Académique Documents
Professionnel Documents
Culture Documents
MEA
• Highest reactivity Highest removal capacity
• Lowest molecular weight
• Highest removal capacity on a unit weight basis Lower circulation rates
Characteristics of Ethanolamines
MEA
• Chemically stable Minimal solution degradation
• Reaction rate of H2S is greater than CO2
• Process is non-selective towards H2S/CO2, even CO2 is rapidly and completely removed
Characteristics of Ethanolamines
MEA
• High vaporization losses due to high vapor pressure limits operating
temperature
• Reacts irreversibly with carbonyl sulfide and carbon disulfide leads to build up
of solids Requires efficient filtration
Characteristics of Ethanolamines
DEA
• Less reactive than MEA Causes problem in achieving pipeline specification
• Reaction with carbonyl sulfide and carbon disulfide is slower leads to different
product not build up of solids Less filtration problem
• Low vapor pressure Less vaporization losses
Characteristics of Ethanolamines
TEA
• Completely replaced by MEA and DEA, due to lesser reactivity and difficulty in
achieving pipeline specification
Characteristics of Ethanolamines
DGA
• Recently found many applications
• Reactivity as DEA
• Low vapor pressure
Alkanol-Amine Process
Solution Concentration
• MEA : 15 % by weight
• DEA : 20 - 30 % by weight
• DIPA and MDEA : 30 - 50 % by weight
• DGA : 40 - 70 % by weight
Mixture of glycol and amine used for simultaneous de-hydration and desulfurization
• MEA : 10 – 30 % by weight
• TEG : 45 - 85 % by weight
• H2O : 5 - 25 % by weight
Alkanol-Amine Process
Chemical Reactions
ABSORPTION
• Ethanolamine reacts with H2S to give bisulfide of ethanolamine
RNH2 + H2S = RNH4S + heat
• MEA and DEA reacts with CO2 to give carbamate salt of ethanolamine
(TEA does not react with CO2)
2 RNH2 + CO2 = RNHCO2- + RNH3+
• Ethanolamine reacts with CO2 in aqueous solution to give carbonate
salt of ethanolamine (Slower reaction)
RNH2 + CO2 + H20 = RNH3HCO3 + heat
Alkanol-Amine Process
Differences Dehydration vs sweetening
• Absorber contains more trays
• More filtration and heat exchanger is required
• Reflux requirement are greater
• Operating conditions are different
Alkanol-Amine Process
• Sour gas enters the contactor tower and rises through the descending
amine solution
• Purified gas flows from the top of the tower
• The amine solution, carrying absorbed acid gases, leaves the tower for the
heat exchanger or optional flash tank
• Rich amine is heated by hot regenerated lean amine in the heat exchanger.
• Rich amine is further heated in the regeneration still column, by heat
supplied from the re-boiler. The steam rising through the still liberates water
and CO2 , regenerating the amine.
• Steam and acid gases separated from the rich amine are condensed and
cooled, respectively, in the reflux condenser.
Alkanol-Amine Process
• Condensed steam is separated in the reflux accumulator and returned to
the still. Acid gases may be vented, incinerated, or directed to a sulfur
recovery system.
• Hot regenerated lean amine is cooled in a solvent aerial cooler and
circulated to the contactor tower, completing the cycle.
• A variety of heat sources can be used for the still re-boiler – direct fired,
waste heat, hot oil, and steam systems.
CORROSION
• The presence of acid gas constituents causes
corrosion.
• Impossible to eliminate but can be minimized or at
least limited, by proper design and operation.
• Corrosion will be more severe at places where the
highest concentrations of acid gases encounter the
highest temperatures like amine-amine heat exchanger,
stripping column and reboiler.
SOLUTION DEGRADATION
• Amine solution will slowly oxidize when exposed to air or
oxygen, product are generally considered to cause
corrosion problems.
• Oxidation can be minimized by use of an inert blanket on
amine storage containers and surge drums.
• MEA reacts with carbonyl sulfide or carbon disulfide to
form an insoluble salt, results in loss of MEA unless the
solution is reclaimed. This reaction can be reversed by
placing the MEA in a basic solution and heating.
• Degradation product can remove H2S and/or CO2 but
they are not as effective as original ethanol amine and
for this reason a loss in solution activity.
FOAMING
Gas –Gas
Exchanger
Bottom temp.
Scrubber
230-240 F
PROCESS CONCERNS
• Corrosion.
• Erosion.
CORROSION
• Severe corrosion of carbon steel in several areas.
• This corrosion occurred where the conversion to bicarbonate
was high and where CO2 and steam were released by pressure
reduction.
• Remedy – Corrosion inhibitors includes arsenic and vanadium
salts as well as dichromates.
• Stainless steel is recommended for reboiler tubes.
• Control valves and solution pumps should also be of stainless
steel, particularly those parts which encounter the carbonate
solution such as impellers and inner valves.
CORROSION
• The absorber and stripper can be made of carbon steel.
• When CO2 is the only acid gas constituents, potassium
dichromate will serve as an effective corrosion inhibitors
(but from 1000 to 3000 ppm).
• If sufficient quantity of H2S is present, formation of the
potassium bisulfide inhibits corrosion to a significant
extent.
• In cases where corrosion is a problem with H2S present, the
commercially available film-forming fatty amines are
usually effective as corrosion inhibitors.
EROSION
• Occasional pieces of scale and other solid material causes
severe erosion.
• Efficient filtration schemes is required, minimizes erosion
problem.
• Flashing and cavitation are frequently encountered when
high pressure multi-stage pumps are used for pumping
solution from the low pressure of the stripper to the high
pressure of the absorber.
• Single stage, slow speed booster pump of low NPSH
design to serve as a feed pump for high pressure pumps.
HOT CARBONATE PROCESSES
WITH ACTIVATORS
Among carbonate processes, those containing an activator
to increase the activity of the hot potassium carbonate
solution are more popular. Some of these are:
1. Benfield-several activators, usually DEA.
2. Catacarb-amine borates used as activators.
3.Giammarco-Vetrocoke- for CO2 removal, arsenic trioxide
most commonly used; selenous acid and tellurous acid are
also used. For H2S removal, alkaline arsenites and
arsenates (usually KH2AsO3 and KH2AsO4) used.
THE HOLMES-STRETFORD PROCESS
• This process converts H2S to elemental sulfur of almost
99.9% purity.
• The process is selective for H2S, and can reduce the H2S
content to as low as 1 ppm.
• CO2 content remains almost unaltered by this process.
• Operating costs are lower and the process has better
flexibility in application, that is, it can be designed for
larger pressure and temperature ranges.
THE HOLMES-STRETFORD PROCESS
Air Compressor
Inlet gas
scrubber
Acid Solution return pump
Gas
LO-CAT PROCESS
• This process is used for the removal of small amount of
acid gas from a large amounts of the gas and producing
elemental sulphur.
• The reactions involved are:
During absorption of H2S
Fe3+ + S2- Fe2+ + S
During regeneration of catalyst
Fe2+ + ½ O2 + H2O 2OH- + Fe3+
CLAUS PROCESS
In the Claus process H2S was reacted over a catalyst with
air (oxygen) to form elemental sulfur and water.
H2S + 1/2 O2 S + H2O
The overall reaction was separated into two steps:
A highly exothermic combustion reaction in which H2S
reacts with air to form SO2
H2S + (3/2) O2 SO2 + H2O, ∆H (77°F) = -223100 Btu
A moderately exothermic catalytic reaction in which sulfur
dioxide (SO2) formed in the combustion section reacts with
unburned H2S to form elemental sulfur.
2 H2S + SO2 (3/x) Sx + 2 H2O, ∆H (77°F) = - 41300 Btu
CLAUS PROCESS
The side reactions involving hydrocarbons, H2S, and CO2
present in the acid gas feed can result in the formation of
carbonyl sulfide (COS), carbon disulfide (CS2), carbon
monoxide (CO) and hydrogen (H2).
CLAUS PROCESS CONFIGURATIONS
STRAIGHT-THROUGH CONFIGURATION