DEVELOPMENT OF NOVEL AMINE SOLID SORBENTS FORNOVEL AMINE SOLID SORBENTS FOR

POST-COMBUSTION CO2 CAPTURE

H. Yamada, J. Fujiki, R. Numaguchi, K. Kida,F. A. Chowdhury, K. Goto, K. Yogo

Research Institute of Innovative Technology for the Earth

Kyoto, JAPAN

11th European Conference onCoal Research and its ApplicationsCoal Research and its Applications

September 7, 2016University of Sheffield, UK

Contents

Overview of the project

Strategy for the development of novel

solid sorbents

f f h l d b Performance of the new solid sorbents

S & f t l Summary & future plan

COCS Project (20042009)

Conventional New amine R1 R3

MEA 4.0 GJ/ton CO2

R2

2.5 GJ/ton CO2

/ 2 2

Goto et al. Int J Greenhouse Gas Control 5 (2011) 1214

Recent Advances in Post-Combustion CO2 Capture Chemistry, ACS Symp Ser (2013)

Development of Soid Sorbents for CO2 Capture(2010 2015)(20102015)

ObjectiveI ti S lid S b t

R & D

Separation energy < 1.5 GJ/ton CO2

Innovative Solid Sorbent

Amine/ 2

for post-combustion capture Solid sorbent+

4.0

5.0

/ton

CO

2)

Vaporization heatSensible heat

Poroussupport

2.0

3.0

ener

gy (G

J/ Sensible heatHeat of absorption

System Evaluation Tool

PC

0.0

1.0

gene

ratio

n e

RITE S lid b

Capture & Compression Storage

PC power plant

Reg MEA

sol.RITEsol.

Solid sorbent(target)

Separation

Requirements for the Target: 1.5 GJ/ton CO2

High working capacity (> 3 mol CO /kg) High working capacity (> 3 mol CO2/kg)

Low heat of adsorption

Gray et al. Int J Greenhouse

Gas Control 2 (2008) 3

Strategy Increasing amine content

by the wet impregnation method using polyaminesby the wet impregnation method using polyamines

Improving regeneration efficiency

by the structural modification of amino groups

NH2

NH

NH2n

OHN

R''

R'

Substituentintroduction

OH R

Blending

NH

NH

NH

n RR

H H

Design of Effective AmineHeat of reaction for CO2 capture

R1R2NH + CO + B R1R2NCOO + BH+

H

R1R2NH + CO2 + B R1R2NCOO + BH

Stability of carbamate G

R1R2NCOO + H2O HCO3 + R1R2NH

Effects of functional groups R1 R2 and base BEffects of functional groups R1, R2, and base B analyzed using the density fictional theory, solvation models and spectroscopic methods in terms of enthalpy, free energy and reaction pathway

Yamada et al. Ind Eng Chem Res 49 (2010) 2449Yamada et al. Ind Eng Chem Res 49 (2010) 2449

Yamada et al. J Phys Chem A 115 (2011) 3079

Yamada et al. J Mol Model 19 (2013) 4147

Yamada et al. Int J Greenhouse Gas Control 17 (2013) 99

Yamada et al. Ind Eng Chem Res 53 (2014) 1617

New Amine Impregnated Solid Sorbents

OHNH

OHNH2

NH

NH

NH

NH2

DEA

HHSubstituentintroduction Blending

TEPA

H H

TEPA X

NH

NH

NH

NH

NH

XX

TEPA-X

Evaporation

Amine/porous material/methanol Sorbent (powder)

Thermogravimetric Analysis

70 wtamine

30 wtMSU-F: Mesoporous silica,28 nm pore, 270 m2/g surface

Thermally stable High amine content ( 15 mmol N/g)

Blending of Amines

NH2

NH

NH

NH

NH2TEPA TEPA-DEA/MSU-F

OHNH

OH

DEA

+ =70 (wt)

Synergistic effect

DEA

Synergistic effect between polyamine and alkanolamine

@ 40 C & 100 kPa

on CO2 uptake

Yamada et al. Sep Sci Technol

50 (2015) 2948

ASAP 2020 (Micromeritics)

50 (2015) 2948

Substituent Introduction

NH

NH

NH

NH

NH

XXNH2

NH

NH

NH

NH2

TEPA TEPA-X

@ 40 C

Amine70/MSU-F (granulated)ChemiSorb HTP (Micromeritics)

Adsorption after Vacuum Regeneration

NH

NH

NH

NH

NH

XXNH2

NH

NH

NH

NH2

TEPA TEPA-X

Working capacity

@ 40 C

Amine70/MSU-F (granulated)ChemiSorb HTP (Micromeritics)

Process Optimization Using Lab-Scale Apparatus

Simulant gasSimulant gas12% CO23-9 L/min (= 1-3 kg CO2/d)20-100% relative humidity

Adsorption100 kP 40 60˚C100 kPa, 40-60˚C

Desorption5-10 kPa5 10 kPa

Cycle time3-12 min

ProcessesVacuum swing adsorption (VSA)Vacuum swing adsorption (VSA)Steam-aided VSA (SA-VSA)

CO2 Capture Performance of RITE Solid Sorbent

1.5 GJ/t-CO2

Temperature of sorbets

Recovered CO2

CO2-in

CO2-out

SA-VSA is suitable for CO2 recovery using the RITE sorbent.High purity > 98%Hi h i ld 93%High recovery yield > 93%

SummarySummary Amine-impregnated solid sorbents were developed for

energy efficient CO2 capture.

Bl di f l i d lk l i bl d th Blending of polyamine and alkanolamine enabled the

increase of CO2 capacity.

The efficiency of regeneration was drastically increased

by the newly designed polyamineby the newly designed polyamine.

RITE sorbets achieved 1.5 GJ/t-CO2 regeneration energy

with high purity (98%) and high recovery yield (93%) from

a simulated flue gas.a simulated flue gas.

Current Project (2015)

RITE is partnering with Kawasaki Heavy Industries, Ltd on the development of the dust es, td o t e de e op e t o t esolid sorbent system.

Project Objectives:

Material optimizationMaterial optimizationto develop low cost production of the solid sorbent, sorbent durability, and commercial scale productioncommercial scale production

Process optimizationby operating bench scale (5 ton CO2/d) y p g ( 2/ )and pilot scale (3040 ton CO2/d) units on exhaust gas

Okumura et al. Energy Procedia 63 (2014) 2249

This project was sponsoredThis project was sponsored by METI, Japan.

Thank you.

hyamada@rite.or.jp y @ jpHidetaka YAMADA