Amine Treating - Troubleshooting Guide

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AMINES GAS TREATING

Best Practices Guide
Contents
Process Capabilities for gas treating process

Typical Amine Treating
Typical Amine System Improvements
Primary Equipment Overview
Inlet Gas Knockout
Absorber
Three Phase Flash Tank
Lean/Rich Heat Exchanger
Regenerator
Filtration
Amine Reclaimer
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AMINES GAS TREATING

Contents
Operating Difficulties Overview

Foaming
Failure to Meet Gas Specification
Solvent Losses
Corrosion
Degradation of Amines and Alkanolamines during
Sour Gas Treating
APPENDIX
Best Practices - Troubleshooting Guide
Amines: Gas Treating

Wastes Types Generated in Different CO2 Removal Process units
Typical Amines Treating

Sour gas sweetening process
Typical Amine System


Inlet Gas Knockout

Absorber
Regenerator
Filtration
Amine Reclaimer

Inlet Gas Knockout
Before entering the absorber, the gas is

passed through an inlet separator where
entrained droplets or slugs of liquid are
removed from the gas stream by
impaction devices (to the right >>>>>)
Baffles remove a portion of the liquids. Mist eliminator pads, located

near the gas outlet of the tank, trap the rest. Typical contaminants in
natural gas streams may be liquid hydrocarbons, salt water, sands, well
treating compounds, pipeline treating chemicals, and compressor oils.

Tray Tower Absorber
The sour gas, freed of entrained
liquids by the inlet separator, enters
the bottom of the absorber. Usually
the absorber is a tray column;
although packed columns are also
used. In either case, the objective is
to provide intimate contact between
the gas and the amine solvent so that
the H2S and C02 molecules can
transfer from the gas phase to the
solvent liquid phase. In tray columns,
a liquid level is maintained on each
tray by a weir usually 2 or 3 inches
high (Figure >>>>>).

In many units the rich amine solution is
sent from the absorber to a flash
skimmer tank to recover hydrocarbons
that may have dissolved or condensed
in the amine solution in the absorber.
The pressure of the solution is dropped
as it enters the tank, allowing the
lightest of the hydrocarbons to flash.
The heavier hydrocarbons remain as a
liquid, but separate from the aqueous
amine, forming a separate liquid layer.

The rich solvent is preheated before entering
the stripper. Because the lean amine exiting the
reboiler must be cooled before entering the
absorber, there is an opportunity to exchange
heat from the lean to the rich stream, thereby
reducing the heat load on the reboiler.
This is usually done in a shell and tube
lean/rich heat exchanger with the rich solvent
passed through the tubes, which are usually
made of stainless steel.
Note: Recommended maximum velocity to minimize corrosion
in the tubes is 3 or 3.5 feet/sec.

Regenerator
Like the absorber, the stripper is either
a tray or packed column with
approximately 20 trays or the equivalent
height in packing. To minimize amine
vaporization loss, there may be a water
wash section at the top of the column
with an additional four to six trays.
The preheated rich amine enters near
the top of the column and flows down
countercurrent to a gas stream of
steam, H2S, and C02. The steam is
generated in the reboiler, lowering the
partial pressure of H2S and C02 in the
gas stream, enhancing driving force of
the acid gases from the amine solution.

Filtration
A filtration scheme of mechanical and
activated carbon filters is important in
maintaining good solution control.
Mechanical filters such as, cartridge
filters or precoat filters remove
particulate material while call filters
remove chemical contaminants such
as entrained hydrocarbons and
surface-active compounds.
Filters are located in the rich line in some plants, and in the line in
others. One manufacturer recommends filters in both rich and lean
lines. Locating the filters in the rich line upstream of the lean rich
heat exchanger will protect both the heat exchanger and the
stripper from plugging, and reduce the erosion/corrosion rate in
the heat exchanger.

Filtration
A 10 to 20 micron mechanical filter
should be adequate for particulate
removal. If cotton filters are used, the
cotton should be virgin cot ton rather
than recycled. Recycled cottons
may contain fibers with coatings which
may be the source of amine solution
foaming problems.
Circulation rates through mechanical filters range from 5% of the
circulating system to full fl depending on the degree of contamination.
Recommendations for flow to carbon filters range from less than I
percent to 5 to 10 percent and some units have been built with full flow.

Filtration
Criteria In determining when a carbon bed should be changed
The following can be used as a guide:
1) a high pressure drop across the bed, caused by solids plugging
the voids;
2) a color comparison between a sample taken from the outlet
of the filter and a plant sample run through fresh carbon in the lab.
Active carbon will remove color;
3) an increase in foaming tendency in the plant, or the start of
a foaming problem.

Amine Reclaimer

Amine Reclaimer

Operating Difficulties
Amine gas sweetening plants can experience operating
difficulties including foaming, failure to meet sweet gas
specification, high solvent losses, corrosion, fouling of
equipment, and contamination of the amine solution.
Often one operating difficulty is the cause of another.
Not all plants experience the same problems to the same degree,
and what may be a continual problem in one plant may occur
only rarely in another.

Foaming
Solvent Losses
Corrosion

Foaming
Solvent Losses
Corrosion

Symptoms of Foaming

Operating Difficulties: Foaming I
Pure aqueous amine solutions do not foam. It is only in the presence of
contaminants such as condensed hydrocarbons, small suspended
particulate matter, or other surface active agents such as some pipeline
corrosion inhibitors or compressor oils, that a foaming problem may
develop.
Foaming usually occurs in the absorber or the stripping tower, and is
accompanied by a sudden noticeable increase in the differential
pressure across the column.
Other indications of a foaming condition may be a high solvent
carryover, a drop in liquid levels, and the detection of off-specification
gas.

Operating Difficulties: Foaming II
An immediate method to control a foaming problem is the addition of

an antifoam at a location just upstream of the foam.
Effective foam inhibitors for amine sweetening systems are silicone
antifoams and polyalkylene glycols. Also widely used are high-boiling
alcohols such as oleyl aIcohol and octylphenoxyethanol.
It is advisable to test the antifoam on a plant sample in the laboratory
before applying it in the field to verify that it will break the foam.
In the event that one antifoam is ineffective, switching to another
antifoam may solve the problem.

Operating Difficulties: Foaming III
The silicone antifoams have proven to be quick and effective in

controlling foaming problems in the gas treating industry. When using
a silicone antifoam, the antifoam should be added downstream of the
carbon filters because carbon filters will adsorb the silicone.
Care should be exercised with respect to the amount of silicone
antifoam added to a system.
The silicone antifoams should be used only in small quantities, as
recommended by the manufacturer.
It is important to be aware that silicone antifoams used in excessive
quantities have the potential to promote the formation of foam.

Operating Difficulties: Foaming IV
The use of an antifoam may only be a temporary solution to a
continuing problem. The objective in controlling foaming should be to
minimize the level of contaminants in the amine solution.
Of critical importance is the prevention of entrained contaminants in
the feed gas from entering the amine system.
The inlet separator, equipped with a demister pad and possibly filters,
is instrumental in trapping most contaminants, and should be
monitored to insure that it is operating efficiently and not being
overloaded.
Mechanical and carbon filters are necessary in maintaining a clean
solution. In order to prevent hydrocarbons from condensing in the
absorber, the lean amine feed temperature should be held between 10'F
and 20'F above the temperature of the feed gas.

Foaming
Solvent Losses
Corrosion

Causes of Failure to Meet Specifications

Failure to Meet Gas Specification I
Difficulty in meeting the sweet gas specification may be the result of
poor contact between the gas and the amine solvent, which may in turn
be caused by foaming or mechanical problems in the contacting
equipment.
In the case of foaming, the gas remains trapped in bubbles, unable to
contact the rest of the solvent, resulting in poor mass transfer of acid
gas from the gas to the amine solution.
In terms of mechanical damage, if trays are broken or have fallen, there
may not be enough contact zones (trays) for adequate sweetening. If the
trays are plugged, there is less contact between the gas and liquid on
each tray, resulting in poorer sweetening.

Failure to Meet Gas Specification II
Other explanations for off-specification gas may be related to the amine
solution:
The circulation rate may be too low,
The amine concentration too low,
The lean solution temperature may be too high,
The acid gas loading in the lean solution may be too high.
Monoethanolamine systems usually run with solution concentrations
between 10 and 20 weight percent MEA, and a lean loading of 0.1 moles
acid gas/mole of MEA.

Failure to Meet Gas Specification III
Diethanolamine systems are between 20 and 30 weight percent DEA,
with lean loadings of 0.02 to 0.05 moles acid gas/mole DEA.
In order to reach these lean loadings, regeneration resulting in a steamto-acid gas ratio ranging from 1:1 to 3:1 (moles steam: moles acid gas)
in the stripper overhead gas is usually required (1). In some cases, even
higher ratios may be necessary to bring the loading down, as in lowpressure treating applications.

Failure to Meet Gas Specification IV
One way to estimate the overhead steam-to-acid gas ratio, knowing the
stripper overhead temperature and pressure, is to use steam table data
and Raoult's law:
PP H2O = x H2O psat
where: PP H2O = partial pressure of water in the overhead gas;
X H2O = mole fraction of water in the amine solvent;
psat = vapor pressure of pure water at the temperature
of the overhead gas.

Failure to Meet Gas Specification V
Approximating the overhead gas as an ideal gas containing water, H2S
and C02, the partial pressure of the acid gases can be obtained by
subtracting the partial pressure of water, calculated from Raoult's law,
from the stripper overhead pressure:
PPacid gas = Poverhead PP H2O
The ratio of water partial pressure to acid gas partial pressure is equal to
the mole ratio of steam to acid gas.

Failure to Meet Gas Specification VI
As an example calculation of the steam-to-acid gas ratio, a stripper with
an overhead temperature and pressure of 200'F and 20 psia, carrying a
27 weight percent (6 mole percent) DEA solvent, has a corresponding
water vapor pressure of 11.5 psia as obtained from the steam tables.
From Raoult's law, the partial pressure of water is 10.8 psia:
PPH2 0 = (0.94) (11.5) = 10.8 psia
The partial pressure of acid gas would be 20 psia less 10.3 psia or 9.19
psia, and the overhead steam-to-acid gas ratio would be 1.2 moles
steam/mole acid gas (10.8 -t 9.19).

Foaming
Solvent Losses
Corrosion

Solvent Losses
Amine losses are largely through entrainment, caused by

foaming or excessive gas velocities, and by leakage due to
spills or corrosion. In MEA units the reclaimer bottoms
disposal significantly adds to the makeup requirement.
On a much smaller scale are vaporization losses from the
absorber, the overhead condenser, and the flash tank, and
degradation losses by chemical and thermal degradation

Foaming
Solvent Losses
Corrosion

Factors in Corrosion

Corrosion I
Corrosion is a problem experienced by many alkanolamine gas

sweetening plants.
When loaded with C02 and H2S, aqueous amine solutions can
become corrosive to carbon steel.
Corrosion rates are increased by high amine concentration, high
acid gas loading, high temperatures, degradation products, and
foaming.
Also corrosive are acid gases flashed from solution.

Corrosion II
Monoethanolamine is more reactive than diethanolamine and similarly more
corrosive. As a result, the concentration of MEA is restricted to 10 to 20
weight percent, while DEA strengths range from 20 to 30 weight percent.
Rich solution loadings are normally limited to the range of 0.25 to 0.45
moles acid gas/mole MEA, while in DEA systems loadings may range from
0.5 to 0.6 moles acid gas/mole DEA.
The corrosiveness of a loaded amine solution is strongly influenced by the
relative proportion Of C02 to H2S in the feed gas. C02 is more corrosive to
carbon steel than is H2S in aqueous systems.

Corrosion III
Thus, for gases containing a higher ratio Of C02 to H2S, the rich
acid gas loading should be maintained at the lower end of the
recommended loading range.
In cases where the feed gas is predominantly H2S, loadings at
the higher end of the loading range may be acceptable.
In terms of design, a number of measures can be taken to
minimize corrosion. Solution velocities should not exceed 3 or
3.5 ft/sec.

Corrosion IV
The rich solution should be on the tube side of the lean/rich heat
exchanger, and pressure should be maintained on the exchanger to
prevent acid gases from flashing, creating an erosion/corrosion cycle.
A low temperature heating medium should be used in the reboiler,
thereby preventing accelerated corrosion rates and thermal degradation
of the amine.
All equipment should be stress relieved.

Corrosion V
There are certain areas of amine sweetening plants which are more
susceptible to corrosion than others, and, as a result, are often
constructed of corrosion-resistant materials such as Type 304 stainless
steel.
These areas include:
1) the lean/rich heat exchanger tube bundle,
2) the reboiler tube bundle,
3) the stripping column, particularly the upper section and
overhead gas line,
4) the reflux condenser, and
5) the rich solvent let-down valve and subsequent piping to the
stripper.
Several Key Operating

Parameters that can Help
maintain good Operation
(Click here for full size Table)
Degradation of Amines and

Alkanolamines
during Sour Gas Sweetening
AMINES GAS TREATING

Contents
Degradation of Amines and Alkanolamines

during Sour Gas Treating
Figure 1. Sour gas sweetening process
Figure 2. Causes of amine degradation
Figure 3. Problems irreversible degradation reaction
Figure 4. Foam formations in the interior of the stripper by degradation
products
Figure 5. Foam formations by degradation products
Figure 6. Crevice corrosion in the junction of pipelines
Figure 7. Pitting corrosion occurring at the end of the pipe junction
Figure 8. Fouling effect in the pipe line of gas sweetening plant
Figure 9. CO2 induced degradation of MEA
Figure 10. Reaction responsible for the degradation of DEA by C02
Figure 11. CO2 induced degradation of PZ and MDEA
AMINES GAS TREATING

Contents
Degradation of Amines and Alkanolamines

during Sour Gas Treating
Table 1. Degradation products of MEA induced by CO2
Table 2. Degradation products of MEA induced by CO2 and O2
Table 3. Degradation products of DEA induced by CS2
Simplified amine gas sweetening PFD

CAUSES OF AMINE DEGRADATION

EFFECT OF DEGRADATION PRODUCTS
Amines Gas Treating

Foam formations in the interior of the stripper by degradation products
Amines Gas Treating

Foam formations by degradation products

Crevice corrosion in the junction of pipelines

Pitting corrosion occurring at the end of the pipe junction

Fouling effect in the pipe line of gas sweetening plant
CO2 Induced Degradation of MEA

Major problems associated with chemical absorption using alkanolamines
Degradation through irreversible side reactions

With CO2, H2S and O2 leads to numerous problems
with the process:
solvent loss
foaming
fouling
increased viscosity
corrosion

CO2 induced degradation of MEA

Degradation products of MEA induced by CO2

Degradation products of MEA induced by CO2 and O2
Degradation of DEA and its blends
Degradation products of DEA and DEA blend

DEA is a secondary alkanolamine, it has a reduced
affinity to reaction with H2S and CO2.

Reaction responsible for the degradation of DEA by C02

Degradation products of DEA induced by CS2
Table 3.

CO2 induced degradation of PZ and MDEA
Figure 11.
APPENDIX
Best Practices - Troubleshooting Guide
Amines: Gas Sweetening
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown Activation
Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst Remaining
Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing & Petrochemical Industries
Catalysts / Process Technology - Hydrogen Catalysts / Process Technology - Ammonia Catalyst / Process Technology - Methanol Catalysts / process
Technology Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass Balance Analysis Catalyst
Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance Characterization Refining & Gas Processing &
Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts / Process Technology - Ammonia Catalyst / Process Technology Methanol Catalysts / process Technology Petrochemicals Specializing in the Development & Commercialization of New Technology in the Refining
& Petrochemical Industries

Reference List
1. Nexant Inc. Task 1: Acid Gas Removal Technology Survey and

Screening for Thermochemical Ethanol Synthesis. Subcontract
Report NREL/KAFT-8-882786-01. March 2009.
2. Phillips, S., Aden, A., Jechura, J., Dayton, D., and Eggeman, T.,
Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol
Synthesis of Lignocellulosic Biomass, NREL Report No. TP-510-41168,
April 2007.
3. Kohl, A. L., and Nielsen, R. B., Gas Purification, 5th ed., Gulf
Publishing, Houston, TX, 1997.
4. Bishnoi, S. and G. T. Rochelle, "Absorption of Carbon Dioxide in
Aqueous Piperazine/Methyldiethanolamine," AIChE Journal, Vol. 48, No.
12, December 2002, pp. 2788 - 2799.

Reference List
5. Phillips, S., Aden, A., Jechura, J., Dayton, D., and Eggeman, T.,
Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol
Synthesis of Lignocellulosic Biomass, NREL Report No. TP-51041168, April 2007.
6. Kohl, A. L., and Nielsen, R. B., Gas Purification, 5th ed., Gulf
Publishing, Houston, TX, 1997.
7. Nexant Database.
8. Kidnay, A. J., and Parrish, W. R., Fundamentals of Natural Gas
Processing, Taylor & Francis Group, Boca Raton, FL, 2006.
9. Engineering Data Book, 10th ed., Section 21, Hydrocarbon Treating,
Gas Processors Supply Association, 1987.

Reference List
10. Kubek, D. J., Polla, E., and Wilcher, F. P., Purification and Recovery
for Gasification, Gasification Technologies Conference, October 1996,
San Francisco, CA.
11. Ranke, G., Advantages of the Rectisol-Wash Process in Selective H2S
Removal from Gas Mixtures, Linde Reports on Science and Technology,
Vol. 18, 1973.
12. UOP Gas Treating information, available at
http://uop.com/gasprocessing/6010.html
13. Catalyst information from Johnson Matthey Group, Absorbent for
Sulphur Polishing, available at
http://www.synetix.com/refineries/pdfs/manuals/669w.pdf

Reference List
14. Watson, J., Jones, K., Removing H2S from Syngas Using Proven
Technology in Japanese Waste Gasification Facility, available at
http://www.gtp-merichem.com/ support/technical_papers
15. Douglas L. Heguy, Gary J. Nagl, The State of Iron Redox Sulfur Plant
Technology New Developments to an Established Technology, available at
http://www.gtp-merichem.com/support/technical_papers
16. Dortmundt, D., Doshi, K., Recent Developments in CO2 Removal
Membrane Technology, 1999.
17. Edwards, M.S., H2S Removal Processes for Low-Btu Coal Gas,
prepared by Oak Ridge National Laboratory, Oak Ridge, Tennessee, for the
Department of Energy/Fossil Energy Office of Program Planning and
Analysis, Contract No. W-7405-eng-26, January 1979.
18. Tennyson & Schaaf, Guidelines Can Help Choose Proper Process for
Gas Treating Plants, Oil and Gas Journal, January 1977.
19. W. Breckenridge, A. Holiday, J. Ong and C. Sharp Use of SELEXOL
Process in Coke Gasification to Ammonia Project Laurance Reid Gas
Conditioning Conference, February 17, 2000.

Reference List
20.
Degradation studies of amines and alkanolamines during

sour gas treatment process
M. S. Islam, R. Yusoff, B. S. Ali1*, M. N. Islam and M. H.
Chakrabarti Department of Chemical Engineering, Faculty of
Engineering, University of Malaya, 50603 Kuala Lumpur,
Malaysia. Department of Chemistry, Faculty of
Engineering, Bangladesh University of Engineering and
Technology (BUET), Dhaka-1000, Bangladesh.
21.
DOW Technical Article : Gas Sweetening Reprint: Printed 1998

Gas Sweetening
22.
Amine Best Practices Group

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WWW.GBHENTERPRISES.

AMINES GAS TREATING

Process Capabilities for gas treating process

AMINES GAS TREATING

Operating Difficulties Overview

Amines: Gas Treating

Amines: Gas Treating

Amines: Gas Treating

Amines: Gas Treating

Amines: Gas Treating

Amines: Gas Treating

Amines: Gas Treating

Amines: Gas Treating

Typical Amines Treating

Amines: Gas Treating

Amines: Gas Treating

Typical Amine System

Typical Amine System

Inlet Gas Knockout

Typical Amine System

Before entering the absorber, the gas is

Baffles remove a portion of the liquids. Mist eliminator pads, located

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

An immediate method to control a foaming problem is the addition of

Typical Amine System

The silicone antifoams have proven to be quick and effective in

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Amine losses are largely through entrainment, caused by

Typical Amine System

Typical Amine System

Typical Amine System

Corrosion is a problem experienced by many alkanolamine gas

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System

Typical Amine System Improvements

Several Key Operating

Amines: Gas Treating