Presentation given at the Conference of the European Biogas Association 2014.

1. 1
October 01, 2014
Marco Linders
Solvent development for biogas
TNO Customers
TNO is a technology development and consulting company
with over 30 years of experience in (Renewable) Gas
technology
TNO Facts
! Independent Research Organization
! Technology development, consulting, and contract R&D
! Approximately 3800 employees
! 600 million Euro Revenue, 1/3 government funding
Markets
! Energy, Defence & Safety, Industry, Healthy Living, Living
Environment

2. 2
October 01, 2014
Marco Linders
Solvent development for biogas
Gas Treatment: Our Focus Areas
Processes
for
purifica1on,
separa1on
&
treatment
of:
Flue
Gas
Natural
Gas
/
Syngas
/
Biogas
U1liza1on

3. 3
October 01, 2014
Marco Linders
Solvent development for biogas
Algae for CO2 capture & utilization
Technology
Innova1ons
CO2-­‐lean
solvent
CO2-­‐rich
solvent
Smart CO2 Feeding
Combining CO2 capture with algae cultivation to:
! Decrease in energy requirement for solvent regeneration
! Increase in algae growth rates & CO2 feeding efficiency
! Create potential revenue from bio-products

4. 4
October 01, 2014
H2S removal technology
Technology Innovations
Marco Linders
Solvent development for biogas
Principle of technology:
2 Fe(III)NTA + H2S à 2 Fe(II)NTA + S0 + 2 H+
2 Fe(II)NTA + ½ O2 + 2 H+ à 2 Fe(III)NTA + H2O
• High removal efficiency up to 99,9%
• Sulphur removal of 0,1 to 20 t/d
• H2S is directly converted to
elemental sulphur
• No Claus-SRU required
• Low CAPEX/OPEX

5. 5
October 01, 2014
Marco Linders
Solvent development for biogas
Process Development
TNO Approach
Molecular
modelling
Synthesis
Proof
of
Principle
-­‐
VLE
&
batch
tes1ng
Proof
of
Concept
-­‐
Mini
pilot
Pilot
plant
design
&
scale
up
Pilot
plant
(Lab
scale)

6. 6
October 01, 2014
Marco Linders
Solvent development for biogas
Carbon Clean Solutions MethPure Solvent development
for biogas scrubbers – approach
! Goal: outperform current used state-of-the-art solvents (e.g. aMDEA)
with respect to general performance, stability, operating costs
! Benchmark: amine, pressure swing adsorption and water scrubbers for
CO2 removal
! Approach:
Miniplant
tes1ng
Demonstra1on
Solvent
Mixture
op1misa1on
Solvent
component
iden1fica1on
Equilibrium
Thermal stability
Physical characteristics
(Kinetics)
Stripper pressure
Stripper temperature
Solvent loading
European Partner;
Capacity 6000 m3/day
Benchmark against
aMDEA

7. Equilibrium testing
7
October 01, 2014
Marco Linders
Solvent development for biogas
Equilibrium 19% thermal
energy savings compared to
benchmark aMDEA
! Mixtures significantly better than MDEA at required partial pressure
! Mixture 2 selected because it has higher thermal stability (see next)

8. Thermal stability testing
8
October 01, 2014
Marco Linders
Solvent development for biogas
! CO2 loaded samples stored at 160°C for 3 weeks (accelerated aging)

9. Physical characteristics
9
October 01, 2014
Marco Linders
Solvent development for biogas
! At high CO2 loadings, viscosity can be an issue

10. Miniplant testing
10
October 01, 2014
Marco Linders
Solvent development for biogas
! Solvent performance testing in a continuous absorption-desorption
miniplant
! Solvent handling and practical issues such as foaming

11. Miniplant testing
11
October 01, 2014
Marco Linders
Solvent development for biogas
Characteristics:
! Mobile and fully automated
! Capacity of 4 m3/h of flue gas
! Absorber section: packed bed (Sulzer Mellapak 2X), totally 3.5 m
high with 4 packed beds each of 0.5 m
! Diameter of 4.5 cm
! Stripper section same dimension/packing as absorber
! Total liquid inventory of the system is about 20 L
! Measurement of process parameters such as temperatures, flows,
liquid level, pH lean and rich, CO2 concentration

12. Miniplant testing
12
October 01, 2014
Marco Linders
Solvent development for biogas
! Parametric testing for two weeks to find optimum performance
Parameter Range CO2 Capture
rate (%)
Stripper pressure
change 0.9-1.0 bar at 120 °C 90-94
Lower stripper
temperature
110-115°C
81-95
Higher stripper
temperature
130°C at 1.7 bar
93
Maximum rich loading Recirculation of solvent
and no stripping -
! Based on results solvent considered suitable for demonstration scale
! Performed much better than the benchmark aMDEA

13. 13
October 01, 2014
Marco Linders
Solvent development for biogas
Commercial Demonstration – European Biogas Partner
! Source of biogas: Agricultural waste
! Capacity: 6000 m3/day / Ongoing operation since July, 2014
! Commercial validation of ‘MethPure’ solvent successfully with match
customer requirement
! Detailed solvent characterization obtained: results are as expected,
leading to a database useable for further scaling up

14. Conclusion
14
October 01, 2014
Marco Linders
Solvent development for biogas
! Solvent has higher capacity compared to benchmark aMDEA
! Solvent has better thermal stability compared to benchmark aMDEA
! Important aspects as well are viscosity, kinetics and energy efficiency
! Miniplant tests showed good continuous performance, gave insight in
optimal process conditions, and showed stable operation
! Commercial validation proven successful and on-going
! Multi-dimensional approach by means of expertise in solvent and process
development and lab scale to pilot plant testing and detailed
benchmarking against aMDEA

15. 15
October 01, 2014
Marco Linders
Solvent development for biogas
Thank you for your time and attention
Questions?
! Marco Linders
! marco.linders@tno.nl
! Phone +31 88 866 1324
! Mobile +31 6 225 450 18
! Prateek Bumb
! prateek@carboncleansolutions.com
! Mobile +44 774743 4099/+91-9167555141
http://www.hak.nl/index.php?nav=actueel&subnav=nieuwsarchief&id=62

16. Back-up slides
16
October 01, 2014
Marco Linders
Solvent development for biogas

17. 3.5
3
2.5
2
1.5
1
0.5
0
17
Mixture 1 Mixture 2 Mixture 3 Mixture 4
Mixture 1 @ 24.53 kPa
Mixture 2 @ 27.5 kPa
Mixture 3 @ 25.07 kPa
Mixture 4 @ 17.18 kPa
Rate of reaction X 105 (kmol/m2 s)
Kinetics Testing
Corrosion – SS316L
Rate of corrosion (*mpy) 0.035
(Extraordinary)
* mpy = mils per year
October 01, 2014
Marco Linders
Solvent development for biogas