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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 222
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
CO2 + H2O HCO3- + H+
Wet CO2 corrosion
CO2 + H2O HCO3- + H+
Fe Fe + 2e
Catodic
2H+ + 2e- 2H0
Wet CO2 corrosion
CO2 + H2O HCO3- + H+
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
CO2 + H2O HCO3- + H+
Wet CO2 corrosion
CO2 + H2O HCO3- + H+
Wet CO2 corrosion
CO2 + H2O HCO3- + H+
Amine corrosionAmine corrosion
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 444
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 5
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 6
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
-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3
-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3-R1R2R3N + CO2 + H2O R1R2R3NH+ + HCO3
-
CO2
CoolingCO2CO2
CoolingCooling
Process Flow Sheet
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 7
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 8
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 999
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 10
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 11
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
R i i Ab i i E i VLE S bili
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 12
Reactivity Absorption capacity Energy consumption VLE Stability
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
R i i Ab i i E i VLE S bili
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 13
Reactivity Absorption capacity Energy consumption VLE Stability
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 14
g p g p
Outline
Motivation
Novel concepts
Novel solvent
Challenges and Vaporisation lossgimprovement
Vaporisation lossPhase transitionRegeneration techniques
SummaryProcess development
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 151515
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 16
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 17
( )
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 18
Challenges and improvement III
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 19
Challenges and improvement III
Extractive regeneration with regeneration promoter (B)Solution: B1+A1+water (+CO2)
Extractive regeneration with regeneration promoter (B)
After absorption: homogeneous loaded solution
GasPhase
Start of desorption CO2 is first liberated from B1
B1 CO2
A1+CO2
2
H2O
SingleLiquidPhase
(Heat)
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 20
Challenges and improvement III
Extractive regeneration with regeneration promoter (B)Solution: B1+A1+water (+CO2)
Extractive regeneration with regeneration promoter (B)
After absorption: homogeneous loaded solution
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)
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 21
Challenges and improvement III
Extractive regeneration with regeneration promoter (B)Solution: B1+A1+water (+CO2)
Extractive regeneration with regeneration promoter (B)
After absorption: homogeneous loaded solution
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)
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 22
Challenges and improvement III
Extractive regeneration
HA
DPA
A1
Acti.
Extractive regeneration with regeneration promoter (B)
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 23
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 24
Challenges and improvement V
P d l tProcess developmentR
egeenerationn withoutsteam
strripping
Fl h i di
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 25
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.
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 2626
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar 272727
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar
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
Development of Thermomorphic Biphasic Solvents for Low-Cost CO2 Absorption Process Jiafei Zhang
Lab. Technical Chemistry BProf. Dr. David W. Agar
Campus of TU DortmundTCB