Modeling, Simulation & Experimentation of Separation Processes for CO2 Removal from Natural Gas

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1 1 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. Araújo Escola de Química UFRJ Lab. H2CIN

2 Objectives of this Presentation 2 # 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

3 Lab. H2CIN at Fundão Island Bay of Guanabara 3

4 Lab. H2CIN at Fundão Island 4

5 Lab. H2CIN General Research Lines 5 # 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)

6 Lab. H2CIN General Research Lines 2 X 12m Plexiglass Pilot Riser System 6

7 Lab. H2CIN General Research Lines 2 X 12m Plexiglass Riser System 7

8 Lab. H2CIN General Research Lines 2 X 120m High P Loop for Leak Detection 8

9 Lab. H2CIN General Research Lines 200bar Hydrocracking Pilot Unit 50bar Hydrotreating Pilot Unit 9

10 Lab. H2CIN General Research Lines 700L Outdoor Microalgae Photo-Bioreactor 10

11 11 Lab. H2CIN Specific Research Lines Natural 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

12 Line 1 : Modeling of High-Pressure Membrane Permeators for CO2/CH4 Separations Hollow-Fiber Modules 12

13 Line 1 : Modeling of High-Pressure Membrane Permeators for CO2/CH4 Separations Hollow-Fiber Modules 13 Rigorous Component Balances for Permeate & Retentate Permeation Fluxes Expressed in Terms of Fugacity Gradients Rigorous Momentum Balances for Permeate & Retentate Rigorous Energy Balances for Permeate & Retentate Temperature Profiles of Permeate & Retentate are Accessed Temperature Decreases along Permeate & Retentate Flows Risk of Gas Condensation in the Retentate

14 2. Modeling of CO2 Transport by Pipeline CO2 Critical & Triple-Point Properties 14

15 15 Permeator Sample Problem Permeation Profiles at Stage 1 %Mol Retentate 82%Mol CH4 6%Mol CO2

16 16 Permeator Sample Problem Permeation Profiles at Stage 1 %Mol Permeate 67%Mol CO2 32.7%Mol CH4

17 Permeator Sample Problem Permeation Profiles at Stage 1 17 Temperature Profiles

18 Permeator Sample Problem Profiles for Permeation at Stage 1 18 Investigating Condensation VLE Locus for the Feed

19 Line 2: Thermodynamic VLE Model for AGWA Systems 19 # 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 K1 CO2 + H 2O + MEA CO2 MEA H 2O K2 CO2 + H 2O + MDEA CO2 MDEA H 2O K3 H 2 S + H 2O + MEA H 2 S MEA H 2O K4 H 2 S + H 2O + MDEA H 2 S MDEA H 2O

20 Line 2: Thermodynamic VLE Model for AGWA Systems 20 Estimation Results for ChE Constants

21 Line 2: Thermodynamic VLE Model for AGWA Systems 21 Estimation Results for ChE Constants

22 Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems G1 V12 G2 V6 W2 W1 L12 L6 1 L1 V5 7 2 V4 L8 3 L3 V3 4 L4 Q 3 U1 L6 # Vertices : VLE-ChE Stages 9 L9 # Edges : Connecting Streams, V9 Q Feeds & Products V8 11 V7 L11 V1 6 # Digraph Framework V10 L10 V2 L5 Representation of a Process with Absorption & Stripping Columns for AGWA Systems 8 Esgotamento Absorção L2 V11 L7 22 F1 F2 Q 2 12 U2 L12 L13

23 Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems 23 The Real Process

24 Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems 24 A Typical Simulated Temperature Profile (K) for MEA/MDEA/H2O with CO2/H2S

25 Line 3 : Equilibrium-Staged Rigorous Column Model for Absorption & Stripping with AGWA Systems 25 Typical Simulated Profiles of ChE Constants for MEA/MDEA/H2O with CO2/H2S

26 Line 4: Rigorous Modeling of Membrane Contactors26 with AGWA Solvents for CO2/CH4 Separations Hollow-Fiber Contactor

27 Line 4: Rigorous Modeling of Membrane Contactors27 with AGWA Solvents for CO2/CH4 Separations 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 & ExothermicJ.L.Effects de Medeiros - UFRJ

28 Line 4: Rigorous Modeling of Membrane Contactors28 with AGWA Solvents for CO2/CH4 Separations # 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 TwoPhase Permeate & in Gas Retentate # ChE Constants estimated with a Database from the Literature K1 CO2 + H 2O + MEA CO2 MEA H 2O K2 CO2 + H 2O + MDEA CO2 MDEA H 2O

29 Line 4: Rigorous Modeling of Membrane Contactors29 with AGWA Solvents for CO2/CH4 Separations Typical ChE Behavior of YCO2 vs T&P in the Two-Phase Reactive Permeate

30 Line 4: Rigorous Modeling of Membrane Contactors30 with AGWA Solvents for CO2/CH4 Separations Typical ChE Behavior of YCO2 vs T&P in the Two-Phase Reactive Permeate Good for Absorption of CO2 Good for Stripping of CO2

31 Line 4: Rigorous Modeling of Membrane Contactors31 with AGWA Solvents for CO2/CH4 Separations Rigorous Component Balances for Permeate (Two-Phase) & Retentate (Gas) Permeation Fluxes Expressed in Terms of Fugacity Gradients Rigorous Momentum Balances for Permeate (Two-Phase) & Retentate (Gas) Rigorous Energy Balances for Permeate (Two-Phase) & Retentate (Gas) Temperature Profiles of Permeate & Retentate are Accessed Temperature Increases along Permeate & Retentate Flows No Risk of Gas Condensation

32 Line 4: Rigorous Modeling of Membrane Contactors32 with AGWA Solvents for CO2/CH4 Separations Typical Process Flowsheet with Contactor for CO2 Capture from Natural Gas GN_Contact_1 CGL mrsolv3 MR1 S1 Q2 Q1 MR2 MEA+H2O

33 Line 4: Rigorous Modeling of Membrane Contactors33 with AGWA Solvents for CO2/CH4 Separations Typical Simulated Flowsheet with Contactor : Stream Data

34 Contactor Sample Problem Retentate Flow Rate Profiles 34 77%Mol CH4 3.5%Mol CO2

35 Contactor Sample Problem Permeate %mol for Liquid & Vapor Phases 35

36 Contactor Sample Problem T Profiles for (Two-Phase) Permeate & Retentate 36 Retentate Permeate

37 Contactor Sample Problem Profiles of %Recovery in the Permeate 37

38 38 THANK YOU!

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