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What our programs

do
Amine and Sulfur
Recovery Units

Gas Treating

Natural Gas Processing


Refinery Liquids & Gas Treatment
Ammonia CO2 Removal
Steel Industry - Coke Ovens

Gas Treating is the removal of undesired


compounds from gas and liquefied gas
streams - primarily H2S and CO2

Treatment for Amine Units

Defoamers / Antifoams *
Emulsion Breakers *
Corrosion inhibitors *
HSAS Neutralizers
Antifoulants
Amine Solvents

Simple Flow Diagram


Lean Amine

Acid Gas

Rich Amine
Gas/Liquid
Out

Regenerator
Absorber

Gas/Liquid
In

Foaming in Amine Systems


Where?
Absorber / Contactor
Stripper / Regenerator
Flash Drum

Why?

Condensed hydrocarbons
corrosion products
oil contamination (FCC)
organic acids
chemical additives

Foaming

Clean amine solutions have a low foaming tendency.


very polar, high surface tension solution

Foaming occurs from contamination by surfactants.


reduces surface tension (foaming tendency)
increases viscosity (foam stability)
liquid hydrocarbons, organic acids, solids

Defoamers / Antifoams
Additives that increase the elasticity of the
bubble
allows bubble to expand making the film
unstable
must have low solubility in bulk solution
1 Defoamers are generally only fed when needed.
2 Antifoams can be injected as a preventative.

Foaming or Fouling?
Foaming
Increases amine hold in tower
Increases tower dP suddenly

Fouling
Solids on trays, packing and exchangers
Increases tower dP slowly

Defoamer / Antifoam Application

Inject upstream to problem area


Avoid loosing additive in filters or wide
spots
Defoamer
Shot Feed 1 to 4 qts per shot
Antifoam
Shot Feed 1 to 4 qts per shot or
Continuous feed 1 to 3 gpd

Defoamer Injection
FUNNEL

SMALL
VESSEL

SHOT FEED EQUIPMENT

CHEMICAL
PUMP

CONTINUOUS INJECTION

Emulsions in Amine Systems


Why?

Where?
Liquid Treater
Flash Drum
Stripper / Regenerator

organic acids
condensed hydrocarbons
corrosion products
oil contamination (FCC)
chemical additives

Sounds like foaming - but ...

Emulsification
Amine solutions have a low
emulsification tendency.
very polar, high surface tension solution
Emulsions occur from contamination.
reduces surface tension
increases viscosity
increases hydrocarbon solubility in amine
phase
Still sounds like foaming ...

Defoamer or Emulsion Breaker?


Foam
vapor in amine mixture

Defoamer / Antifoam
amine insoluble

Injection Location
amine solution

Emulsion
oil in amine mixture
amine in oil mixture

Emulsion Breaker
amine insoluble or
oil insoluble

Injection Location
hydrocarbon feed

Treatment reduces amine losses and


allows for higher throughput!

Acid Gas

Lean Amine
Rich Amine
Gas/Liquid
Out

CI
CP

DF

CP

Regenerator

dP

Absorber

Gas/Liquid
In

CP

CI

CP

CI

Corrosion in Amine Systems


Where?

Reboiler
Stripper / Regenerator
Hot Lean Piping
Hot Rich Piping
Overhead Condenser

Why?

highest temperature
organic acids
acid gases (CO2)
amine degradation

Corrosion
Clean amine solutions are non-corrosive.
high pH
Corrosion occurs from contamination.
acids, acid gases and chelants (degraded
amine)
phase changes, temperature and velocity
increases with low H2S concentrations

Acidic Contamination
Common Acids
formic acid
acetic acid
oxalic acid
glycolic acid
thiocyanic
thiosulfurous
sulfuric
hydrochloric

Net Problem
Reacts with amine
reduces treating capacity
Heat Stable Salt

Foaming / Emulsions
Corrosion
lowers pH
amine-acid salt corrosive

Strong Acids
Hydrogen Cyanide (HCN)

Formic Acid
(HCOOH)
Acetic Acid (CH3COOH)
Oxalic
(HOOCCOOH)
Thiocyanic
(HSCN)

Example: Formic Acid


HCN + 2H2O --> NH3 + HCOOH

Sulfur Dioxide based


acids
Sulfurous (H2SO2)
Sulfate (H2SO4)

Oxygen based acids


Sulfate (H2SO4)
Thiosulfate (H2S2O3)
Organic Acids

Heat Stable Amine Salts


Strong Acid + Amine = HSAS
less amine for H2S absorbtion
amine not regenerated
promotes amine polymerization
acid lowers pH
acid increases corrosion
acid + amine = chelant

Other Corrosives
Acid Gases
Carbon Dioxide
very aggressive acid
increase CO2,
corrosion

Hydrogen Sulphide
promotes FeS scale
can reduce corrosion
avoid over stripping!

Amine Degradation
Thermal, oxygen or CO2
diamines chelate iron
organic acids

Ammonium Bisulfide
Concentrates in overhead
control to < 10,000 ppm
purge reflux to SWS

Process Variables
Phase Change
boiling, condensation, flashing

Temperature
Antoine's Equation
reactions rate doubles with each 10C increase

Velocity
physical damage + concentration effect

Corrosion Cycle
1 Corrosion in HOT areas.
Low H2S content
acids more aggressive
acids + amine = chelant
water soluble corrosion product

2 Fouling in COLD areas


water soluble corrosion product + H2S = FeS
acid + amine = chelant

Corrosion Inhibition
Process Changes
increase amine wt%
restores capacity
increases pH

Chemical Changes
Filming Inhibitor
continuous injection
disperses solids
coats metal

reduce velocity
reduce acid concentrations
control acid
replace / reclaim amine
concentration
neutralize acids
reduce steam rate
remove solids - filtration

Corrosion Inhibitor Application


Corrosion Inhibitors (general)
Inject based on volume
Inject upstream to known problem area
Adjust feed rate based on monitoring

Commodity Amine Solvents


MEA, DEA, DGA, MDEA
Chemical Management

Concepts for Amine Treating


Absorbtion & Regeneration

Absorbing H2S
Gas is physically and chemically
absorbed by amine.
Amount of gas absorbed
depends on:
Temperature

Pressure
Amount of H2S in amine

Example: 35C, 0.2 atm

4 Possible Variables
1 Increase gas pressure!
Not possible
Pressure set by process

2 Increase amine
circulation rate!
Rate determines how
much not how pure.

3 Reduce temperature!
Reduce Lean Amine
Temperature.

4 Reduce lean amine


loading!
Improve regenerator
performance.

Caution!
Too low a temperature may result in
FOAMING.
At lower temperature:
Amine viscosity increases.
Cold amine may condense feed gas.
(dT=+5C)

Regeneration
1 High Temperature
Reverses absorbtion

2 Steam
Stripping gas

3 Low Pressure
Reduces vapor
pressure

Reduce Lean Amine Loading


Regenerator must be hot at bottom and top.
Top Temperature: 105C +/- 3C
(221F +/- 5F)
Bottom Temperature: 125C +/- 3C
(255F +/- 5F)

Steam Rate affects temperature and stripping action.


Steam Ratio: 0.07 to 0.12 kg steam/liter amine
Steam Ratio: 4.3 to 7.2 kg/hr / lpm
(about 1 lb steam/gallon of circulation)

Caution!
1 Hydrocarbons
reduce top temperature, cause foaming.

2 Reboiler temperature < 121C or > 128C


degrade amine, increase corrosion.

3 Steam temperature greater than 150C


degrade amine, increase corrosion.

Increase Circulation Rate


More circulation:
Increases heat requirement.
Lean Loading increases!
H2S in treated gas can increase!

Action Plan
Reduce H2S in treated gas by:
1
2
3
3

Reduce lean amine temperature.


Increase steam rate.
Maximize amine concentration
Increase circulation rate.

The 5 Common Problems

1
2
3
4
5

Off spec gas


Limited capacity
Amine losses
Heat Stable Amine Salts
Corrosion & Fouling

Amine Losses

Foaming +
Emulsification

condensing hydrocarbon
entrained hydrocarbon
contaminated LPG
solids

Entrainment
too much gas/liquid flow
knock out drum

Solubility
high amine
concentrations
amine type

House Keeping
filter changes
recovered amine
waste

Amine Losses
High Amine Losses Action Plan
1
2
3
4
5
7

Adjust lean amine temperature


Recover lost amine (knock out drum)
Monitor dP
Inject defoamer or emulsion breaker
Reduce amine concentration or circulation rate
Purge Hydrocarbons

Heat Stable Amine Salts


Heat Stable Amine Salts Action Plan
1 Wash inlet gases
2 Exclude hydrogen cyanide (APS)
3 Inject corrosion inhibitor
4 Neutralize HSAS
5 Reclaim or replace amine