A Carbon Molecular Sieve Membrane-Based Reactive

Separation Process for Pre-Combustion CO2 Capture

Mingyuan Cao1, Linghao Zhao1, Dongwan Xu1, Seçgin Karagöz2, Patricia Pichardo2, Richard J. Ciora, Jr.3, Doug Parsley3, Paul K.T. Liu3,

Vasilios I. Manousiouthakis2, and Theodore T. Tsotsis1

1Mork Family Department of Chemical Engineering and Materials Science, University of Southern California; 2Chemical and Biomolecular Engineering Department,

University of California; 3Media and Process Technology, Inc.

Key Technology Components

Multi-Scale MR-AR Model for Process Scale-Up

Technology BackgroundMembrane Reactor Studies

The CMSM employed demonstrated robust and stable performance during the long-term run (>500 hr at T=250°C and P=25 bar)

Adsorption-enhanced WGS membrane reactor (MR-AR) process for

pre-combustion CO2 capture

Advantages

➢ No syngas

pretreatment required

➢ Improved WGS

efficiency

➢ Significantly reduced

catalyst weight usage

requirements

➢ Efficient H2

production, and

superior CO2

recovery and purity

Conventional IGCC Power Plant

Carbon Molecular Sieve (CMS) Membranes

Hydrotalcite (HTC) Adsorbent

High-Pressure Adsorption Isotherm at 250oC

1

10

100

1000

0 50 100 150 200 250 300 350 400 450

Per

mea

nce

[G

PU

]

Cumulative Syngas Exposure Time [hours]

#7 Helium #22 Helium #37 Helium

#7 Nitrogen #22 Nitrogen #37 Nitrogen

He or N2 Test Conditions

Pressure: 20 to 50 psig

Temperature: 230 to 265oC

Part ID He

[GPU]

N2

[GPU]

H2

[GPU]

CO2

[GPU]

H2/N2

[-]

H2/CO2

[-]

HMR-61 578 2.5 550 1.0 219 558

HMR-67 450 1.6 581 2.8 354 211

HMR-68 591 3.0 675 2.7 227 248

MR-70 445 1.5 502 0.7 344 738

HMR-72 500 1.7 602 2.5 359 246

HMR-104 542 1.5 540 2.0 361 270

Lab-Scale Experimental Set-Up

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28

0

1

2

3

4

5

6

7

8

9

10

11

12

Pressure (bar)

Exc

ess

so

rptio

n (

wt%

/g)

Before correcting

After correcting

Co-Mo/Al2O3 Sour-Shift Catalyst

Field-tested at NCCC

Reaction rate data generated and global kinetics model developed

0

10

20

30

40

50

60

70

80

0 20 40 60 80

Sim

ula

ted C

O c

onver

sion

Measured CO conversion

−𝑟𝑐𝑜= 𝐴 𝑒−𝐸𝑅𝑇 𝑝𝑐𝑜

𝑎 𝑝𝐻2𝑂𝑏 𝑝𝑐𝑜2

𝑐 𝑝𝐻2𝑑 1 − 𝛽

𝛽 =1

𝐾𝑒𝑞

൫𝑃𝐶𝑂2 . 𝑃𝐻2 )

൯ሺ𝑃𝐶𝑂 . 𝑃𝐻2𝑂

𝐾𝑒𝑞 = ex p4577.8

𝑇− 4.33

Lab-Scale Experiments

AR Studies

CO in the AR and total MR-AR conversion, and species molar flow rates. (Left Top) AR I,

first cycle, (Right Top) AR II, first cycle, (Left Bottom) AR I, second cycle, (Right Bottom)

AR II, second cycle. Temp.=250 °C, pressure=25 bar, H2O/CO ratio=2.8, W/FCO=55

g·h/mol.

Solid Phase

Fluid Phase

Adsorbent Pellet

Fluid Phase

Catalyst Pellet

Adsorbent PelletCatalyst Pellet

Fluid Phase

Syngas Water

Carbon Depleted Syngas

Carbon Depleted

Syngas

Water

Reaction Zone

Permeation Zone

J,j

Fluid Phase

Pellet

2 2 2CO HO CO H⎯⎯→+ +⎯⎯

Catalyst Pellet

Sweep (H2O)

J,j

J,j

J,j

J,j

J,j

J,j

J,j

CH4, H2, CO, CO2, H2O

2 2 2CO HO CO H⎯⎯→+ +⎯⎯

ADSORPTION

REGENERATION

Water+CO2

Water+CO2

CO2>= 20 bar

CO2 Drying andCompression

CO2 to storage 150 bar

Preliminary TEA - MR-AR IGCC Process Scheme

Field-Scale Study of the MR-AR Process

The MR-AR model accounts for mass/energy balances in the catalyst, sorbent and the reactor fluid phases. The

Dusty-Gas-Model is used to describe membrane transport. It describes well the laboratory data without resorting

to adjustable parameters. It is used in the TEA calculations.

Uky-CAER Gasifier

AcknowledgementThe financial support of the U.S. Department of Energy (FE0026423

and F0037137), the technical guidance and assistance of our Project

Manager Andrew Jones, and helpful discussions with Ms. Lynn

Brickett are gratefully acknowledged. MR-AR Skid