A High Efficiency, Ultra -Compact Process For Pre ... · November 16, 2015. A High Efficiency,...

•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 EnergyNational Energy Technology Laboratory

Office of Fossil EnergyNovember 16, 2015

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

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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

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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% CO2purity 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 theinitial technical and economic feasibility study. (Budget Period 2).----- M&PT, UCLA, USC

Project Objectives

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Conventional IGCC Power Plant

Background

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Hybrid Adsorbent Membrane Reactor (HAMR)

Background, cont.

The HAMR combines adsorbent, catalyst and membrane functions in the same unit. Previouslytested for methane steam reforming (MSR) and the WGS reaction.

The simultaneous in situ removal of H2 and CO2 from the reactor significantly enhances reactoryield and H2 purity. CO2 stream ready for sequestration.

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CMS Membranes for Large Scale Applications

Background, cont.

M&PT test-unit at NCCC for hydrogen

separation

CMS membranes and modules

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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-derivedsyngas. Shown to have stable performance for >1000 hr of continuous operation.

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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.

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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.

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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 ofH2 and CO2.

• Significantly reduced catalyst weight usage requirements: Reaction rate enhancement (over theconventional WGSR) that results from removing both products, potentially, allows one to operate atmuch lower W/FCO (Kgcat/mol.hr).

• Efficient H2 production, and superior CO2 recovery and purity: The synergy created between theMR and AR units makes simultaneously meeting the CO2 recovery/purity targets together withcarbon utilization (CO conversion) and hydrogen recovery/purity goals a potential reality.

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Challenges

Key Technical Challenges Ahead (BP1):

• Modify an existing lab-scale test unit at USC to permit operation at higherpressure (up to 25 bar).

• Design and incorporate a dedicated AR subsystem.

• Prepare and characterize membranes and adsorbents and validate theirperformance at the relevant experimental conditions.

• Validate catalyst performance at the relevant pressure conditions. Verifyapplicability of global reaction kinetics.

• Develop and experimentally validate mathematical model.

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Proposed Lab-Scale Experimental System

Challenges, cont.

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Modify an existing MR system at USC (up to 25 bar)

Incorporate a dedicated AR subsystem

Adsorption

Regeneration

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

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).

15

Pellet-Scale Steady-State Modelj-Component Mass Conservation:

( ) ( ),0 1 1,p p pj j s V A f j s

rate of mass generation of j rate of addition of mass ofby reaction per pellet volume jby diffusion per pellet volume

M r j j Nρ ε ε= − − ∇⋅ =

Dusty-gas model (DGM) :

( ) ( ), , , ,3 33 3

2 (1,1)* 2

1 14 2 23 3

3 2 16 16effiK eff

ij

ppjp p p p pTot o i

f j f j f j f f jp p pf jporeV B ij B ijV Vi

ji ji jiD

D

xm B xm j x P jMd RT k T m k T m

M p p

γε π πε ετ π τ πσ τ πσ

−∇ = + ∇ + − Ω Ω

,1

(1,1)*

effij

ipf i

ji

D

j

∑

Energy Conservation:

( )( ) , ,1

10 . 1sN

p p p p p p p pA s A f A f j f j

j jrate of energy addition by heat conduction

per volume rate of energy addition by species massfluxes per volume

k k T h jM

ε ε ε=

= ∇ − + ∇ − ∇⋅

∑

( ), , 0

. .surfacer r

f j f j

B C

x x at S=

( ) 0

. .surfacep p

B C

T T at S=

1-D Reactor-Scale Steady-State Model

16

j-Component Mass Conservation:

( )0 r rA f fvε ρ= ∇ ⋅

Total mass conservation:

( )( )

( )( )

2

3 32

1 1150 1.75

r rV Vr r r r r

f f f fr rrate of pressure drop V p V pinside reactor

drag exerted by the fluid on the solid surface per volume

P v vd d

ε εµ ρ

ε ε

− − ∇ = − −

Momentum conservation:

( ) ( )

( ) ( ),

,

1 r r rj j j s V A f j

rate of production of mass of net rate of addition of mass ofj by reaction per volume jby diffusion per vor r rA f j f f

net rate of addition of mass ofj by convection per volume

M r j

x v

η ρ ε ε

ε ρ

− − ∇⋅

∇ ⋅ =

( )2, 2,

2

2

0,

exp 12

lume

jaH o r

j n nH r H p

mem

rate of addition of mass of j by permeation per volume

if j HEB if j H

R T P PR

λλ

δ

− ≠ = − = ⋅ − −

( ) ( ) 2

. .

, ,R R r rf f inin

B C

v v P P at S= =

3 40Rfv at S and S∇ =

( ), , 2

. .r rf j f j in

B C

x x at S=


17

Maxwell-Stefan Equation:

( )( ) ( )

( ), , , ,

, , , , ,3 33 31 1 , ,

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

2 23 316 16

s sr r r r TN N Tr rf j f i f j f i jr r r r r i

f j f i f j f j f j r r r rr rj j f i f j

B ij B ijrV Vf

ji ji ji ji

x x x x DDP Tx v v w xP w w Tk T m k T m

p p

π πε ερτ πσ τ πσ

= =

∇ ∇∇ = − + + −

Ω Ω

∑ ∑

( )

( )( ) ( )sr r p r r rI A f

rate of energy addition by heatrate of energy addition by heatconduction per voconvection per volume

r r r rA f f f

rate of energy addition by convectivetransport per unit volume

h T T k T

h v

ε ε

ε ρ

− + ∇⋅ ∇

∇⋅ =

( )

, ,1

1

1

4 4

sNr r rA f j f j

j j

lume rate of energy addition by speciesmass fluxes per volume

r W mem

t

rate of energy addition betweenreaction zone and external

wall per volume

h jM

d UU T Td d

ε=

− ∇ ⋅ −

− − −

∑

( )2

r perm

t

rate of energy addition betweenreaction zone and internal

wall per volume

T T

−


( ) 2

7

. .

0

r r

in

r

B C

T T at S

T at S

=

∇ =

18



( ) ( ) ( ) ( ), ,1r r r r r r rA f j f f j j j s V A f j

rate of production of mass of jnet rate of addition of mass of net rate of addition of mass ofby reaction per volumej by convection per volume jby diffusion pe

x v M r jε ρ η ρ ε ε∇ ⋅ = − − ∇ ⋅

1, s

r volume

j N=

( ), , 2

. .r rf j f j in

B C

x x at S=

( ) ( ) ( )

( ) ( )2, 2,

2, 4

2

, 3

exp 0,

1

0

m

aH o r

e jr r r n nf j f f H r H p j

p

r r rf j f f

EBP if j HR Tx v P P at Sif j Hd

x v at S

λρ λ

δ

ρ

− ≠ ⋅ ∇ ⋅ = − = =

∇ ⋅ =

19


( ) 2

. .

,r r

in

B C

T T at S=

( ) ( )( ) ( )sr r r r r r p r r rA f f f I A f

rate of energy addition by heatrate of energy addition by convective rate of energy addition by heatconduction per votransport per unit volume convection per volume

h v h T T k Tε ρ ε ε∇ ⋅ = − + ∇ ⋅ ∇

, ,

1

1sNr r rA f j f j

j j

lume rate of energy addition by speciesmass fluxes per volume

h jM

ε=

− ∇ ⋅

∑


( ) ( ) 1150

Tr r r r r r r r rA f f f V V f f f

rate of momentum addition rate of momentum addition by molecular transport per volumeby convection per volume

v v P v vε

ε ρ ε ε µ− ∇ ⋅ = − ∇ −∇⋅ ∇ + ∇ + −

( )( )

( )( )

2

2 22

11.75

r rV Vr r r r

f f f fr rV p V p

drag exerted by the fluid on the solid surface per volume

v vd d

εµ ρ

ε ε

− −

( ) ( ) 2

. .

, ,R R r rf f inin

B C

v v P P at S= =

Momentum Conservation:

3 4

. .

0Rf

B C

v at S and S∇ =

( ) ( ) ( ) ( )14 32

.

4 , 4r r r r perm r r r r Wmemf f f f f f

t t

B Cd U Uh v T T at S h v T T at S

d dρ ρ∇⋅ = − ∇ ⋅ = −

1-D Steady-State Permeation Zone Model

20

j-Component Mass Conservation :

( ) ( ) ( )2, 2,

2

2

exp 02 ,1

aH o r

M M M n nii H r H p i

memrate of addition of mass of i by rate of addition of mass of j by permeation per volumeconvection per volum

EB if i HR Tx v P Pif i HR

λρ λδ

− ≠ ⋅ ∇ ⋅ = − = =


( ) ( )TM M M M M M M


v v P v vρ µ ∇ ⋅ = −∇ −∇⋅ ∇ + ∇


( ) ( )1

1sNM M M M M M M

ij j

rate of energy addition by heatrate of energy addition by convectiveconduction per volume rate of energy addition by speciestransport per unit volume

m

h v k T h jM

ρ=

∇ ⋅ = ∇ ⋅ ∇ − ∇⋅

∑

( )1

24 perm rmem

t

rate of energy addition betweenreaction zone and internalass fluxes per volume

wall per volume

d U T Td

− −

( ) ( ) 1

. .

, ,M M M M

inin

B C

v v P P at S= =

( ) 1

. .M Mi i in

B C

x x at S=

( ) 1

6

. .

0

M M

in

M

B C

T T at S

T at S

=

∇ =

21



( ) 1

. .

,M Mi i in

B C

x x at S=

( ) ( )M

M M M Mii

rate of addition of mass of i byrate of change of mass ofconvection per volumi per volume

x x vt

ρ ρ∂= ∇ ⋅

∂

( ) ( ) ( )2, 2, 2

25

2

. .

exp 0,

1m

aH o r

e jM M n ni f H r H p H j

p

B CEBP if j HR Tx v P P J at S

if j Hdλ

ρ λδ

− ≠ ⋅ ∇ ⋅ = − = = =

22


( ) ( )TM M M M M M M


v v P v vρ µ ∇ ⋅ = −∇ −∇⋅ ∇ + ∇


( ) ( )1

1sNM M M M M M M

ij j

rate of energy addition by heatrate of energy addition by convectiveconduction per volume rate of energy addition by speciestransport per unit volume

m

h v k T h jM

ρ=

∇ ⋅ = ∇ ⋅ ∇ − ∇⋅

∑

ass fluxes per volume


( ) ( )15 62

.

4 , 0M M M r perm Mmem

t

B Cd Uh v T T at S T at S

dρ∇⋅ = − ∇ =

( ) ( ) 1

. .

, ,M M M M

inin

B C

v v P P at S= =

5

. .

0Rf

B C

v at S∇ =

( ) 1

. .

,M M

in

B C

T T at S=

23



( ) ( ) ( ) ( )( )1

1 . 1Na

a aa a a a a a a aV s V V f V A s A f A j s js f

jrate of energy addition by heat conductionrate of change of energy per adsorbent volume

per adsorbent volume

TC C k k T h Rt

ε ρ ε ρ ε ε ε ρ=

∂ − + = ∇ − + ∇ − ∇⋅ ∂

s

rate of energy addition by adsorptionper adsorbent volume

∑

( )01/ 1/0,

1

1, , 1,1

i

s

HR T Tj j j

seq j s j j sN

j jj

m b PC j N b b e j N

b P

−∆ −

=

= = = =+∑

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

Adsorbent-Scale Dynamic Model

( ), 1 1,af ja a

V f j s j V s

rate of addition of mass of jrate of change of mass of j by adsorption per adsorbent volumeper adsorbent volume

xM R j N

tε ρ ρ ε

∂= − =

∂

( ), 1, ,jj j seq j j s

dCR k C C j N

dt= = − =

1-D AR-Scale Dynamic Model

24


( )( )( ) ( ) ( )

( )

,,

,

1PSARf jPSA PSAR a PSAR PSAR PSAR

V V V f A f j f f

rate of mass addition of j byrate of change of mass of j per volumeconvection per volume

PSAR PSARA f j

rate of mass add

xx v

t

j

ε ε ε ρ ε ρ

ε

∂+ − + ∇ ⋅ =

∂

= ∇ ⋅

( )1 1,PSAR

j s j V s

rate of mass addition of j byition of jby adsorption per volumediffusion per volume

M R j Nρ ε

+ − =


( )( )

( )( )

2

3 32

1 1150 1.75

PSAR PSAR PSARV V fPSAR PSAR PSAR PSAR

f f fPSARPSAR PSARsV p V p

drag exerted by the fluid on the solid surface per mass of absorbent

P v vd d

ε ε ρµ

ρε ε

− − ∇ = − −


25


( ) ( )

( )( )

V

PSARPSARPSAR PSAR PSAR PSARV f A f f ff

rate of energy addition by convectiverate of change of energytransport per mass of adsorbentper mass of adsorbent

sPSAR PSAR aI

rate of ene

TC h vt

h T T

ε ρ ε ρ

ε

∂+ ∇ ⋅ =

∂

= −

( )1

sNPSAR PSAR PSAR PSARA f A j s j

jrate of energy addition by heat conductionrgy addition by heat convection

per mass of adsorbent rate of energy addition by specper mass of adsorbent

k T h Rε ε ρ=

+ ∇ ⋅ ∇ − ∇⋅

∑

ies

per mass of adsorbent


26


( )( )( ) ( ) ( )

( )

,,

,

1PSARf jPSAR PSAR a PSAR PSAR PSAR

V V V f A f j f f

rate of mass addition of j byrate of change of mass of j per volumeconvection per volume

PSAR PSARA f j

rate of mass ad

xx v

t

j

ε ε ε ρ ε ρ

ε

∂+ − + ∇ ⋅ =

∂

= ∇ ⋅

( )1 1,PSAR

j s j V s

rate of mass addition of j bydition of jby adsorption per volumediffusion per volume

M R j Nρ ε

+ − =


( )( )

( )( )

2

3 32

1 1150 1.75

PSAR PSAR PSARV V fPSAR PSAR PSAR PSAR

f f f fPSARPSAR PSARsV p V p

drag exerted by the fluid on the solid surface per mass of absorbent

P v vd d

ε ε ρµ

ρε ε

− − ∇ = − −


27


( ) ( )

( )

V

PSARPSARPSAR PSAR PSAR PSAR PSAR PSARV f A f f ff

rate of energy addition by convectiverate of change of energytransport per mass of adsorbentper mass of adsorbent

PSAR PSAR aI

TC h vt

h T T

ε ρ ε ρ

ε

∂+ ∇ ⋅ =

∂

= −

( ) ( )1

sNs PSAR PSAR PSAR PSARA f A j s j

jrate of energy addition by heat conductionrate of energy addition by heat convection

per mass of adsorbent rate of energy addiper mass of adsorbent

k T h Rε ε ρ=

+ ∇ ⋅ ∇ − ∇⋅

∑

tion by species

per mass of adsorbent

Initial and Boundary Conditions

28

Cycle Step I. Adsorption step t=0

at 0S at 1S at 2S at 3S

,PSARf jx =0, jC =0, PSART = ( )PSAR

ambientT , PSARP = ( )PSAR

ambientP

,PSARf jx = ( ),

surfacePSARf jx , aT = ( )surfaceaT

,PSARf jx = ( ),

PSARf j in

x , PSART = ( )PSAR

inT , PSARP = ( )PSAR

inP , PSAR

fv

= ( )PSARf

inv

,PSARf jx∇

=0, PSART∇

=0

,PSARf jx∇

=0, PSART∇

=0

II. Desorption step t=0 at 0S at 1S at 2S at 3S

,PSARf jx = ( ),

IPSARf jx , jC = ( )I

jC , PSART = ( )IPSART , PSARP = ( )IPSARP

,PSARf jx = ( ),

surfacePSARf jx , aT = ( )surfaceaT

,PSARf jx∇

=0, PSART∇

=0

,PSARf jx∇

=0, PSART∇

=0

,PSARf jx∇

=0, PSART∇

=0, PSAR

fv

= ( )PSARf

valvev

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

Thin Film Deposition for Pore Size Control

MPT Core Technology

10 μm

CeramicSubstrate

10 μmCeramic Substrate

CeramicSubstrate

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

Some Typical Performance and Operation Capabilities. CMS Membranes

Progress to Date: CMS Membranes

CMS Performance: 86-Tube BundlesQA/QC Testing ConditionsTemperature: 220 to 250oC

Pressure: 20 to 50 psig

0.0001

0.0010

0.0100

0.1000

1.0000

0 200 400 600 800 1,000 1,200

N2

Perm

eanc

e (w

ith d

ense

tube

s) [G

PU]

Pressure [psig]

Dense Ceramic Tube Sheet (DCT)

High-Pressure Leak Rates

Potted Ceramic/Glass (PCG)

PCG 150CPCG 250CDCT 150CDCT 250C

M&P H2 CMS Selective MembranesPilot Module Photographs: 3-CMS Membrane Bundles

Membrane Bundle

Multiple Bundle Module

Multiple Bundles Installed in High-Pressure Module

Membrane Bundle Enclosure

20

40

60

80

100

120

140

160

0

200

400

600

800

1,000

1,200

0 2,000 4,000 6,000 8,000

He/

N2

Sele

ctiv

ity [-

]

He

Perm

eanc

e [G

PU]

Run Time [hours]

Part ID: Bundle CMS J-1Temperature: 250oCPressure: 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

34Performance 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

Membrane86-tube CMS

Operating ConditionsT~ 250 to 300oC

P~ 200 to 300 psig

PretreatmentParticulate trap only, no other gas cleanup.

CompositionH2 ~ 10 to 30%CO ~ 10%CO2 ~10%N2,H2O ~Balance

Trace ContaminantsNH3 ~ 1,000ppmSulfur Species ~ 1,000ppmHCl, 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

CMS Performance Stability: H2S Removal during NCCC TestingTesting Parameters

Membrane86-tube CMS

Operating ConditionsT~ 250 to 300oC

P~ 200 to 300 psig

PretreatmentParticulate trap, no other gas cleanup.

CompositionH2 ~ 10 to 30%CO ~ 10%CO2 ~10%N2,H2O ~Balance

Trace ContaminantsNH3 ~ 1,000ppmSulfur Species ~ 1,000ppmHCl, HCN, Naphthalenes/Tars, etc.

NCCC Slip Stream Testing: H2S Feed and Permeate Composition

35


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

36

Progress: CMS Membranes Stability, cont.

Temperatures ≤230oCTar or other residue build-

up evident

Operating Temperatures Above 250oC Required to Prevent Condensation of Tar-like Contaminants

Temperatures >250oCNo evidence of tar or

other residue build-up

Effect of Temperature in the Presence of Model Tar Compounds

37


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 2 4 6 8 10 12 14 16

Naphthalene Exposure [hours]

He

Perm

eanc

e [m

3 /m2 /h

r/bar

]

Operating ConditionsTemperature: 150oCPressure: 20 to 30 psigNaphthalene: 0.8vol%Toluene: 6.4vol%

Operating ConditionsTemperature: 250oCPressure: 20 to 30 psigHe Only

Naphthalene/toluene as model tar and organic vapors

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

CMS Membrane Stability in the Presence of Model Tar Compound

38


0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0 2 4 6 8 10 12 14 16 18 20

Naphthalene Exposure [hours]

He

Perm

eanc

e [m

3 /m2 /h

r/bar

]

40

55

70

85

100

115

130

145

160

He/

N2 S

elec

tivity

[-]

Operating ConditionsTemperature: 250oCPressure: 20 to 30 psigNaphthalene: 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.

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 SouthernCalifornia, Los Angeles, CA, USA, 2012.

Equilibrium Adsorption (Isotherm) Data & Adsorption Kinetics Data

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

40

Experimental results with model fitsCO2 isotherm data

Experimental results with model fitsCO2 breakthrough data

Chem. Eng. Sci.,4126, 62 (2007).

Cyclic Adsorption Behavior & Regeneration

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

41

Effect of cycle number on adsorption capacity ofhydrotalcite 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.

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:H2S2.6:1:2.14:0.8:1.2:0.05

Reject and Permeate Stream Compositions

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

43


Comparison of Experimental Results

vs.Model Predictionsfor WGS/MR usingCMS Membranes

(Co/Mo Sulfided Catalyst)

Effect of Pressure on the CO Conversion and Hydrogen Recovery

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

44


Simulations for WGS/MR using

a CMS Membrane under a

Coal GasificatioinEnvironment

(Co/Mo sulfided Catalyst)

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 alreadyavailable in-house, and characterize their performance for the proposedapplication.

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

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

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 operating 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 LowInvestigate causes of poor fit. Re-evaluate intrinsic system parameters

Experimental difficulties with high-pressure reactor operation 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 ModerateUse 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 ModerateImprove 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

48

Resource-Loaded Schedule

49

Milestone Log

Budget Period ID Task Description

Planned Completion

Date

Actual Completion

DateVerification Method

1 a 1 Updated PMP submitted 10/31/2015 PMP document

1 b 1 Kick-off meeting convened 12/31/2015Presentation file/report documents

1c 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

1d 2

Preparation/characterization of the CMS membranes at the anticipated process conditions (up to 300ºC and 25 bar total pressure) completed

6/30/2016Results 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


1f 4

MR subsystem testing and reporting of key parameters (permeance, selectivity, catalyst weight, temperature, pressures, residence time, CO conversion, effluent stream compositions, etc.) completed


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


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


50

Milestone Log, cont.

Budget Period ID Task Description

Planned Completion

Date

Actual Completion

DateVerification Method

2 i 5

Parametric testing of the integrated, lab-scale MR-AR system and identification of optimal operating conditions for long-term testing completed


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 5Integrated system modeling and data analysis completed


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


2 m 5

Operation of the integrated lab-scale MR-AR system for at least 500 hr at the optimal operating conditions to evaluate material stability and process operability completed


2 n 6Preliminary process design and optimization based on integrated MR-AR experimental results completed

9/30/2018Results reported in Final Report

2 o 6Initial technical and economic feasibility study and sensitivity analysis completed

9/30/2018Results reported in Final Report

1,2 QR 1 Quarterly report Each quarterQuarterly Report files

2 FR 1 Draft Final report 10/31/2018Draft Final Report file

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 80-100Measurement 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 of 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 approachesSubmission of updated membrane and adsorbent state-point data tables based on the results of integrated lab-scale MR-AR testingSubmission of a Final Report

52

Notation3

3 :pV

m fluidm pellet

ε

pellet volume void fraction

2

2 :pA

m permeable surfacem total surface

ε

pellet area void fraction

2

3Im fluid solid interfacial area

m reactorε −

is the area to volume interfacial factor

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

3 :fkg fluidm fluid

ρ

( ) :pT K

:. .

ps

Jkm s K

thermal conductivity of solid phase

, 2 ; 1, N :pf j s

kg jj jm s

= ⋅

; 1, :j sj Nη =

density of fluid phase

, ; 1, N :rf j s

kg jx jkg fluid

=

mass fraction of the jth species

; 1, :j skg jM j N

kmol j

=

molar mass of the jth species

( ); 1, :j s

mol jr j Nkg solid s

= ⋅

1, :j sJh j N

mol j

=

molar enthalpy of jth species

2 :Jhm s K

⋅ ⋅

heat transfer coefficient between fluid and pellet

( ) :rP Pa pressure inside reactor

( ) :pd m diameter of the pellet

( ) :td m diameter of the reactor tube

:aJE

mol

is the membrane permeability activation energy

2 2 :.H

kgJm s

hydrogen flux through the membrane

22 :. .oH n

mol HBm s Pa

is the membrane permeability pre-exponential factor

:meP mass effective radial Peclet number

:memR

2 , :H rP Hydrogen partial pressure in Reaction zone

2 , :H pP 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

:. .

ps

Jkm s K

thermal conductivity of fluid phase

temperature of pellet

:fmvs

velocity of fluid phase

3

3 :pV

m fluidm reactor

ε

reactor volume void fraction

2

2 :rA


ε

reactor area void fraction

effectiveness factor of jth species

, 2 ; 1, N :pf j s

kg jj jm s

= ⋅

diffusive mass flux of the jth species in reactor

selective membrane radius

2 :JUm s K

⋅ ⋅

heat transfer coefficient between fluid and reactor external wall

53

Notation

; 1, N :Mi s

kg ix jkg fluid

=

1, :Mi s

Jh i Nmol i

=

temperature of permeation zone1 2 :JU

m s K ⋅ ⋅

heat transfer coefficient between fluid and membrane wall

( ) :td m diameter of permeation zone

( ) :WT K temperature at reactor external wall

( ) :permT K temperature at membrane wall

( ) :rT K

temperature of adsorbent

( ) ( ) :spT K temperature at pellet surface

mass fraction of the ith species in permeation zone

3 :M kg fluidm fluid

ρ

density of fluid phase in permeation zone

:M mvs

velocity of fluid phase in permeation zone

( ) :MP Pa pressure in permeation zone

molar enthalpy of ith species in permeation zone

:M Jhkg fluid

enthalpy of fluid in permeation zone

:. .

M Jkm s K

thermal conductivity of fluid phase in permeation zone

( ) :pT K

,a adsorbent PSAR pressure swelling adsorping reactor= =

3

3 :pV

m fluidm pellet

ε

adsorbent volume void fraction

2

2 :pA


ε

adsorbent area void fraction

( )v :s

JCkg K

⋅ constant volume heat capacity of the solid phase

, ; 1, Naf j s

kg jx jkg fluid

=

mass fraction of the jth species

:.j

molRkg adsorbent s

−

adsorption rate of jth species per kg adsorbent per second

, :seq jmolC

kg adsorbent −

molar equilibrium concentration of jth species

:.j

molCkg adsorbent

−

( )1 ; 1, :j sb Pa j N− = adsorption equilibrium constant of jth species

( )0 1 ; 1, :j sb Pa j N− =

adsorption equilibrium constant of jth species at standard state

( ) :aT K

temperature of reactor

3

3 :PSAV

m fluidm PSA

ε

PSAR volume void fraction 2

2 :PSAA


ε

PSAR area void fraction

molar concentration of jth species

:.j

molmkg adsorbent

−

Total adsorbent capacity

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