Exploration of Aqueous Amine Solutions for CO Capture using … · 2015. 11. 18. · The Second...

The Second Project Report Meeting of the HPCI System Including K Computer(Miraikan, National Museum of Emerging Science and Innovation, October 26, 2015)

Exploration of Aqueous Amine Solutions for CO2 Capture using Chemical Reaction Simulations

Hiromi Nakai a-d

a Research Institute of Science & Engineering, Waseda Universityb School of Advanced Science & Engineering, Waseda University

c JST-CRESTd ESICB, Kyoto University

hp140164

2nd Project Report Meeting of the HPCI System (Miraikan, October 26, 2015)

Project Member (hp140164)

Dr. Masato Kobayashi (Waseda U → Hokkaido U)

Prof. Stephan Irle (Nagoya U)

－－－－－－－－－－－－－－－－－－－－－－－－－

Dr. Yoshifumi Nishimura(IMS, Waseda U)

Dr. Hiroaki Nishizawa (IMS, Waseda U)

Mr. Takeaki Kaiho (Waseda U)

Dr. Daisuke Yokogawa (Nagoya U)

Dr. Yoshio Nishimoto (Nagoya U)

2


Energy and Global Warming Issues

3

Economic Growth by Mass Consumption of Energy since Industrial Revolution

Depletion of fossil fuel resources：Energy issue

Petroleum Natural gas Coal

World energy resource reserves[1]

[1] 原子力・エネルギー図面集 2014, [2] 5th Report of IPCC

Increase of greenhouse gases: Global warming issue

CO2（Fossil fuels）

65.2%CO2

（Forest decline, Land‐use change）

10.8%

CH415.8%

N2O6.2%

Fluorocarbons2.0%

Type percentage of greenhouse gases[2]

Introduction Theory & Method Results & Discussion Summary


Global Warming Prediction

4

Average temperature rise is approximately proportional to CO2emissions.

[2] 5th Report of IPCC

CO2 cumulative total emissions by human activities since 1870 (GtC)

Average temperature rise amount for CO2 cumulative total emissions [2]Tempe

rature changes wrt1861–1880 (℃

)

Basic technology development is highly required to reduce CO2emissions.



Global Warming Countermeasure

International Energy Agency(IEA): 450 Scenario[3]

Limiting concentration of greenhouse gases in the atmosphere to around 450 ppm of CO2

Limiting the global increase in temperature to 2 ℃

5

[3] World Energy Outlook 2012 (International Energy Agency), p. 253.



CO2 Capture & Storage (CCS)

Flow of CCS

6

Capture & Separation Storage

Exhaust Gas with CO2

Transport

Fossil fuel power plants



CO2 Chemical Absorption Technique

Flow of CO2 chemical absorption technique

7


⼤気へ放出

熱交換器CO2低濃度

吸収液（低温）

CO2⾼濃度吸収液

輸送プロセスへ

CO2低濃度吸収液（⾼温）

吸収塔再⽣塔

排気ガス

CO2

N2

O2 etc.

気体

液体

CO2

N2

Absorption tower（~40℃）

Regeneration tower（~120℃）

Heating

To AtmosphereTo Transport

CO2 rich solvent

CO2 lean solvent (high temp.)

O2 etc.

gas

liquid

Exhaust gas

Heat exchanger

CO2 lean solvent (low temp.)


CO2 Chemical Absorption Technique

8

R2NR1

O

OR2

NR1

O

O

CO2 ＋ CO2＋


Regeneration tower

Absorption tower

Same pathway in absorption and regenerationAbsorption（~40 ℃）

Regeneration（~120℃）

Twitter ion

+

Protonated ammine Carbamate

Ammine

H2O +Bicarbonate ion

CO2+

Ammine


Performance of Amine Solution

Required performance of amine solution Absorption process

Fast reaction rateCostdown due to lower tower

(infrastructure)

Regeneration process Low reaction energy (enthalpy)Costdown due to lower heat energy

(running cost)

Higher CO2 capture capacity Robustness to degradation Lower environmental concern etc.

9

✕Absorption○Regeneration

Ideal??

○Absorption✕Regeneration

Piperazine(PZ)

2‐amino‐2‐methyl‐1‐propanol (AMP)



Chemical Reaction Simulation

10


Regeneration tower

Absorption tower


Chemical Reaction Simulation

11


Regeneration tower

Absorption tower


Reaction Simulation of Nano System

Bond formation/cleavage Electron transfer Dynamical behavior Tens of thousands of atoms

12

QM-MD Classical MDWFT DFT DFTB MM

Cluster collision[1] Electrolyte decomposition[2] Growth of nanotube[3] Virus[4]

< 100 < 1,000 < 1,000 ~10,000,000[1] H. Nakai, Y. Yamauchi, A. Matsuda, Y. Okada, K. Takeuchi, J. Mol. Struct. (THEOCHEM) 592, 61 (2002).[2] K. Ushirogata, K. Sodeyama, Y. Okuno, Y. Tateyama, J. Am. Chem. Soc. 135, 11967 (2013).[3] A. J. Page, Y. Ohta, S. Irle, K. Morokuma, Acc. Chem. Res. 43, 1375 (2010).[4] Y. Andoh, N. Yoshii, S. Okazaki, et al. J. Chem. Phys. 141, 165101(2014).

Quantum Mechanics (QM)

Molecular Dynamics (MD)Linear-Scaling Method

??



Cost of Conventional Calculation

13

Number of atoms

CPU time [sec.]

Target ：C2nH2n+2

DFTB Calculation• Small prefactor• O(N3) scaling

↓• Need ~2.5 hours (CPU)

for DFTB calculation of 8,000 atoms



Cost of New Calculation

14

Number of atoms

CPU time [sec.]

Target ：C2nH2n+2

DC‐DFTB Calculation• Small prefactor• Achieve O(N) scaling

↓• Need ~1 minute (CPU)

for DC‐DFTB calculation of 20,000 atoms

Subsystem : 1 unit

Unit : C2H2

Subsystem

BufferBuffer



Cost of New Calculation

15

Number of atoms

CPU time [sec.]

Target ：C2nH2n+2

DC‐DFTB Calculation• Small prefactor• Achieve O(N) scaling

↓• Need ~1 minute (CPU)

for DC‐DFTB calculation of 20,000 atoms

Subsystem : 1 unit

Unit : C2H2

Subsystem

BufferBuffer



Massive-Parallel Code

16

…

…

H0α, Sα, γα, Γα

MPI： all-to-all

Fα

Determine common Fermi level

Dα

qα

qMPI： all-to-all

SCC

1) Assign each fragment to each node2) Determine localization region and save its information

3) Calculate Erep

4) Calculate H0α & Sα

5) Calculate γα & Γα

6) Calculate EDFTB

7) Construct Fock matrix, Fα

8) Diagonalize Fα

9) Construct subsystem’s density matrix, Dα

10) Calculate subsystem’s charge, qα

11) Calculate total charge, q


2nd Project Report Meeting of the HPCI System (Miraikan, October 26, 2015) 17

40 CPU seconds for 1,500,000 atoms (500,000 H2O). O(N1.4) scaling High parallel efficiency


Massive-Parallel Calculation

Target: (H2O)n (n = 1 – 500,000)

42.4 sec

CPU core

CPU time

Number of atoms [million]


Simulation for Absorption Process

18

90100110120130140150160170180

O-C

-O A

ngle

[deg

.]

1.0 1.5 2.0 2.5 3.0 4.0Time [ps]

3.5

Absorption（~40 ℃）


Twitter ion

+Protonated

ammine Carbamate

Ammine


CO2+Ammine



Simulation for Absorption Process

19

-1.5

-1.0

-0.5

0.0

Oxy

gen

char

ge

0.5

1.0

1.5

2.0

0.0 1.0 2.0 3.0

Coor

dina

tion

nu

mbe

r of

Oxy

gen

Time [ps]

HCO3-

H2O

OH-

2

1

O1O2O3O4

O1

O2

O3

O4

(a)

(b) 1.17 ps 2.30 ps

Grotthuss (indirect) mechanism: OH- transfer through hydrogen-bond network



Absorption Mechanism

20

O

O

OO

O

OC

H

H

H

H

H

H

H

OH-

CO2

O

O

OO

O

OC

H

H

H

H

H

H

HHCO3

-

O

O

OO

O

OC

H

H

H

H

H

H

H

OH-

O

O

OO

O

OC

H

H

H

H

H

H

H

OH-

O

O

OO

O

OC

H

H

H

H

H

H

H OH-



Simulation for Regeneration Process

21

-1.0-0.50.00.51.01.52.02.53.0

N2: PZ(C)

N1: AMP(P)

0個

1個

2個

N原

子周

りの

H原

子数

3個

100110120130140150160170180

CO

2角

度[°

]16.5 17.0 17.5 18.0

時刻 [ps]

(b)

Absorption（~40 ℃）


Twitter ion

+Protonated

ammine Carbamate

Ammine


CO2+Ammine

Time [ps]16.5 17.0 17.5 18.0

O-C

-O A

ngle

[deg

.]


2nd Project Report Meeting of the HPCI System (Miraikan, October 26, 2015) 22

Ion-pair (direct) mechanism: Collision between carbamate (anion) and protonated amine (cation) OH- transfer through hydrogen-bond network

Time [ps]

Dis

tanc

e

Non-reactive collision

Reactive collision

Simulation for Regeneration Process Introduction Theory & Method Results & Discussion Summary


Regeneration Mechanism

23

N

CO

O

NH

C

C

CC

CO2desorption

N

CO

O

NH

C

C

CC

Twitterionintermediate

N

CO

O

N

H

C

C

CC

Proton transfer

N

CO

O

N

H

C

C

CC Protonated

amine

Carbamate



Realistic Model

24

• Number of atoms: 10,496• Number of molecules:

AMP(P) 128PZ(C) 64CO2 128H2O 2,112HCO3

- 64• Unit cell: (45.2 Å)3

• Node: 840 node (6,720 core)

• CPU time: 18 h/1 ps



Summary

Development of DC-DFTB-K program Divide-and-conquer (DC) method Density-functional based tight-binding (DFTB) methodMassive-parallel code

Performance of DC-DFTB-K Program Linear-scaling cost with extremely small prefactorHigh parallel efficiency Possible for ~1,000,000 atom simulation on K computerGeneral-purpose property

Simulation of chemical absorption methodGrotthuss mechanism for CO2 absorption process Ion-pair mechanism for CO2 regeneration process

25



Summary

26

QM-MD Classical MDWFT DFT DFTB DC-DFTB MM

Cluster collision Electrolyte decomposition

Growth of nanotube

CO2chemisorption Virus

< 100 < 1,000 < 1,000 ~100,000 ~10,000,000


Exploration of Aqueous Amine Solutions for CO Capture using … · 2015. 11. 18. · The Second...

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