HiPerCap High Performance Capture

Source CO2 capture Transport Storage Natural gas

Oil

Bio-fuel

Coal

Absorption Systems

Earl Goetheer, Principal scientist at TNO

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Capture in 1930

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Challenges Post-combustion Capture

Ab

sorb

er

Reg

ener

ato

r

Makeup water

CO2-lean gas

CO2-rich gas

Rich solvent

Bottom Tray

Top Tray

Bottom Tray

Top Tray

Pump

Pump

Condenser

Reflux Reflux drum

Reboiler

Lean solvent

Liquid

Vapor

Steam

Condensate

Rich solvent

Lean

so

lven

t

CO2 gas

Scru

bb

er

advanced heat

integration

reduce heat consumption

avoid emission solvent traces

reduce absorber, scrubber investment

Emission

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Aerosol emission Volatile emission

Particle number conc./[1/cm3]

104 105 106 107 108

ME

A/[

mg/N

m3]

0

200

400

600

800

1000

1200

1400

Low Soot

High Soot

Low level H2SO4 aerosol

Middle level H2SO4 aerosol

High level H2SO4 aerosol

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FGD

FFSCR

~

infiltration air

infiltration air

CO2 to storage

DCC

1 2 3

water/steam

air

CO2

coal

coal millI air

II air

PZ process

flue gas

APH

Integration

Energy Consumption

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Spe

cifi

c e

ne

rgy

du

ty G

J th/t

CO

2

Technologies

• Enzymatic catalysed CO2 capture

• Biomimicking

• Strong bicarbonate formers

• Precipitating solvent systems

• Capture integrated with algae cultivation

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Precipitating solvent systems

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9

CO2 absorption with amino acid salts Resistant to oxidative

degradation

Less waste generated products

Zero emissions of active reactant

Potential energy savings

• Limited solubility in water

Ionic equilibria In water:

R-(NH2)COOH R-(NH3)+COO- zwitterion

- H+ - H+

R-(NH3)+ COOH ↔ R-(NH3)

+COO- ↔ R-(NH2)+COO-

R-(NH3)+COO- + KOH R-(NH2)COO-K+ reactive

Taurine

Glycine

10

Effect of solid precipitation

Experimental: Aqueous potassium taurate.

Dark points: precipitation

From: Kumar et al. Ind. Eng. Chem. Res. 42, 2003, 2841-2852

40 oC ; 6M AmA

10

100

1000

10000

100000

0 0,1 0,2 0,3 0,4 0,5

Loading [mole CO2/mole AmA)C

O2 P

ressure

[P

a]

Combined process

No precipitation

With precipitation

Schematic picture: effect of solvent precipitation

Enhanced absorption capacity: DECAB principle

11

Reactions with CO2 (similar to “normal” amine systems):

Carbamate formation (primary and secondary amines)

CO2 + 2 -OOC-R-NH2 ↔ -OOC-R-NH-COO- + -OOC-R-NH3+ (1)

amine carbamate protonated amine

Carbamate hydrolysis -OOC-R-NH-COO- + H2O ↔ -OOC-R-NH2 + HCO3

- (2) carbamate amine bicarbonate

Bicarbonate formation (tertiary amines, sterically hindered secondary amines)

CO2 + -OOC-R-NH2↔ -OOC-R-NH3+ + HCO3

- (3) amine protonated amine bicarbonate

Why do you get higher capacity?

Removed by precipitation

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Working with solids in the process

• Controlled precipitation of the solvent

• Solids should appear where they can be handled

• Equipment selected for solids handling

• Process complexity increased

Working with solids IF there is an economic breakthrough

13

DECAB Process (Design & Modelling Results)

Absorption column

Spray column

Flash vessel

Stripper

HX-2

Loaded solvent

Flue Gas

Clean Gas

Pre-loaded solventHX-3

Carbon dioxide

HX-1

10MW

76 MW

16MW

36MW

190 Nm3/s

8vol%

90 C => 50 C 89MW

504 kg/s

Loading

0,13mol/mol

120 C

Loading 0,13 mol/mol

Loading

0,26mol/mol

Loading

0,43mol/mol

Loading

0,33mol/mol

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From DECAB to DECAB+

Absorption column

Spray column

Stripper

HX-1

Loaded solvent,

slurry

Loaded solvent,

Particle free

Lean solvent

Flue Gas

Depleted

Flue gas

Clean Gas

Strip gas

Pre-loaded solvent,

particle freeHX-2

Make – up water

Lean solventCondenser

Reflux

CO2 to compresion

Conditions to enhance absorption and desorption

Absorption: High pH (basicity) Desorption: Low pH (acidity)

15

Effect of DECAB+. Enhanced desorption

VLE 100ºC

0,01

0,1

1

10

0 0,1 0,2 0,3 0,4 0,5 0,6

Loading [mol CO2 / mol Amino acid]

CO

2 P

art

ial p

ress

ure

[b

ar]

VLE 4M / 4M 100ºC

Fit 4M / 4M 100ºC

VLE 3.5M / 5M 100ºC

Fit 3.5M / 5M 100ºC

VLE 80ºC

0,001

0,01

0,1

1

10

0 0,1 0,2 0,3 0,4 0,5 0,6

Loading [mol CO2 / mol Amino acid]

CO

2 P

arti

al p

ress

ure

[b

ar]

VLE 4M /4M 80ºC

Fit 4M / 4M 80ºC

VLE 3.5M / 5M 80ºC

Fit 3.5M / 5M 80ºC

The pH shift increases the partial pressure of CO2 at a given

loading

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Proof of principle

Liquid removed

Vol (%)

Conc.

M

T

C

Rich

Loading

mol/mol

Lean

Loading

mol/mol

0% 4 74.1 0.65 0.36

21% 4.3 77.1 0.65 0.3

42% 4.9 76 0.65 0.17

0% 4 89.7 0.65 0.24

21% 4.3 95.4 0.65 0.13

42% 4.9 93.7 0.65 0.09

Low lean loadings are

possible at relatively low

temperatures

CO2

N2

To analyzer

flask

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Key advantages of DECAB+

• Low desorption temperature • Possibility to use low grade heat / waste heat (Ideal for the

refinery case) • Possibility to achieve lower lean loadings without increasing

reboiler temperature (Ideal for streams with low CO2 concentrations such as flue gas from gas turbines combustion)

• High pressure desorption

• Lower operating costs due to enhanced desorption

• All environmental advantages from amino acids

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DECAB+ Process Concept

CO2 capture algae cultivation

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M. Tredici. Symposium “ I Biocarburanti di seconda e terza generazione” Roma 14 April 2011

Biomass community Location Yield

(t d.w. ha-1 y-1)

Photosynthetic efficiency (%)

Hybrid poplar (Populus spp.) (C3) Minnesota 8 -11 0.3- 0.4

Water hyacinth (Eichornia

crassipes) Mississippi 11 – 33 (>150) 0.3- 0.9

Switch grass (Panicum virgatum)

(C4) Texas 8-20 0.2- 0.6

Sweet sorghum (Sorghum

bicolor) (C4) Texas-California 22 - 47 0.6-1.0

Coniferous forest England 34 1.8

Maize (Zea mays) (C4) Israel 34 0.8

Tree plantation Congo 36 1.0

Tropical forest West Indies 60 1.6

Algae Different locations

70 2-2.5

Sugar cane (Saccharum

officinarum) Hawaii-Java 64-87 1.8-2.6

Napier grass (Pennisetum

purpureum) Hawaii, Puerto

Rico 85-106 2.2-2.8

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EXAMPLES OF HIGH

PRODUCTIVITY BIOMASS

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Per kg dry biomass ~ 4,4 kg of CO2 is needed

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Ab

sorb

er

Reg

ener

ato

r

Makeup water

CO2-lean gas

CO2-rich gas

Rich solvent

Bottom Tray

Top Tray

Bottom Tray

Top Tray

Pump

Pump

Condenser

Reflux Reflux drum

Reboiler

Lean solvent

Liquid

Vapor

Steam

Condensate

Rich solvent

Lean

so

lven

t

CO2 gas

Scru

bb

er

~75% OPEX is

predominantly

CO2 desorption/

solvent regeneration

~20% efficiency loss of

power plant due to high

energy demand for

desorption

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Al

Ab

sorb

er

Algae based Regenerator

Makeup water

CO2-lean gas

Flue gas

Rich solvent

Bottom Tray

Top Tray

Pump

Lean solvent

Rich solvent

Lean

so

lve

nt

Scru

bb

er

Biomass/ products

Need for major cost reduction of

CO2 capture and limited efficiency

loss for power plants and

industrial emission sources.

Leads to new business models for

Algae to biofuels production.

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From algae to products – improvement options

Cultivation

Open systems

Closed systems

Algae-strain

Oils & hydrocarbons

Proteins

Carbohydrates

Biomass

Biofuels

Pharmaceutical Industry

Animal feed

Electricity generation

Aquaculture feed

Chemical Industry

Inoculation Harvesting & Processing Valorization Nutrients/ CO2

Growing System

Advanced Nutrient Delivery

Technology.

Advanced algal Strain Technology

Energy efficient

harvesting, extraction and

processing system.

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Advanced algal Strain Technology

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21/06/2012

Solution: Light efficient strains

Improved Strain Wild strain

Same algal density 1,5 gr/ltr

Max. algal cell density of 8 gr/ltr for Light Efficient Strain

Non-GMO

Limitation: Mutual shading

Decreased light penetration

=

Slower growth

=

Lower biomass density

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Advanced Nutrient Delivery Technology.

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Efficient CO2-nutrient feeding

Pure CO2 bubbling Flue gas washing/bubbling (diluted CO2 stream)

Current state-of-the-art

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Enzyme promoted CO2 capture

Carbonic Anhydrase enhances the uptake rate of CO2 into an absorption liquid

Algae regenerate the carbonate-based absorption liquid

Two possible routes researched at TNO

Amine based CO2 capture

– Cultivation of algae directly on CO2 “captured” in amine-based solvents

– Algae regenerate solvent which can be reused for CO2 capture

(source: Premkumar et al. (2005) PNAS, 102 (21) p,7493-7498)

Carbonic Anhydrase II

(source http://www.energen.it/inglese/

olio_da_alghe.html)

Spirulina platensis

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Route 1: Enzyme promoted CO2 capture

Carbonic Anhydrase effects on CO2 loading

Kinetic experiments showing the rate of CO2 loading in the reference (▲, 2M sodium carbonate) and catalyzed (, 2M sodium carbonate plus 400mg/L carbonic anhydrase) tests

Carbonate solutions are cheap compared to other CO2 absorption liquids, but have a slow CO2 uptake rate

Addition of carbonic anhydrase to sodium carbonate solution increases the rate of CO2 uptake

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Route 1: Enzyme promoted CO2 capture

Concept process design of a carbonate based CO2 capture system using carbonic anhydrase as promoter and algae as

solvent regenerator

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Route 2: Combining CO2 capture with amine based solvents & algae cultivation

The uptake of CO2 by a amine-based solvent

CO2 stripping of solvent by consumption through algae in a solvent & medium solution

Recycle of the solvent for new cycle of CO2 uptake

The algae biomass can be used for product.

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Algae Bioreactor

Algae Biomass

Nutrients

Light

Down stream processing

Biomass

C o n c e p t

Products

Ab

sorb

er

Makeup water

CO2-lean gas

CO2-rich gas

Rich solvent

Bottom Tray

Top Tray

Lean solvent

Route 2: Algae-mediated CO2 desorption from amine-based solvents

Concept process design of a amine based CO2 capture system using algae as solvent regenerator

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Capture solvent selection criteria

• 1. Non-toxic to algae culture • 2. Slow biodegradable by algae culture • 3. Cheap/abundant • 4. Efficient capture of CO2

(partly absorbed CO2 should be bicarbonate species)

It is of importance to note that 90% CO2 capture is not the objective

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From problem to business

www.stichtingmilieunet.nl/.../sailing-algae.bmp

www.altdotenergy.com/wp-content/uploads/2009/...

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Some references

US2014295531 (A1) - ENZYME PROMOTED CO2 CAPTURE INTEGRATED WITH ALGAE PRODUCTION – Goetheer et al.

WO2013022349 (A1) - COMBINING ALGAE CULTIVATION AND CO2 CAPTURE – Goetheer et al.

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Acknowledgement

21/06/2012