ATTOCK REFINERY LIMITED

MORGAH RAWALPINDI

Amine Unit and world wide

Problems

Prepared by: KHIZER IQBAL

ENGINEER (OPERATIONS)

Submitted to: MOHSIN ALI KHAN

SENIOR ENGINEER (AMU/SWU)

INTRODUCTION:
Sweets the sour gas by removing acidic gases from Natural Gas.

• Acidic gases: like H2S, CO2, CO, H2, NH3 and water vapors.
• Sour gas: Natural gas having acidic gases in access.
• Sweet gas: Natural Gas not contains acidic gases or in Limited quantity which is acceptable.

WHY WE SWEET THE NATURAL GAS:

• H2S is highly Toxic gas and is very corrosive to carbon steel.
• CO2 is also corrosive and also reduce the BTU of natural Gas.
• Gas sweetening process removes these gases to make Natural gas suitable for transportation
and use.

Amines Used For Acid Gas Removal:

1. MEA (Mono Ethanol Amine)
• It is Primary amine.
• It is good for CO2 Removal.
2. DEA (Di Ethanol Amine)
• It is Secondary Amine
• It is good for H2S Removal.
3. MDEA (Methyl Di Ethanol Amine)
• It is tertiary amine
• It is used for selective removal.
• MDEA has very fast reaction with H2S and reacts slowly with CO2.

Comparison of Different Amines:

Amine Acid Gas Regeneration Degradation Recommended Density
Loading Temperature Temperature Strength
Moles of g/mL
H2S/Mole of Degree C Degree C wt. %
amine

MEA 0.30 90 170 15-20 1.0117

DEA 0.35 120 272 30 1.097
MDEA 0.70 110 247 50 1.038
Operation in Amine Units:
• A typical amine gas treating process includes an absorber unit and regenerator unit as well as
accessory equipment.
• In the absorber the down flowing amine solution absorbs H2S and CO2 from the up flowing sour
gas to produce a sweetened gas stream as a product.
• Amine solution rich in the absorbed acid gases moves to Regeneration side. “Rich" amine is then
routed into the regenerator to produce regenerated or “Lean" amine that is recycled for reuse
in the absorber.
• The stripped overhead gas from the regenerator is concentrated H2S and CO2 and burnt to
atmosphere.

Typical Layout of amine unit:

Main Problems Faced in Amine Units:

1. Amine loss from the system
2. Amine foaming problem
3. Corrosion problem
4. Concentration of residual gas in lean amine solution
5. Winterization.

1. Amine loss from the system:

A certain amount of Amine will be continuously lost from the amine sweetening system due to the
vapor pressure of the amine. The largest amine losses are usually through the amine absorber as
carry over with the treated gas. Some amine is also lost through the Amine Stripper, Amine Flash
Tank, Pumps Packing and Drainages. The losses vary for different plants, but usually are between
0.05 to 0.5 gallons per MMscf of treated gas.

FACTORS
1. Sour gas flow rate
2. Reboiler temperature
3. High differential temperature between amine solution and the sour gas in the amine absorber
4. Bad mist eliminator on the absorber top
5. Bad filtration system
6. Foaming

REMIDIES
1. Maintain the top temperature of the amine absorber as low as possible.
2. Maintain proper amine solution concentration.
3. Ensure good clean amine solution (good filtration).
4. Proper Reboiler control to avoid chemical breakdown (Degradation) of amine.
5. Avoid all amine contamination.
6. Regularly check all operating parameters & process variables to maintain steady running of the
amine unit.

2. Amine Foaming:
Foaming is a common problem that results in a decrease of treating capacity of the plant and
amine losses.

INDICATIONS
1. It is usually detected by a sharp rise in the pressure drop across the amine absorber.
2. Fluctuations in level of absorber.
 Causes
• Hydrocarbons.
• Reaction of the amine solution with organic acids.
• Contamination of ferric Sulphides or other salts
• Contamination of Fats or oils.
• Contamination of Sludge.
• Degradation of amine

REMIDIES
• Do not overload the inlet separator in your plant.
• Avoid condensation of liquid hydrocarbons in the amine absorber by keeping the
temperature in the absorber above the hydrocarbon dew point.
• Keep field corrosion inhibitors, soap based lubricants and lube oil out of the amine system.
• Maintain the charcoal filter in good working condition, because this is the filter which
absorbs the liquid contaminants.
• Avoid degradation by preventing oxidation of Amine and by proper reboiler control.
• Try an Anti-foaming agent and evaluate the results.

Note
Anti-foaming agents are only a temporarily answer for the foaming problem. The best cure
for the problem is to avoid the main causes.

3. Corrosion problem:
Corrosion problem is commonly encountered in the amine system.

Most corrosion occurs in areas where the acid gases are actually released from the solution i.e.
Amine Regenerator, Heat exchanger, Amine stripper, Amine pumps, Reflux pump and Acid Gas
Condenser.

Causes
Corrosion is traced to gaseous H2S & CO2 which comes out of the amine solution while the rich
amine solution is receiving heat in the heat exchanger prior to the regenerator.

These acid gases combine with water to form acids, which will attack the metal surfaces.
 Remedies
1. Keep the amine solution clean.
2. Do not over load the inlet separator, which prevents solids entering in the system.
3. Other solids that contribute to corrosion are removed by amine filters.
4. Its very important to maintain a good amine filtration system.
5. The presence of air will cause the amine to degrade into heat stable salts, so there should be
a gas blanket on all the amine storage tanks to exclude air.
6. Maintain acid-gas loading within the proper ranges.
7. Corrosion problems become severe at high temperatures with the rich amine solutions, so
keep the amine solution concentration up to the recommended value.
8. Amine Reboiler temperature should be kept at the recommended range to avoid any amine
decomposition or any extra water losses which will affect the amine solution concentration.
9. Maintain a regular corrosion testing programmed for an early detection of any corrosion
problems in the system.

4. Winterization:
Cold weather operation requires special attention for plants using MEA, DEA. The freezing
point of these solutions is about the same as that of the water.

Remedies
1. Lines or vessels in which there is no continuous flow should be given a special consideration
during cold weather.
2. If the amine unit is shut down for an extended period during freezing weather, the amine
solution should be completely drained from the system.
3. This problem is an occasional one, but it is important and must be considered while working
in the amine system.

5. Concentration of residual gas in lean amine

solution:
The rich amine solution fed to the amine stripper contains acid gas from two sources:

A. Acid gas absorbed in the absorber.

B. Residual acid gas from the amine stripper.
 If the concentration of residual gas is low then more acid gas can be absorbed by the lean amine
solution in the absorber.

Reasons
• The amount of residual acid gas in the solution depends upon the heat used in the Stripper and
Reboiler.
• The inlet sour gas rate and amount of acidic gasses changes in feed gas.

Remedies
• Increasing the heat in reboiler and stripper reduces the residual acid gas in lean amine and vice
versa.
• The amine solution flow rate and the reboiler heat should be changed in same proportion to
match the sour gas changes in feed gas.

• Normal operation parameters:

LEVEL (%)
Equipment Normal Range
Contactor Tower 30-40

Gas knock out drum 10-30

Gas scrubber 40-50

Rich Amine Flash Drum 30-40

Reflux Drum of Stripper 40-50

Temperatures (Degree C)
Equipment Normal Range
Lean Amine Inlet Amine to Contactor tower 50-65

Sour Gas And Lean Amine in Contactor Tower 5-10

(Differential)
Plate and frame Exchanger rich amine outlet 85-95

Stripper Top 120-130

Amine Condenser Out 50-65
Reboiler 130-135
Lean Amine Cooler Outlet 55-65

Pressure (Kg/CM²)
Equipment Normal Range

Contactor tower Differential 0.1-0.5

Carbon filter and sock filter (Differential) 0.1-0.5

Acid Flare Line 1.0-1.6

Flow (M³/Hr)
Equipment Normal Range
Lean amine Flow rate to contactor Tower Depends on the amount acidic gasses in feed
natural gas (10-20)

Main Problems due to variations in parameters:

Absorber Towers

Unit Parameters Too Low Too high

Inlet temperature - • Foaming • Low acid gas absorption
product or amine
Rich Amine loading • Corrosion risk • Corrosion in hot rich section
• High amine circulation rates
Liquid / vapor • Channeling • Amine loss
velocities • Low acid gas absorption • Entrainment
Tower Pressure • Foaming • Fouling
• Low acid gas absorption
Bottoms level • Foaming • Fouling

Defoamer injection • N/A • Fouling

rate • Foaming
• Amine degradation
Amine / product • Low contact time • Amine loss
interface level • Low acid gas absorption • Entrainment

Amine Stripper (Regenerator)

Unit Parameters Too Low Too high

Reboiler heat flux • High lean amine • Fouling

loading • Amine degradation
• Insufficient acid • Corrosion risk
gas stripping
Reflux ratio • High amine loss • High lean amine loading
• Insufficient acid gas stripping
• Increased energy demand
Tower Pressure • Foaming • Fouling
• High lean amine loading
• insufficient acid gas stripping
Bottoms level • Foaming • Fouling

Defoamer injection rate • N/A • Fouling

• Foaming
• Amine degradation
Reflux ammonium bi • N/A • Corrosion potential
sulfide concentration • Fouling potential

Solvent Filtration
Unit Parameters Too Low Too high

Filter element micron rating • Operating cost increase • Fouling

• High filter change frequency • Insufficient particulate removal

Carbon bed life • Amine degradation • N/A

• Feed contaminants high
• Increased fouling potential
Lean amine filter bypass loop • Insufficient particulate removal • Operating cost increase
flow rate • High filter change frequency
• Low carbon bed efficiency

Rich Amine Flash Drum / Separators

Unit Parameters Too Low Too high

Oil skimming rate • Fouling • High amine loss

• Foaming

Residence time • Fouling / Foaming in stripper, • N/A

Plate and frame heat exchanger
• Poor hydrocarbon Removal
Flash gas rate • Corrosion potential in hot rich • High amine loss in
section • flare gas

Amine Solvent
Unit Parameters Too Low Too high

Heat stable amine salts • N/A • Corrosion potential

concentration • Fouling potential
• Insufficient acid gas absorption
• High amine loss
• High make up rate of fresh
solvent
Amine concentration • Insufficient acid gas absorption • Increased corrosion
• High energy costs • High rich amine loading
• Increased stripping requirements • Foaming
Corrosion monitoring • Uncontrolled corrosion • N/A

Important Tripping Of Amine Units:

A. Low Low level of contactor tower.
B. Low Low Level of sweet gas Scrubber.
C. Low Low level in the Lean Amine Charge Pump suction Vessel.
D. Low Low Suction Pressure of Lean Amine Charge Pump.
E. High High Temperature of Reboiler.
 F. High High H2S.
G. Vibration Switches where Unit is Skid Erected.

Some Problems can easily be Understood by Experimental

results:
1. Pick Up Rate
2. Amine pH Control

1. Pick Up Rate
• The quantity of acid gas removed by each gallon of amine solution is referred to as’ The Pick-up
Rate’.
• The Pick-up rate can be determine from the difference of the acid gas concentration in the rich
and lean Amine solution.
• Increasing the concentration, Will also increase pickup of acid gases and decreasing the conc.
Will reduce the pickup rate.

An experiment carried out by Bryan Research and Engineering Inc. for MDEA

Conc. of lean solution Pick up rate

Wt. % Ft3 of acid gas / gal. solution
40 4.9
45 5.4
50 6.3
55 6.5
60 6.7

8
6
4
2
0
40 45 50 55 60
RESULTS:
It can be seen that the optimum concentration of MDEA is 50 % , with a result of pick-up rate 6.3 ft3 of
acid gas per gallon of solution.

Note:
The pick-up rate shown above is for plants operating above 500 psig(35 Kg/Cm²) pressure.

Disadvantages of increasing concentration:

1. A higher concentration of the amine in the solution would be more effective in acid gas removal
but not optimum.
2. The increase in pick-up rate decrease slightly.
3. It may be more corrosive.
4. It will require more heat for its regeneration.
5. Higher concentration requires a higher temperature in the stripper reboiler.
6. Increased temperature in reboiler will lead to amine decompose and form undesirable
compounds.

2. Amine pH Control:
It is important to control the amine pH within a certain specified value. Controlled pH of amine gives
better acid gas removal and protects the equipment from corrosion.

Recommended pH values
The recommended pH values for amine are given in the table below:

Amine Type required pH values

Lean = 7.0 - 7.5

Rich = 5.5 (minimum)

Consequences of pH
1. Too high pH (more than the specified values) :
• Increase the amine foaming.
• More amine losses.
• Less intimate contact between the gas and amine.
 2. Too Low pH (Less than the specified values) :
• Corrosion.

Solution of the problem

Problem can be shooting by improving the stripping process.

Acid gas loading:

“Acid gas loading” is the number of moles of acid gas in solution divided by the number of moles of total

amine in solution.

Formula for Rich acid gas Loading

Rich amine loading = (Sour gas rate (m3/hr) * H2S concentration (Mole %) * 105.14) / (amine rate
(m3/hr) * amine strength * 22.414 *1000)

• The result will be in mole H2S/mole amine

H2S Safety:
• Hydrogen sulfide is a highly toxic and flammable gas.
• Being heavier than air, it tends to accumulate at the bottom of poorly Ventilated spaces.
• Although very pungent smell.
• It quickly deadens the sense of smell, so victims may be unaware of its presence until it is
too late.

Detection by Smell
• Can be smelled at low levels
• But with continuous low level exposure or at higher concentrations you lose your ability to
smell.
• At high concentrations – your ability to smell the gas can be lost instantly.

Health Effects
1. Low concentrations
• Irritation of eyes
• Nose
• Throat or Respiratory system.
 2. Moderate concentrations
• More severe eye and respiratory effects
• Headache
• Dizziness
• Nausea
• Coughing
• Vomiting
• Difficulty in Breathing.
3. High concentrations
• Shock
• Convulsions
• Unable to breathe coma
• Death
• Effects can be extremely rapid (within a few breaths).

Before Entering Areas with Possible Hydrogen Sulfide

• The air needs to be tested for the presence and concentration of hydrogen sulfide by a
qualified person using test equipment.
• This individual also determines if fire/explosion precautions are necessary.
• If gas is present, the space should be ventilated.

If the gas cannot be removed:

• Use appropriate respiratory protection
• Other necessary personal protective equipment (PPE),
• Rescue and communication equipment.
• Atmospheres containing high concentrations (greater than 100 ppm) are considered
immediately dangerous to life and health.
• A self contained breathing apparatus (SCBA) is required.