Jiafei Zhang and David W. Aggar · Jiafei Zhang and David W. Aggar Technische Universität Dortmund, Germany Frankfurt a.M. 20.06.2011 Lab. Technical Chemistry B Prof. Dr. David W.

Sh ll’ h jShell’s research project:Development of novel amineabsorbents for CO2 capture

Efficient Carbon Capture for Coal Power PlantsSession M1: Chemical Absorption Materials

Development of Thermomorphic Biphasic SolventsDevelopment of Thermomorphic Biphasic Solvents

for Low-Cost CO2 Absorption Process

Jiafei Zhang and David W. Agarg gTechnische Universität Dortmund, Germany

Frankfurt a.M.

20.06.2011

Lab. Technical Chemistry BProf. Dr. David W. Agar

Outline

Motivation

Novel concepts

Novel solvents

Challenges and improvementg p

SummarySummary

Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang

Lab. Technical Chemistry BProf. Dr. David W. Agar 111

Outline

MotivationGlobal warmingShortcomings of conventionalsolvents

Novel concepts

solventsAdvantages of novel biphasic solvents

Novel solvents

Challenges and gimprovement

Summary



Motivation

CO2 emission global warming CO2 Capture & Storage (CCS)

Amine-based absorption process is the dominant commercial technology for CO2 capture

Technical shortcomings of Major superiorities of novel

Challenges? New generation absorbents

Technical shortcomings of conventional solvents:

e.g. monoethanolamine (MEA)

Major superiorities of novel biphasic solvents:

Regeneration temperature 80°CHigh energy consumptionHigh quality of heat: 130-150 °CSignificant amine loss by degradation

Use of waste heat for desorptionGood chemical stabilityHigh net CO2 loading capacity

Anodic

Fe Fe2+ + 2e-

Wet CO2 corrosion

CO2 + H2O HCO3- + H+

Anodic

Fe Fe2+ + 2e-

Anodic

Fe Fe2+ + 2e-

Anodic

Fe Fe2+ + 2e-

Wet CO2 corrosion


Wet CO2 corrosion


Fe Fe + 2e

Catodic

2H+ + 2e- 2H0

Wet CO2 corrosion


Amine corrosion

Fe Fe + 2e

Catodic

2H+ + 2e- 2H0

Fe Fe + 2eFe Fe + 2e

Catodic

2H+ + 2e- 2H0

Catodic

2H+ + 2e- 2H0

Wet CO2 corrosion


Wet CO2 corrosion


Wet CO2 corrosion


Amine corrosionAmine corrosion



Amine corrosion

Fe + 2RNH3+ Fe2+ + 2H0 + 2RNH2

Amine corrosion

Fe + 2RNH3+ Fe2+ + 2H0 + 2RNH2

Amine corrosion

Fe + 2RNH3+ Fe2+ + 2H0 + 2RNH2

3

Outline

Motivation

Novel conceptsLipophilic aminePhase changeTBS b b t

Novel solvents

TBS absorbentOther CO2 capture process with LLPS

Challenges and gamelioration Liquid-liquid phase separation (LLPS):

Summary



Concepts I

N l iNovel amines

Alkanolamine vs lipophilic amine

(H)R R(H)(H)R R(H)

Hydrophobic Hydrophilic

N

R

N

ROH

NH2

NH

Examples of lipophilic amineHexylamine (I) HADipropylamine (II) DPA

NDipropylamine (II) DPAN,N-Dimethylcyclohexylamine (III) DMCA

N



Concepts II

Ph hPhase change

Thermomorphic phase transitionThermomorphic phase transitionLow temperature single phaseHigh temperature dual phases

Lower critical solution temperature (LCST)

60

80 Hexylamine (I) A1 DPA (II) DMCA (III) Frozen

]

20

40

Tem

pera

ture

[癈 Two phases

Expected 0,0 0,2 0,4 0,6 0,8 1,0-20

0Single phase



Mass fraction of lipophilic amine in aqueous solution [g/g]

Concepts III

N l b b t th hi bi h i l t (TBS)Novel absorbent: thermomorphic biphasic solvent (TBS) Absorption: single phase Regeneration: single phase two phases

Lean solvent cooling to 30 40°C: homogeneousLean solvent cooling to 30-40 C: homogeneousRich solvent heating to 70-80°C: biphasic

(a) Homogeneous absorption (b) Heterogeneous desorption

Heating

CO2

(a) Homogeneous absorption (b) Heterogeneous desorption

Heating

CO2CO2

Heating

Aqueous phase

Organic phase

Cooling

R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3

-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3

-

Heating

Aqueous phase

Organic phase

Aqueous phase

Organic phase

CoolingCooling

R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3



-

CO2

CoolingCO2CO2

CoolingCooling

Process Flow Sheet



Concepts IV

‘Self-Concentration’ CO2C t P

DMXTM process with d i i l t

Other CO2 capture process with LLPS

Capture ProcessUniv. of Kentucky

demixing solventsIFP Energies Nouvelles

H tHeat



Ref.: Hu, 2010 Annual NETL CO2 Capture Technol. R&D Meeting. Lemaire, et al., 12th Intl. Network for CO2 Capture, 2009

Outline

Motivation

Novel conceptsIdeal solventAbsorption

Novel solvents

DesorptionChemical stabilityAmine selection

Challenges and

Amine selection

gimprovement

200

300

400

500

r)

Summary DMX-1, 40癈 A1+DsBA, 30癈 A1+DsBA, 80癈 MEA 30wt%, 40癈 MEA 30wt%, 120癈

0 1 2 3 4 540

50

60708090

100 PC

O2 (m

bar



0 1 2 3 4 5

Loading (mol-CO2/kg-sol.)

Novel solvents

Th id l h i l l t f PCCThe ideal chemical solvent for PCC (Davidson, 2007)

High reactivity (kinetics) – reduces height requirements for theHigh reactivity (kinetics) reduces height requirements for the absorber and/or solvent circulation flow ratesHigh absorption capacity – directly influences solvent circulation fl t i tflow rate requirementsLow regeneration costs – reduced energy consumptionHigh thermal stability and low solvent degradation – reducedHigh thermal stability and low solvent degradation reduced solvent waste due to thermal and chemical degradationLow solvent costs – should be easy and cheap to produceLow environmental impactTechnical feasibility

Reactivity Absorption capacity Energy consumption Stability



Reactivity Absorption capacity Energy consumption Stability

Novel solvents I

Ab ti1,0

Absorption

Reactivity0,6

0,8

mol

CO

2 / m

ol a

min

e] TBS

MEA

ReactivityRapid reaction rateComparable to MEA (when α<0.5)

0,0

0,2

0,4

Load

ing

of C

O2 [

m

MDEA+MEA

3,5

0 20 40 60 80 100 120 140 160,

Time [min]

Loading capacity (net)Alkanolamine 40-120 °C

w/ steam stripping 1,5

2

2,5

3

ol-C

O2/k

g -so

l

TBS absorbent 30-80 °C w/o steam stripping

CO2 absorbed in TBS: 3.4 mol/kg0

0,5

1mo

Higher than MEA and AMP

R i i Ab i i E i VLE S bili



Reactivity Absorption capacity Energy consumption VLE Stability

Novel solvents II

D tiDesorption

Liquid-liquid phase separationLiquid liquid phase separation

Low regeneration temperatureca 80°Cca. 80 CLow value heat

Hi h bilit

Before regeneration

During regeneration

After regeneration

High regenerability> 80% at 80°C for most TBS> 98% at 80°C for optimised TBS

Estimated energy consumption MEA: 4.0 GJ/t CO20 GJ/t-CO2

TBS: 2.5 GJ/t-CO2 Ref.: Geuzebroek, et al., TCCS-5, 2009





Novel solvents III

V li id ilib iVapour-liquid equilibriumHigher CO2 loadingLower residual loading

200

300

400

500

ar)Lower residual loading

Better than benchmarks DMX-1, 40癈 A1+DsBA, 30癈 A1+DsBA, 80癈60

708090

100 PC

O2 (

mba

100

Basicity reduction by oxidative degradationR ti it d ti b CO i d d d d ti

MEA 30wt%, 40癈 MEA 30wt%, 120癈

0 1 2 3 4 540

50

Loading (mol-CO2/kg-sol.)

Chemical stabilityLow temperature (80°C) for desorption less 60

80

100

]

Reactivity reduction by CO2 induced degradation Reactivity reduction by oxidative degradation Reactivity reduction by catalyzed oxidative degradation

desorption less thermal degradationLow oxidability less 20

40

Per

cent

[%

B1 A1 MEA

oxidative degradation B1 A1 MEA MDEA

0

Solvent





Novel solvents IVScreening tests – searching new aminesScreening tests searching new amines

> 60 lipophilic amines (alkylamines)≈ 10 comparable to MEA or MDEACriteria

HN

CriteriaHigh loading capacity: > 0.6 mol/mol (15% CO2)Fast absorption rate: comparable to MEAGood regenerability: better than MDEA

DPA

g yLow degradability: comparable to AMP & MDEAModerate heat of reaction: lower than MEA

A

N

DMCAA: partially soluble in water, rapid absorption rateas absorption activator e.g. HX, DPA, A1

DMCA

B: less miscible with water, high regenerabilityas regeneration promoter e.g. DMCA, EPD, B1

N

Recommended absorbent: blended solvent A+BBlending A+B exploits the strengths of both components

EPD



g p g p

Outline

Motivation

Novel concepts

Novel solvent

Challenges and Vaporisation lossgimprovement

Vaporisation lossPhase transitionRegeneration techniques

SummaryProcess development



Challenges and improvement I

A i i ti l C tAmine vaporisation lossHigh volatilitySi ifi t l til l

Countermeasures

T f f d (t ) t 30 °CSignificant volatile loss T for feed (top) at 30 °CReduced vaporisation

Amine Temp. Loss

Hydrophobic solvent scrubbing

°C %/day

A130 <0.5

e.g. Diphyl Recovery >80%

A140 1.8

DMCA30 4.840 12

Water wash when using A1 as primary solvent

40 12

DMCA+A1(3:1)

30 4.140 10

Reduced amine lossComparable to MEA or AMP

( )50 14

MEA 40 1.2AMP 40 1.6



AMP 40 1.6

Challenges and improvement II

Ph t iti C tPhase transition

Lower critical solution

Countermeasures

ConcentratingLower critical solution temperature (LCST): most lipo. Amines < 20°CProblem:

ConcentratingNegative on vaporisation lossLimited at 4MProblem:

biphasic solvent in absorber Using more A1Negative on regenerationLCST ≈ 20°C50

LCST ≈ 20 C

Partial deep regenerationResidual loading 0.130

40

50

emulsion

癈)

PTT of DMCA+A1 with 9wt% AMP CST of DMCA+A1 with 9wt% AMP PTT of DMCA+A1 CST of DMCA+A1

Two phases gIncreasing LCST to 30°C

Adding solubiliser10

20

Tem

pera

ture

(癈

Single phase

emulsion

<10wt%Increasing LCST to 40°C

3M(2:1) 3M(1:1) 4M(2:1) 4M(1:1)

0

Concentration (mol/L)

Single phase

PTT: phase transition temperatureCST: critical solution temperature



( )

Challenges and improvement III

Regeneration techniquesRegeneration techniques

Challenges Regeneration intensification

Low temperature 80°CWithout steam

Extractive regeneration+ Regeneration promoter

How to intensify the regeneration?

AgitationNucleationregeneration? NucleationNucleation + Agitation




Extractive regeneration with regeneration promoter (B)Solution: B1+A1+water (loaded with CO2)

Extractive regeneration with regeneration promoter (B)

After absorption: homogeneous loaded solution

GasPhase

SingleLiquidPhase




Extractive regeneration with regeneration promoter (B)Solution: B1+A1+water (+CO2)



GasPhase

Start of desorption CO2 is first liberated from B1

B1 CO2

A1+CO2

2

H2O

SingleLiquidPhase

(Heat)







GasPhase

Start of desorption: CO2 is first liberated from B1 B1 is insoluble in water regenerated

B1

B1 CO2B1 is insoluble in water, regenerated B1 accumulatesSeparate supernatant organic phase is

A1+CO2

H2O

2

formed

Aq.PhasePhase

(Heat)







GasPhase

Start of desorption: CO2 is first liberated from B1B1 is insoluble in water regenerated B1

B1 Org.PhaseB1 is insoluble in water, regenerated B1

accumulatesSeparate supernatant organic phase is CO2 A1

formedA1 preferentially dissolves in the organic rather than the aqueous phase

Aq.Phase

H2O

organic rather than the aqueous phaseB1 adopts the role of a solvent, extracting A1 from the aqueous phase

Phase

(Heat)




Extractive regeneration

HA

DPA

A1

Acti.


LLSP temperatureB1

DMCA

EPD

HA

Prom.

promoter (B)

Activator (A): 90°CPromoter (B): 60-80°C

0 20 40 60 80 100

B1

LLSP temperature (°C)( )

Regenerability at 80°C 80

100

Activator (A): 45-50%Promoter (B): 90-95% 40

60

Reg

ener

abili

ty (%

)

Acti.+Prom. (A:B=3:1): 85-90%

0

20

Activator Promoter Acti.+Prom.R



Challenges and improvement IV

Nucleation & AgitationNucleation & Agitation

1,6

2,0

Solution: A1+B1, 2+1M at 75 癈

Agitation0,8

1,2

Des

orbe

r CO

2 (mol

/L)

Stirring

Nucleation0 10 20 30 40

0,0

0,4

D

Time (min)

750 rpm 500 rpm 250 rpm N

2 stripping

1,6

2,0

)

Solution: A1+B1, 2+1M at 75 癈250

DMCA+A1 DMCA+DPA

Porous particles

0,8

1,2

Des

orbe

r CO

2 (mol

/L)

100

150

200

2 rele

ase

rate

[g/L

/hr]

Agitati

on

Porous particles for CO2 bubble

formation

0 10 20 30 400,0

0,4

Time (min)

1/40 wt. 1/60 wt. 1/80 wt. N2 stripping

none 100 rpm 250 rpm 500 rpm 750 rpm 1000 rpm Stripping0

50

CO

2

Method



Challenges and improvement V

P d l tProcess developmentR

egeenerationn withoutsteam

strripping

Fl h i di



Flow sheeting diagram

Challenges and amelioration V

Bench scale experimentation in packed absorption columnsBench-scale experimentation in packed absorption columns

Absorber

Regeneratorg

B tt f b bBottom of absorber

At TU Dortmund

At Shell G.S.



At TU Dortmund

Summary

Novel absorbent: lipophilic amine TBS

Rapid absorption rate (due to activator A)High regenerability (due to regeneration promoter B)Excellent net CO2 loading capacity (> 3 mol-CO2/kg-sol)Low energy requirement (≈ 2.5 MJ/kg-CO2)High chemical stabilityHigh chemical stability

Novel concept: phase transitionNovel concept: phase transition

LLPS enhanced regenerationRegeneration at 80°C use of waste heat reduces CO2capture process costs



Acknowlegement

Development of Thermomorphic Biphasic Solvents

f L C t CO Ab ti Pfor Low-Cost CO2 Absorption Process

CO2 Capture Research Group:

Prof. Dr. David W. Agar Technical Staff:Mi h l S hlütM.Sc. Jiafei Zhang

TU Dortmund University

Dr Frank Geuzebroek

Michael SchlüterJulian GiesJerzy Konikowski

Dr. Frank Geuzebroek Ir. Mark Senden Dr. Xiaohui Zhang Shell Global Solutions Int. B.V.

Students:Robert Misch, Jing ChenYu Qiao, Wanzhong Wang O k hi N iOnyekachi Nwani

Frankfurt a.M

20.06.2011



End

Thank youThank youThank youThank youfor your attentionfor your attention

Jiafei ZHANG

Emil-Figge-Str. 66 (TCB)D-44227 Dortmund, GermanyTel.: (+49) 231 - 755 2582 E-Mail: [email protected]/tcb

Campus of TU DortmundTCB



Campus of TU DortmundTCB

Jiafei Zhang and David W. Aggar · Jiafei Zhang and David W. Aggar Technische Universität Dortmund, Germany Frankfurt a.M. 20.06.2011 Lab. Technical Chemistry B Prof. Dr. David W.

Documents