Modeling Energy Performance of

Aqueous MDEA/PZ for CO2 Capture

Peter Frailie
Gary T. Rochelle
The University of Texas at Austin
Luminant Carbon Management Program
TCCS-6
June 16, 2011
Overview
 Why MDEA/PZ?
 MDEA/PZ Aspen Plus® Framework
 Thermodynamics
 Hydraulics
 Kinetics
 Process Modeling
 Absorber
 Intercooling
 Stripper
 Simple stripper vs. 2-Stage Flash
 Conclusions
Why MDEA/PZ?
 High capacity
 7m MDEA/2m PZ0.83 mol CO2/kg solvent
 7m MEA (0.60) 8m PZ (0.76)
 High CO2 Absorption Rate
 kg’ comparable to 8m PZ at 40oC
 Does not exhibit solubility limitations of conc. PZ
 Commercially used for H2 and CH4 treating
 MDEA is less expensive than PZ
Amine Modeling
 Aspen Plus® Modeling - Thermo
 Overall goal: construct 1 model that represents MDEA, PZ and
MDEA/PZ using Aspen Plus® eNRTL method
 Over wide temperature, loading, and amine concentration ranges
 Sequential regression: amineamine/H2Oamine/H2O/CO2
 Minimizes the number of regressed parameters
 Process models more likely to converge
 Improves confidence in parameter values
 Thermodynamically consistent methodology
 Speciation and thermodynamic properties calculated using same set
of thermodynamic parameters
Aspen Plus® Modeling - Thermo
 Incorporated all available experimental data
 CP, VLE, amine volatility, speciation, ∆HABS, pKa,γCO2
 Improves thermodynamic consistency
 Final model utilized 54 independently adjusted
parameters
 MDEA (17), PZ (33), MDEA/PZ (4)
 Focused on operationally significant conditions
 Loading  0.5 and 5 kPa CO2
 Temperature  40 oC to 150 oC
 Amine concentration  35-50 wt%
Aspen Plus® Modeling - Hydraulics
 FORTRAN subroutines used to fit data
 Functions of amine concentration, loading, and
temperature
 Density  Dugas (2009)
 Viscosity Weiland (1998)
 Diffusivity  Dugas (2009)
 Fit over same temperature, loading, and amine
concentration ranges as thermodynamic data
Aspen Plus® Modeling - Kinetics
 Fit using WWC simulation in Aspen Plus® RateSepTM
 Adjusted k0 and EA for select kinetic reactions
 Reactions selected based on predicted speciation
 EA  1 1 
k = k0 exp −  − 
 R  T 298.15 K 
 Final model uses 7 independently adjusted parameters
 3 k0, 3 EA, and D0
CO2 Loading
Amine System Temperature (oC)
(mol/mol alk)
8m PZ 40-100 0.20-0.40
7m MDEA/2m PZ 40-100 0.10-0.26
5m MDEA/5m PZ 40-100 0.18-0.37
 1,3
40oC
Lean Rich
1,2 60oC
80oC
100oC
1,1
Fluxpred/Fluxexp

1,0
∆ = 8m PZ
0,9 ◊ = 7m MDEA/2m PZ
= 5m MDEA/5m PZ
0,8
Erroravg = 6.7%
0,7
0,01 0,1 1 10 100
PCO2 (kPa)
Process Modeling - Absorber
 Absorber Lean
~1.2 kPa CO2 40oC
(90% removal)

L/Lmin=1.1 Column diameter

Intercooling to 40oC 100 kPa set to 80% flood
Mellapak in bottom stage.
250X
12 kPa CO2
40oC
100 kPa Rich
45-55oC
 12
5m MDEA/5m PZ
11
0.24 mol CO2/mol alk
10 Not Intercooled
L/G (mol basis)

4
0 5 10 15 20 25
Absorber Height (m)
 12
5m MDEA/5m PZ
11
0.24 mol CO2/mol alk
10 Not Intercooled
L/G (mol basis)

5
6.4
4
0 5 10 15 20 25
Absorber Height (m)
 12
5m MDEA/5m PZ
11
0.24 mol CO2/mol alk
10 Not Intercooled
L/G (mol basis)

8
7.04
7

6
6.4 11.5 m
5

4
0 5 10 15 20 25
Absorber Height (m)
Capacity (mol CO2/kg H2O + Amine) 1
7m MDEA/2m PZ
0,9
5m MDEA/5m PZ
0,8 Isothermal 8m PZ

0,7

0,6

0,5

0,4
0,1 0.5 1
PCO2 at 40oC (kPa)
Capacity (mol CO2/kg H2O + Amine) 1
7m MDEA/2m PZ
0,9
5m MDEA/5m PZ
0,8 8m PZ

0,7

0,6

Not Intercooled
0,5

0,4
0,1 0.5 1
PCO2 at 40oC (kPa)
Capacity (mol CO2/kg H2O + Amine) 1
7m MDEA/2m PZ
0,9
5m MDEA/5m PZ
Intercooled 8m PZ
0,8

0,7

0,6

Not Intercooled
0,5

0,4
0,1 0.5 1
PCO2 at 40oC (kPa)
Process Modeling - Stripper
 Simple Stripper 40oC
150 bar
Rich Pump 99.9% CO2

Rich conditions 120-150oC

set by absorber 4-14 bar
results Mellapak
HeatX 250X
Cold ∆T = 5oC

Trim Cooler Lean Pump

 40oC
2 Stage Flash 150 bar
99.9% CO2
Rich Pump
HP LP
Rich conditions Flash Flash
set by absorber
results •HP and LP flashes at
HeatX
same temperature
Cold ∆T = 5oC
•Equal vapor flow
rates
Trim Cooler Lean Pump
 Equivalent Work Analysis (0.5 kPa Lean Loading)
Amine Stripper T IC? WEQ, SS WEQ, 2SF Abs Ht
(oC) (kJ/mol CO2) (kJ/mol CO2) (m)
No 36 37.2 14
7m MDEA/2m PZ 120
Yes 33.9 35.2 16
No 36 37.1 10
5m MDEA/5m PZ 120
Yes 33 34.2 17
No 36.6 38.4 11
8m PZ 120
Yes 33.7 35.3 16
No 37.3 38.5 11
8m PZ 150
Yes 33.5 34.6 16

nreboilers
 Ti + 5 K − Tsin k 
Weq = ∑ 0.75 ∗ Qi   + W pumps + Wcomps
i =1  Ti + 5 K 
 Conclusions
 Thermodynamic, hydraulic, and kinetic data can be
simultaneously fit for MDEA, PZ, and MDEA/PZ using
eNRTL model and RateSepTM in Aspen Plus®
 Intercooling significantly improved the capacity of each
solvent tested
 Also improved associated WEQ
 Increased absorber height
 WEQ for 2SF systematically higher (~1.5 kJ/mol CO2) than
that of SS.
 Higher stripper temperature did not necessarily improve
energy performance
 Best WEQ observed for 5m MDEA/5m PZ with an
intercooled absorber
Questions?
 Reaction Rate Constants
→ AmCOO − + BH +
Am + B + CO2 

(kf1) → MDEAH + + HCO3−

MDEA + H 2O + CO2 
(kf2) → PZH + + HCO3−
PZ + H 2O + CO2 
(kf3) → PZH + + PZCOO −
2 PZ + CO2 
(kf4) → MDEAH + + PZCOO −
PZ + MDEA + CO2 
→ H + PZCOO − + PZ (COO )2
2−
(kf5) 2 PZCOO − + CO2 
→ MDEAH + + PZ (COO )2
2−
(kf6) PZCOO − + MDEA + CO2 

 Nine possible amine/base combinations for MDEA/PZ

 Cut down to 6 reactions by analyzing predicted speciation
 12 total parameters (6 k0 and 6 EA) further reduced to 8