2.1.

Alkanolamines Operational Problems

Main operational problems encountered in amine processes are:

corrosion

foaming

losses

2.1.1.1 Corrosion
Corrosion in amine processes may depend on different factors such as:

sour gas concentration in the solution

decay of amino/CO2 intermediate compounds

heat stable salts formation (HSS)

erosion

Corrosion may be mostly present in the zones not wetted by amine solution such as
reboiler upper part and its vapor return line including vapor inlet in the column,
rich/lean amine exchanger (if there is a change of phase), column OVHD system.
2.1.1.1.1

Sour Gas Concentration

The chemical nature of the treated sour gases (H2S, CO2) may cause severe
corrosion. Especially when using primary amine, due to the high reactivity,
regeneration is more difficult and the regenerated solution may still contain high
concentrations of acid gas causing corrosion all over the plant.
Limit concentrations of acid gas in different amines are:
MEA

0.35 acid moles/amine moles

DEA

0.40 acid moles/amine moles

MDEA

0.50 acid moles/amine moles

The efficiency of a regeneration column is evaluated based on the acid gas residual
concentration. For the different amines the maximum allowable concentration is:
MEA

0.15 acid moles/amine moles

DEA

0.07 acid moles/amine moles

MDEA

0.01 acid moles/amine moles

2.1.1.1.2

Decay of intermediate amino-CO2 compounds

Primary and secondary amines react with CO2 to form intermediate compounds
(amides) and consequently amino-carbamates that decompose into corrosive
alkaline compounds.
Due to their reactivity primary amines favor carbamates formation more than
secondary amines. Tertiary amines do not form either amides or carbamates.
2.1.1.1.3

Heat Stable Salt - HSS

May be defined as HSS salts that do not change at the normal operating conditions
of the regeneration column. They are: carboxylic acids (formic, acetic etc.),
thiocyanates (HSCN), chlorides (HCl), sulfates (H2SO4) and thiosulfates (H2S2O3).
HSS formation is directly due to the presence of specific precursors both in the liquid
and in the gas fed to the amine absorbers.
Presence of HSS above 500 ppm imply unavoidable corrosion problems.
Next table shows the most common pollutant sources leading to HSS formation.
ANION
chloride
nitrates/nitrites

SOURCE
Make-up water (if not BFW)
Water in sour gas
Make-up water (if not BFW)
Corrosion inhibitors
Sulphur oxidation products

sulphates/sulphites/thiosulphates

H2S + O2 S2O3
Sour gas components
Sour gas components

formates/oxalates/acetates

Amine thermal decay

Amine chemical decay

2.1.1.1.4

thiocyanates

H2S and CO2 reaction products

phosphates

Corrosion inhibitors

Erosion

Erosion may be due to the presence of suspended solids and, at the same time,
high flow velocity through pipes and exchangers. That way the formation of a
protective layer of iron sulfide (passivation) over the surface of piping and equipment
is prevented and the metal is continuously removed by H2S.
To overcome the above problem, velocity in pipes should never exceed 1 m/s for
carbon steel pipes and 2.4 m/s for other steels.
In order to avoid presence of suspended solids, make up water should always be of
BFW quality. In any case the parameters of the following table should not be
exceeded.

PARAMETER

ppm MAX

Suspended solids

100

Hardness as Ca

++

Cl+

50
2

Na

Fe+

10

Most often, in process plants, filters are used both of the mechanical and the active
carbon types as mechanical filters stop the suspended solids while active carbon
filters stop the other contaminants.
2.1.1.2 Foaming
Foam formation is normally more common in absorption columns but it may happen
in regeneration columns as well.
Foaming is generally due to contamination by:

light hydrocarbons

finely suspended solids

amine decay products

surface active agents contained in sour gas

Light hydrocarbon condensation may be avoided in the absorbers keeping lean

amine temperature 58C higher than the temperature of sour gas to the absorption
column to avoid change of phase.
Finely suspended solids are normally eliminated by mechanical filtration while heavy
organic molecules are removed by active carbon filters.
Amine decay may be avoided by monitoring reboiling temperature (thermal decay)
and by avoiding amine air contact (chemical decay).
Foaming is shown by the following parameters:

column pressure drop fluctuation

amine entrainment from absorber or stripper

column liquid level fluctuation

reduced efficiency in H2S removal

Antifoam agents may be used but they only avoid foaming formation without
removing the foaming cause which has to be eliminated and it may be one of the
following:

lean amine low temperature

ineffective filtration

lack of equipment/plant cleaning after maintenance

reboilers high temperature

ineffective blanketing system

2.1.1.3 Losses
Amine losses are a serious operational and economic problem and it may be
caused by:

Evaporation

Solubility

Entrainment

Decay

Leakage from equipment (pipes, valves, pumps, etc.)

2.1.1.3.1

Evaporation

Evaporation losses are direct consequence of amine vapor pressure in the solution
in presence of a gas phase.
The evaporation quantity depends on the operating conditions of absorbers and
regenerators OVHD systems as well as Rich Amine Flash Drum operating
conditions such as temperature, pressure, amine concentration and solution vapor
pressure.
On the basis of amine vapor pressure and operating conditions (T,P) of the column it
is possible to calculate the evaporation losses according to Raoult Law:

Pv x P y
where
Pv

vapor pressure

total pressure

amine mole fraction in liquid phase

amine mole fraction in gas phase

the following table shows amine losses for different types of amines at the same
operating conditions.
AMINE

Concentration %

Losses
kg of amine/MMNm3 of treated gas

MEA

15

8.65

DEA

30

0.06

MDEA

30

0.56

50

0.98

Source: Hydrocarbon Processing - May 1994 - Stewart/Lanning - Reduce amine plant solvent losses

The above table refers to equilibrium conditions in absorbers so the real losses
should be less than calculated.
In case of regeneration column (stripper) amine losses by evaporation should be
negligible as:

liquid reflux washes the gas

amine content in the reflux is normally low (traces)

gas is only a small part of the column overhead vapors

Amine losses in regeneration columns may be evaluated as follows.

AMINE

Losses
kg of amine/MMNm3 of treated gas

MEA

< 1.6

DEA

< 0.02

MDEA

< 0.16

Regenerator overhead drum conditions: P=25 psia; T=1205F

Source: Hydrocarbon Processing - May 1994 - Stewart/Lanning - Reduce amine plant solvent losses

A commonly used method to reduce amine losses is the water washing of the
treated gas from the absorber.

2.1.1.3.2

Solubility

Amine losses for solubility happen in liquid-liquid systems and according to

temperature and pressure a certain quantity of amine may remain dissolved in the
hydrocarbon phase.
2.1.1.3.3

Entrainment

While evaporation and solubility depend on the amine physical properties and
operating conditions, entrainment of amine in the treated gas is function of the gas
and liquid hydraulics in absorbers and regenerators.
Entrainment is the result of the formation of amine droplets with a size of
0,15000m that may be carried away by the gas flow.
Main symptoms of entrainment are:

Overloading of downstream gas KO drums

Presence of amine in the downstream gas treatment processes

Main entrainment causes are:

Columns (absorbers) undersized for the given flowrate

Low operating pressure

Column trays working in or almost in flooding conditions

Faulty or plugged trays and/or other internals

Poorly working KO drums and demisters

2.1.1.3.4

Amine Decay

Amine decay may be:

Chemical (oxidation)

Thermal

Chemical (reaction with formation of HSS)

Chemical Decay
Alkanolamines may be decayed by oxidation in various ways. Oxygen can react with
the H2S and form free Sulfur that reacts with amine and form di-thiocarbamates,
thiourea and other compounds not re-convertible into amine.

Similarly thiosulfuric acid may react with amine to form HSS.

Impurities contained in the sour gas such as carboxylic acids, sulfur compounds
(COS, CS2), hydrochloric acid react with amine to produce simple HSS.
Amine recovery can only be carried out by treatment with strong alkali like caustic
soda and subsequent distillation.

Thermal Decay
Amine temperatures exceeding 130C 130 (even locally induced by abnormal metal
temperatures) may cause thermal decay.
To avoid such phenomenon it is necessary to:

Maintain the Reboiler temperature as low as possible

Maintain the regenerator pressure within the appropriate range.