Gas-FACTS project: Gas - Future Advanced Capture Technology SystemsWP 2.1: Gas-Specific Solvents

2nd Post Combustion Capture ConferenceSession 3: 2nd & 3rd Generation

Capture Technologies

Selection and Development of Specific Solvents for CO Capture from Specific Solvents for CO2 Capture from

Natural Gas Power Systems:

monophasic & biphasic monophasic & biphasic

Jiafei Zhang, Paul Fennell, Martin Truslerg

Bergen, 18th Sept. 2013

OutlineOutline

IntroductionIntroduction• PCC for gas-fired power plants• Overview of Gas-FACTS Project Results and discussionResults and discussion • Solvents selection • Measurement parameters

Densit ViscositAbsorption Desorption

• Density, Viscosity • Heat capacity (Cp)• Vapour-Liquid Equilibrium (VLE)

N t CO it• Net CO2 capacity • Degradation • Surface tension, Contact angle

P d l t• Process developmentSummary

2Image Source: Siemens

PCC for Gas fired power plantsPCC for Gas-fired power plants

Natural gas becomes the new Higher O concentration Natural gas becomes the new ‘coal’ for power generation… burns much cleaner than coal but...

Higher O2 concentration Degradable solvents can not be

considered Solvents resisting oxidation

Lower CO2 partial pressure Reduce α-CO2

Seeking specific solvents

g Exhaust Gas Recycle (EGR) to

increase the CO2 concentration Two baseline cases

to reduce: solvent flow column size CapEx & OpEx

to achieve: ~90% of CO2 removal

Without EGR: ~4% CO2, ~12% O2

With EGR: 6-8% CO2, 8-10% O2

CO2 Emissions (kg/MWh)w/o w/ CCS

C l fi d 800 1000 100

After Combustion:CO2 H2O O2 N2 Ar

Coal-fired 13.53 15.17 2.40 68.08 0.82

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Coal-fired 800-1000 ~100Gas-fired 350-400 ~40 Gas-fired 4.04 8.67 12.09 74.32 0.89

Project overviewProject overview

Work packages EPSRC Reference:EP/J020788/1

2.1 Gas-Specific Solvents

EP/J020788/1

Solvents

2.2 Flexible Capture SystemsSystems

2.3 Advanced Testing

Consortium Members:

4

Solvents selectionSolvents selection

Advanced solventsAdvanced solvents• Monoethanlamine (MEA) as benchmark primary amine

• 2-Amino-2-methyl-1-propanol (AMP) sterically hinderedHO

NH2

NH2HO

2 Amino 2 methyl 1 propanol (AMP) sterically hindered• Dimethylaminoethanol (DMAE) tertiary • Diethylaminoethanol (DEAE) tertiary • Piperazine (PZ) as activator diamine

2

Piperazine (PZ) as activator diamine• Piperazinyl ethylamine (PZEA) triamine

• Blended amines – recommended HN NH

• Formulations• DMAE+PZ• DEAE+PZ

High net CO2loadings

Rapid reaction kinetics

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• AMP+PZg

Chemically stable

Low energy consumption

Solvents selectionSolvents selection

Thermomorphic biphasic solvents (TBS) Hydrophobic HydrophilicThermomorphic biphasic solvents (TBS)

• Using lipophilic amines as activating components • Examples

NH2

Hydrophobic Hydrophilic

• Hexylamine (I) HA• Dipropylamine (II) DPA• N,N-Dimethylbutylamine (III) DMBtA

NH

N

N

• Liquid-liquid phase separation

70-80 C

Screened lipophilic amines• Alkylamines – linear, branched,

N

Before D i Aft

oC Alkylamines linear, branched, cyclic

• Aromatic amines - derivatives of benzylamineC li i d i ti

6

Before regeneration

During regeneration

After regeneration

• Cyclic amines – derivatives of piperidine

~40 oC

Measurement parametersMeasurement parameters

Density F d fl• Density• 25-80 °C• +/- 0.000005 g/cm³

• Viscosity BPR

Feed flow

Column packingsViscosity • 30-80 °C • Deviation < 1.5%

• Heat capacity T2

m

Peltier Device

Pump Bath

T1

P

BPRColumn packings

Energy consumptionp y• 25-120 °C, 10-40 bar• < 0.5% (low T), < 1.5% (high T)

• Surface tension / Contact angle

2gy p

Packing wettability

(Sensible heat)

• 25-80 °C • < 1%

• VLE / net CO2 capacity°C

Column size

• 30-120 °C, 4-100 kPa

7VLE rig + GC

DensityDensity

Measurement Various

amine solutions:solutions: single & blended

with CO2with CO2loadings

8Anton-Paar model DMA

5000 M densimeter

Viscosity advanced amine solvents Viscosity - advanced amine solvents

30wt% MEA and other amine solutions: 4.8 cP at

35 oC• Influence of α• fitted by Weiland’s (1998) correlation

1 wgTfweXdwcTbwaT

35 C

2

1exp 2

2T

wgTfweXdwcTbwaTT AmAmCOAmAm

OH

solution

0.78 cP at 80 oC

9U-Tube capillary viscometer

Viscosity biphasic amine solvents Viscosity – biphasic amine solvents N

H2

O

N

NH

NH

HO

10

Heat capacityHeat capacity

Flow calorimeter BPRFlow calorimeterm

Peltier Device

Pump Bath

T1 TmQC net

p

Influence: T ↑ Cp ↑α ↑ C ↓ (/g)

T2 P

α ↑ Cp ↓ (/g)α ↑ Cp ↑ (/ml)

11

Heat capacityHeat capacity

Solvents:

DMAE + PZAMP + PZPZEAetc.

12

VLEVLE

Advanced amine solvents30% DMAE (+,)25% DMAE + 5% PZ (,)

Biphasic amine solvents4M pMCA (blended solvent)Compared to 30% MEA (eq. 5M)

300

400

500

100

200

P CO

2 (mba

r)

MEA

40

50

60708090

100 MEA, 40 oC MEA, 120 oC DMX-1, 40 oC pMCA, 40 oC pMCA, 90 oC

MEA

pMCA

13in-house data from D. Tong

0 1 2 3 4 5

Loading (mol-CO2/kg-sol.)

Net CO capacity Net CO2 capacity

Higher than benchmarks

40 120 C f40-120oC for alkanolamine

30 80oC for30-80oC for lipophilic amine

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DegradtionDegradtion

Analysis

N

Analysis • Heat stable salts (HSS): titration• Volatile components: GC-MS

Main reactions N

• Demethylation / Methylation• Ketonisation & Oximation for MCA

6

HN

4

5

6 w/o Fe(II/III) w/ Fe(II/III)

2

3

HS

S /

%

TBS

15AMP Blend DMCA MEA MCA0

1

Surface tension & Contact angleSurface tension & Contact angle

+ CO loading+ CO2 loading • Increase ST• Increase CA

θ

Some plastic materials such as PE-HD: also wettable to lipophilic amines

16α ↑

PFD for TBSPFD for TBS

17Process flow diagram for TBS with phase splitting and stripping

SummarySummary

ViscosityViscosityLean solvents: PZEA > AMP ≈ DEAE > DMAE > MEA > TBS > H2O Rich solvents: TBS > AMP > DMAE > MEACO2 loading: α ↑ η ↑CO2 loading: α ↑ η ↑

Heat capacity Solvents: H2O > DMAE > AMP ≈ PZEA > MEA > TBSCO loading: α ↑ C ↓ (/g) or C ↑ (/ml)CO2 loading: α ↑ Cp ↓ (/g) or Cp ↑ (/ml)

Loading capacity & chemical stability Higher α than conventional solvents at low p Lower degradation than MEALower degradation than MEA

Further studiesExplore & formulate new solventsOptimise solvent recipe & modellingOptimise solvent recipe & modelling Advanced Testing at UKCCSRC’s PACT Facilities

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8 m absorberup to 1 ton/day of CO2

AcknowledgementAcknowledgement

The gas-specific solvents were studied in the Imperial College London and financial supported by the EPSRC

The biphasic solvent system was studied in the Technical University of Dortmund and supported by the Shell Globalby the EPSRC. supported by the Shell Global Solutions Int. B.V.

Advisors: Prof. Dr. David W. AgarProf. Dr. David W. Agar Dr. Frank Geuzebroek Ir. Mark Senden Dr. Robert Moene

Consortium Members:

Dr. Robert MoeneDr. Xiaohui Zhang

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Thank you for your attention!

Selection and Development of Specific Solvents for CO2 Capture from

Natural Gas Power Systems:Natural Gas Power Systems:

monophasic & biphasic

Jiafei Zhang

Department of Chemical EngineeringImperial College London UK The Queen's Tower in the

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Imperial College London, UKTel: +44 (0)20 7594 1185 E-mail: jiafei.zhang@imperial.ac.uk

The Queen s Tower in the South Kensington Campus