A High Efficiency, Ultra-Compact Process For Pre-Combustion CO 2 - - PowerPoint PPT Presentation

SLIDE 1

• Professor Theo Tsotsis, University of Southern California, Los Angeles, CA
• Professor Vasilios Manousiouthakis, University of California, Los Angeles, CA
• Dr. Rich Ciora, Media and Process Technology Inc., Pittsburgh, PA

DE-FOA-0001235

U.S. Department of Energy National Energy Technology Laboratory Office of Fossil Energy November 16, 2015

A High Efficiency, Ultra-Compact Process For Pre-Combustion CO2 Capture

1

SLIDE 2

2

Presentation Outline

• Project Objectives
• Process Description

– Background – Project Technical Approach – Advantages – Challenges

• Progress to Date on Key Technical Issues
• Scope of Work
• Tasks to be Performed

SLIDE 3

3

Overarching Project Objectives:

1. Prove the technical feasibility of the membrane- and adsorption-enhanced water gas shift (WGS) process. 2. Achieve the overall fossil energy performance goals of 90% CO2 capture rate with 95% CO2 purity at a cost of electricity of 30% less than baseline capture approaches.

Key Project Tasks:

1. Design, construct and test the lab-scale experimental MR-AR system.-----USC 2. Select and characterize appropriate membranes, adsorbents and catalysts.-----M&PT, USC 3. Develop and experimentally validate mathematical model.-----UCLA, USC 4. Experimentally test the proposed novel process in the lab-scale apparatus, and complete the initial technical and economic feasibility study. (Budget Period 2).----- M&PT, UCLA, USC

Project Objectives

SLIDE 4

4

Conventional IGCC Power Plant

Background

SLIDE 5

5

Hybrid Adsorbent Membrane Reactor (HAMR)

Background, cont.

 The HAMR combines adsorbent, catalyst and membrane functions in the same unit. Previously tested for methane steam reforming (MSR) and the WGS reaction.  The simultaneous in situ removal of H2 and CO2 from the reactor significantly enhances reactor yield and H2 purity. CO2 stream ready for sequestration.

SLIDE 6

6

CMS Membranes for Large Scale Applications

Background, cont.

M&PT test-unit at NCCC for hydrogen separation CMS membranes and modules

SLIDE 7

7

Hydrotalcite (HT) Adsorbents & Co/Mo-Based Sour Shift Catalysts

Background, cont.

Hydrotalcite Adsorbent:

• The HT adsorbents shown to have a working CO2 capacity of 3-4 wt.% during the

past HAMR studies with the MSR and WGS reactions. Theoretical capacity >16 wt.%.

Co/Mo-Based Sour Shift Catalyst:

• A commercial Co/Mo-based sour shift catalyst has been used in our past and ongoing

lab-scale MR studies (P<15 bar) with simulated coal-derived and biomass-derived

• syngas. Shown to have stable performance for >1000 hr of continuous operation.

SLIDE 8

8

Proposed Process Scheme

Project Technical Approach

 No CGCU (or WGCU) step is required to clean-up the syngas prior to entering the WGS reactor.  No post-treatment absorption step is needed to separate the H2 from CO2.  No CO2 recompression step is needed for its further transport and storage.  Note that the use of 2 HT/AR is for illustrative purposes only. The full process will require more (typically 4) HT/AR in use.

SLIDE 9

9

Proposed MR-AR Process

Project Technical Approach, cont.

 Potential use of a TSA regeneration scheme allows the recovery of CO2 at high pressures.  The MR-AR process overcomes the limitations of competitive singular, stand-alone systems, such as the conventional WGSR, and the more advanced WGS-MR and WGS-AR technologies.

SLIDE 10

10

Our Proposed Process vs. SOTA

Advantages

Key Innovation:

• Highly-efficient, low-temperature reactor process for the WGS reaction of coal-gasifier syngas for

pre-combustion CO2 capture, using a unique adsorption-enhanced WGS membrane reactor (MR- AR) concept.

Unique Advantages:

• No syngas pretreatment required: CMS membranes proven stable in past/ongoing studies to all of

the gas contaminants associated with coal-derived syngas.

• Improved WGS Efficiency: Enhanced reactor yield and selectivity via the simultaneous removal of

H2 and CO2.

• Significantly reduced catalyst weight usage requirements: Reaction rate enhancement (over the

conventional WGSR) that results from removing both products, potentially, allows one to operate at much lower W/FCO (Kgcat/mol.hr).

• Efficient H2 production, and superior CO2 recovery and purity: The synergy created between the

MR and AR units makes simultaneously meeting the CO2 recovery/purity targets together with carbon utilization (CO conversion) and hydrogen recovery/purity goals a potential reality.

SLIDE 11

11

Challenges

Key Technical Challenges Ahead (BP1):

• Modify an existing lab-scale test unit at USC to permit operation at higher

pressure (up to 25 bar).

• Design and incorporate a dedicated AR subsystem.
• Prepare and characterize membranes and adsorbents and validate their

performance at the relevant experimental conditions.

• Validate catalyst performance at the relevant pressure conditions. Verify

applicability of global reaction kinetics.

• Develop and experimentally validate mathematical model.

SLIDE 12

12

Proposed Lab-Scale Experimental System

Challenges, cont.

1 1 1 1 2 2 2 2 3 3 3 3 4 4 4 4 7 7 7 7 6 11 11 12 12 12 12 15 15 15 15 5 5 5 9 9 9 9 14 14 8 8 8 8 13 13 10 10 10 10 10 8 8 Modify an existing MR system at USC (up to 25 bar) Incorporate a dedicated AR subsystem

Adsorption Regeneration

SLIDE 13

Membrane Reactor Multi-scale (Pellet-Reactor Scale) Model

13

2D Representation of control volumes in Membrane Reactor 1D Representation of control volumes in Membrane Reactor

SLIDE 14

Membrane Reactor Multi-scale (Pellet-Reactor Scale) Model

14

1D (pellet radial direction) pellet equations solved at each grid point of the discretized reactor domain (z axis).

SLIDE 15

15

Pellet-Scale Steady-State Model

j-Component Mass Conservation:

( )

( )

,

1 1,

p p p j j s V A f j s rate of mass generation of j rate of addition of mass of by reaction per pellet volume jby diffusion per pellet volume

M r j j N ρ ε ε = − − ∇⋅ =          

Dusty-gas model (DGM) :

( ) ( )

, , , , 3 3 3 3 2 (1,1)* 2

1 1 4 2 2 3 3 3 2 16 16

eff iK eff ij

p p j p p p p p Tot

• i

f j f j f j f f j p p p f j pore V B ij B ij V V i ji ji ji D D

x m B x m j x P j M d RT k T m k T m M p p γ ε π π ε ε τ π τ πσ τ πσ     −∇ = + ∇ + −                           Ω Ω                

, 1 (1,1)*

eff ij

i p f i ji D

j                      

∑

    

Energy Conservation:

( )

( )

, , 1

1 . 1

s

N p p p p p p p p A s A f A f j f j j j rate of energy addition by heat conduction per volume rate of energy addition by species mass fluxes per volume

k k T h j M ε ε ε

=

    = ∇ − + ∇ − ∇⋅       

∑

               

( )

, ,

. .

surface r r f j f j

B C x x at S =

( )

. .

surface p p

B C T T at S =

SLIDE 16

1-D Reactor-Scale Steady-State Model

16

j-Component Mass Conservation:

( )

r r A f f

v ε ρ = ∇⋅     Total mass conservation:



( ) ( ) ( ) ( )

2 3 3 2

1 1 150 1.75

r r V V r r r r r f f f f r r rate of pressure drop V p V p inside reactor drag exerted by the fluid on the solid surface per volume

P v v d d ε ε µ ρ ε ε   − −   ∇ = − −              

Momentum conservation:

( ) (

)

( )

( )

, ,

1

r r r j j j s V A f j rate of production of mass of net rate of addition of mass of j by reaction per volume jby diffusion per vo r r r A f j f f net rate of addition of mass of j by convection per volume

M r j x v η ρ ε ε ε ρ − − ∇⋅ ∇ ⋅ =            

( )

2, 2,

2 2

, exp 1 2

lume j a H o r j n n H r H p mem rate of addition of mass of j by permeation per volume

if j H E B if j H R T P P R λ λ δ   −       ≠     =       − =       ⋅     − −             

( )

( )

2

. . , ,

R R r r f f in in

B C v v P P at S = =    

3 4 R f

v at S and S ∇ =    

( )

, , 2

. .

r r f j f j in

B C x x at S =

SLIDE 17

1-D Reactor-Scale Steady-State Model

17

Maxwell-Stefan Equation:

( )

( ) (

) ( )

, , , , , , , , , 3 3 3 3 1 1 , , 2 (1,1)* 2 (1,1)*

2 2 3 3 16 16

s s

r r r r T N N T r r f j f i f j f i j r r r r r i f j f i f j f j f j r r r r r r j j f i f j B ij B ij r V V f ji ji ji ji

x x x x D D P T x v v w x P w w T k T m k T m p p π π ε ε ρ τ πσ τ πσ

= =

      ∇ ∇ ∇ = − + + −                     Ω Ω    

∑ ∑

           

( )

( )

( )

( )

s r r p r r r I A f rate of energy addition by heat rate of energy addition by heat conduction per vo convection per volume r r r r A f f f rate of energy addition by convective transport perunit volume

h T T k T h v ε ε ε ρ − + ∇⋅ ∇ ∇⋅ =               

( )

, , 1 1

1 4 4

s

N r r r A f j f j j j lume rate of energy addition by species mass fluxes per volume r W mem t rate of energy addition between reaction zone and external wall per volume

h j M d U U T T d d ε

=

  − ∇⋅ −       − − −

∑

               

( )

2 r perm t rate of energy addition between reaction zone and internal wall per volume

T T               −           

Energy Conservation:

( )

2 7

. .

r r in r

B C T T at S T at S = ∇ =  

SLIDE 18

18

2-D Reactor-Scale Steady-State Model

j-Component Mass Conservation:

( ) (

)

( )

( )

, ,

1

r r r r r r r A f j f f j j j s V A f j rate of production of mass of j net rate of addition of mass of net rate of addition of mass of by reaction per volume j by convection per volume jby diffusion pe

x v M r j ε ρ η ρ ε ε ∇ ⋅ = − − ∇⋅                 1,

s r volume

j N =   

( )

, , 2

. .

r r f j f j in

B C x x at S =

( ) (

)

( ) ( ) (

)

2, 2,

2 , 4 2 , 3

exp , 1

m

a H o r e j r r r n n f j f f H r H p j p r r r f j f f

E B P if j H R T x v P P at S if j H d x v at S λ ρ λ δ ρ   −   ≠   ⋅   ∇ ⋅ = − =   =   ∇ ⋅ =        

SLIDE 19

19

2-D Reactor-Scale Steady-State Model

( )

2

. . ,

r r in

B C T T at S =

( )

( )

( )

( )

s r r r r r r p r r r A f f f I A f rate of energy addition by heat rate of energy addition by convective rate of energy addition by heat conduction per vo transport perunit volume convection per volume

h v h T T k T ε ρ ε ε ∇⋅ = − + ∇⋅ ∇               

, , 1

1

s

N r r r A f j f j j j lume rate of energy addition by species mass fluxes per volume

h j M ε

=

  − ∇⋅     

∑

           

Energy Conservation:

( ) ( )

1 150

T r r r r r r r r r A f f f V V f f f rate of momentum addition rate of momentum addition by molecular transport per volume by convection per volume

v v P v v ε ε ρ ε ε µ −     ∇ ⋅ = − ∇ −∇⋅ ∇ + ∇ + −                                  

( ) ( ) ( ) ( )

2 2 2 2

1 1.75

r r V V r r r r f f f f r r V p V p drag exerted by the fluid on the solid surface per volume

v v d d ε µ ρ ε ε   −   −           

( )

( )

2

. . , ,

R R r r f f in in

B C v v P P at S = =    

Momentum Conservation:

3 4

. .

R f

B C v at S and S ∇ =    

( )

( )

( )

( )

1 4 3 2

. 4 , 4

r r r r perm r r r r W mem f f f f f f t t

B C d U U h v T T at S h v T T at S d d ρ ρ ∇⋅ = − ∇⋅ = −        

SLIDE 20

1-D Steady-State Permeation Zone Model

20

j-Component Mass Conservation :

( ) (

)

( )

2, 2,

2 2

exp 2 , 1

a H o r M M M n n i i H r H p i mem rate of addition of mass of i by rate of addition of mass of j by permeation per volume convection per volum

E B if i H R T x v P P if i H R λ ρ λ δ   −   ≠   ⋅   ∇ ⋅ = − =   =            

Momentum Conservation:

( ) ( )

T M M M M M M M rate of momentum addition rate of momentum addition by molecular transport per volume by convection per volume

v v P v v ρ µ     ∇ ⋅ = −∇ −∇⋅ ∇ + ∇                             

Energy Conservation:

( )

( )

1

1

s

N M M M M M M M i j j rate of energy addition by heat rate of energy addition by convective conduction per volume rate of energy addition by species transport perunit volume m

h v k T h j M ρ

=

  ∇⋅ = ∇⋅ ∇ − ∇⋅     

∑

                   

( )

1 2

4

perm r mem t rate of energy addition between reaction zone and internal ass fluxes per volume wall per volume

d U T T d − −       

( )

( )

1

. . , ,

M M M M in in

B C v v P P at S = =  

( )

1

. .

M M i i in

B C x x at S =

( )

1 6

. .

M M in M

B C T T at S T at S = ∇ =  

SLIDE 21

21

2-D Steady-State Permeation Zone Model

j-Component Mass Conservation:

( )

1

. . ,

M M i i in

B C x x at S =

( ) (

)

M M M M M i i rate of addition of mass of i by rate of change of mass of convection per volum i per volume

x x v t ρ ρ ∂ = ∇ ⋅ ∂           ( ) (

)

( )

2, 2, 2

2 5 2

. . exp , 1

m

a H o r e j M M n n i f H r H p H j p

B C E B P if j H R T x v P P J at S if j H d λ ρ λ δ   −   ≠   ⋅   ∇ ⋅ = − = =   =     

SLIDE 22

22

2-D Steady-State Permeation Zone Model

( ) ( )

T M M M M M M M rate of momentum addition rate of momentum addition by molecular transport per volume by convection per volume

v v P v v ρ µ     ∇ ⋅ = −∇ −∇⋅ ∇ + ∇                             

Momentum Conservation:

( )

( )

1

1

s

N M M M M M M M i j j rate of energy addition by heat rate of energy addition by convective conduction per volume rate of energy addition by species transport perunit volume m

h v k T h j M ρ

=

  ∇⋅ = ∇⋅ ∇ − ∇⋅     

∑

                   

ass fluxes per volume

   

Energy Conservation:

( )

( )

1 5 6 2

. 4 ,

M M M r perm M mem t

B C d U h v T T at S T at S d ρ ∇⋅ = − ∇ =     

( )

( )

1

. . , ,

M M M M in in

B C v v P P at S = =  

5

. .

R f

B C v at S ∇ =    

( )

1

. . ,

M M in

B C T T at S =

SLIDE 23

23

j-Component Mass Conservation: Energy Conservation:

( )

( ) ( )

( )

( )

1

1 . 1

N a a a a a a a a a a a V s V V f V A s A f A j s j s f j rate of energy addition by heat conduction rate of change of energy per adsorbent volume per adsorbent volume

T C C k k T h R t ε ρ ε ρ ε ε ε ρ

=

∂     − + = ∇ − + ∇ − ∇⋅     ∂               

s

rate of energy addition byadsorption per adsorbent volume

     

∑

   

( )

1/ 1/ , 1

1, , 1, 1

i s

H R T T j j j seq j s j j s N j j j

m b P C j N b b e j N b P

  −∆     −   =

= = = = + ∑

Adsorbing Reactor (AR) Multi-Scale (Adsorbent-Reactor Scale) Model Adsorbent-Scale Dynamic Model

( )

,

1 1,

a f j a a V f j s j V s rate of addition of mass of j rate of change of mass of j by adsorption per adsorbent volume per adsorbent volume

x M R j N t ε ρ ρ ε ∂ = − = ∂       

( )

,

1, ,

j j j seq j j s

dC R k C C j N dt = = − =

SLIDE 24

1-D AR-Scale Dynamic Model

24

j-Component Mass Conservation:

( )

( )

( )

( ) (

) ( )

, , ,

1

PSAR f j PSA PSAR a PSAR PSAR PSAR V V V f A f j f f rate of mass addition of j by rate of change of mass of j pervolume convection per volume PSAR PSAR A f j rate of mass add

x x v t j ε ε ε ρ ε ρ ε ∂ + − + ∇ ⋅ = ∂ = ∇⋅                

( )

1 1,

PSAR j s j V s rate of mass addition of j by ition of jby adsorption per volume diffusion per volume

M R j N ρ ε       + − =                 Momentum Conservation: ( ) ( ) ( ) ( )

2 3 3 2

1 1 150 1.75

PSAR PSAR PSAR V V f PSAR PSAR PSAR PSAR f f f PSAR PSAR PSAR s V p V p drag exerted by the fluid on the solid surface per mass of absorbent

P v v d d ε ε ρ µ ρ ε ε   − −   ∇ = − −           

SLIDE 25

1-D AR-Scale Dynamic Model

25

Energy Conservation:

( )

( )

( )

( )

V PSAR PSAR PSAR PSAR PSAR PSAR V f A f f f f rate of energy addition by convective rate of change of energy transport per mass of adsorbent per mass of adsorbent s PSAR PSAR a I rate of ene

T C h v t h T T ε ρ ε ρ ε ∂ + ∇⋅ = ∂ = −            

( )

1

s

N PSAR PSAR PSAR PSAR A f A j s j j rate of energy addition by heat conduction rgy addition by heat convection per mass of adsorbent rate of energy addition by spec per mass of adsorbent

k T h R ε ε ρ

=

  + ∇⋅ ∇ − ∇⋅   

∑

            

ies per mass of adsorbent

                 

SLIDE 26

2-D AR-Scale Dynamic Model

26

j-Component Mass Conservation:

( )

( )

( )

( ) (

) ( )

, , ,

1

PSAR f j PSAR PSAR a PSAR PSAR PSAR V V V f A f j f f rate of mass addition of j by rate of change of mass of j pervolume convection per volume PSAR PSAR A f j rate of mass ad

x x v t j ε ε ε ρ ε ρ ε ∂ + − + ∇ ⋅ = ∂ = ∇⋅                

( )

1 1,

PSAR j s j V s rate of mass addition of j by dition of jby adsorption per volume diffusion per volume

M R j N ρ ε       + − =                 Momentum Conservation: ( ) ( ) ( ) ( )

2 3 3 2

1 1 150 1.75

PSAR PSAR PSAR V V f PSAR PSAR PSAR PSAR f f f f PSAR PSAR PSAR s V p V p drag exerted by the fluid on the solid surface per mass of absorbent

P v v d d ε ε ρ µ ρ ε ε   − −   ∇ = − −           

SLIDE 27

2-D AR-Scale Dynamic Model

27

Energy Conservation:

( )

( )

( )

V PSAR PSAR PSAR PSAR PSAR PSAR PSAR PSAR V f A f f f f rate of energy addition by convective rate of change of energy transport per mass of adsorbent per mass of adsorbent PSAR PSAR a I

T C h v t h T T ε ρ ε ρ ε ∂ + ∇⋅ = ∂ = −            

( )

( )

1

s

N s PSAR PSAR PSAR PSAR A f A j s j j rate of energy addition by heat conduction rate of energy addition by heat convection per mass of adsorbent rate of energy addi per mass of adsorbent

k T h R ε ε ρ

=

  + ∇⋅ ∇ − ∇⋅   

∑

            

tion by species per mass of adsorbent

                 

SLIDE 28

Initial and Boundary Conditions

28

Cycle Step

• I. Adsorption step

t=0 at

S

at

1

S

at

2

S

at

3

S

, PSAR f j

x

=0,

j

C =0,

PSAR

T

=(

)

PSAR ambient

T

,

PSAR

P

=(

)

PSAR ambient

P

, PSAR f j

x

=(

)

, surface PSAR f j

x

,

a

T =(

)

surface a

T

, PSAR f j

x

=(

)

, PSAR f j in

x

,

PSAR

T

=(

)

PSAR in

T

,

PSAR

P

=(

)

PSAR in

P

,

PSAR f

v  

=(

)

PSAR f in

v  

, PSAR f j

x ∇  

=0,

PSAR

T ∇  

=0

, PSAR f j

x ∇  

=0,

PSAR

T ∇  

=0

• II. Desorption step

t=0 at

S

at

1

S

at

2

S

at

3

S

, PSAR f j

x

=(

)

, I PSAR f j

x

,

j

C =(

)

I j

C

,

PSAR

T

=(

)

I PSAR

T

,

PSAR

P

=(

)

I PSAR

P

, PSAR f j

x

=(

)

, surface PSAR f j

x

,

a

T =(

)

surface a

T

, PSAR f j

x ∇  

=0,

PSAR

T ∇  

=0

, PSAR f j

x ∇  

=0,

PSAR

T ∇  

=0

, PSAR f j

x ∇  

=0,

PSAR

T ∇  

=0,

PSAR f

v  

=(

)

PSAR f valve

v  

SLIDE 29

Multiple Ceramic Tube Membrane Bundles – versatile, low cost

MPT Core Technology

• 1. Close-Packed Bundles

Single Tubes Example: conventional micro- and ultrafiltration Ex: porous heat exchangers & catalytic membrane reactors Ex: high pressure intermediate temperature gas separations

#1: Packaging individual membrane tubes into commercially viable modules for field use.

Our Core Expertise/Technology

29

• 2. Spaced Bundles

Ceramic Membrane Features

• Inorganic membranes, tubular format
• Ultra-thin film, nanoporous layers
• Flexible bundle packaging; many size

and shape options

• Only US Manufacturer
• 3. Candle Filter Bundles

SLIDE 30

Thin Film Deposition for Pore Size Control

MPT Core Technology

10 μm

Ceramic Substrate

10 μm

Ceramic Substrate Ceramic Substrate

5 μm

Palladium Membrane

5 μm

Carbon molecular sieve (porous, sulfur resistance) Palladium (dense, excellent selectivity)

Others, including zeolites, flourinated hydrocarbons, etc.

Important Features of MPT Inorganic Membranes

• Low cost commercial ceramic support
• High packing density, tube bundle
• Module/housing for high temperature and pressure use

30

#2: Thin film deposition on less-than desirable but low-cost porous tubular substrates Our Core Expertise/Technology

SLIDE 31

Some Typical Performance and Operation Capabilities. CMS Membranes

Progress to Date: CMS Membranes

CMS Performance: 86-Tube Bundles QA/QC Testing Conditions Temperature: 220 to 250oC Pressure: 20 to 50 psig

0.0001 0.0010 0.0100 0.1000 1.0000 200 400 600 800 1,000 1,200 N2 Permeance (with dense tubes) [GPU] Pressure [psig]

Dense Ceramic Tube Sheet (DCT)

High-Pressure Leak Rates

Potted Ceramic/Glass (PCG)

PCG 150C PCG 250C DCT 150C DCT 250C

SLIDE 32

M&P H2 CMS Selective Membranes

Pilot Module Photographs: 3-CMS Membrane Bundles

Membrane Bundle Multiple Bundle Module Multiple Bundles Installed in High-Pressure Module Membrane Bundle Enclosure

SLIDE 33

20 40 60 80 100 120 140 160 200 400 600 800 1,000 1,200 2,000 4,000 6,000 8,000

He/N2 Selectivity [-] He Permeance [GPU] Run Time [hours]

Part ID: Bundle CMS J-1 Temperature: 250oC Pressure: 20 psig

Repack Bundle. Orings Failed

CMS 86-Tube Bundle Long Term Stability (8,000 hrs)

Key Technical Hurdles Focused on Long Term Stability

Progress to Date: CMS Membranes Stability, cont.

33

SLIDE 34

34 Performance stability of multiple-tube CMS membrane bundles during H2 recovery from NCCC slip-stream testing. He and N2 Permeances measured periodically during >400 hr test. Testing Parameters

Membrane 86-tube CMS Operating Conditions T~ 250 to 300oC P~ 200 to 300 psig Pretreatment Particulate trap only, no other gas cleanup. Composition H2 ~ 10 to 30% CO ~ 10% CO2 ~10% N2,H2O ~Balance Trace Contaminants NH3 ~ 1,000ppm Sulfur Species ~ 1,000ppm HCl, HCN, Naphthalenes/Tars, etc.

Membrane Bundle NCCC Slip-Stream Testing: No Gasifier Off-Gas Pretreatment

Progress to Date: CMS Membranes Stability, cont.

NCCC Testing: CMS Membranes Highly Stable in Coal Gasifier Syngas

SLIDE 35

CMS Performance Stability: H2S Removal during NCCC Testing

Testing Parameters

Membrane 86-tube CMS Operating Conditions T~ 250 to 300oC P~ 200 to 300 psig Pretreatment Particulate trap, no

• ther gas cleanup.

Composition H2 ~ 10 to 30% CO ~ 10% CO2 ~10% N2,H2O ~Balance Trace Contaminants NH3 ~ 1,000ppm Sulfur Species ~ 1,000ppm HCl, HCN, Naphthalenes/Tars, etc.

NCCC Slip Stream Testing: H2S Feed and Permeate Composition 35

Progress to Date: CMS Membranes Stability, cont.

SLIDE 36

CMS Performance Stability: Tar-like Species in Gasifier Off-gas

36

Progress: CMS Membranes Stability, cont.

Temperatures ≤230oC Tar or other residue build- up evident Operating Temperatures Above 250oC Required to Prevent Condensation of Tar-like Contaminants Temperatures >250oC No evidence of tar or

• ther residue build-up

SLIDE 37

Effect of Temperature in the Presence of Model Tar Compounds

37

Progress to Date: CMS Membranes Stability, cont.

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 2 4 6 8 10 12 14 16 Naphthalene Exposure [hours] He Permeance [m

3/m 2/hr/bar]

Operating Conditions Temperature: 150oC Pressure: 20 to 30 psig Naphthalene: 0.8vol% Toluene: 6.4vol% Operating Conditions Temperature: 250oC Pressure: 20 to 30 psig He Only

Naphthalene/toluene as model tar and organic vapors

 Membrane fouling occurs at low temperature.  Membrane regeneration can be achieved rapidly at high temperature.

SLIDE 38

CMS Membrane Stability in the Presence of Model Tar Compound

38

Progress to Date: CMS Membranes Stability, cont.

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 2 4 6 8 10 12 14 16 18 20 Naphthalene Exposure [hours] He Permeance [m

3/m 2/hr/bar]

40 55 70 85 100 115 130 145 160 He/N2 Selectivity [-] Operating Conditions Temperature: 250oC Pressure: 20 to 30 psig Naphthalene: 0.8vol% Toluene: 6.4vol%

Membrane performance is stable at high operating temperatures (250oC) in the presence of naphthalene/toluene as model tar and organic vapors compounds.

SLIDE 39

Characterization of the Hydrotalcite (HT) Adsorbents

Progress to Date: Hydrotalcite (HT) Adsorbents

39 The structure of the hydrotalcites (HT) adsorbents Characterization of the hydrotalcites

Aadesh Harale, PhD Thesis, University of Southern California, Los Angeles, CA, USA, 2012.

SLIDE 40

Equilibrium Adsorption (Isotherm) Data & Adsorption Kinetics Data

Progress to Date: Hydrotalcite (HT) Adsorbents, cont.

40 Experimental results with model fits CO2 isotherm data Experimental results with model fits CO2 breakthrough data

• Chem. Eng. Sci.,4126, 62 (2007).

SLIDE 41

Cyclic Adsorption Behavior & Regeneration

Progress to Date: Hydrotalcite (HT) Adsorbents, cont.

41 Effect of cycle number on adsorption capacity of hydrotalcite at 250°C, Pressure = 1 atm CO2 desorption profiles using Argon as a purge gas

• Chem. Eng. Sci., 4126, 62 (2007).

Aadesh Harale, PhD Thesis, University of Southern California, Los Angeles, CA, USA, 2012.

SLIDE 42

CO Conversion and Hydrogen Recovery

Progress to Date: CMS Membrane for WGS-MR

Comparison of Experimental Results vs. Model Predictions for WGS/MR using CMS Membranes

(Co/Mo Sulfided Catalyst)

42

• J. Membr. Sci., 363, 160 (2010);
• Ind. Eng. Chem. Res., 819, 53 (2014).

Temperature (°C): 300 Pressure (atm): 5 Weight of catalyst (g): 12 W/FCO (g-cat.h/mol-CO): 150 -311 Feed Composition H2:CO:CO2:CH4:H2O:H2S 2.6:1:2.14:0.8:1.2:0.05

SLIDE 43

Reject and Permeate Stream Compositions

Progress to Date: CMS Membrane for WGS-MR, cont.

43

• J. Membr. Sci., 363, 160 (2010);
• Ind. Eng. Chem. Res., 819, 53 (2014).

Comparison of Experimental Results vs. Model Predictions for WGS/MR using CMS Membranes

(Co/Mo Sulfided Catalyst)

SLIDE 44

Effect of Pressure on the CO Conversion and Hydrogen Recovery

Progress to Date: CMS Membrane for WGS-MR, cont.

44

• J. Membr. Sci., 363, 160 (2010);
• Ind. Eng. Chem. Res., 819, 53 (2014).

Simulations for WGS/MR using a CMS Membrane under a Coal Gasificatioin Environment

(Co/Mo sulfided Catalyst)

SLIDE 45

45

Budget Period 1 (BP1):

1. Design, construct, and test the lab-scale MR-AR system.

• 2. Select baseline membranes, adsorbents and catalysts from those already

available in-house, and characterize their performance for the proposed application.

• 3. Upgrade and experimentally validate the in-house mathematical model.

Budget Period 2 (BP2):

• 1. Experimentally test the proposed novel process in the lab-scale apparatus using

simulated fuel gas.

• 2. Complete the initial technical and economic feasibility study.

Scope of Work: Key Objectives

SLIDE 46

46 Budget Period 1(BP1):

Task 2.0 - Materials Preparation and Characterization.

Subtask 2.1- Preparation and Characterization of the CMS Membranes at the anticipated process conditions. Subtask 2.2- Preparation and Characterization of Adsorbents and Catalysts.

Task 3.0 - Design and Construction of the Lab-Scale MR-AR Experimental System. Task 4.0 - Initial Testing and Modeling of the Lab-Scale Experimental System.

Subtask 4.1 - Unit Operation Testing. Subtask 4.2 - Mathematical Model Development and Simulations.

Budget Period 2 (BP2):

Task 5.0 - Integrated Testing and Modeling of the Lab-Scale Experimental System.

Subtask 5.1 - Materials Optimization and Scale-up. Subtask 5.2 - Integrated Testing. Subtask 5.3 - Model Simulations and Data Analysis.

Task 6.0 - Preliminary Process Design/Optimization and Economic Evaluation.

Subtask 6.1 - Process Design/Optimization. Subtask 6.2 - Sensitivity Analysis.

Tasks to be Performed

SLIDE 47

47

Project Risks and Mitigation Strategies

Description of Risk Probability (low, moderate, high) Impact (low, moderate, high) Risk Management Mitigation and Response Strategies Technical Risks: Adsorbent not chemically stable in presence of syngas components Moderate High Explore the addition of a warm or cold gas clean-up step into the process design Concerns with the adsorbent’s physical integrity under the

• perating conditions

Moderate Moderate Reduce heating/cooling rates; improve physical strength during preparation via increased binder content. Replace TSA with PSA or hybrid TSA/PSA operation Model does not fit experimental data Low Low Investigate causes of poor fit. Re-evaluate intrinsic system parameters Experimental difficulties with high-pressure reactor

• peration and temperature

control Moderate Moderate Identify and fix leaks; replace malfunctioning valves and high- pressure components; adjust control hardware/software Resource Risks: Equipment malfunction Moderate Moderate Use back-up systems, when available. Repair malfunctioning equipment Personnel performance issues Low Moderate Address/remedy performance issues. Replace personnel, if need arises Delays in delivery of materials from M&PT to USC Low Moderate Improve coordination between M&PT and USC Budgetary issues, i.e., not enough funds to complete a certain Task Low Low Seek DOE guidance and approval for shifting funds from less critical tasks and consolidating certain activities Management Risks: Poor coordination among PI’s Low High Address communication/coordination issues. Increase frequency of meetings and data exchange and coordination IP ownership issues develop Low Moderate Face-to-face meetings among PIs and appropriate administrative

• people. Address/remedy issues and disagreements

SLIDE 48

48

Resource-Loaded Schedule

SLIDE 49

49

Milestone Log

Budget Period ID Task Description Planned Completion Date Actual Completion Date Verification Method 1 a 1 Updated PMP submitted 10/31/2015 PMP document 1 b 1 Kick-off meeting convened 12/31/2015 Presentation file/report documents 1 c 3 Construction of the lab-scale MR-AR experimental system (designed for pressures up to 25 bar) completed 3/31/2016 Description and photographs provided in the quarterly report 1 d 2 Preparation/characterization of the CMS membranes at the anticipated process conditions (up to 300ºC and 25 bar total pressure) completed 6/30/2016 Results reported in the quarterly report 1 e 2 Preparation/characterization of the HT- based adsorbents at the anticipated process conditions (300-450ºC and up to 25 bar total pressure) completed. Adsorbent working capacity, adsorption/desorption kinetics determined. Global rate expression for Co/Mo-based sour shift catalysts at the anticipated process conditions (up to 300ºC and 25 bar total pressure) generated 12/31/2016 Results reported in the quarterly report 1 f 4 MR subsystem testing and reporting of key parameters (permeance, selectivity, catalyst weight, temperature, pressures, residence time, CO conversion, effluent stream compositions, etc.) completed 3/31/2017 Results reported in the quarterly report 1 g 4 AR subsystem testing and reporting of key parameters (adsorbent and catalyst weight, temperatures, pressures, residence time, desorption mode, working capacity, energy demand, effluent stream compositions, etc.) completed 3/31/2017 Results reported in the quarterly report 1 h 4 Mathematical model modifications to simulate the hybrid MR-AR process and validate model using experimental MR and AR subsystem test results completed 3/31/2017 Results reported in the quarterly report

SLIDE 50

50

Milestone Log, cont.

Budget Period ID Task Description Planned Completion Date Actual Completion Date Verification Method 2 i 5 Parametric testing of the integrated, lab- scale MR-AR system and identification

• f optimal operating conditions for long-

term testing completed 9/30/2017 Results reported in the quarterly report 2 j 5 Short-term (24 hr for initial screening) and long-term (>100 hr) hydrothermal and chemical stability (e.g., NH3, H2S, H2O, etc.) materials evaluations at the anticipated process conditions completed 3/31/2018 Results reported in the quarterly report 2 k 5 Integrated system modeling and data analysis completed 3/31/2018 Results reported in the quarterly report 2 l 5 Materials optimization with respect to membrane permeance/selectivity and adsorbent working capacity at the anticipated process conditions (up to 300ºC for membranes and 300-450ºC for adsorbents, and up to 25 bar total pressure) completed 6/30/2018 Results reported in the quarterly report 2 m 5 Operation of the integrated lab-scale MR-AR system for at least 500 hr at the

• ptimal operating conditions to evaluate

material stability and process operability completed 6/30/2018 Results reported in the quarterly report 2 n 6 Preliminary process design and

• ptimization based on integrated MR-AR

experimental results completed 9/30/2018 Results reported in Final Report 2

• 6

Initial technical and economic feasibility study and sensitivity analysis completed 9/30/2018 Results reported in Final Report 1,2 QR 1 Quarterly report Each quarter Quarterly Report files 2 FR 1 Draft Final report 10/31/2018 Draft Final Report file

SLIDE 51

51

Success Criteria

Decision Point Basis for Decision/Success Criteria Completion of Budget Period 1 Successful completion of all work proposed in Budget Period 1. Measurements of membrane permeance for H2, CH4, CO, CO2 both in the absence and presence of H2O, NH3, H2S for full-range of operating temperatures (up to 300ºC) and total pressures (10-25 bar). Creation of Robeson (selectivity vs. permeance) plots. Target range for H2 permeance 1-1.5 m3/m2.hr.bar; Target range for H2/CO selectivity 80-100 Measurement of adsorption/desorption kinetics and working capacity at relevant conditions (300°C<T<450°C, pressures up to 25 bar). Measurement of catalytic kinetics, and the development of global rate expression at relevant conditions (temperatures up to 300ºC and pressures up to 25 bar). Target for working capacity >3 wt% Complete fabrication of the lab-scale apparatus and testing of the individual units (MR or AR) at relevant experimental conditions. Measurements of CO conversion (%), H2 recovery (%) and purity (%), CO2 capture ratio/purity (%) and energy demand for regeneration (kJ/mol CO2). Generation of experimental data sufficient to validate the model. Target for CO conversion >95%; Target for H2 purity >95%; Target for H2 recovery >90%; Target for CO2 purity >95%; Target for CO2 recovery >90%. Completion of simulations of the MR-AR system that indicate its ability to meet the 90% CO2 capture and 95% CO2 purity targets. Submission and approval of a Continuation Application in accordance with the terms and conditions of the

• award. The Continuation Application should include a detailed budget and budget justification for budget

revisions or budget items not previously justified, including quotes and budget justification for service contractors and major equipment items Completion of Budget Period 2 Successful completion of all work proposed in Budget Period 2. Completion of short-term (24 hr) and long-term (>100 hr) hydrothermal/chemical stability evaluations. Membranes/adsorbents are stable towards fuel gas constituents (e.g., NH3, H2S, H2O) at the anticipated process operating conditions. Target <10% decline in performance over 100 hr of testing. Completion of integrated testing and system operated for >500 hr at optimal process conditions. Results of the initial technical and economic feasibility study show significant progress toward achievement

• f the overall fossil energy performance goals of 90% CO2 capture rate with 95% CO2 purity at a cost of

electricity 30% less than baseline capture approaches Submission of updated membrane and adsorbent state-point data tables based on the results of integrated lab- scale MR-AR testing Submission of a Final Report

SLIDE 52

52

Notation

3 3

:

p V

m fluid m pellet ε      

pellet volume void fraction

2 2

:

p A

m permeable surface m total surface ε       pellet area void fraction

2 3 I

m fluid solid interfacial area m reactor ε   −     is the area to volume interfacial factor

, , p pellet r reactor M permeation zone = = =

3

:

f

kg fluid m fluid ρ      

( ) :

p

T K 

: . .

p s

J k m s K       thermal conductivity of solid phase

, 2

; 1, N :

p f j s

kg j j j m s   =   ⋅   

; 1, :

j s

j N η =

density of fluid phase

,

; 1, N :

r f j s

kg j x j kg fluid   =    

mass fraction of the jth species

; 1, :

j s

kg j M j N kmol j   =    

molar mass of the jth species

( )

; 1, :

j s

mol j r j N kg solid s   =     ⋅  

1, :

j s

J h j N mol j   =     

molar enthalpy of jth species

2

: J h m s K     ⋅ ⋅  

heat transfer coefficient between fluid and pellet

( ) :

r

P Pa pressure inside reactor

( ) :

p

d m

diameter of the pellet

( ) :

t

d m

diameter of the reactor tube :

a

J E mol       is the membrane permeability activation energy

2

2

: .

H

kg J m s      

hydrogen flux through the membrane

2 2

: . .

• H

n

mol H B m s Pa      

is the membrane permeability pre-exponential factor

:

m

e

P

mass effective radial Peclet number

:

mem

R

2 , :

H r

P

Hydrogen partial pressure in Reaction zone

2 , :

H p

P

Hydrogen partial pressure in permeation zone mass generation rate of jth species per mass of solid diffusive mass flux of the jth species in pellet

: . .

p s

J k m s K       thermal conductivity of fluid phase

temperature of pellet

:

f

m v s        

velocity of fluid phase

3 3

:

p V

m fluid m reactor ε      

reactor volume void fraction

2 2

:

r A

m permeable surface m total surface ε       reactor area void fraction effectiveness factor of jth species

, 2

; 1, N :

p f j s

kg j j j m s   =   ⋅   

diffusive mass flux of the jth species in reactor selective membrane radius

2

: J U m s K     ⋅ ⋅  

heat transfer coefficient between fluid and reactor external wall

SLIDE 53

53

Notation

; 1, N :

M i s

kg i x j kg fluid   =     1, :

M i s

J h i N moli   =     

temperature of permeation zone

1 2

: J U m s K     ⋅ ⋅  

heat transfer coefficient between fluid and membrane wall

( ) :

t

d m

diameter of permeation zone

( ) :

W

T K  temperature at reactor external wall

( ) :

perm

T K  temperature at membrane wall

( ) :

r

T K  temperature of adsorbent

( ) ( ) :

s p

T K  temperature at pellet surface mass fraction of the ith species in permeation zone

3

:

M

kg fluid m fluid ρ      

density of fluid phase in permeation zone

:

M

m v s       

velocity of fluid phase in permeation zone

( ) :

M

P Pa pressure in permeation zone molar enthalpy of ith species in permeation zone

:

M

J h kg fluid      

enthalpy of fluid in permeation zone

: . .

M

J k m s K      

thermal conductivity of fluid phase in permeation zone

( ) :

p

T K 

, a adsorbent PSAR pressure swelling adsorping reactor = =

3 3

:

p V

m fluid m pellet ε      

adsorbent volume void fraction

2 2

:

p A

m permeable surface m total surface ε       adsorbent area void fraction

( )

v

:

s

J C kg K     ⋅   constant volume heat capacity of the solid phase

,

; 1, N

a f j s

kg j x j kg fluid   =    

mass fraction of the jth species

: .

j

mol R kg adsorbent s     −  

adsorption rate of jth species per kg adsorbent per second

,

:

seq j

mol C kg adsorbent     −  

molar equilibrium concentration of jth species : .

j

mol C kg adsorbent     −  

( )

1 ;

1, :

j s

b Pa j N

−

=

adsorption equilibrium constant of jth species

( )

1 ;

1, :

j

s

b Pa j N

−

= adsorption equilibrium constant of jth species at standard state

( ) :

a

T K  temperature of reactor

3 3

:

PSA V

m fluid m PSA ε      

PSAR volume void fraction

2 2

:

PSA A

m permeable surface m total surface ε       PSAR area void fraction molar concentration of jth species : .

j

mol m kg adsorbent     −   Total adsorbent capacity