In Amenas BASF Training 2010 PDF

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 1
BASF presentation
for In Amenas, Algeria
®
aMDEA Process for
Acid Gas Removal
In Amenas - 17th November 2010
Justin Hearn
Arslan Trigui

Training Objective
By the end of this session . ..
. . you should have a better

understanding of the
aMDEA® Process
for acid gas removal (AGR)
Training structure
 Introduction: BASF – “The Chemical Company”

 Summary of plant cleaning procedure
 Preparing the aMDEA® solution
 Start-up preparations
 Maintaining treated gas specifications
 Effects of a variation of operating parameters
 Foaming / Antifoam application
 Safety
 Solvent analysis

BASF
“The Chemical Company”

BASF - a strong tradition since 1865
Since 2004
The Chemical Company
1965 – 2004
From Ludwigshafen to the world
1953 – 1965
The beginning of the plastics age
1945 – 1953
Reconstruction and new beginning
1925 – 1945
New high-pressure syntheses
1901 – 1925
The age of fertilizers
1865 – 1901
Founding of
BASF – the age of dyes
BASF
The world’s
largest chemical
company
BASF Site, Ludwigshafen, Germany
8 km
250 chemical plants making 6,500 different products

BASF - The Chemical Company
Our portfolio includes:

Chemicals
Plastics
Agricultural products
Personal Care
Catalysts
Oil & Gas
 Sales €57,951 million

 Income from operations (EBIT) € 7,316 million
 Employees as of December 31 95,175
Based on 2007 Figures

BASF’s Global Presence
Antwerp
Nanjing
Ludwigshafen
Tarragona
Freeport
Geismar
Kuantan
Integrated site Production Sales

BASF and gas treatment?
 Production of process chemicals
 BASF operates 15 CO2 removal plants
 Laboratory and Mini Plant team
 Technology Team
 Support and technical marketing team

Where are the aMDEA® process
applications?
 LNG plants
 Natural (sales) gas plants
 Ammonia plants
 Synthesis gas plants
 Hydrogen units
 Iron Ore reduction units
 2-EH plants
Operational
Challenges for
INA’s AGR Units
using aMDEA ®
Operational Challenges
 Maintain treated gas specifications
 Minimise operational upsets (foaming, etc)
 Minimise operational costs ( solvent make-up)
 Minimise maintenance (corrosion, scale)
 Maximise on-stream time (availability)
 Maximise profitability!
In Amenas
AGR Process
Configuration
Amine solution cycle
Absorber: Stripper:
high P, low T low P, high T
C1, C2, C3 . . .
CO2, H2S
aMDEA®

INA - Simplified PFD
Ref 1838 - In Am enas - M WKL
Treated Gas Acid Off-Gas
4
10
34 50
Condenser 155
Make-Up E12
16 Water 9
Lean Solution
85
Cooler
E1 Absorber Stripper
lp flash
C1 C7 C9
17 Reboiler
Feedgas 1 E20
25
29
Lean Solution
Pum p
Solvent/Solvent
Heat Exchanger E19
IAP Process Configuration
Special design features:
 LP Flash column – energy saving
 Acid gas recycle to LP Flash from stripper
 HC skimming points in all 3 columns
 Larger capacity slipstream (20%) for filtration

Variable feed gas temperatures
 The temperature in the absorber should be

higher than the hydrocarbon dew point of the
feed gas to avoid hydrocarbon condensation
 Keep the lean amine temperature (design 56°C

- 60°C) higher than the feed gas temperature
(varies between 25°C – 55°C)
 Little chance of hydrocarbon condensation with

a T of 10°K

Training structure

 Solvent chemistry, aMDEA® solution
 Safety
Solvent
Chemistry of
the aMDEA ®
Solution
Amines - an introduction
 Amines are organic bases
 Three main groups: Primary, Secondary and Tertiary
 Amines react reversibly with CO2 to form amine salts
 The CO2 absorption reaction is exothermic (liberates heat)
 CO2 is absorbed at high pressures & low temperatures
 CO2 is regenerated at low pressures & high temperatures

Primary, secondary and tertiary amines
MEA: MonoEthanolAmine DEA: DiEthanolAmine
H CH2CH2OH
N CH2CH2OH H-N
H CH2CH2OH
Primary Amine Secondary Amine
MDEA: Methyl-DiEthanolAmine
Tertiary Amine CH2CH2OH

H3C-N
CH2CH2OH
Characteristics of Primary,
Secondary & Tertiary amines?
 Primary amines, like MEA, are very strong bases
- React fastest with CO2, but bad corrosion problems
 Secondary amines, like DEA, are strong bases.
- React quickly with CO2 , corrosion, but less than MEA.
 Tertiary amines, like MDEA, are very stable, no corrosion
 Corrosion is a result of amine degradation

Consequences of Degradation
 Loss of treating capacity, solvent deactivation

 Solvent losses
 Formation of chelating polyethylene amines which will
pick-up Fe2+ ions and other heavy metal ions (Cr, Ni, ...)
 Corrosion followed by Scaling
 Excessive foaming caused by

degradation and corrosion products
MDEA - a potentially
excellent amine. . .
CH2CH2OH
H3C-N Tertiary Amine
CH2CH2OH
 good CO2 capacity
 very stable, non-degrading.
 High molecular weight 119.2 kg/kmole
 High boiling point pure MDEA 245 °C (low vapour pressure!)
 Low solution boiling point 110 - 120 °C (normal reboiler)

Absorption mechanisms for CO2
There are two possible mechanisms

for CO2 absorption with amines
One is fast . . .
but the second is very much slower!

Absorption Mechanism 1
CO2 + H2O HCO3- + H+

R2NH + H+ R2NH2+
R2NH + CO2 + H2O R2NH2+ HCO3-
 This reaction is possible for all amines

primary, secondary and tertiary amines
 Water is not only a “solvent”, but also a reactant
 This reaction is slow

Absorption Mechanism 2
R2N + CO2 R2NCOOH

R2NCOOH + H2O R2NCOO- + H3O+
R2NH2 + CO2 + H2O R2NHCOO- + H3O+
• Formation of carbamates is a fast reaction

• But - tertiary amines, like MDEA, do not
form carbamates!

 Key learning Point
 Primary and secondary amines form carbamates

 Carbamates react very quickly with CO2
Absorption of CO2 with MEA & DEA is fast
 Tertiary amines do not form carbamates at all

MDEA is very stable and does not degrade at
normal AGRU operating temperatures.
 But, absorption of CO2 in MDEA is rather slow

Absorption of CO2
So how can we combine the “good” properties of

MDEA together with fast CO2 absorption?
 Addition of activators!

Absorption mechanism (Summary)
GAS PHASE LIQUID PHASE
MDEAH+ + HCO3-
CO2 SLOW
MDEA + H2O
activator MDEAH+ + HCO3-
CO2 FAST
activator + CO2 MDEA + H2O
CO2 + H2O + MDEA MDEAH+ + HCO3-

What if we used
un-activated MDEA?
MDEA has a high CO2 absorption capacity
- the reaction takes longer due to poor kinetics
So what difference would this make to the design

(and cost) of the INA AGR unit if we used un-
activated MDEA to absorb the CO2?
 The absorber column would

be around three times higher!
What does an activator do?
 Activators “catalyse” the rate of absorption of CO2 by

forming a fast-acting intermediate compound called a
“carbamate”
 Primary and secondary amines form carbamates by

themselves, and therefore require no activation
 Potential activators must be able to form carbamates

Which activator?
 So MEA and DEA could be used as activators

for MDEA . . . . however
 an “ideal” activator would form carbamates
 and would not degrade causing corrosion
and foaming problems.
 BASF researched for several years to find
activators with these characteristics . . . . . . .

aMDEA® activator chemistry
 BASF activator systems can form carbamates
 However, aMDEA® activators do not contain

any primary or secondary alkanolamines
 This means there is no activator degradation at

normal system operating temperatures
 The precise formulation of the activator systems

used in aMDEA® is proprietary to BASF

INA AGRU Solvent: aMDEA®
 aMDEA® is a BASF brand name for a large ‘family’ of

non-degrading gas treating solvents
 All members of the aMDEA® solvent family consist of

three components:
- MDEA - a very stable tertiary amine
- Water
- activator system, (containing no alkanolamines)
 BASF developed a tailor-made aMDEA® for INA

Training structure

 Solvent chemistry, aMDEA® solution
 Safety

Summary of
plant cleaning
procedure
Summary –
AGRU Cleaning Procedure
 Pre-cleaning of unit – manual* and air blowing
 Preparation for flushing by demin. water circulation
 Potash solution flush
 First demineralised (R.O.) water flush
 Second demineralised water flush
 Unit now ready for filling with aMDEA®
 The better the cleaning, the smoother the start-up!

Preparing
the aMDEA ®
solution
Delivery of the solvent
 aMDEA® Premix is supplied in 210 kg

(200 litre) drums
 BASF aMDEA® sales products are
concentrated, pre-activated solutions
containing approx. 92 % amine
 This premix has to be diluted to a
concentration of 40 % with degassed,
demineralised (R.O.) water.
Solution strength (1)
aMDEA® consists of three parts:

- Methyl-Diethanolamine (MDEA)
- Water
- activator system
 MDEA + activators = Total Amine
The lab will measure Total Amine

Design (total amines) : 40 %(wt.)
Recommended range: 37% to 45%(wt.)
Permissible range:  35% to 55%(wt.)
 very flexible operating conditions

Activator content
 Primarily influences the CO2 absorption rate rather than

the CO2 absorption capacity
 Low activator content can be balanced by higher solution

flow rate – up to a point.
 Concentration of activators reduces slowly over time
 Make-up activators with aMDEA® “Enriched Premix”
 Enriched Premix is a 1:1 ratio of MDEA : activators
 N.B. Two different types of aMDEA® on site!

Water quality for diluting the
aMDEA® Premix and make-up
 Use degassed, demineralised / RO water

 The presence of oxygen will increase the
corrosion in the AGRU
 The presence of solids may stabilise emulsions

 aMDEA® solvent is hardly affected by short
term contact with oxygen

Make-up water quality
For ions and particles the following maximum levels
should not be exceeded:
 max. 1 to 2 ppm (wt.) of Cl-
 max. 3 ppm (wt.) of Na+
 max. 3 ppm (wt.) of K+
 max. 5 ppm (wt.) of Si
 max. 10 ppm (wt.) of dissolved Fe
 max. 50 ppm (wt.) for total hardness, expressed in terms of
Ca2+
 max. 100 ppm (wt.) of suspended solids, max. particle size
10 µm, max. 35 % (wt.) of these, i.e. 35 ppm (wt.) in range of
5 to 10 µm, remainder below 5 µm.
Chloride level
 The recommended max. chloride content in the

make-up (demin.) water is 1 - 2 ppm (wt.)
 Chlorides can lead to pitting corrosion and stress
corrosion cracking of stainless steel
 Chlorides can disturb the formation of the
protective layer on carbon steel equipment
 It is recommended to keep the chloride level
below 100 ppm(wt.)
 Above 500 ppm (wt.) a “de-ionising” treatment of
the system is recommended
Preparing the aMDEA® solution (1)
 The aMDEA® Premix is viscous at low temperatures.

 The water used for diluting the cold premix should have
a temperature of at least 20 °C. A higher temperature is
preferred, e.g. 50 °C, because the viscosity of the
solution is lower at higher temperatures and a
homogeneous mixture is achieved more quickly.
 The aMDEA® storage tanks are (electrically) heat-traced.
 At a temperature below +10°C precipitation of the
activator system could occur!
 It is preferable to prepare an over-diluted solution

than an over-concentrated solution.(30% is better
than 50%)
- If there is too much water content, it can be evaporated.
- If there is too much amine, it is difficult to remove.
 Try to empty the drums completely, i.e. without
leaving any aMDEA® residue in the bottom of the
drum. Add hot R.O water and thoroughly agitate
drum before pumping.
 Rinsing each emptied drum with 200 litres of warm

demineralised water will both clean the drums and
optimise the use of aMDEA®
 At the same time, this method, if carefully applied,
will dilute the amine to around 46% (wt).
 Often, the exact hold-up of the plant has not been
accurately estimated. (e.g. ISG), so be prepared to
adjust the total volume of prepared solution.

Reasons for aMDEA® losses
and how they can be minimised
 Leakages from seals or gaskets, pumps, valves, etc.
Improvement of plant maintenance.
 Excessive sampling for analytical reasons
Reduction of the sample amount
(return unused samples to system)
 Entrainment of the aMDEA® solution
Installation and maintenance of demister pads on top
of the columns
 Excess water should be avoided due to the presence of
amine in the reflux water (usually 0.1 - 1 % (w/w))
Bring the plant back to the recommended
operating conditions
Start-up
Preparations
Recap: Measures prior to start-up
 Cleaning of the plant according to cleaning procedure

 Disconnect the lines used for pressurisation of the
absorber (and the hp flash), e.g. by means of blind
flanges. Reconnect instruments / orifice plates /
analysers/ plate and frame heat exchanger.
 Check for leaks
- Pressurise with nitrogen (or process gas)
- Don’t use air due to the oxygen content: corrosion
 Filling the AGRU with aMDEA® Premix and dilution to
~40%(wt) with R.O water.
Start-up (1)
 The system should be under inert nitrogen

atmosphere:
 Establish the liquid levels in the columns at
50% of level control range and pressurise with
feed gas or HP nitrogen
 Start minimum amine flow – check distributor
vendor’s recommendations and add 5%.
 Establish AGRU operating temperatures by
operating reboilers and coolers.
Start-up (2)
 If it is possible, BASF recommends circulating

the amine before introducing feed gas. This will
build a very strong, stable corrosion-resistant
layer of magnetite (Fe3O4) on the carbon steel
surfaces throughout the AGRU.
 When “passivating”, increase amine circulation
to design rates and temperatures. This
establishes the usual flow regimes at design
operating conditions.
 Continue aMDEA® circulation, if possible, for 24
to 72 hours before introducing feed gas.
Start-up (2)
 Confirm the aMDEA® solution strength.

 Test antifoam pump injection rates into measuring
cylinder and cross check against pump manufacturer’s
data.
 Pay attention to correct operation of the check valves.
 Prepare an initial charge of antifoam agent:
- This should be added to the system after the
circulating solvent is heated up approximately one to
two hours before gas shall be charged to the system
(check “cycle time” of amine solution)
 The concentration of antifoam in amine should typically
be around 50 ppmw based on the solution inventory.
Start-up (3)
 During start-up, the liquid flow rate should always

be maintained 5% to 10% higher than the amount
required for the current feed gas rate.
e.g. if the gas flow rate is 45% of design, amine flow
rate should be around 50% to 55% of the design.
 Initially, first establish minimum amine circulation
according to tray vendor’s recommendations + 5%.
(Maximum “turn-down” flow)
 Gradually introduce feed gas to the system,
stabilising system temperatures and levels.

Start-up (4)
Do not over-circulate the amine solution!
This leads to
- higher methane co-absorption – (This can lead to a
very high calorific value of the acid off-gas, and
seriously impact the performance and integrity of the
thermal oxidiser.)
- co-absorption of higher hydrocarbons – foaming
- higher reboiler duty than needed (waste of energy)
- less stable operating conditions (gas-to-liquid ratio
considerably lower than design)
Start-up (5)
 Once amine circulation reaches 100% design value,

gradually increase feed gas to 100% design value.
 Check DCS carefully for potential foam activity:-
increased LP flash gas flow rates; ‘bouncing’ column
gas/liquid levels, followed by increasing column P.
 If necessary, add a shock dose of antifoam agent on
an as-needed basis.
 Re-check filter P for good operation, plenty of
particles will still be filtered out in first few months,
mesh sizes should be gradually decreased from 100
microns to design size of 5(?) microns.
Typical observations following start-up
S.Fe ,T.Fe & S.S OF @MDEA IN H2 PLANT Of Esfahan

7,00
6,00
5,00
PPM
4,00
3,00
2,00
1,00
0,00
12/09/ 27/09/ 14/10/ 30/10/ 28/11/ 17/12/ 18/01/ 10/02/ 07/03/ 11/03/ 13/03/ 15/03/ 17/03/ 22/03/ 25/03/ 26/03/ 27/03/ 28/03/ 29/03/ 31/03/ 04/04/ 09/04/
1381 1381 1381 1381 1381 1381 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382 1382
S.Fe 0,70 0,78 1,80 2,37 2,48 2,30 3,00 0,88 0,40 0,64 0,85 0,96 0,93 0,56 0,50 0,48 0,96 0,86 0,70 0,95 0,90 0,80
T.Fe 0,76 0,90 2,40 2,55 2,64 2,75 3,00 1,20 0,70 0,92 0,90 0,93 0,97 0,56 0,52 0,50 1,08 0,92 0,70 1,00 1,06 0,80
S.S 0,00 0,00 6,00 1,60 0,40 0,50 0,00 0,80 0,40 0,40 0,40 0,40 0,80 0,00 0,00 0,00 0,00 0,00 0,00 0,60 0,00 0,00

Key Learning Point
First Signs of foaming

 1. Increased lp flash gas flow rates*
 2. ‘Bouncing’ column gas/liquid levels
 3. Increasing column P
* Early warning of approaching foaming
Measures prior to a turnaround (1)
 Stop the feed gas flow to the AGRU

 Keep circulating the amine solution for 2 to 3 hours at
normal process temperatures and continue
regenerating the amine solution to remove all
absorbed acid gases and co-absorbed hydrocarbons.
 Introduce nitrogen so that any flammable gases will
be replaced by N2. This will avoid co-absorbed
methane being sent to the storage tank
 Maintain an appropriate pressure in the absorber to
enable circulation. This can be higher pressure
nitrogen.
 Cool down the solvent by turning off the steam to the

reboiler.
 Drain the aMDEA® solvent to the storage tank. The
temperature must be below 85°C.
 Wait as long as practical, say up to 24 hr,until the
aMDEA® solution has trickled off the column internals.
The longer the delay, the more amine can be pumped to
storage.
 In case the columns are to be inspected and entered by
personnel, the column internals must be flushed with
demin. water

 Ventilate the columns via the open manholes

for approx. 2 days. Forced ventilation can be
used.
 Re-drain the bottom sections and ensure that
the O2 content inside the vessels is high
enough to enter without breathing apparatus
 Check for toxic gases such as H2S, where
applicable, before entering the columns

 The inspection of the plant can be achieved by

taking the normal protection measures, which
are common for plant inspection
 Breathing apparatus should be available, but is
not normally necessary to wear it during the
inspection, assuming the equipment is well-
ventilated.
 Normal working clothes can be worn.

 aMDEA® solution is not flammable, so no

special precautions have to be taken for hot
work, i.e. welding inside the columns
 It is recommended to conform to the safety
rules, guidelines and regulations issued for
this plant.

Maintaining treated
gas specifications

Importance of CO2 (& H2S) slippage
 The CO2 and H2S slip are the most important design
and operating parameters in an AGR Unit
 CO2 slip (CO2 concentration in the treated gas)

should be less than 1000 ppmv. The treated gas is
then re-combined with the gas which has by-passed
the unit to produce sales gas with a CO2 content of
2%.
 H2S in the AGRU feed will be reduced below 4 ppmv.

Importance of CO2 (& H2S) slippage. 2
 Please note that there is no CO2 analyser at the absorber outlet.
The concentration of 1000 ppmv can be measured manually.
 The main CO2 analyser is located downstream of the point

where the treated gas is mixed with the by-pass gas, and should
be < 2%.
 If the recombined CO2 slip is greater than 2%(vol), it should be

checked if the treated gas leaving the absorber is less than 1000
ppmv. If it is lower, the proportion of gas flowing to the AGRU
should be gradually increased until the treated gas concentration
is close to 1000ppmv.

Increased CO2 slip?
Possible reasons for increased CO2 slip:
 Feed gas composition, temperature or pressure out of spec.
 Feed gas pressure too low
 Solvent circulation rate too low
 Feed gas flow rate to AGRU need to be “rebalanced”
 Lean solution temperature too low
 Lean solution temperature too high

Increased CO2 slippage
Reasons for increased CO2 slip (contd.)
 Solvent strength too low
 Concentration of activator system too low
 Insufficient regeneration of solvent (also for H2S)
 Foaming tendency too high
 Mechanical damage or plugging of packing, distributors etc.

CO2 breakthrough:
Thermodynamic limitation (1)
Example: Gas rate is steadily

CO2 conc. [ppm (v/v)]
1700 increased at constant liquid

1600 flow rate
1500
1400
1300
1200
1100
Specification (Example!)
1000
0
92 94 96 98 100 102 104
gas capacity [%]
 higher solution flow rate needed

CO2 breakthrough:
Thermodynamic limitation (2)
 A steep increase of the CO2 slip, as

shown, is an indication that the potential
acid gas loading capacity of the solvent is
exceeded!
 Either the amine circulation rate must be
increased, or the gas flow must be
reduced.

CO2 breakthrough:
Kinetic limitation (1)
 Activator content of the solution drops slowly over

time. (Vapour pressures slightly higher than MDEA)
 If no other operating parameters are changed, the
decreasing activator content will slowly lead to an
increase of the CO2 slip (see next slide)
 Up to a certain point, a lack of activator can be
balanced by an increased solvent circulation rate.
 Finally, some activator make-up is required, known
as “aMDEA® Enriched Premix”.

CO2 breakthrough:
Kinetic limitation (2)
1800
1600
CO2 conc. [ppm (v/v)]
1400
1200
1000
800
600
0
0 3 6 9 12 15 18
Operating time [months]
 More activator (1:1 premix) needed

Incomplete Solvent Regeneration
 If there is too much CO2 (also H2S) in the regenerated

“lean” solution fed to the absorber, too little CO2 (and
H2S) can be absorbed (see next slide)
 Lean solution must be adequately regenerated to remove
sufficient CO2 and H2S (= lean amine loading)
 A lack of activator can be balanced by an increased
solvent circulation rate.
 Finally, some activator make-up is required, known as
“aMDEA® Enriched Premix”.

Effects of a
variation of
operating
parameters
Important parameters
 Lean solution temperature

 Feed gas temperature
 Feed gas pressure
 Stripper overhead pressure
 Stripper reboiler duty
 Solution strength
Lean solution temperature (1)
If higher than design:

 higher temperature in absorber bottom
 lower CO2 loading capacity
 higher absorption velocity
 higher water content in treated gas (saturation
temperature)
 lower efficiency of solvent heat exchanger
 higher temperature in the flash section of stripper

Lean solution temperature (2)
Lower than design:

 higher CO2 loading of the solvent
 but the absorption velocity decreases
 These effects work against each other
 Overall influence is usually rather small
 Lean solution temperature variation may be

possible within relatively wide limits
Feed gas temperature
 Feed gas temperature higher than design leads to a
higher temperature in the bottom of the absorber:
Usually this influence is small
 In case the feed gas is saturated with water
- the water input with the feed gas might increase
significantly with higher temperature
- amount of make-up water has to be adjusted
- It might even be required to drain condensate
from the regenerator reflux drum to fulfil water
balance of the unit, if the feed gas temperature is
too high.
Feed gas pressure
 Feed gas pressure lower than designed

 lower driving force for the absorption due to the
lower partial pressure of CO2
 lower the performance of the absorption process
 Can be balanced by a higher solvent circulation rate
- at the cost of a higher specific energy consumption of
the process (kCal/kmole CO2)
- hydraulic limits of the columns have to be considered
 An absorber pressure higher than design is beneficial for the
acid gas absorption (check pressure rating of absorber!)
Stripper overhead pressure (1)
Stripper overhead pressure influences

significantly the regeneration of the solvent
higher than design:

 higher stripper temperature (top and bottom)
 lower driving temperature difference in reboiler
 higher efficiency of solvent heat exchanger
 only slightly higher energy requirement in stripper
reboiler
Stripper overhead pressure (2)
higher than design:

 slightly lower vapour content in stripper
overhead
 slightly lower condenser duty
 lower hydraulic load of the column

Stripper reboiler duty (1)
higher than design:

 higher energy consumption
 higher stripper overhead temperature
 higher vapour content in stripper overhead
 higher vapour load in the column
- This could lead to increased entrainment or even flooding
 higher reflux condenser duty

Stripper reboiler duty (2)
 A higher reboiler duty than design leads only

to a slightly better regeneration of the lean
solvent
 In the case of a single stage absorber the
plant capacity cannot be raised by
increasing the reboiler duty

higher than design:

 increased solution viscosity
 reduced mass transfer properties
 higher solution hold-up in the packing
 higher pressure drop
 weak performance in case of a lack of water (water is not only a
solvent, but also a reactant) Typically occurs above 65(wt)%
 but, inherent foaming tendency of the aMDEA® solution is
typically lower

lower than design:

 risk of corrosion due to insufficient “re-passivation”
 reduced CO2 loading capacity
 higher solvent circulation rate required
 increased energy consumption
 higher CO2 slip
 Inherent foaming tendency of the aMDEA® solution
typically increases to a maximum as concentration
reduces to 20% (wt)
Foaming
Foaming: General Aspects
 All amine solutions tend to foam

 Decisive for plant operation is the foam stability
 Two main ways to prevent foaming problems:
- Minimise surface-active ingredients in the plant
(Pre-cleaning; carbon filtration)
- No particles, which stabilise foam in the plant
(Pre-cleaning; mechanical filtration; reduce
corrosion)
- Note:many corrosion inhibitors are surfactants
Foaming Problems
Excessive foaming will cause:
 (Apparently) ‘unsteady’ liquid levels in column sump
 Increasing pressure drop in the columns
 Treated gas out of specification (absorber foaming)
 Foaming should to be kept low

Indications of high
foaming activity
 Difficulties in controlling the column liquid levels
 Increasing differential pressure in the columns
 Increasing methane content in the acid off-gas

(CH4 carry-under from absorber)
 Rapidly increasing CO2 slip
 Carry-over of amine content into downstream

KO vessels (increase in liquid levels)
Typical compounds causing
foaming problems (1)
 Oil, fat or grease, e.g. from insufficiently cleaned

vessel internals
 Heavy hydrocarbons or long chained organic acids

(naphthenic acids) entering with the feed gas
 Solid particles like rust, activated carbon, etc.
 Solid contaminants in make-up water

Typical compounds causing
foaming problems (2)
 The level of these contaminants has to be kept as

low as possible.
 Continuous filtration of side stream, both mechanical

and charcoal.
 Because this is not always 100% effective:

some antifoam dosage is normally necessary.
 Antifoam over-use should be avoided

Foaming
- Antifoam dosage
Antifoam: General remarks (1)
 Antifoam dosage has to be optimised during plant operation

 Success has been reported with both “threshold” and
“shock” dosage strategies
 There are no “standard” recommendations for the
dosage of antifoam
 Dosage of antifoam ideally to be coordinated with
operation of mechanical & charcoal filters.
 Amerel is a mixture of silicon particles and silicone oil,
therefore both mechanical and carbon filters should be
online together, or only particles will be removed.

Typical dosage rates of
AMEREL 1500
1000 ml/day per 350,000 Nm3/hr Feed Gas
 As required (e.g. ‘bouncing’ levels, rising column P,)

 Raise or lower ‘shock’ dose as needed
 Higher frequency is better than higher amount
 Goal is good foam control with lowest dosage
 If 500ml is “good”, 5,000 ml is NOT 10x better!

Typical dosage rates of
SAG 7133
SAG 7133 (Momentive Performance Materials) is a more

“dilute” antifoam additive that has been successfully
used in many of BASF’s natural gas references,
including In Salah Gas.
As it is more dilute, the injection rate is necessarily higher.

A typical dosage rate will be:
1000 ml/day per 100,000 Nm3/hr Feed Gas

Antifoam: General remarks (2)
 Continuous high over-dosage of antifoam over a longer

period of time should be avoided:
 Rapid plugging of the mechanical filter

 Unnecessary OPEX in antifoam costs
 Potential blocking of reboiler bundle
 The real reason for the high antifoam requirement has
to be traced, and the appropriate remedial action taken.
(also check for mechanical damage)
Safety …
…is everybody’s
business!
Important Safety Information (1)
The main reference document
aMDEA® Material Safety Data Sheet
“MSDS”

Safety Considerations (1)
aMDEA® Material Safety data Sheet
#1 Substance and company
#2 Information on chemical composition
#3 Hazards identification
#4 First Aid Measures
#5 Fire-fighting measures
#6 Accidental release measures
#7 Handling and storage
#8 Exposure controls & personal protection

# 9 Physical & chemical properties
#10 Stability & reactivity
#11 Toxicological information
#12 Ecological information
#13 Disposal considerations
#14 Transport Information
#15 Regulatory information
#16 Other information


#3 Hazards Identification
#4 First Aid measures
#5 Fire fighting measures
#7 Handling and storage

# 3 Hazards Identification
 Risk of serious damage to eyes
 May cause sensitization by
inhalation & skin contact

#4 First Aid measures
 Clothing - remove contaminated clothes and wash
 Inhalation - get fresh air, seek medical attention
 Skin contact - wash with ample water
 Eye contact - water wash for 15 mins, call doctor
 Ingestion - rinse mouth with water, call doctor


#5 Fire-fighting measures
 Suitable extinguishing media
- water; CO2; dry powder; foam
 Protective equipment
- BA; chemical protective clothing
 Collect all effluent water & neutralise


Avoid inhalation, eye contact
Prevent untreated discharge to environment
Clean-up measures
- pump off large volumes to storage
- then use suitable absorbent; sand; sawdust etc.

#7 Handling & Storage
Ensure thorough ventilation in storage area
Protect against fire & explosion
Prevent electrostatic discharge
Protect from acids


BA if ventilation inadequate
Hands: chemical resistant gloves
Eye protection: Safety glasses with side shield
(For drum handling, face shield recommended)
Avoid eye contact; avoid inhalation;
Long sleeved, long trousered clothing only

 Key learning Point
 aMDEA® is an industrial chemical
 Take note of MSDS recommendations
 Wear appropriate PPE and clothing

Solvent
analyses
Analyses: General
 Regular sampling and analyses is essential for steady and

reliable plant operation
 Recommended plant laboratory analyses are:
 Solvent strength:
- Determining total amine content
- or water content
 Foam test
 Periodic analyses in BASF laboratories (see next slide)
 Analyses described in the manual provided to INA
Frequency of solvent analyses
General recommendations:
 Total amines by titration: once per week
 Water content by Karl Fischer: once per day
 Foam test: once per week
 Activator, metals, chloride, HSS: twice per year (BASF)
Further analyses as needed, frequency according to

experience
In beginning, more frequent analyses establish confidence


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17/11/2010 CONFIDENTIAL - In Amenas Internal use only 1

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 2

By the end of this session . ..

. . you should have a better

 Introduction: BASF – “The Chemical Company”

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 4

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 5

250 chemical plants making 6,500 different products

Our portfolio includes:

 Sales €57,951 million

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 9

Integrated site Production Sales

 Production of process chemicals

 BASF operates 15 CO2 removal plants

 Laboratory and Mini Plant team

 Support and technical marketing team

 Maintain treated gas specifications

 Minimise operational upsets (foaming, etc)

 Minimise operational costs ( solvent make-up)

 Minimise maintenance (corrosion, scale)

 Maximise on-stream time (availability)

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 16

Treated Gas Acid Off-Gas

Special design features:

 LP Flash column – energy saving

 Acid gas recycle to LP Flash from stripper

 HC skimming points in all 3 columns

 Larger capacity slipstream (20%) for filtration

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 18

 The temperature in the absorber should be

 Keep the lean amine temperature (design 56°C

 Little chance of hydrocarbon condensation with

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 19

 Introduction: BASF – “The Chemical Company”

 Amines are organic bases

 Three main groups: Primary, Secondary and Tertiary

 Amines react reversibly with CO2 to form amine salts

 The CO2 absorption reaction is exothermic (liberates heat)

 CO2 is absorbed at high pressures & low temperatures

 CO2 is regenerated at low pressures & high temperatures

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 22

MEA: MonoEthanolAmine DEA: DiEthanolAmine

Tertiary Amine CH2CH2OH

 Primary amines, like MEA, are very strong bases

- React fastest with CO2, but bad corrosion problems

 Secondary amines, like DEA, are strong bases.

- React quickly with CO2 , corrosion, but less than MEA.

 Tertiary amines, like MDEA, are very stable, no corrosion

 Corrosion is a result of amine degradation

 Loss of treating capacity, solvent deactivation

 Corrosion followed by Scaling

 Excessive foaming caused by

 good CO2 capacity

 very stable, non-degrading.

 High molecular weight 119.2 kg/kmole

 High boiling point pure MDEA 245 °C (low vapour pressure!)

 Low solution boiling point 110 - 120 °C (normal reboiler)

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 26

There are two possible mechanisms

but the second is very much slower!

17/11/2010 CONFIDENTIAL - In Amenas Internal use only 27

CO2 + H2O HCO3- + H+

R2NH + CO2 + H2O R2NH2+ HCO3-