Amine Treatment/Regeneration

Operation Department
By: SOHAIL ZAFAR
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Contents

 Basics of Acid Gas treatment.

 Amine Selection
 Amine Treatment
 Amine Regeneration
 Operational Philosophy
 Safety Concerns

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Basics of Acid Gas treatment
• Acid Gases (H2S and CO2) causes corrosion .
• Acid Gases removal is desire to meet Product purity specification.
• For over seventy years the alkanolamine process has been considered the
best approach in removing H2S and CO2 acid gases from refinery
products. It is based on the reaction of a weak base (alkanolamine) and a
weak acid (H2S and/or CO2) to give a water-soluble amine acid gas salt.
This reaction creating the weak amine-sulfide salt is reversible at elevated
temperatures, which allows the amine to be regenerated and recycled to
the contactor for additional acid gas removal.
110 F (Absorption)
2(RNH2) + H2S (RNH3)2S
240 F (Regeneration)
(Amine) (Unstable Salt)

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 Amine Selection Criteria
o Amines are compounds formed from ammonia (NH3) by replacing one or more of the
hydrogen atoms with another hydrocarbon group
o Monoethanolamine (MEA), Diethanolamine (DEA), Di-Isopropanolamine (DIPA), N-
ethyldiethanolamine (MDEA), Diglycolamine (DGA), Formulated Amines (UCARSOL
DOW).
o Mixtures of amines are generally mixtures of MDEA and DEA or MEA and are used to
enhance CO2 removal by MDEA.

• The initial selection is based on the pressure and acid gas content of the sour gases as well as
the purity specification of the product.
• As different process conditions have been tested and proven with each amine, they have
become widely accepted in the acid gas processing industry.

• The selection of an amine for gas sweetening is complex and must be based on several
process considerations. Some of the important criteria for the selection of amines are:

 Easy recovery
 Acid Gas selectivity
 Least corrosive and least cost.
 High solubility
 Low volatility and viscosity

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Amine Selection Criteria

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Amine Selection Criteria

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Amine Treatment
 LPG (hydrocarbon) is treated with Amine (Lean Amine) in counter current flow in an
absorption column.
 H2S is absorbed in amine ( Rich amine ) & LPG is sweeten.
 45-50 wt % (MDEA) or 15-18 % (MEA), amine solution is used in the process.
 Lean Amine temperature directly affect absorption efficiency (For Optimum H2S
absorption 110 F is recommended)
 Higher temperature will accelerate desorption and thus reduce efficiency.
 Temperature below 60 F may cause foaming as well as inhibit reaction rate and result
is incomplete H2S absorption.
 The amine circulation rate to absorber should not be decreased below 2.5 mol per
mol of H2S in LPG stream.
 In most cases, unless special design considerations have been employed, the rich
amine acid gas loading ( H2S plus CO2 ) should not exceed 0.3 to 0.4 mols total acid
gas per mol of amine present.
 The lower the sulfide content of the lean amine, the greater the available amine
concentration for removal of H2S. In most cases, properly regenerated lean amine
will not contain more than 0.03 mol H2S per mol amine nor more than 0.1 mol CO2
per mol amine.
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 Amine Regeneration

• The regeneration of the amine solution, actually the breakdown of the weakly bonded
amine-hydrosulfide salt
• The breakdown of the amine-hydrosulfide salt into H2S and amine, the reverse
reaction of the equation below, is promoted by higher temperatures.
• At high temperature (260 F) amines can be thermally decomposed, The decomposition
temperature need not be approached to provide adequate regeneration of amine
solutions and to avoid losses.
• The stripper reboiler outlet temperature is generally less than 260 F . This temperature
is subject to variation with column operating pressure, amine concentration, and acid
gas loadings.
• It should be noted that amine solutions are mostly water. Therefore, temperature
changes with composition are small and it is the operating pressure of the stripper that
determines the temperature of operation.
• The stripping column is operated at the lowest overhead receiver pressure possible , in
any case this pressure must not exceeds 12 psi.
• Reflux with amine to avoid overhead corrosion.

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Description of Process Flow

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 Operational Philosophy
• The unit is designed to recover 920 lbs per hr of H2S.
• The design Amine circulation Rate to achieve this H2S is 2.5 mol Amine per
Mol of H2S.
• Amine solution Composition: 25 % (wt.) Amine solution used in the process is prepared by
diluting pure Amine with steam condensate. Any non-volatile impurities in the water used to
make up the solution will tend to concentrate and deposit out in the form of scale. The process
design for the amine system anticipates a loss of about 24 lbs/hr of water to the acid gas stream
leaving the regeneration accumulator. Accordingly , condensate must be added to system.
• Conditioning : Solids and chemical contaminations are controlled by continues filtration and
reclaiming of amine. Main solid impurities are iron sulfide and iron oxide. It is recommended that
the solids content in the solution be maintained (< 0.1 % wt.). Continues slipstream pass to filter
before flowing to feed surge tank , up to 25 microns solids are removed. The reclaimer restores
the amine purity by removing the high-boiling and non-volatile impurities, such as heat-stable
salts, suspended solids, volatile acids and iron products.
• Start-up of unit:
• Degreasing and steaming out of system before commissioning the unit.
• Amine solution is circulated and Levels maintained in the columns.
• Reboiler commissioned and reflux is sustained.
• Feed is introduced to the contractor/ absorber.
• Proper sampling is done to monitor the process streams.

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Heat Stable Salts
• HSS are salts which do not decompose and release acids in the amine
regenerator (stripper).
• Heat stable salts (HSS) have become identified as a leading cause for
reduced capacity in amine systems. They also contribute to corrosion,
increased viscosity, and foaming.
• As a general rule, total HSS anion of 5000 ppm or less recommended for
the most trouble-free operations.
• Here are the common approaches to remove HSS from amine solutions:
 Bleed and Feed
 Reclaiming
 Neutralization
 Ion Exchange
 Distillation

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Amine Reclaiming
• Reclaimers are installed in Amine units to permit cleaning up amine contaminated with heat
stable salts.
• They work by converting the amine salts to sodium salts, and boiling the amine away from the
resulting salt solution.
• A batch consists of the following steps:
 Filling the reclaimer with amine
 Adding caustic or soda ash
 Adding steam to the bundle to boil off the water and volatile Amine, while making up
with lean Amine to hold levels. This continues until the temperature of the slowly
concentrating salt solution in the reclaimer nears the thermal degradation temperature of
the Amine.
 Sometimes live steam is injected into the reclaimer at the end of the run to strip out any
remaining MEA.
 The sludge in the reclaimer is dumped and the cycle can be repeated.

 The positive effects of reclaiming seen to reduced amine losses / consumption /

replacement, reduced anti-foam usage, reduced foaming, reduced filtration costs,
reduced heat exchanger fouling, reduced amine unit operating costs, fewer production
curtailments, fewer upsets of waste water treatment plant, increased overall
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production, ability to run sourer crude, increased sulfur production.
Foaming
• Foaming in amines systems cause system upsets that lead to loss
production and amine losses.
• Foaming is caused by an impurity or impurities that act as surfactants in
the amine system.
• Foaming has been attributed to number contaminants such as
hydrocarbons (polar and non-polar), HSS, and solids.
• There is a wide variety of anti-foaming or de-foaming agents available.
These additives are believed to break the foam by being a heterogeneous
droplet or solid enter entering the foam bubble and weakening the wall
until the bubble ruptures.
• The advantages of de-foaming agents are their ease of use and low initial
capital expense. The primary disadvantage of antifoam agents is that they
do not remove impurities that cause the foaming in the amine system.

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Reducing Amine Losses:
• The loss of amine can be a serious and costly operating
problem.
• Losses can be occurred due to entrainment of the solution,
vaporization, chemical decomposition, or mechanical leaks.
• Ways to reduce losses are:
 Avoid overheating the surge tank contents. Maintained temperature
at not more than the design 110 F by careful operation of lean amine
fan cooler.
 Maintain sufficient reflux in the regenerator to prevent carryover.
 Exercise good solution control to prevent contamination and foam.
 Maintain solution concentration b/w 15 to 18 wt. %
 Do not exceed plant capacity unless absolutely necessary.

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Troubleshooting Guide lines

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Safety Concerns
• There are two important problems about safety in this unit:
I. The existence of H2S, SO2, NH3, HCN and other toxic gases.
II. The danger of explosion due to the presence of H2, H2S, NH3, hydrocarbons and
other inflammable gases.
• It is thus necessary to have sufficient knowledge of the above problems when
operating or carrying out maintenance of the unit, in order to avoid dangerous
situations.
• Hydrogen Sulfide (H2S): Hydrogen sulfide is a very dangerous gas even in small
concentrations. Hydrogen sulfide (H2S) is a colorless, inflammable and very toxic gas, having
an offensive odor, like that of rotten eggs, and a salty taste. It is an extremely poisonous gas
in the same class as hydrogen cyanide. The odor is not reliable as a warning indication of
dangerous concentration, as persons differ greatly in their ability to detect smells.
• Furthermore, the sense of smell tires rapidly, and also higher gas concentration paralyses the
olfactory nerves so that the victim does not realize that he is breathing the gas.
• Gas masks suitable for use with hydrogen sulfide must be used in all work where exposure to
it is likely to occur. Such masks must be checked frequently to make sure they are not
exhausted. Whenever work is to be done on or in equipment containing appreciable
concentrations of hydrogen sulfide, men must wear gas masks and will work in pairs so that
one may effect a rescue or call for help will thepage
other be overcome.
Safety Concerns
Precautions:

• Work, e.g. repairs, on equipment and lines containing hydrogen sulfide will only be started on
instructions from a qualified person.
• When sampling streams containing hydrogen sulfide keep the volume released to the air to a
minimum.
• Do not stand, or allow anyone else to stand, downwind of the sample point while sampling.
• The operator must wear a mask while sampling streams containing hydrogen sulfide.
• Whenever a leak of hydrogen sulfide is suspected, a mask must be worn while looking for the
leak.
• Basically if there is any possibility of the presence of hydrogen sulfide, masks are an absolute
necessity.
• REMEMBER - IF YOU CANNOT SMELL H2S IT DOES NOT NECESSARILY MEAN IT IS NOT THERE.

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