modeling, simulation & experimentation of separation
TRANSCRIPT
J.L. de Medeiros - UFRJ
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Modeling, Simulation & Experimentation of Separation Processes for CO2 Removal
from Natural Gas
High Pressure Membrane Units High Pressure Membrane Contactors High Pressure Absorption with Amines
José Luiz de Medeiros & Ofélia Q.F. AraújoEscola de Química – UFRJ
Lab. H2CIN
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Objectives of this Presentation
# To present our Lab. H2CIN at UFRJ
# To present the General Research Lines of Lab. H2CIN
# To present the Specific Research Lines of Lab. H2CIN in the context of High Pressure Natural Gas Purification Technologies
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Lab. H2CIN at Fundão Island
Bay of Guanabara
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Lab. H2CIN at Fundão Island
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Lab. H2CIN – General Research Lines
# Hydrogenation of Oil Fractions (Model & Pilot)
# Hydrocracking of Heavy Gasoils (Model & Pilot)
# Pipeline Network Modeling & CO2 Pipelines
# Leak Detection by Software (Model & Pilot)
# Dynamics & Control of Offshore Separation Plants
# Riser Dynamics & Control (Model & Pilot)
# Separation Processes & Thermodynamics
# Engineering of Chemical Sequestration of CO2
# Engineering of Biochemical Sequestration of CO2
# Photo-Bioreactor Engineering (Model & Pilot)
J.L. de Medeiros - UFRJ
6Lab. H2CIN – General Research Lines2” X 12m Plexiglass Pilot Riser System
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7Lab. H2CIN – General Research Lines2” X 12m Plexiglass Riser System
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8Lab. H2CIN – General Research Lines2” X 120m High P Loop for Leak Detection
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9Lab. H2CIN – General Research Lines 200bar Hydrocracking Pilot Unit
50bar Hydrotreating Pilot Unit
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10Lab. H2CIN – General Research Lines700L Outdoor Microalgae Photo-Bioreactor
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11Lab. H2CIN – Specific Research LinesNatural Gas (NG) Purification & CO2 Capture
# 1. Rigorous Modeling of High-Pressure Membrane
Permeators for CO2/CH4 Separations
# 2. Thermodynamic VLE Model for AGWA Systems
(AGWA = Acid Gas + Water + Amine)
(Acid Gas = CO2 & H2S)
(Amine = MEA, DEA, MDEA, AMP)
# 3. Equilibrium-Staged Rigorous Column Model for
Absorption & Stripping with AGWA Systems
# 4. Rigorous Modeling of Membrane Contactors
with AGWA Solvents for CO2/CH4 Separations
J.L. de Medeiros - UFRJ
12Line 1 : Modeling of High-Pressure Membrane Permeators for CO2/CH4 Separations Hollow-Fiber Modules
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Rigorous Component Balances for Permeate & Retentate
Rigorous Momentum Balances for Permeate & Retentate
Rigorous Energy Balances for Permeate & Retentate
Temperature Profiles of Permeate & Retentate are Accessed
Permeation Fluxes Expressed in Terms of Fugacity Gradients
Temperature Decreases along Permeate & Retentate FlowsRisk of Gas Condensation in the Retentate
Line 1 : Modeling of High-Pressure Membrane Permeators for CO2/CH4 Separations Hollow-Fiber Modules
J.L. de Medeiros - UFRJ
142. Modeling of CO2 Transport by PipelineCO2 Critical & Triple-Point Properties
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15Permeator Sample ProblemPermeation Profiles at Stage 1
%Mol Retentate
6%Mol CO2
82%Mol CH4
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16Permeator Sample ProblemPermeation Profiles at Stage 1
%Mol Permeate
32.7%Mol CH4
67%Mol CO2
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17Permeator Sample ProblemPermeation Profiles at Stage 1
Temperature Profiles
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18Permeator Sample ProblemProfiles for Permeation at Stage 1
Investigating Condensation
VLE Locus for the Feed
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19Line 2: Thermodynamic VLE Model for AGWA
Systems
OHMDEASHMDEAOHSH
OHMEASHMEAOHSH
OHMDEACOMDEAOHCO
OHMEACOMEAOHCO
K
K
K
K
2222
2222
2222
2222
4
3
2
1
⋅⋅→←++
⋅⋅→←++
⋅⋅→←++
⋅⋅→←++
# Modeling of Chemical Equilibrium(ChE) + Vapor-Liquid Equilibrium(VLE)
# ChE Reactions forming Non Volatile Complex Species
# Conventional Equations of State for property prediction (PR, SRK, etc)
# ChE Constants estimated with a Database containing more than 1200 VLE-AGWA Experiments from the Literature
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Estimation Results for ChE Constants
Line 2: Thermodynamic VLE Model for AGWA Systems
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Estimation Results for ChE Constants
Line 2: Thermodynamic VLE Model for AGWA Systems
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1Q
2
11
10
5
9
7
6
4
3
8
12
1L
2L
3L
7L
6L
8L
9L
10L
11L1V
5V
4V
3V
2V
7V
12L
8V
9V
10V
11V
12V
2Q
Abso
rção
Esg
ota
mento
1W 2W
1U
1
6V1G
4L
5L
2G
13L2U
2F1F
12L 6L
3Q
Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems
Representation of a Process with Absorption & Stripping Columns for AGWA Systems
# Digraph Framework
# Vertices : VLE-ChE Stages
# Edges : Connecting Streams, Feeds & Products
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The Real Process
Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems
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A Typical Simulated Temperature Profile (K) for MEA/MDEA/H2O with CO2/H2S
Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems
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Typical Simulated Profiles of ChE Constants for MEA/MDEA/H2O with CO2/H2S
Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems
J.L. de Medeiros - UFRJ
26Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
Hollow-Fiber Contactor
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Hollow-Fiber Contactor
# AGWA Solvent in axial flow inside fibers
# CO2 captured by solvent after diffusion through membrane
# Similar to column absorber, but without direct contact of phases and smaller
# Membrane is selective # High pressure gas # Gravity not necessary
# Reactive Two-phase permeate with ChE & Exothermic Effects
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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OHMDEASHMDEAOHSH
OHMEASHMEAOHSH
OHMDEACOMDEAOHCO
OHMEACOMEAOHCO
K
K
K
K
2222
2222
2222
2222
4
3
2
1
⋅⋅→←++
⋅⋅→←++
⋅⋅→←++
⋅⋅→←++
# Same AGWA Reactive Model for Two-Phase Permeate = ChE + VLE
# ChE Reactions forming Non Volatile Complex Species
# Conventional EOS (PR, SRK, etc) for property prediction in the Two-Phase Permeate & in Gas Retentate
# ChE Constants estimated with a Database from the Literature
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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Typical ChE Behavior of YCO2 vs T&P in the Two-Phase Reactive Permeate
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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Good for Absorption of CO2
Good for Stripping of CO2
Typical ChE Behavior of YCO2 vs T&P in the Two-Phase Reactive Permeate
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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Rigorous Component Balances for Permeate (Two-Phase) & Retentate (Gas)
Rigorous Momentum Balances for Permeate (Two-Phase) & Retentate (Gas)
Rigorous Energy Balances for Permeate (Two-Phase) & Retentate (Gas)
Permeation Fluxes Expressed in Terms of Fugacity Gradients
Temperature Profiles of Permeate & Retentate are Accessed
Temperature Increases along Permeate & Retentate FlowsNo Risk of Gas Condensation
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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Typical Process Flowsheet with Contactor for CO2 Capture from Natural Gas
Q1
S1MR1CGL
GN_Contact_1
mrSOLV3
V@GN_Contact_1
L@GN_Contact_1
L@mrL@GN_Contact_1
V@mrL@GN_Contact_1
mrL@GN_Contact_1
MEA+H2OMR2
Q2
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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Typical Simulated Flowsheet with Contactor : Stream Data
Line 4: Rigorous Modeling of Membrane Contactors with AGWA Solvents for CO2/CH4 Separations
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34Contactor Sample ProblemRetentate Flow Rate Profiles
3.5%Mol CO2
77%Mol CH4
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35Contactor Sample ProblemPermeate %mol for Liquid & Vapor Phases
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36Contactor Sample ProblemT Profiles for (Two-Phase) Permeate & Retentate
Retentate
Permeate
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37Contactor Sample ProblemProfiles of %Recovery in the Permeate
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THANK YOU !