribution of the various carboxylic acids depends on the oxygen concentration, the operating
temperature and the amine type used. Under conditions of high temperature and high oxygen concentration the
product distribution for the organic acids shows that oxidation is not very selective and splitting of the αN-CH2
bond occurs together with the further decomposition of the acid formed. Alternatively, C-C bond fission occur
leading to the formation of acetic acid and formic acid.

In the presence of oxygen at high temperatures the formation of hydroxyl radicals may occur. These
hydroxyl radicals will abstract a α-hydrogen atom next to the nitrogen to give the corresponding radical. This radical
can react with oxygen to give the peroxy radical that abstracts another hydrogen atom from the primary amine,
thereby completing the cycle.

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Amine degradation chemistry is more complex than salt formation, because a series of intermediates
compounds are formed that continues to react to eventually form ethylenediamines, typical degradation compounds
are listed below in table 2

Table 2. Amine Degradation Products.

4. Solving Problems
4.1. Methods of handling contaminated amine systems
There are several methods depending on the type of contaminants. One or more of the following methods
can be used for cleaning an amine system:
• Disposal and Replace
• Continuous Disposal and Replace (Bleed & Feed)
• Filtration of Particulates
• Neutralization of Heat Stable Salts
• Electrodialysis
• Ion exchange
• Vacuum Distillation Reclaiming.

Until recently, both Dispose/Replace, and Bleed/Feed were commonly used for controlling contaminants.
However, increased cost of amines and disposal has made these methods less economical. These methods of
purification should now only be considered as a last resort.

Particulate filtration is the preferred method if suspended solids are the only contaminant. Carbon filtration
can be used to control hydrocarbons and injection chemicals. When carbon filtration is used, particulate filtration is
recommended both before and after the carbon bed.

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Heat Stable Salts should be controlled by neutralization to not more than 2 wt% as the amine in use. This
minimizes the amount of non-productive amine in the solution. The use of neutralization allows additional operating
time before reclaiming needs to be done. Salts produced by addition of a strong base neutralizer can be removed by
electrodialysis, ion exchange or vacuum reclamation.

4.2. Unit Management

Amine based gas treating systems can have problems with Heat Stable Amine Salts (HSAS). HSAS cause
corrosion, reduced amine capacity, facilitate poor unit operations, reduced solvent life and solvent disposal
problems.

Some companies have developed programs those minimize the problems associated with HSAS, maximize
solvent life, and restores operational reliability. Dow’s Heat Stable Salt Management Program is based on a low
total cost approach to treat HSAS, reduce HSAS contamination, and minimize the corrosion from HSAS.

Benefits of Heat Stable Salt Management

• Reduce corrosion and equipment replacement costs
• Reduce or eliminate solvent disposal and associated environmental costs
• Optimize amine system capacity for acid gases and avoid unit shutdowns
• Minimize maintenance costs due to system cleanings and frequent filter change outs
• Avoid high energy and amine solvent consumption

Heat Stable Salt Management Program Elements

1) Monitoring and Prediction:
Solvent analyses determine the HSAS profile and predict when remedial action is necessary.

2) Control Strategies:
System configuration is studied to determine if operations can be adjusted to reduce the formation of
contaminants or to achieve more effective removal of contaminants upstream of the amine system.

3) Neutralization Technology:
The resulting neutralized salt is substantially less corrosive than the amine salt. Therefore, the solvent can
tolerate a higher level of HSAS forming anions, and amine solution life is extended significantly, if not indefinitely.
Ucarsol ™ DHM Neutralizer has been developed to easily and effectively neutralize HSAS.

4) Removal:
The system might eventually require some type of solvent purification, especially if solvent losses are low.
Purging the solvent to remove HSAS loses valuable amine and is no longer economically or environmentally
justifiable. The patented UCARSEP™ Amine Reclamation System is used for on site and on line salt removal. This
process has been used to clean up formulated amines, MDEA, and DEA solvents without interruption of amine
system operations.

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5. Conclusions

Amine contamination and associated problems in the amine gas treating unit cannot be completely avoided
or eliminated. They can be cost effectively mitigated using a thorough Amine Management Program. Economic and
performance benefits realized from an amine management program include:

• Increased reliability with reduced operating and maintenance costs

• Increased throughput the system performs economically at the optimum operating concentration
• Lowest cost reclaiming technology without operating interruptions
• Reduced amine disposal, emission and environmental costs
• Reduced solvent losses, costs and contamination of downstream processes
• Reduced corrosion-related costs and downtime
• Improved understanding of unit operations by operating personnel
• Improved operation of downstream units

Better yields, lower costs, and fewer environmental concerns are some of the additional advantages of
using a comprehensive amine management system to help run the amine gas treating unit.

6. Acknowledgement

"The authors wish to express their sincere appreciation to Ana Rosa Zárate and Dr. Sid Bosen for their
significant contribution and technical review of the paper."

7. References
1. R. Haws -CCR Technologies Inc.; Paper: Contaminants in Amine Gas Treating
2001GPA Houston Regional Meeting

2. R. B. Nielsen, K R. Lewis - Fluor Daniel, Inc.; John G. McCullough - Proton Technology, Ltd.; D. A.
Hansen - Fluor Daniel, Inc. – Paper: Controlling Corrosion in Amine Treating Plants

3. H.J. Liu and J.W. Dean - Union Carbide Corporation; Sidney F. Bosen - Union Carbide Corporation
Technical Paper Number 572 Presented at: NACE International, Corrosion/95 - Neutralization
Technology to Reduce Corrosion from Heat Stable Amine Salts

4. The Dow Chemical Company, Midland, Michigan 48674 U.S.A. “Amine Management Program – Heat
Stable Amine Salts Maintenance Guidelines”

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