You are on page 1of 60

Simulation of Amine Plants: Fundamental Models and Limitations

2das Jornadas Tcnicas Sobre Acondicionamiento del Gas Natural 30 de Septiembre al 3 de Octubre de 2008 El Calafate, Argentina

Jenny Seagraves INEOS Oxide GAS/SPEC Technology Group


IAPG 2008

Topics of Presentation
General history and overview of fundamental models
refer to paper and references in papers for more details

Case Studies
Important considerations or ideas for designing or optimizing an amine plant

IAPG 2008

History and Fundamentals of Amine Simulation Models

IAPG 2008

Improved simulation model are developed as solvent technologies evolve and amine plant become more complex.
MEA DEA Specialty Amine

TEA

DGA

1930

1940

1950

1960

1970

1980 & Beyond.

MDEA

DIPA

Simple Models (Hand Calculations)


IAPG 2008

Complex Computer Models

Simulation of MDEA and newer specialty solvents...


MDEA-based and specialty solvents more difficult to simulate
contain MDEA and sometimes blends of chemicals that yield specific treating characteristics have components with different reaction kinetics MDEA solvent have different temperature profile than MEA or DEA. Simplified computer calculations are dangerously misleading for MDEA and specialty amine designs

IAPG 2008

Improved Simulation is Needed as Amine Plant Designs Evolve...


While 20 trays absorber & regenerator designs are still most common . We now are designing amine plants with
multiple feeds and side draws Complex multi-staged flash to reduce energy New mass transfer devices to get more capacity
new packing material or trays or a combination of the two.

IAPG 2008

Example of Amine Plant with Multi-feeds and Flash


CO2 Lean Amine T = 130 F (50 C)

Absorber Semi-lean Regenerator

Syngas

Rich Amine Reboiler

IAPG 2008

Definitions
Vapor Liquid Equilibrium (VLE)
Defines the solution chemistry / chemical species present model determines the maximum limit of H2S and CO2 absorbed

Reaction Rates
Defines how quickly H2S and CO2 are absorbed H2S react instantaneously with amines and CO2 react at various rates depending on type of amine.

Mass Transfer Rate


Define the surface area and how quickly the surface area is refreshed for H2S and CO2 absorption

IAPG 2008

MDEA Amine Chemistry (Simplified)

H2S + Amine

AmH + + HS -

CO2 + H20 + Amine

AmH + + HCO3

Note: Heat is generated by the reaction of the acid gas with the amine. Conversely, heat is required to free the acid gas from solution.

IAPG 2008

Vapor Liquid Equilibrium


ionization of water 2 H2O H3O+ + OHdissociation of hydrogen sulfide H2O + H2S H3O+ + HSdissociation of bisulfide H2O + HS- H3O+ + S2dissociation of carbon dioxide 2 H2O + CO2 H3O+ + HCO3dissociation of bicarbonate H2O + HCO3- H3O+ + CO32dissociation of protonated alkanolamine H2O + RRRNH+ H3O+ + RRRN carbamate reversion to bicarbonate RRNCOO- + H2O RRNH + HCO3(eq. 1)

(eq. 2)

(eq. 3)

(eq. 4)

(eq. 5)

(eq. 6)

(eq. 7)

IAPG 2008

Vapor Liquid Equilibrium

The equations governing chemical equilibria for equations 1 to 7 may be written as: K = 4i (xi Ki )Ri (eq. 8)

where, K is the equilibrium constant xi is the mole fraction of species i Ki is the activity coefficient of species i Ri is the stoichiometric coefficient

IAPG 2008

Chemical Kinetics and Mass Transfer

Ni = Ei ki,L a (yi interface - yi Bulk)

(eq 8)

NI = transfer rate Ei = enhancement factor (accounts for chemical reaction) ki,L = Mass transfer coefficient a = interfacial area yi interface= acid gas conc. at interface (from Henrys law) yi bulk = acid gas conc. in bulk (from VLE)

IAPG 2008

Evolution of Amine Simulation


Pre 1980s - Equilibrium Stage Approach was only method
Uses simplified estimates Estimate chemical species in solution Uses tray efficiencies lump reaction and mass transfer rates Adequate for simulation of MEA and DEA Not accurate for MDEA, specialty solvents, and complex amine mixtures Still used in many commercial simulators today
IAPG 2008

After 1980s - Mass Transfer Rate Based Approach


More rigorous Calculate exact chemical species present in solution Calculate reaction and mass transfer rates Accurate for MEA, DEA, MDEA, and Specialty amine solvents Can be extended to systems with heat stable salts and other components if data is available Used in only a few simulators

History of Mass Transfer Rate Based Simulation Approach


Idea to combine mass transfer with chemical reactions in amine simulation came about as a result of works by Astarita, Weiland, Katti, and others. In early 1980s, GAS/SPEC funded a series of research projects to developed the first amine simulator that combined
rigorous vapor-liquid-equilibrium (VLE) modeling with mass transfer and chemical reactions calculations

Mass Transfer Rate-based simulation has been used and refined over the last 20+ years by the GAS/SPEC group Available in certain simulators such as
GAS/SPEC APS Simulator (proprietary simulation program) Commercially available ProTreat Simulator (Optimized Gas Treating Inc.)

IAPG 2008

What is mass transfer rate-based?

IAPG 2008

Example of GAS/SPEC APS Simulation

IAPG 2008

Most Basic Amine Simulation Models


Use tray efficiencies to account for mass transfer reaction rates Efficiencies are empirically derived Ignore tower internals use equivalent stages to represent a given number of trays or packing height
IAPG 2008

Tray Efficiency

Properties

Simulation Material Balance Phase Equilibrium

Predicted Plant Performance

Mass Transfer Rate-based Simulations


More detailed approach Avoid the use of efficiencies Considers differences in reaction rates of H2S and CO2 Consider Mass Transfer rate of absorption in different tower internals (trays, packing, etc.)
IAPG 2008

Mass Transfer (Tower internals) Reaction Kinetics Simulation Material Balance Phase Equilibrium Properties

Predicted Plant Performance

Advantages of MT Rate-based Models


Makes more rigorous and accurate prediction inside column
temperature profile
Tray Number

Example of Actual vs Predicted


21 19 17 15 13 11 9 7 5 3 1 100 110 120 130 140 150

ProTreat Actual

reaction or absorption zone identify trouble area in the column


equilibrium limits areas of corrosion concerns due to high temperatures

Temperature (F)

IAPG 2008

Equilibrium Stage Approach


No one-to-one correspondence of theoretical stage with position in column
3 trays per stage ? Or 4 trays per stage?etc. Top Tray Stage 3 Tray location? Stage 2 Tray location? Temp? Composition?

Difficult to locate exact temperature and composition of feeds and side draws

Stage 1
Feed

IAPG 2008

M.T. Rate-based Approach


Know temperature and composition on every actual tray Can accurately locate optimum points for feeds and side draws
Top Tray

Tray is known Tray is known Temp is known

Feed

IAPG 2008

Case Studies

IAPG 2008

Case Study 1
High pressure coal bed methane gas
requires CO2 removal only plant have ability to treat a portion of the natural gas and blend to meet 3 mol% CO2 spec

IAPG 2008

Case 1 - Flow Diagram

TREATED GAS REFLUX CONDENSER LEAN AMINE REFLUX ACCUMULATOR REGEN ABSORBER FILTER TRAIN FEED AMINE COOLER REBOILER RICH AMINE LEAN /RICH CROSS-EXCHANGER

IAPG 2008

Benchmark Performance Tests


Test 1 Raw Gas Flow (Nm3/h) Temperature (oC) Pressure (kPa) CO2 (mol%) Lean Solvent Flow (m3/h) Temp (oC) Wt% MDEA 235500 40 6881 4.29 Test 2 232100 40 6881 4.29 Test 3 200900 40 6881 4.21

227 40 48

186 43 48

227 39 48

IAPG 2008

Performance Compared to Simulation


Test 1 227 235500 Test 2 186 232100 Test 3 227 200900

Solvent Rate (m3/h) Gas Rate (Nm3/h) Treated Gas Measured CO2 (mol%) Predicted CO2 (mol%) Lean Amine Actual mol/mol Predicted mol/mol Rich Amine Predicted mol/mol
IAPG 2008

1.54 1.57 0.008 0.0075 0.310

1.98 1.95 0.008 0.0059 0.403

1.20 1.20 0.007 0.0046 0.294

Performance Compared to Simulation


Test 1 227 235500 Test 2 186 232100 Test 3 227 200900

Solvent Rate (m3/h) Gas Rate (Nm3/h) Treated Gas Measured CO2 (mol%) Predicted CO2 (mol%) Lean Amine Actual mol/mol Predicted mol/mol Rich Amine Predicted mol/mol
IAPG 2008

1.54 1.57 0.008 0.0075 0.310

1.98 1.95 0.008 0.0059 0.403

1.20 1.20 0.007 0.0046 0.294

Actual versus Simulation Predicted Temperature


Test 1 - Absorber
21

Test 2 - Absorber
21 19 17 15 Tray Number 13 11 9 7 5 3 1 38

Test 3 - Absorber
21 19 17 15 13 Tray Number 11 9 7 5 3 1 38

19 17 Tray Number 15 13 11 9 7 5 3 1 38 49 60 71 Temperature (C)

49 60 71 Temperature (C)

82

49 60 Temperature (C)

Actual temperature measurements Simulated Temperatures


IAPG 2008

Significance of Temperature Profile


Concern with Temperature Profile because
higher and broader profile have corrosion implications outlet gas temperature increase load on downstream dehydration equipment high temperature may limit capacity or cause plant to go off spec difficult to absorb CO2
near equilibrium loading

IAPG 2008

Tower Temperature Profiles


Broad temperature profile throughout

Poor liquid distribution

GAS/SPEC technical service engineers use these temperature scans of towers to troubleshoot amine plant. This is a method to monitor performance
IAPG 2008

Options for More Capacity


Customer wants more capacity out of the plant
However CO2 level in inlet gas is rising!

Option 1 - Continue to treat with MDEA


Treat to just below 3% CO2 specification

Option 2 - Upgrade to a Specialty Solvent


Treat CO2 to low levels of < 1000 ppm then blend with untreated gas to meet 3% CO2 specification

IAPG 2008

Max Capacity with MDEA


600000

Pipeline Max
500000 Gas Flow, Nm3/h 400000 300000 200000 100000 0 3.5 4 4.5 5 5.5 6 6.5 Inlet CO2, mol%
Treated Bypassed Combined

IAPG 2008

Max Capacity with Specialty Solvent


900000 800000 700000 Gas Flow, Nm3/h 600000 500000 400000 300000 200000 100000 0 3.5 4 4.5 5 Inlet CO2, mol% 5.5 6 6.5 Treated Bypassed

Pipeline Max

Combined

IAPG 2008

Results after Conversion

Flow to Absorber (Nm3/h) Inlet CO2, mol% Outlet CO2, mol% Amine Flow, Nm3/h Max Total Gas Capacity (Nm3/h)
\ Currently

MDEA 235500 4.29 1.54 227

CS-2010 232100 4.5 < 0.1 202

446400

502200 \

limited by capacity of downstream pipeline

IAPG 2008

Conclusions - Case 1
Demonstrates use of simulation tool to
accurately predict temperature and CO2 in the column. identify opportunities for optimization of existing plant make decision on how to best utilize assets for present and future treating conditions

IAPG 2008

Case Study 2
Offshore natural gas application
H2S and CO2 removal

Simulations used to
design original plant modify plant to adapt to changing process conditions

IAPG 2008

Case 2 - Flow Diagram

TREATED GAS REFLUX CONDENSER LEAN AMINE REFLUX ACCUMULATOR REGEN ABSORBER FILTER TRAIN FEED AMINE COOLER REBOILER RICH AMINE LEAN /RICH CROSS-EXCHANGER

IAPG 2008

Original Design Treating Conditions


Inlet Gas Flow (Nm3/h) Inlet Gas Pressure (kPa) Inlet Gas Temp (C) Gas Composition: CO2 (mol%) H2S (mol%) Treated Gas Specification: CO2 (mol%) H2S (ppmv) 502200 7419 49 3.25 1.35 <1 <4

IAPG 2008

Key Design Decisions


Prior to INEOS involvement, customer decided on
30 tray absorber (3.35 meters diameter with 10 cm weir height) design based on generic MDEA plant was already designed with Equilibrium Stage-based simulator

Use of 30 trays is unusual in an offshore application due to weight consideration

IAPG 2008

Simulation - Design Rate

Gas Flow (Nm3/h) Feed Tray from Top MDEA Conc. (wt% ) Circulation Rate (m3/h) Treated Gas CO2 (mol%) H2S (ppmv)

502200 30 50% 545 0.92 < 1 ppm

Lean Loadings / Rich Loadings H2S (mol/mol) 0.0002 / 0.13 CO2 (mol/mol) 0.005 / 0.23
IAPG 2008

Variations operating conditions were also simulated...

IAPG 2008

Simulations for Changing Condition


Limited heat source at certain times
57% of design duty available Plant will operate at reduced rate Increased CO2 pickup at reduced rate

How to operate plant to minimize CO2 pickup

IAPG 2008

Alternatives for Operating at Reduced Rates

Scenario 1

502200 Nm3/h Reboiler Duty = X 30 trays CO2 Out = 0.92 mol%


Scenario 2

30 trays 279000 Nm3/h 340 m3/h of 50wt% MDEA Reboiler Duty = 0.57 X CO2 Out = 0.59 mol% 19 trays 279000 Nm3/h 340 m3/h of 50 wt% MDEA Reboiler Duty = 0.57X CO2 Out = 0.99 mol%

IAPG 2008

Alternative Cases
Design Rate 502200 30 50% 545 0.92 < 1 ppm 0.0002 0.005 0.13 0.23 X Simulation Scenario 1 279000 30 50% 341 0.59 <1 ppm 0.0002 0.005 0.11 0.23 0.57 X Simulation Scenario 2 279000 19 50% 341 0.99 < 1 ppm 0.0002 0.005 0.11 0.20 0.57 X

Gas Flow (Nm3/h) Feed Tray from Top MDEA Conc. (wt% ) Lean Amine (m3/h) Treated Gas CO2 (mol%) H2S (ppmv) Lean Loadings H2S (mol/mol) CO2 (mol/mol) Rich Loadings H2S (mol/mol) CO2 (mol/mol) Reboiler Duty
IAPG 2008

Outcome of Simulations

Feed points added to trays 30, 24, 19 to allow for flexibility under changing conditions
Tray 30 ABSORBER Tray 24 Tray 19 Feed

IAPG 2008

Prior to Startup
Plant needed lower CO2 level
Minimize corrosion in downstream pipeline Old spec 1% CO2 ; New spec 1000 ppmv CO2

In order to maximize CO2 removal, customer has 2 options


Option 1 - Continue with MDEA
Higher amine circulation rate, L/V Use all 30 trays

Option 2 - Specialty amine solvent


Treat with less trays and less circulation

Customer decide to proceed startup with MDEA and then upgrade to a specialty solvent.
IAPG 2008

After Startup
After startup, the plant experienced foaming Plant had difficulty treating at high capacity Not making the 1% CO2 spec with MDEA Problem was caused by
Hydrocarbon coming into the plant High amine flow and high tray count required by MDEA seem to worsen foaming problem
operate with only 19 trays over-circulate to keep the CO2 level down

IAPG 2008

Conversion to Specialty Solvent


After operating with MDEA for 5 months, customer converted to GAS/SPEC* CS-2000 solvent
Running conversion. Now plant treating at full capacity of 450 MMSCFD Meeting < 1000 ppmv CO2 spec Only the bottom 19 trays were needed Reduction in foaming tendency
better separation / filtration higher loading decrease HC solubility

IAPG 2008

Conclusions - Case 2
Ideally want to design a plant with fewer trays and higher rich loadings
to reduce capital cost to minimize hydrocarbon absorption

Simulation used to determined alternative feed points to improve plant flexibility Simulations helped adapt plant to new treating requirements with a specialty solvent

IAPG 2008

Case Study 3
Natural gas plant plant faced with rising CO2 composition
Originally 7.8 mol% CO2 is now over 10%

Plant operation was unstable because high outlet CO2 caused coldbox to freeze Goal is to increase capacity and stabilize plant operations

IAPG 2008

Operating Conditions versus Simulated


Flow (Nm3/h) Temperature (C) Pressure (kPa) Inlet CO2 (mol%) Actual CO2 Out (ppm) Predicted CO2 Out (ppm) Lean Solvent Flow (m3/h) Temperature (C) Wt% GAS/SPEC CS-2020 Rich Solvent Temperature (C) Predicted Temp (C) 34600 11 4440 10.2 10 10

82 48 50

79 to 81 81

IAPG 2008

Operating Conditions versus Simulated


Flow (Nm3/h) Temperature (C) Pressure (kPa) Inlet CO2 (mol%) Actual CO2 Out (ppm) Predicted CO2 Out (ppm) Lean Solvent Flow (m3/h) Temperature (C) Wt% GAS/SPEC CS-2020 Rich Solvent Temperature (C) Predicted Temp (C) 34600 11 4440 10.2 10 10

82 48 50

79 to 81 81

IAPG 2008

Effect of Rate on CO2 Concentration


CO2 in Vapor, ppmv 1 1 3 5 7 Tray # (Top down) 9 11 13 15 17 19 21 23
IAPG 2008

10

100

1000

10000

100000

36800 Nm3/h 35700 Nm3/h 34600 Nm3/h

Effect of Rate on CO2 Loadings


Loading, mol/mol

0.00
1 3 5 7 Tray # (Top down) 9 11 13 15 17 19 21 23

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40
36800 Nm3/h 35700 Nm3/h 34600 Nm3/h

0.45

Little CO2 absorption

IAPG 2008

Effect of Rate on Column Temperature


Temperature, F 120 1 3 5 7 Tray # (Top down) 9 11 13 15 17 19 21 23 130 140 150 160 170 180 190 200 36800 Nm3/h 35700 Nm3/h 34600 Nm3/h 210

IAPG 2008

Outcome - Case 3
Plant personnel confirmed maximum rate of 34600 Nm3/h Client considering upgrading pumps and exchangers in order to increase/maintain capacity as inlet CO2 rises

IAPG 2008

Conclusions - Case 3
MT Rate based simulation gave insight on effect of gas rate on treat and temperature profile Allows plant to make informed decisions for future

IAPG 2008

Conclusions
Discussed the advantages of Mass Transfer Rate Based Simulation over other simulation methods Case studies have shown
accuracy of column temperature/composition prediction effect of mass transfer (tray count) on performance how to use simulator to design/modify in changing conditions the importance in considering temperature effects

IAPG 2008

Acknowledgement
Ulises Cruz - INEOS Andy Sargent - INEOS Ralph Weiland - Optimized Gas Treating, Inc.

* GAS/SPEC and CS-2000 are trademarks of INEOS Oxide


TM

ProTreat is a trademark of Optimized Gas Treating, Inc.

IAPG 2008

QUESTIONS?

IAPG 2008

You might also like