Fundamentals

of Gas Separa2on and CO2 Capture Technology

Developments in Membrane Separa2on

Jennifer Wilcox Department of Energy Resources Engineering RECS Summer School June 19th, 2013

Clean Energy Conversions Team - 2013

Bryce Anzelmo (PhD) Panithita Rochana (PhD) Ekin Ozdogan (PhD) Jiajun He (PhD) Kyoungjin Lee (PhD) Abby Kirchofer (PhD) Ana Suarez Negreira (PhD, ChemE) Mengyao Yuan (PhD)

Beibei Wang (MS) Tao Narakornpijit (MS) Jeremy Homan (UG, Chem) Reza Haghpanah (Post-doc) Dong-Hee Lim (Post-doc) Mahnaz Firouzi (Post-doc) Dawn Geatches (Post-doc) Erik Rupp (Research Assistant)

Agenda

Scale of Emissions Work of Carbon Capture N2-SelecYve Membranes

To Prevent 2 C Warming
Between 2000-2050 if cumulaYve emissions are less than: 1,000 Gt 25% probability global warming beyond 2 C 1,440 Gt 50% probability global warming beyond 2 C
Ref: Allen et al., Nature, 2009

Where were projected to go (BAU): Assuming annual increases: Coal 0.3% Oil 0.9% Natural Gas 2.3% ~ 29 Gt CO2 emieed in 2009 ~ 44 Gt CO2 projected in 2050 1790 cum. Gt CO2 in 2050!
Ref: BP StaYsYcal Rev. of World Energy, 2012

BAU

2009

2050

Expanding the Impact of CCS

BAU - 1790 Gt CO2

1440 Gt CO2 50% probability of 2C 1000 Gt CO2 25% probability of 2C

Scenario Replace Coal w/ NG 90% Capture ( Point Source Electric Sector) 90% Capture (Point Source Electric Sector) + 50% Transport (on-board capture; EV; DAC)

Avoided Cum. Gt CO2 1512 1288 1083

Apprecia2ng the Scale

US populaYon ~311,591,000 CH populaYon - ~ 1,344,130,000 Annual emissions per capita: Flight from SF to Birmingham (via Houston) RT ~ 0.7 tons CO2 Drive Honda Accord ~ 1.5 tons CO2 Drive Honda Civic Hybrid ~ 0.74 tons CO2 Depending on sorbent loading and performance (cycling)
17.5 tons total 150 tons material US ~ 17.5 tons CO2 CH ~ 5 tons CO2

Just the CO2 per person in US!

Just the sorbent + CO2 per person in US!

Capture and Regenera2on are Both Key

Capturing CO2 is only the story MUST regenerate OpYons for usage: Chemical feedstock? Challenge market is small Enhanced oil recovery (aka EOR) Seems to be best near-term opYon Storage Challenges include public percepYon and overcoming risks of potenYal seismic events
Amine Scrubbing - Current State-of-the-Art Technology for Point-Source Capture of CO2

Agenda

Scale of Emissions Work of Carbon Capture N2-SelecYve Membranes

Minimum Work for Separa2on

combined rst and second laws

CO 2 B CO2 B CO 2 CO2 CO 2 C CO2 C CO 2 2 W min = RT [n CO ln( y ) + n ln( y ) + RT n ln( y ) + n ln( y )] ] [ B B B B C C C C CO2 A CO2 A CO2 2 RT [ n CO ln( y ) + n ln( y )] A A A A

Wilcox, Carbon Capture, Springer, 2012

Minimum Work for Separa2on

APS Report, Feasibility of DAC with Chemicals, 2011

Minimum Work
DAC is always ~ 20 kJ/mol CO2, regardless of %capture and purity Reason: capturing less of a given total gas AddiYonal work required due to density changes w/ mixtures of CO2 and N2 95%CO2 + 5%N2: 681 kg/m3 80%CO2 + 20%N2: 343 kg/m3 ~ 0.5 kJ/mol CO2 addiYonal compression energy!

19 17 15 13 11 9 7 5 3 1

Direct Air Capture 19 21 kJ/ mol CO2

Minimum Work (kJ/mol CO2 Captured)

50% capture; 80% purity 75% capture; 80% purity 90% capture; 80% purity 50% capture; 95% purity 75% capture; 95% purity 90% capture; 95% purity 50% capture; 99% purity 75% capture; 99% purity 90% capture; 99% purity

Natural Gas Combus2on 6-9 kJ/mol CO2 Coal Combus2on 5-7 kJ/mol CO2 Coal Gasica2on1- 4 kJ/mol CO2

Ref: Wilcox, Carbon Capture, 2012

0.05

0.1

0.15 0.2 0.25 CO2 Concentra2on

0.3

0.35

0.4

Sherwood Plot for Flue Gas Scrubbing

CalculaYons carried out using IECM, all cases assume 500-MW plant burning Appalachian bituminous, NGCC (477-MW) O&M + annualized capital costs are included in the cost esYmates

Cost and Scale

Process CO2-PCC CO2-NGCC SOx (MS) SOx (LS) NOx Hg Price [$/kg] 0.045 0.059 0.66 2.1 1.1 22000 Concentra2on [mole frac2on] 0.121 0.0373 0.00127 Emissions Cost [kg/day] [1000s $/day] 8.59 x 106 3.01 x 106 8.94 x 104 392 178 59.6 50.4 12.5 21.6

0.000399 (399 ppm) 2.32 x 104 0.000387 (387 ppm) 1.11 x 104 5 x 10-9 (ppb) 0.951

the recovery of potentially valuable solutes from dilute solution is dominated by the costs of processing large masses of unwanted materials.1 -Edwin Lightfoot

Values may change based upon coal-type burned and scrubbing methods; 1EN Lighsoot, MCM Cockrem, What Are Dilute SoluYons, Sep. Sci. Technol., 22(2), 165 (1987)

2nd-Law Eciency Drops with Concentra2on

2 nd
Wmin = Wreal

House, K.Z. et al., Proc. Nat. Acad. Sci., 108(51), 20428-20433 (2011)

Benets of Membrane Processes

Focus is on the more concentrated gas, i.e., N2 DAC, Natural Gas, Coal applicaYons Based primarily upon physical separaYon processes, with CO2 maintaining its linear form throughout separaYon Water does not need to be unnecessarily heated; most solvents are aqueous- based w/ the chemical ~ 30 % RegeneraYon is not required in membrane separaYon In general, the footprint is smaller Membrane Process: Major challenge w/ CO2-selecYve polymers: lack of driving force in ue gas w/ CO2 concentraYon ~ 12 % - consider N2-selecYve membrane instead

Agenda

Scale of Emissions Work of Carbon Capture N2-Selec2ve Membranes

N2-Selec2ve Membrane for Carbon Capture

Flux:

Residue (retentate)

Q = permeability = Diusivity Solubility L = membrane thickness

Feed Permeate

InspiraYon ARPA-E brainstorm session in 2010 Capture CO2 on the high-pressure side of the membrane may lead to cost savings in terms of compression energy Can we do it? Start w/ a literature review

N and O Diusivity in Vanadium Permeability = Diusivity Solubility

1Keinonen et al. Appl. Phys. A 34, 39 (1984); 2Nakajima et al. Philosophical Magazine A 67, 557 (1993). 3Holleck, J. Phys.

Chem. 74, 503 (1970); 4 Fukai and Sugimoto, Adv. In Phys. 34, 263 (1985)

N and O Solubility in Vanadium

Hydrogen solubility in vanadium3

Decreasing ()

1 Henry, J. L., et al. J. Less-Common Metals 25, 39 (1971); 2 Henry, J. L., et al. J. Less-Common Metals 21, 115 (1970); 3Tanaka,

S.; Kimura, H. Trans. JIM 20 (1979).

Theory, Experiments, and Op2miza2on -the team-

Theory and Experiments: OpYmizaYon:
PhD students: Mengyao Yuan, Tao Narakornpijit Post-doc: Reza Haghpanah

PhD students: Ni Rochana, Ekin Ozdogan, Kyoungjin Lee

Poten2al Applica2ons for N2-Selec2ve Membranes

Poten2al Applica2ons: Carbon capture Ammonia synthesis Methane/N2 mixtures Air separaYon (selecYve O2) (IGCC, oxy-combusYon)
N2
Step 1 Adsorp2on Step 2 Dissocia2on

Membrane

N2

N N

Step 3 Bulk Diusion

N H

N N

2 NH3 Goals: Use DFT to provide insight into tuning materials electronic structure for enhanced nitrogen reacYvity Perform permeaYon tests on the Group V materials

PhD students: Ni Rochana, Ekin Ozdogan, Kyoungjin Lee

N2 Dissocia2on is Dicult!
Bond dissociaYon energies N2 ~ 225 kcal/mol; 944 kJ/mol; 9.7eV O2 ~ 119 kcal/mol; 498 kJ/mol; 5.1 eV H2 ~ 104 kcal/mol; 435 kJ/mol; 4.4eV Common N2 dissociaYon catalysts (H-B, ammonia synthesis) Fe, Ru d-band center model (Hammer and Nrskov) provides insight

Density of States
The density of states (DOS) of a system describes the number of states at each energy level that are available to be occupied. Fermi level

occupied

unoccupied

TransiYon metal reacYvity is disYnguished by its d-states, with each transiYon metal having a characterisYc d-band center

d-band Center Model

When bonding and anY-bonding states are formed, bond strength depends on the relaYve occupancy of states Bonding states lled strong bonds; anY-bonding states lled weakening d-band center increases from R to L of periodic table (transiYon metals) both bonding and anY-bonding states are higher from R to L Strength of adsorbate-metal bond increases Why use Fe and Ru for ammonia synthesis? Why not Group V? answer volcano

Hammer and Nrskov, Nature 376 238 (1995); Hammer and Nrskov, Adv. Catal. 45 71-129 (2000)

Material Screening and DFT

1. Surface ac2vity N2 adsorpYon mechanism N2 dissociaYon pathway Comparison to other typical ammonia synthesis catalysts 2. Solubility and Diusivity Atomic N binding mechanism Comparison to atomic H binding 3. Eect of alloying Ru Eect on binding ImplicaYons for permeability

Computa2onal Methodology

VASP (Vienna ab iniYo SimulaYon Package) Density funcYonal theory (DFT) Projector-augmented wave (PAW) potenYal GGA PBE
Bulk vanadium Lattice constant [] 2.98 2.93-2.941 3.0212 3.0243

This study Previous calculation

Experiment

1Mehl and Papaconstantopoulos, Phys. Rev. B 54, 4519 (1996); 2Vitos et al., J., Surf. Sci. 411, 186 (1998); 3Online CRC

Handbook of Chemistry and Physics, 91st ediYon, 2010-2011

Molecular N2 Adsorp2on Energy

V(110) Eads (eV/molecule) = E(surf+N2) [E(surf)+E(N2)] n(N2)

1-top 2-short-bridge (SB) 3-long-bridge (LB) 4-three-fold (TF)

V(111)

strength of N2-metal bond increases

1-top, 2-hcp 3-fcc, 4-bridge
1Grunze, et al., Appl. Phys. A 44, 19 (1987); 2 Bozso, et al. J. Catal. 49, 18 (1977); Ertl et al., Surf. Sci. 114, 515 (1982); 3Sheey

et al., J. Phys. Chem. C 112, 17768 (2008)

Absorp2on of Atomic N in Bulk V

IntersYYal binding

Vanadium: bcc structure

1) O-site

2) T-site

Ebinding (eV/atom) = E(bulk + n N atoms) [ E(bulk) + 0.5n*E(N2) ]

Congura2on

Conc. (at.%) 6.25 6.25

(eV / N) -1.99 -0.90

Ebinding

V16N (O) V16N (T)

Absorp2on of Two N Atoms in Bulk V

1 2 3 4

No.

Congura2on

Conc. (at.%) 12.5 12.5 12.5 12.5

N-N dist. () 2.991 2.499 2.800 4.240

(eV / N) -1.55 -2.10 -2.70 -2.78

Ebinding

1 2 3 4

V16N2 (T,T) V16N2 (O,O) V16N2 (O,O) V16N2 (O,O)

Bader Charge Analysis on V16N2

As V donates its d-electrons to p-state of N, charge is accumulated on N Charge interac2on could explain the strong binding of N in V, as well as the repulsive interacYon between N atoms Strong binding could enhance the solubility. However, too strong binding can lead to a slow diusion process
+0.011 +0.008 +0.011 +0.016 +0.016 +0.005 +0.011 +0.376 -0.002 +0.381 +0.378 +0.011 +0.008

+0.016 +0.376 +0.378

+0.381

+0.381 +0.378 -1.545 +0.381

+0.381

-1.545 +0.381 +0.006 +0.379 +0.008 +0.011

+0.001 +0.380 +0.016 +0.011 +0.008

+0.016

+0.011

+0.016

+0.011

Pauling-Scale ElectronegaYviYes: N = 3.04; V = 1.63; Ru = 2.2

Eect of Ru Addi2on
Pure Vanadium Distance (N-Ru)= 0.5 Distance (N-Ru)= 0.71

-0.09 -0.254 +2.836 -0.255 -0.141 -0.257 -0.255

-0.374 -0.292 +2.710 -0.292 -0.292 -0.292 Ru +3.347

-0.372

-0.235

+3.075 -0.214 -0.174 Ru +3.075 -0.372

Lattice Constant= 3.01 Eb= -2.132 eV Lattice Expansion= 1.01%

Lattice Constant= 3.02 Eb= -0.889 eV Lattice Expansion= 1.34%

Lattice Constant= 3.01 Eb= -1.48 eV Lattice Expansion= 1.01%

H binding in V: O-site = -0.076eV; T-site = -0.280eV

Aboud and Wilcox, J. Phys. Chem. C, 114(24) 10978-10985 (2010); Pauling-Scale Electronegativities: N = 3.04; V = 1.63; Ru = 2.2

Flux Measurements
Test Temperatures: 500C -1000C
Retentate Sweep Gas Feed Gas

Test Pressures: 20 90 psi

Inside of Membrane Holder

Permeate

(Group V metals) (uniformly rigidized sheet of

Membrane Foils

Porous Support (Hastelloy X) Diffusion Barrier

alumina ber and binder)

Membrane Defect Correc2ons

Flux measurements: Argon gas used to correct for pinhole and general leaks in the membrane system Each pure foil is tested at a temperature range of 500C-1000C. At each temperature, feed pressure is changed between 23.4-93.4 psig. Retentate Pressure is kept at 3.4psig Use Knudsen diusion for correcYons:

Nitrogen Permeability measurement

Nitrogen permeability through vanadium is higher by two orders of magnitude than its permeability through niobium. Compare to the hydrogen permeability through Pd membrane (1.610-8 mole/msPa0.5), enhancing the nitrogen permeability by alloying or other techniques is necessary. V has a la{ce constant of 2. 98; Nb has a la{ce constant of .. .

CO2 Permeability measurement

CO2 permeability is lower than nitrogen permeability by ve orders of magnitude in vanadium. CO2 is expected to diuse through the defects in the metals, which is highly limited.

Flux Measurements w/ Gas Mixtures

Niobium (P=90 psi)
Natural gas ue gas
3.00E-04 2.50E-04 N2 Flux (mole/ms) 2.00E-04 1.50E-04 1.00E-04 5.00E-05 0.00E+00 0.001 0.0011 0.0012 0.0013 1/T (K-1) 1.00E-06 5.00E-07 0.00E+00 0.0014

Coal ue gas
2.50E-06 CO2 Flux ((mole/ms) 2.00E-06 1.50E-06 2.50E-04 2.00E-04 1.50E-04 1.00E-04 5.00E-05

4 mol% CO2-96 mol% N2

N2 CO2

15 mol% CO2-85 mol % N2

N2 CO2

8.00E-06 7.00E-06 6.00E-06 5.00E-06 4.00E-06 3.00E-06 2.00E-06 1.00E-06 CO2 Flux ((mole/ms)

N2 Flux (mole/ms)

0.00E+00 0.001

0.0011

0.0012 1/T (K-1)

0.0013

0.00E+00 0.0014

Membrane Surface Arer Permea2on

Scanning Electron Microscopy (SEM) on V membranes
Exposure to high T induces structural changes associated with defect formaYon Gas exposure environments aect crystalline structures

Membrane Surface Arer Permea2on

X-ray Photoelectron Spectroscopy (XPS)
Surface nitride is conrmed by the tail of vanadium 2p spectra O 1s V 2p

V 2p Nitride

V 2p Nitride

Membrane Bulk Arer Permea2on

X-ray Dirac2on (XRD) on V membranes
Bulk vanadium nitride phases formed a}er exposure to N2 at high temperature

Modeling and Op2miza2on

Scope of research Process modeling: Modeling of post-combusYon capture from coal-red power plants using N2-selecYve membranes and their combinaYons with CO2-selecYve membrane Bi-objec2ve op2miza2on: Assessment of the engineering feasibility of using N2-selecYve membranes in large-scale capture applicaYons by simultaneously minimizing energy and membrane surface area requirements, two important indicators of capture costs Six membrane conguraYons have been modeled in MATLAB; Bi-objecYve opYmizaYon was performed by the built-in geneYc algorithm in MATLAB
PhD students: Mengyao Yuan, Tao Narakornpijit Post-doc: Reza Haghpanah

Membrane Congura2ons: N2-Selec2ve Membranes

Feed Permeate Feed N2 Permeate 1 Permeate 2 Retentate 1 Feed N2 Permeate 1 Permeate 2 N2 N2 N2 Retentate 1 Retentate (Product) Cong. 1: Single-stage N2- selecYve membrane

Retentate 2 (Product)

Cong. 2: 2-stage N2- selecYve membranes, with pressurizaYon on 1st-stage feed

Retentate 2 (Product) Cong. 3: 2-stage N2- selecYve membranes, no pressurizaYon on 1st-stage feed

Hybrid Congura2ons: N2- + CO2-Selec2ve Membranes

Feed N2 Permeate 1 Retentate 1 CO2 Permeate 2 (Product) Retentate 1 Feed Permeate 1 N2 Retentate 2 Cong. 4: 1st-stage N2-selecYve membrane with feed pressurizaYon, 2nd-stage CO2- selecYve membrane

Retentate 2 Cong. 5: 1st-stage N2-selecYve membrane with no feed CO2 pressurizaYon, 2nd-stage CO2- selecYve membrane Permeate 2 (Product) Cong. 6: 1st-stage CO2- selecYve membrane with feed pressurizaYon, 2nd-stage N2- selecYve membrane

Feed CO2 Permeate 1

Retentate 1 Retentate 2 (Product) N2

Permeate 2

Pareto Curves of N2-Selec2ve Membrane Congura2ons (100% Capture, 95% Purity)

6 Energy use (GJ/tCO2 captured) 5 4 3 2 1 0 0 120% 100% Energy penalty

Absorp2on

80% 60%

Cong. 1 Cong. 2 Cong. 3

CO2-selec2ve membranes

40% 20%

0% 50,000 100,000 150,000 200,000 250,000 300,000 Membrane surface area (m2)

Pareto Curves of Hybrid Membrane Congura2ons (90% Capture, 95% Purity)

6 Energy use (GJ/tCO2 captured) 5 4 3 2 1 0 0 100% 80% Energy penalty

Absorp2on

60% 40%

Cong. 4 Cong. 5 Cong. 6

CO2-selec2ve membranes 20%

0% 50,000 100,000 150,000 200,000 250,000 300,000 Membrane surface area (m2)

Footprint Comparison
500 MW plant emits 11,000 tons CO2/day and assume capture 90% ( 10,000 tons) Plant size is 0.15 km2 Current SOA amine scrubbing to capture is 0.02 km2 or 13% of the plants land area Membrane surface area
250,000 m2 = 0.025 km2 But its typically shell-in-tube conguraYon Surface area will likely be less than that of a tradiYonal amine scrubbing system

10 8 6 4 2 0 10 8 6 4 2 0 10 8 6 4 2 0 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10

In Summary
Proof of Concept: nitrogen permeates Group V metals, selecYvely over CO2 via a soluYon-diusion mechanism From DFT, atomic N draws signicant charge from V leading to stabilizaYon and bonding in the la{ce Allying with Ru signicantly reduces atomic N stability in V N2-selecYve membranes are likely to have a smaller footprint than CO2- selecYve membranes. The nal size, however, also depends on the surface areato-volume ra2os of the membrane modules. Energy ineciency comes in part from hea2ng and cooling use, which is dictated by the high operaYng temperatures required by the membrane materials. N2-selecYve membranes have shown great potenYal as feed CO2 enrichers for CO2-selecYve membranes.

Next Steps
ConYnue DFT calculaYons to predict alloys for enhanced N2 separaYon Work with SwRI to spueer deposit alloys of VRu and NbRu on porous stainless steel supports Work with Dr Steve Paglieri (TDA) to assist in tubular reactor design to make materials tesYng easier Measure N2 and CO2 uxes of alloys and compare to pure Carry out opYmizaYon calculaYons on natural gas systems; consider applying membrane before the expansion in the gas turbine

Acknowledgements
Helpful Discussions: Dr Steve Paglieri, TDA Research
NAMS, 2013

Funding: Experiments: NSF Eager, Catalysis Division; EPA P3 (high-T furnace); Army Research Oce DFT: NSF Teragrid, UT AusYn

Addi2onal Informa2on:
From Springer site: hep://www.springer.com/chemistry/book/ 978-1-4614-2214-3 Clean Energy Conversions Website: hep://cec-lab.stanford.edu/

Gigaton Challenge Think Outside the Box!

dont worry.. Youll sTll graduate and nd a job

Ekin Ozdogan, PhD 2013

Shell, Research Engineer, Process EvaluaYons Houston, TX

Ni Rochana, PhD 2013

PTT, Research Engineer, Business Development Bangkok, Thailand

Ques2ons?

Clean Energy Conversions Website: hep://cec-lab.stanford.edu 24th, 2012 Shell Technical Day, October