Evaluation of amine-incorporated porous polymer networks (aPPNs) as sorbents for post combustion CO2 capture

DOE AWARD NUMBER: DE-FE0026472

08/14/2018 1

Project Overview

2

Research Team• Principle Investigator: Dr. Hong-Cai

“Joe” Zhou• Industrial partners: Koray “Ray”

Ozdemir (framergy)• Team leaders: Jeremy Willman,

Gregory Day• Team members: Elizabeth Joseph,

Hannah Drake, Xinyu Yang, Jialuo Li, Zachary Perry

• Past Members: Dr. Lanfang Zou, Dr. Mathieu Bosch, Dr. Xuan Wang, Dr. Yujia Sun, Dr. Ning Huang

Outline

• Introduction• Objectives• Porous Polymer Networks• PPN-151-DETA

• Sorbent Scale-up• Improving 250 g synthesis• Evaluation of Washing procedure• 1 kg reactor design and scale-up

• Remaining Tasks

3

Project Objectives

• A scalable highly-robust and highly-efficient sorbent that can be delivered and validated through lab-scale testing

• A sorbent that will be economically feasible to scale-up and use in commercial carbon capture processes

• An ideal sorbent for post-combustion CO2 capture that will approach the goal of 90% CO2 capture rate with 95% CO2 purity at a cost of electricity 30% less than baseline capture approaches

4

NH

NH2

NH

N NH2

NH2

NH

HN NH2

NH

HN N

HNH2

(PPN-6-CH2EDA)

(PPN-6-CH2DETA)

(PPN-6-CH2TETA)

(PPN-6-CH2TAEA)

R:CH2R

RH2C

PPN-6-R

Amine-decorated Porous Materials

• Porous Polymer Networks (PPNs)

A. M. Fracaroli, H. Furukawa, M. Suzuki, M. Dodd, S. Okajima, F. Gándara, J. A. Reimer, O. M. Yaghi, J. Am. Chem. Soc., 2014, 136, 8863-8866.McDonald, T. M.; Long, J. R., Nature 2015, 519 (7543), 303-308.Lu, W.; Sculley, J. P.; Yuan, D.; Krishna, R.; Wei, Z.; Zhou, H.-C., Angew. Chem. Int. Ed. 2012, 51, 7480. 5

Initial PPN Candidate Materials

6

Si

Si

Si

Si

Si

Si

HO OH

OH OHHO

OH

OH

HO OHOH

HO OH

OH

OHHO

Si

CHO

CHO

OHC

OHC

Dioxane/HCl(aq)

100 °C

PPN-60

Br

BrBr

BrBr

Br

alkylamine,

90°C, 48hr

PPN-200-EDAPPN-200-DETAPPN-200-TETAPPN-200-TAEA

Zou, L. et al. CrystEngComm. 2017

Yang, X. et al., Polymer. 2017

NH

N

N

N

NHHN

NH

N

N

N

HNHN

NH

N

N

N

NHN

hexanes

NH2

HN

NH2

NH2

NH

H2N

N

NH

N

HH

H

H

H

NH2N

N N

NH2

H2NNH

N

N

N

HNHN

NH

N

N

N

HNHN

NH

N

N

N

HNHN

DMSO

150°C, 72hr +

PPN-151-DETA

Cyanuric Acid (CA)

7

OHN

N N

OH

HOPPN-151

PPN-151-DETA

+

Tan, M. X., et al. ChemSusChem. 2013, 6, 1186

O

HH+

Diethylenetriamine (DETA)

CA CA

PPN-151 Porosity Measurements

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0

200

400

600

800

0 0.2 0.4 0.6 0.8 1

Qua

ntity

Ads

orbe

d (c

m3 /

g ST

P)

Relative Pressure (P/P0)

N2 Isotherm PPN-151-DETA

0

0.005

0.01

0.015

0.02

0 50 100 150 200 250 300 350

DV/d

wPo

re V

olum

e (c

m3 /

g*Å)

Pore Width (Å)

PPN-151-DETA BJH Pore Size Desorption

BET SA (m2/g) Pore Volume (cm3/g) Average Pore Size (Å)

804 0.784 67.3

0

2

4

6

8

10

12

14

16

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33

CO2

Adso

rptio

n (w

t%)

Cycle Number

PPN-151-DETA CO2 wet gas cycling

PPN-151-DETA Fixed-bed Testing Long-term Wet Cycling

9

0.5

1

1.5

2

2.5

80 90 100 110 120

Rege

nera

tion

Ener

gy

Dem

and

(kJ •

g-1CO

2

Regeneration Temperature (°C)

Regeneration Energy Demand

Regenerative Energy Demand

• Heat of adsorption at 150 mbar CO2 and 40°C:

• PPN-151-DETA: 1.40 MJ/kg CO2

• Heat capacity increases exponentially with higher temperatures

• Regenerative energy demand at 85°C

• PPN-151-DETA: 1.8 MJ/kg CO2

(Typical MEA process: 3.8 MJ/kg CO2)

10

00.5

11.5

22.5

33.5

80 90 100 110 120Heat

Cap

acity

(J•g

-1•°

C-1)

Temperature (°C)

Sorbent Heat Capacity

250 g Scale-up

• The team utilized framergy’s 10 L jacketed solvothermal reactors to scale-up the sorbent synthesis to >250 g

• ~250 g of the sorbent was produced

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Parameter ValueTemperature 150°CTime 5 dayHeadspace ~80%Melamine 201.62 gParaformaldehyde 108.00 gCyanuric acid 15.48 gDimethyl Sulfoxide (DMSO) 2080 mLBET surface area (m2/g) 500

The Importance of Formaldehyde Morphology

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Granular form slows down dissolution, causing inhomogeneity in the polymer and reducing the overall surface area

The initial 250 g syntheses had low BET surface areas and showed a high degree of inhomogeneity

Initial 250 g batch utilizing granular paraformaldehyde

250 g batch utilizing powdered paraformaldehyde

Comparison of BET Surface Area Through Scale-Up

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0100200300400500600700800900

1000

BET

Surf

ace

Area

(m2 /

g)

BET Surface Area of PPN-151

15 g(avg of 5 runs)

250 g

Granular CH2O

9-d

Top

5-d

7-d

9-d

bott

om

Powder CH2O

250 g Scale-up: Processing

• framergy’s Nutsche filter system utilized to wash sorbent (acetone, THF, DCM, methanol)

• For 250 g batch wash with 4 L of each solvent

• Solvent Exchange (heat to 60°C in sealed Nutsche filtration device for 12 hr while agitating) twice with methanol

• Additional 4 L

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Reducing Solvent Washing: Improving Cost of Processing Steps

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0

100

200

300

400

500

600

700

800

900

1000

*Full Wash Acetone THF DCM MeOH MeOH x1 MeOH x2

BET

Surf

ace

Area

(m2 /

g)BET Surface Area of Washed PPN-151

Solvent ExchangeWash

1 kg Scale-Up Reactor

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1 kg Scale-up at Vapor Point

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Reaction Set-up PPN Removal

Parameters and Performance of 1 kg Batch

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0

100

200

300

400

500

0 0.2 0.4 0.6 0.8 1Qua

ntity

Ads

orbe

d (c

m3 /

g ST

P)

Relative Pressure (P/P0)

1 kg batch of PPN-151

02468

10121416

1 2 3

CO2

Upt

ake

(wt%

)

Cycle Number

1 kg PPN-151-DETA Wet Gas Breakthrough Runs

100 mL column cycling

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• Previous Lab scale wet gas testing performed using a 5 mL column

• Long-term cycling tests will be done with 100 mL column

• Multiple thermocouples will inform us on temperature gradients

• Manual testing resulted in non-uniformity of runs.

• Tests will need to be repeated upon instrument repair

02468

10121416

1 2 3 4 5 6 7 8 9 10CO

2Ad

sorp

tion

(wt%

)Cycle Number

Remaining Tasks

• Final cycling tasks require the fabrication of 1.5 L adsorber:• 400 mm double walled column, adsorber stand, heat insulation, larger mass

flow controller and upgrade kit for software integration

• Instrument Manufacturer, Quantachrome Instruments, was recently bought out by Anton Paar USA Inc. delaying fabrication

• DynaSorb BT has also been shipped back for upgrades and repairs

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Summary

• PPN-151-DETA can achieve > 0.1 g/g CO2 loading at large scale• Parameters that have been ignored during lab scale testing can have a large impact

on polymer porosity

• 1 kg synthesis performed in partnership with framergy and Vapor Point• 1 kg batch shows > 0.12 g/g CO2

• Final cycling tests will be performed• 1.5 L adsorber column has been ordered from Anton Paar

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Acknowledgement and Disclaimer

• Acknowledgment: "This material is based upon work supported by the Department of Energy under

Award Number DE-FE0026472."

• Disclaimer: "This report was prepared as an account of work sponsored by an agency of the United States

Government. Neither the United States Government nor any agency thereof, nor any of their employees,

makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy,

completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that

its use would not infringe privately owned rights. Reference herein to any specific commercial product,

process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constituteor imply its endorsement, recommendation, or favoring by the United States Government or any agency

thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the

United States Government or any agency thereof."

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Acknowledgements

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Publications• W. M. Verdegaal, K. Wang, J.

P. Sculley, M. Wriedt and H.-C. Zhou. ChemSusChem, 2016, 9, 636-643.

• Li, H.; Wang, K.; Feng, D.; Chen, Y.-P.; Verdegaal, W.; Zhou, H.-C., ChemSuschem, 2016, 9, 19, 2832-2840.

• Zou, L.; Yang, X.; Yuan, S.; Zhou, H.-C. CrystEngComm,2017.

• Huang, N.; Day, G.; Yang, X.; Drake, H.; Zhou, H.-C. Science China Chemistry, 2017.

• Yang, X.; Zou, L.; Zhou, H.-C. Polymer, 2017.

• Zou, L.; Sun, Y.; Che, S.; Yang, X.; Wang, X.; Bosch, M.; Wang, Q.; Li, H.; Smith, M.; Yuan, S.; Perry, Z.; Zhou, H.-C. Advanced Materials, 2017

• Framergy• Ray Ozdemir

• Vapor Point• Ken Mattheson

• DOE NETL • Project Manager - Andrew Jones