Design and Synthesis of Chemical

Absorption Processes
Prashant Patil
Supervisor:
Dr. Megan Jobson
2005 Process Integration Research Consortium

P4-1 XXII PIRC Annual Research Meeting 2005

 Outline

1 Introduction
2 Model development
3 Superstructure development
4 Flowsheet synthesis and design
5 Conclusions and future work

P4-2 Design and Synthesis of Chemical Absorption Processes

 1. Introduction

P4-3 Design and Synthesis of Chemical Absorption Processes

 Typical absorption-desorption process

MAKE UP
GAS OUT OFF GASES

ABSORPTION DESORPTION

GAS IN LEAN
SOLVENT

Test case: Gas sweetening - removal of acid gases (CO2, H2S) from
natural gas, fuel gas etc. aqueous amine solution

P4-4 Design and Synthesis of Chemical Absorption Processes

 Comparison of physical and chemical absorption
Physical Absorption Chemical Absorption
Vapour phase Vapour phase
Molecular Species Molecular
Electrolyte (A)

Molecular Species Molecular Electrolyte Ions

Liquid phase Liquid phase

Low heat of absorption High heat of absorption

Desorb by flashing (sometimes) Need low-level steam for
desorption
Selective removal is not possible Selective removal is possible
Difficult to remove acid gas Easily reduces acid gas to low
completely concentration in treated gas
High number of stages Low number of stages

P4-5 Design and Synthesis of Chemical Absorption Processes

 Synthesis and design problem

Which solvent to What will be operating

use? conditions of the column
Pure? Mixed? Solvent circulation rate ?
What concentration? Solvent feed temperature ?
Number of trays?
Feed location?

Which flowsheet Existing plant? Can I

structure? improve the performance?

Split-loop? Side draw? Reduce energy demand ?

Vacuum flash? Reduce solvent circulation ?
Complex vs simple flowsheet Change operating conditions ?
Combination of different variables?

P4-6 Design and Synthesis of Chemical Absorption Processes

 Previous work - modelling of chemical absorption

Rate-based models (Kenig et al., 1998)

• based on two film theory
• accurate but demands high computational time
• not suitable for design and synthesis purposes

Equilibrium stage-by-stage models (Tomcej et al., 1987)

• relatively implistic
• cannot capture mass transfer phenomenon

Non-equilibrium models with component efficiency (Tomcej et al.,1987)

• captures non-equilibrium behaviour through component efficiency

Commercial simulators (HYSYS, TSWEET, PROTREAT)

• effective for simulation purposes
• cannot be used for design and synthesis methods based on optimisation

P4-7 Design and Synthesis of Chemical Absorption Processes

 Previous work - design and synthesis

Design guidelines for chemical absorption processes (Astarita et al.,

1983)
• general guidelines for design and scale up
• graphical method for column design using equilibrium curve

Methodology for flowsheet generation for gas sweetening processes

(Shethna, 1996)
• thermodynamic analysis of chemisorption processes
• simulation of design alternatives in HYSYS

Optimisation using commercial simulator TSWEET (Bullin et al., 1981;

Polasek et al., 1990)
• effect of different parameters on performance of gas sweetening units using model
simulation

Effect of different parameters using simulation for CO2 absorption using

MEA (Ferguia, 2003)
• simulation using RATEFRAC Aspen model at different operating conditions

P4-8 Design and Synthesis of Chemical Absorption Processes

 Limitations of previous work

No systematic optimisation method available for design and

synthesis of chemical absorption processes
Models available cannot be used for design and synthesis as they
are highly computational demanding
No systematic method for retrofit of existing flowsheets

P4-9 Design and Synthesis of Chemical Absorption Processes

 Problem statement
To find cost effective and energy-efficient flowsheet and corresponding
operating parameters for given separation specifications

Objectives of this work

Develop simplified model
• suitable for initial design and synthesis purposes
• to accommodate important features for flowsheet synthesis e.g. multiple
feed, side draws etc.
• suitable for initialisation of rigorous models

Develop methodology for design and synthesis of chemical

absorption processes
• optimisation of total flowsheets using simplified models
• generate systematic procedure for design and synthesis of flowsheets
• develop methods to create heat integration opportunities

P4-10 Design and Synthesis of Chemical Absorption Processes

 Challenges for chemical absorption
design and modelling

Multicomponent systems with multiple reactions involving

electrolytes
Complex vapour-liquid equilibrium behaviour (electrolytes)
Finite mass transfer rates, especially for the transferring
components
Heat of reaction affects temperature profile significantly
Strong interactions between individual unit operations
(absorption and desorption)

P4-11 Design and Synthesis of Chemical Absorption Processes

 2. Model development

P4-12 Design and Synthesis of Chemical Absorption Processes

 Shortcut model for physical absorption

Absorbent Treated Gas Kremser group method*

L0, x0 V1, y1

1
Feed conditions specified
A = L / KV At average conditions equilibrium constant is
calculated
Effective absorption factor(A) is calculated
N-1 based on this information
N Simple relationship calculates outlet vapour
Feed Gas Liquid Product and liquid compositions given effective
VN+1, yN+1 LN, xN absorption factor

Strengths
Easy to use
Almost no computational time

* Seader and Henley, Separation Process Principles, Wiley & Sons, New York, 1993.

P4-13 Design and Synthesis of Chemical Absorption Processes

 Kremser group method cannot be applied directly for chemical
absorption

Assumptions for Kremser Chemical absorption

group method

Constant vapour and Higher removal of acid gases: significant change

liquid molar flow in molar flows

Constant temperature Heat of reaction effects are considerable

Equilibrium stages Mass transfer and reaction effects are finite.

Approach to equilibrium can be represented by
component efficiencies

Constant K values Equilibrium constant is strong function of

composition of acid gases and concentration of
solvent

... but can be applied with suitable modifications.

P4-14 Design and Synthesis of Chemical Absorption Processes

 New simplified model for chemical absorption-desorption processes

Gas out Solvent in Basic block

Equivalent to simple absorption
column
Modified Kremser group applied
Building block for generic model
Gas in Solvent out

Gas out Solvent in

Generic model
B

S Basic block combined with individual

B stages which are rigorously modelled
S
Used for complex column: multiple feed,
sidedraws
B
e.g. multiple feed absorption, regenerator
Gas in Solvent out

B - basic block
S - rigorously modelled stage

P4-15 Design and Synthesis of Chemical Absorption Processes

 Basic block: Introduction
Gas out Solvent in Gas out Solvent in

Equilibrium
Basic block calculations

Gas in Solvent out Gas in Solvent out

Assumptions
Constant component efficiency of transferring components within the section
Top stage temperature is assumed to be equal to inlet liquid temperature.
Model concepts
Key components compositions are related by Murphree stage efficiency relation.
Reaction effects accounted for using enhancement factor1
Non-key component compositions are estimated using Kremser group method.
Bottom stage temperature is estimated using heat of reaction and sensible heats of gas
and liquid streams.
Equilibrium balances are carried out at first and last stage only.
Equilibrium constants on intermediate stages are approximated using linear interpolation

P4-16 Design and Synthesis of Chemical Absorption Processes

 Basic block: Model calculations
Specify gas and liquid feed conditions, number of stages, column pressure and
component efficiencies
Initial estimate for unknown key components flowrates (V1,i , L1,i , VN+1,i).
Number of estimates = 3 Number of key components (NK)
Step 1
Gas out Feed liquid Estimate overall removal of acid gases and heat of reaction. Heat balance
V1,i around column gives bottom stage temperature.
1 ∆ sensible heat for ∆ sensible heat for ∆ Heat of
L1,i
+ =
gas stream liquid stream reaction

Step 2
VN,i Calculate non-key component flowrates using Kremser group method at average
N temperature and column pressure conditons
FN,i
Feed gas Liquid out Step 3
Solve non-equilibrium relations and mass balances for key components (see next
V1,i - key component flowrate in slide)
vapour phase leaving first stage

L1,i - key component flowrate in

liquid phase leaving first stage
Step 4
Check convergence
FN,i - key component flowrate in
feed gas entering Nth stage If convegence not met, update the estimate and go to Step 1

P4-17 Design and Synthesis of Chemical Absorption Processes

 Basic block: Model calculations
Step 3 Non-equilibrium relations and mass balances for key components

Non-equilibrium relations (Murphree component efficiency relation)

Gas out Liquid in
• Calculate K values at first and last stage using physical property method
1
• Calculate vapour and liquid mole fractions using estimated key
component flowrates and non-key component flowrates (Step 2)
Estimates
Nonequilibrium relation at first and last stage is given by
N i Kj,i xj,i - (1 - i ) yj+1,i - yj,i = 0 (1)
FN,i=VN+1,i

Gas in Liquid out

• Generate linearised K-profile for intermediate stages using K-profile
using K values at first and last stage

V1,i Mass balance equation

1 • Given key component flowrate in outlet gas, using generated K-profile
and stage-by-stage mass balances key component flowrates in gas
2
stream entering at bottom stage are calculated.
They must be equal to specified key component flowrate in feed gas. This
gives mass balance equation
VN,i
N VN+1,i - FN,i = 0 (2)

VN+1,i Equation (1) and (2) form 3NK equations

P4-18 Design and Synthesis of Chemical Absorption Processes

 Component efficiency
Murphree component efficiency relation
y i, j − y i, j + 1
ηi = where y* is equilibrium value
y * i, j − y i, j + 1
Actual separation
=
Equilibrium separation
Component efficiency gives deviation from equilibrium separation

Component efficiency is function of tray dimension, fluid properties

and operating conditions
Various correlations are available for efficiency calculation for physical
phenomena1
For separation with chemical reaction, mass transfer is affected due
to reaction. This phenomenon can be captured using enhancement
factor

1 Krishna and Taylor, Multicomponent mass transfer, John Wiley and Sons, Inc. New York, 1993

P4-19 Design and Synthesis of Chemical Absorption Processes

 Component efficiency
Component efficiency on tray is given by2
xi,n-1 yi,n
ηi = 1 − exp( −K OG,i a A P Z T / V )
ZT Where
V - velocity of the gas
A - effective surface area
xi,n ZT - liquid height on the plate
V
yi,n+1 KOG - overall mass transfer coefficient
P - total pressure
a - interfacial area

Overall mass transfer coefficient is given by

1 1 1
= + * where k L* = k Lo • I
K OG kG kL
Enhancement factor accounts
Where for reaction effects3
kG - gas phase mass transfer coefficient
k°L - liquid phase mass transfer coefficient
I - enhancement factor

Enhancement factor can be calculated knowing reaction kinetics3

2 Tomcej et al., Tray design for gas sweetening processes, 1987.
3. Laddha et al. Reaction of CO2 with ethanolamines: Kinetics from gas absorption, Chem. Eng. Sci, 36, 479-482, 1981.

P4-20 Design and Synthesis of Chemical Absorption Processes

 Basic block: Illustrative example

Feed and operating conditions Comparison with HYSYS results

CO2 in Feed Gas mol % 1.43
Stream properties Simplified HYSYS
H2S in Feed Gas mol % 1.43
25.0
model model
Feed Gas temperature (°C)
(°C) 25.0 H2S conc. in sweet gas (mol%) 0.09 % 0.02 %
Absorbent inlet temperature
Amine in Absorbent wt % 25.0 CO2 conc. in sweet gas (mol%) 1.19 % 1.21 %
Feed Gas pressure bar 10.0 Outlet gas temperature (°C) 25 28.21
Absorbent flow rate kmol / hr 446 Rich absorbent outlet temp. (°C) 28.92 32.57
Feed gas flow rate kmol / hr 698 H2S loading in outlet liquid* 0.31 0.32
Number of trays 10 CO2 loading in outlet liquid* 0.058 0.054
Component efficiency H2S % 45
Component efficiency CO2 % 2 * loading = moles of acid gas / moles of amine

Property package: Kent and Eisenberg model in HYSYS v. 2.4

P4-21 Design and Synthesis of Chemical Absorption Processes

 Generic column model: Introduction

B1

S1

J B2

K S2

B3
L
S3

B4

Column represented by blocks (B) and interfacing stages (S)

Calculations within block use new simplified model
Rigorous calculations at interfacing stages - mass, energy balances
and equilibrium relationships
Complex column structure accommodated - side draw, multiple feed,
intermediate heat exchanger

P4-22 Design and Synthesis of Chemical Absorption Processes

 Generic model: Calculations
Mass, equilibrium and heat balances at
interfacing stage Specify feed conditions,
number of stages, pressure

Component mass balance

fi, j + li, j + v i, j − v i, j +1 − li, j −1 = 0 i = 1,....., NC j = 1,....., NS Guess unknown compositions

Equilibrium relation
li, j v i, j
ηi,jK i, j − + (1 − ηi, j ) = 0 i = 1,.....,NC j = 1,.....,NS Calculations at
li,j v i, j Update
i i
basic block calculations
Heat balance
FHF,j − HL, j li,j − HV, j v i, j + HV, j+1 v i, j+1 + HL, j−1 v i, j−1 = 0 Mass, equilibrium and heat balances at
i i i i
interfacing stages
i = 1,....,NC j = 1,....,NS

Satisfy all
Model calculations in basic block are same equations
as before No
Yes
Nomenclature: Solution
NC - number of components
NS - number of interfacing stages
v, l,f - component flowrate for vapour, liquid and feed
H - enthalpy
K - equilibrium constant

P4-23 Design and Synthesis of Chemical Absorption Processes

 Generic model: Illustrative example (1)
Multiple feed absorber

Sweet Gas Absorbent

6

5
13

7
Feed Gas Rich Absorbent

Plant data*
CO2 (mole %) in Feed Gas 3.08
H2S (mole %) in Feed Gas 0.31
Feed Gas temperature (°C) 15.6
Absorbent inlet temperature (°C) 26.1
Amine (wt %) in Absorbent 32.4
Feed Gas pressure (bar) 27.1
Absorbent flow rate (m3/h) 15.9
Fraction fed to tray 1 0.39
Fraction fed to tray 7 0.61
* MacKenzie et al, Design and operation of a selective sweetening plant using MDEA, Energy Progress, 7, 31-36, 1987

P4-24 Design and Synthesis of Chemical Absorption Processes

 Generic model: Illustrative example(1)

Comparison of modelling results with plant data and HYSYS results

Stream properties Plant* HYSYS Simplified

Simulation model
CO2 conc. in sweet gas (mole %) 1.95 2.05 2.16
H2S conc. in sweet gas (ppm) 0.6-1.5 Negligible 1.94
Acid gas outlet temperature (°C) 30 29.13 26.1
Rich absorbent outlet temp. (°C) 25 28.26 29.5

P4-25 Design and Synthesis of Chemical Absorption Processes

 Generic model: Illustrative example (2)
Desorption column

Condenser stage

Feed stage

Reboiler stage

Desorption column is represented by interfacing stages and blocks

• Condenser and reboiler stages are modelled as interfacing stages - rigorous
calculations
• Feed stage is modelled as interfacing stage
Column specifications are: reflux ratio or condenser temperature,
boil-up ratio

P4-26 Design and Synthesis of Chemical Absorption Processes

 Generic model: Illustrative example (2)

Desorption column

Feed and operating conditions* Comparison of model results with HYSYS

H2S in feed mol% 0.33 Model HYSYS
CO2 in feed mol% 1.118 Condenser Duty (kW) 1303 1271
MDEA in feed mol% 6.63 Reboiler Duty (kW) 1717 1691*
H2O in feed mol% 91.85 Loading in Lean Solvent+ 0.00610 0.00335
Flowrate kmol/h 658.5 H2S in off gases (mol%) 21.9 21.62
Feed temperature o
C 96 CO2 in off gases (mol%) 71.4 71.74
Feed tray 1 Condenser Temperature* (°C) 31.1 31.10
Number of trays 20 Reboiler Temperature (°C) 114.6 114.8
Condenser temperature o
C 31.1 Reflux ratio 10.87 9.74
Reboiler duty GJ/h 6.09 Boil-up ratio 0.27* 0.234
* specified value
+ loading = moles of acid gases / moles of amine

* MacKenzie et al, Design and operation of a selective sweetening plant using MDEA, Energy Progress, 7, 31-36, 1987

P4-27 Design and Synthesis of Chemical Absorption Processes

 Flowsheet Simulation
Sweet gas Acid gas

Feed gas Rich Solvent Regenerator

Absorber Regenerator
solvent heater feed
Solvent

Solvent recycle Lean solvent

Solvent make-up Solvent pump Solvent

cooler

Block diagram for simulation of typical absorber-desorber loop

Individual columns are represented using simplified models.

Operating and feed conditions are specified for both columns.
Flowsheet is modelled by sequential simulation of blocks until
recycle stream is converged.

P4-28 Design and Synthesis of Chemical Absorption Processes

 Illustrative example (3): Split-flow flowsheet simulation
Sweet Acid gas
gas Lean solution

Lean Rich solution

section
Semi-lean
solution

Semi
- Regenerator
lean Absorber
section

Sour
gas Lean solution

Acid gases removal using MEA amine

Side draw from desorpton column (split-flow arrangement)
Estep et al., “The recovery of sulphur from sour natural and refinery gases”, Advances in Petroleum Chemistry and
Refining, 6, New York,: Interscience publishers, (1962).
P4-29 Design and Synthesis of Chemical Absorption Processes
 Illustrative example (3): Feed and operating conditions
Absorption column
Number of trays in semi-lean section 20
Diameter of semi-lean section colum m 2 Desorption column
Amine conc. in semi-lean solution wt % 15
Semi-lean absorbent flow rate kmol/hr 18276 Number of trays 23
Number of trays in lean solution 10 Location of side draw 10
Diameter of semi-lean section column m 1 Condenser temperature o
C 40
Amine conc. in semi-lean solution wt % 21.5 Feed tray location 2
Semi-lean absorbent flow rate kmol/hr 4180 Feed temperature o
C 107.8
Absorbent inlet temperature o
C 37.78
Column pressure bar 2
Column pressure bar 37.92
H2S efficiency % 40*
H2S in gas feed mol % 33.4
CO2 efficiency % 30*
CO2 in gas feed mol % 10.4
Gas feed temperature o
C 14.4 * specified value (calculated using HYSYS
amines package
Feed gas flowrate kmol/hr 1562.7
H2S efficiency % 60*
CO2 efficiency % 40*

P4-30 Design and Synthesis of Chemical Absorption Processes

 Illustrative example (3): Simulation results
Plant Model
H2S composition in sweet gas ppm 0.30 0.38
CO2 composition in sweet gas ppm Negligible 0.092
Reboiler duty kW 33820 33197
o
Sweet gas outlet temperature C 38.9 37.8
Acid gas analysis
H2S composition mol% 75.2 74.4
CO2 composition mol% 24.7 23.4
Hydrocarbon and other mol% 0.2 2.2
Acid gas flow MMSCFD+ 13.8 14.0
Lean amine solution analysis
MEA concentration wt% 20.1 20.3#
H2S concentration grains per gal* 25.0 17.6
CO2 concentration grains per gal 140 473
Semi-lean amine solution analysis
MEA concentration (wt%) wt% 13.8 13.7#
H2S concentration grains per gal* 317 252
CO2 concentration grains per gal # acid gas free basis
445 683 + Million square cubic feet per day
Rich amine solution analysis * 1 grain per gal = 0.017118061 kg / m3
MEA concentration wt% 14.7 14.97#
H2S concentration grains per gal* 2327 2275
CO2 concentration grains per gal 1164 1447

P4-31 Design and Synthesis of Chemical Absorption Processes

 Summary: Simplified model
Simplified model for chemical absorption is developed. Model is
suitable for multicomponent systems.
• Model extends applicability of Kremser group method to chemical absorption
processes by incorporating component efficiencies for transferring components
• Simple absorption column is represented by basic block
• Generic model is developed which accommodates complex column features
such as multiple feeds, side draws, etc.
• Model is tested against HYSYS simulation as well as plant data. Model
represents column behaviour satisfactorily.

Flowsheet is simulated sequentially

• Simplified models are used to simulate individual columns

Strengths of model
• Model is computationally efficient, so suitable for flowsheet synthesis, design
and analysis purposes
• Number of variables is reduced considerably compared to rigorous stage by
stage equilibrium model

P4-32 Design and Synthesis of Chemical Absorption Processes

 3. Superstructure development

P4-33 Design and Synthesis of Chemical Absorption Processes

 Superstructure formulation

Simultaneous optimisation of structural options along with operating

conditions can give novel flowsheets

P4-34 Design and Synthesis of Chemical Absorption Processes

 Design options (1)

Multiple feeds to absorption column

Additional feed acts as source of

intermediate cooling
Additional feed enhances selective removal

Multiple sidedraws from absorption column

Solvent is removed at intermediate stage

and recycled
Sidedraw can divide column into bulk
absorption and tail absorption

P4-35 Design and Synthesis of Chemical Absorption Processes

 Design options (2)

Side draw from desorption column (split-flow)

Less purified liquid stream is removed from

regenerator and recycled to intermediate
location of absorption column
Decreases purity of sweet gas
Reduces reboiler duty

Flash

Used at regenerator pressure or at vacuum

conditions
Reduces acid gases and hence stripping
requirements

P4-36 Design and Synthesis of Chemical Absorption Processes

 Design options (3)

Heat integration
• Various streams needs cooling and heating
• Heat integration can reduce energy demand
- considered during, not after, flowsheet design
- pinch analysis allows minimum utility requirement to be
determined
• Extra capital cost

Other options

Number of stages in each column block, operating pressures,

reflux ratios, boilup ratios, etc.
Mixing or splitting of streams

P4-37 Design and Synthesis of Chemical Absorption Processes

 Superstructure for synthesis of absorption-desorption flowsheet

• Multiple absorption feeds

• Intermediate draws

• Regeneration flash drums

• Heat recovery

• Mixing and splitting of streams

P4-38 Design and Synthesis of Chemical Absorption Processes

 4. Flowsheet synthesis and design

P4-39 Design and Synthesis of Chemical Absorption Processes

 Synthesis methodology

Given data (Feed, recovery specifications)

Structural and operational alternatives

e.g. superstructure representation
Systematic flowsheet generation
e.g. using optimisation techniques
Simulate flowsheet using
appropriate model
Evaluate flowsheet e.g. operating,
captial cost

Optimal flowsheet

P4-40 Design and Synthesis of Chemical Absorption Processes

 Framework for simulated annealing

Problem specific Design parameters

properties

Simulator Evaluate
Simulates a specified structure
• Material balances (A) objective (B) constraints
• Energy balances
Step II

Moves Simulated Annealing

• Operational changes Optimiser
Step I • Network changes Step III
• Continuous changes Accept / Reject
• Discrete changes Terminate

Optimal solution
P4-41 Design and Synthesis of Chemical Absorption Processes
 Perturbation moves

Feed - split move Operating conditions

Absorption feed -split Absorption column

Regeneration feed -split feed temperature
circulation rate
Regenerator column
condenser temperature
Perturbation moves boil-up ratio

Number of stages Side - draw move Flash exit

Absorption column stages

Absorption side -draw
Ssection stages
Regenerator column stages Regeneration side -draw

P4-42 Design and Synthesis of Chemical Absorption Processes

 Case studies

P4-43 Design and Synthesis of Chemical Absorption Processes

 Case study 1: Acid gases removal using DEA
Base case*
Make up Acid gases
Outlet gas

Heat
Absorber exchanger Regenerator

Feed gas Lean amine

Rich amine

Simple absorption column (single liquid feed, no side draws)

No side draws or multiple feed to absorption or desorption
column
* Tomcej et al., 33rd Annual Gas Conditioning Conference, Oklahama, 1983.

P4-44 Design and Synthesis of Chemical Absorption Processes

 Case study 1: Acid gases removal using DEA
Feed and operating conditions
Absorption column
Column pressure bar 60.68
H2S in gas feed mol% 7.81
CO2 in gas feed mol% 2.38 Comparison with plant
Gas feed temperature °C 23.9
Amine conc. in absorbent wt % 26 Plant Model
Absorbent inlet temperature °C 43.3
H2S in outlet gas mol% 3.713 3.49
Absorbent flow rate kmol/h 4045
CO2 in outlet gas mol% 0.127 8
Feed gas flowrate kmol/h 951.3
Number of trays 20 Rich amine temperature °C 55.4 52
H2S efficiency % 50* H2S load in lean solvent 0.023 0.013
CO2 efficiency % 35* CO2 load in lean solvent 0.003 0.0175
Reboiler duty kW 7327 7160
Desorption column
Column pressure bar 1.0
Condenser temperature °C 30
Number of trays 20
Feed tray location 1
H2S efficiency % 25*
CO2 efficiency % 15*

P4-45 Design and Synthesis of Chemical Absorption Processes

 Case study 1: Problem formulation

Objective function = total annualised cost (operating + capital)

Constraint = composition of H2S in sweet gas 3.5 ppm

Bounds on variables
Optimisation variable Lower bound Upper bound
Absorption draw fraction 0 0.8
Desorption draw fraction 0 0.4
Split fractions of the stream entering at top stage of 0.7,0, 0 1.0,0.5, 0.5
the absorption column
Split fractions of the stream entering at first stage 0, 0, 0 1.0, 1.0, 1.0
of the absorption column
Split fractions of the stream entering at second 0, 0, 0 1.0, 1.0, 1.0
stage of the absorption column
Absorption column section stages 3, 3, 3, 3 7, 7, 7, 7
Desorption column section stages 3, 3 13, 13
Solvent circulation rate (kmol/hr) 3500 4500
Boil-up ratio 0.16 0.35
Absorption feed temperature (oC) 25 45
Desorption feed temperature (oC) 95 105

P4-46 Design and Synthesis of Chemical Absorption Processes

 Case study 1: Optimised flowsheet
Make up
Sweet gas Acid gases

Heat
Semi-lean amine Integration
Desorber
Absorber

Feed
gas Rich amine
Lean amine

Base Optimised
case value
Total hot utility (kW) 7160 2193
Over 50% reduction in
Total cold utility (kW) 14204 13629
overall operating cost
Number of stages in absorption column 20 21
Number of stages in desorption column 20 20
Overall operating cost (M$ / yr) 0.68 0.31
H2S composition in sweet gas (ppm) 3.5 3.4

P4-47 Design and Synthesis of Chemical Absorption Processes

 Case study 1: Optimised flowsheet with HEN

Optimised flowsheet after detailed HEN design.

Sweet
gas

Acid
gases
Absorption
column Regeneration
Column
Semi-
lean
amine

Rich amine
Gas
Feed Lean amine

Base case = 188 m2 HE Area Optimised case = 144 m2

Base case = 1044 kW Cold utility Optimised case = 529 kW

P4-48 Design and Synthesis of Chemical Absorption Processes

 Case study 1: Acid gases removal using DEA
Base case Optimised flowsheet
Semi-lean solvent
Trace removal Ultra-lean solvent
Outlet gas Make up
with pure solvent

Absorber Desorption
Heat exchanger
Bulk absorption
with less
concentration
solvent
Feed gas Rich Lean Amine
Amine

Design specification for outlet gas H2S concentration 3.50 ppm

Base case = 3.5 ppm H2S in outlet gas Optimised case = 3.4 ppm

Base case = 1.18 · 106 $/yr Annualised cost Optimised case = 0.71 · 106 $/yr

Over 40 % reduction in annualised cost

P4-49 Design and Synthesis of Chemical Absorption Processes

 Case study 2: Rretrofit design for MDEA plant*

Make up Acid gases

Outlet gas

Heat
Absorber exchanger Regenerator

Feed gas Lean amine

Rich amine

Simple absorption column (single liquid feed, no side draws)

Problem -
Feed gas specification has changed for CO2 gas from 3.5% to
4.8% and thus sale gas specifications are not met.
* base case from Pakistan Petroleum Limited.
P4-50 Design and Synthesis of Chemical Absorption Processes
 Case study 2: Feed and operating conditions
Absorption column Desorption column

Number of trays 20 Number of trays 20

Column pressure bar 55.0 Column pressure bar 3.0
H2S in gas feed ppm 380 Condenser temperature o
C 30
CO2 in gas feed mol % 4.8 Feed tray location 4
Gas feed temperature o
C 43.9 Feed temperature C
o
97.2
Amine conc. in absorbent wt % 36.0 H2S efficiency % 39.0#
Absorbent inlet temperature o
C 55.7 CO2 efficiency % 2.7#
Absorbent flow rate kmol/hr 691.5
Feed gas flow rate kmol/hr 1046
H2S efficiency % 56.0#
CO2 efficiency % 8.0#
# specified value
Thermodynamic properties = New extended Kent and Eisenberg
model* is used for VLE calculations in simplified model simulation

* Malik, Z., VLE modelling for retrofit of gas sweetening units, MSc thesis, University of Manchester, 2005
P4-51 Design and Synthesis of Chemical Absorption Processes
 Case study 2: comparison of model results

Normal operating plant

Unit Plant Model HYSYS
H2s in outlet gas ppm 2-3# 0.34 3
CO2 in outlet gas % > 2.0 1.97 1.8
Rich amine temperature 0
C 60.6 63.1 61.2
H2S load in lean solvent* - 0.00004 4.9e - 8
CO2 load in lean solvent - 0.03295 0.003617
Re - boil ratio 0.18 0.18 0.18

# calculated.
* load = moles of acid gas per moles of amine

P4-52 Design and Synthesis of Chemical Absorption Processes

 Case study 2: comparison of model results

Plant conditions after change in feed gas composition

Unit Plant Model Hysys

H2S in outlet gas ppm 2 -3 0.4 57

CO2 in outlet gas % 2.8 3.0 2.8

Rich amine temperature 0
C 60.6 65.6 62.2
H2S load in lean solvent* - 0.00003 4.9e-8
CO2 load in lean solvent - 0.03397 0.003617
Re - boil ratio 0.18 0.18 0.18
* load = moles of acid gas per moles of amine

Due to change in inlet feed conditions CO2 composition in

outlet gas from absorber has gone high from 2.0 to 2.8 %.

P4-53 Design and Synthesis of Chemical Absorption Processes

 Case study 2: retrofit options
Options considered for retrofit -

Change solvent conditions (change flow rate, concentration of

solvent, etc.)
Change solvent feed temperature
Change gas feed temperature
Change split feed fractions in the absorption column
there are provisions for feed split at stage 6 and 10 in the absorption
column
Other options -

Use of static mixer (equivalent to a single equilibrium stage)

Need extra unit to be installed
Large pressure drop
Gas feed distribution in order to meet gas specifications
Side draws from the column - need constructional modifications
P4-54 Design and Synthesis of Chemical Absorption Processes
 Case study 2: operating limits on plant

Change solvent feed temperature ( 50 oC)

Rrecycle stream is air-cooled and temperature achievable depends on
ambinent temperature

Change gas feed temperature ( 35 oC)

Ddifference between feed gas and solvent inlet temperature should be in the
range of 10 - 15 oC in order to avoid foaming

Pump on solvent recycle stream is operating at maximum capacity

Any further increase will require larger capacity pump

Plant is currently operating at 36 wt% of MDEA but has been

designed for 50 wt% MDEA
Cconcentration cannot be increased to 50 wt% as there are no corrosion
inhibitiors -can be operated up to 40 wt %
Regenerator has been designed to handle 50 wt% MDEA

P4-55 Design and Synthesis of Chemical Absorption Processes

 Case study 2: Optimisation problem

Objective = operating cost + constant (CO2 composition - target value)

Optimisation results
Optimisation variable Base Optimised
case value
Solvent feed temperature (oC) 55.7 50.5
Gas feed temperature (oC) 43.9 36.0
Amine concentration (wt %) 36.0 39.8
Absorption feed split 1 1.0 0.10
Absorption feed split 2 0.0 0.35
Absorption feed split 3 0.0 0.55
CO2 in treated gas (mol %) 2.8 2.2

P4-56 Design and Synthesis of Chemical Absorption Processes

 Case study 2: Retrofit design
Make up Acid gases
Outlet gas 0.1

6 0.35

10
Heat
Absorber 0.55 exchanger Regenerator

Feed gas Lean amine

Rich amine

Scenario Outlet H2S Outlet CO2

(ppm) (%)
Current operation 0.5 3.0 Retrofit design is
Optimised 1.1 2.2 well within target
Retrofit target <6 2.2

P4-57 Design and Synthesis of Chemical Absorption Processes

 Summary
A superstructure has been proposed for absorption -
desorption flowsheets
• Superstructure includes various structural options

A systematic framework has been developed for absorption

flowsheet synthesis

A stochastic optimisation methodology is used to solve the

superstructure to systematically synthesize the flowsheet.

P4-58 Design and Synthesis of Chemical Absorption Processes

 5. Conclusions and future work

P4-59 Design and Synthesis of Chemical Absorption Processes

 Conclusions

Simplified model for chemical absorption is developed

• Model is suitable for multicomponent system
• Generic model is developed to accommodate complex structures such as
multiple feeds, side draws, etc.
• Model has been tested against plant data as well as HYSYS simulation. Model
represents process behaviour satisfactorily.

Superstructure is proposed for absorption - desorption flowsheet

• Superstructure includes various structural options

A systematic framework for absorption flowsheet synthesis is

formulated using simplified model
• Stochastic optimisation methodology is developed to solve the superstrcture
• Simultaneous optimisation and heat integration problem formulated
• Optimised flowsheet shows considerable reduction in operating cost
• Methodology can be used effectively for retrofit designs

P4-60 Design and Synthesis of Chemical Absorption Processes

 Future work

Extension of methodology for other retrofit cases

• Of particular interest: centralised regenerating column where amine from
different absorption columns (two or more) is regenerated.
Application of methodology to mixed solvents and choice of solvent.

P4-61 Design and Synthesis of Chemical Absorption Processes

 Thank you !

P4-62 Design and Synthesis of Chemical Absorption Processes