Lecture as given to the students and people of University Maastricht at the Campus Brightlands

1. CO2 based in addition to Bio-based
• Presentation: University Maastricht
• Date: 29th March 2018
• Location: Brightlands Geleen
CO2-based / Bio-based
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2. Pol Knops
#Greenolivine
Green Minerals.
pol@green-minerals.nl
Tel: +31 6-51304842
CO2-based
An addition to bio-based
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3. Background myself
• Pol Knops
• 54 years
• Applied Physics (MSc. Twente)
• Worked @ Environmental projects,
renewable energy
• Since 7 years involved in Mineralization
– Own process
– “Enhancing mineralization
• Brightlands Innovation Factory
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4. Problem
• Climate Change
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5. Problem
• Climate Change
• Resources:
Oil reserves 50 years
Gas reserves 100 years
Coal reserves 150 years
Shale gas, shale oil, gas hydrates
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6. Problem
• Climate Change
• Resources:
Oil reserves 50 years
Gas reserves 100 years
Coal reserves 150 years
Shale gas, shale oil, gas hydrates
• Stranded assets
€, risk29-03-18 2018 Geleen 6

7. Problem
• Climate Change
• Resources:
Oil reserves 50 years
Gas reserves 100 years
Coal reserves 150 years
Shale gas, shale oil, gas hydrates
• Stranded assets
€, risk29-03-18 2018 Geleen 7

8. Problem
• Prof. Klaus Lackner:
Environmental problem,
not resource
We won’t run out of resources,
but we run out of environment
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9. CO2 streams
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10. Global CO2 balance
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11. Carbon deposits
Amount
(X 10E15 kg)
Relative
(%)
Cycle
Limestone (CaCO3) 35.000 47% Long inorganic
Dolomites (CaCO3MgCO3) 25.000 33% Long inorganic
Sedimentary carbon 15.000 20% Long organic
Recoverable fossil fuels 4 0,005% Long organic
Oceanic HCO3- CO32- 42 0,056% Long/short organic
Dead Surficial Carbon
(humus, peat)
3 0,004% Long organic
Atmospheric CO2 0,72 0,00095% Short organic
Biomass 0,56 0,0007% Short organic
Anthropogenic emissions 0,03/year Long organic
Natural (volcanic) 0,0025 /yr Long inorganic
“Live”
“Dead”
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12. Pre and post Industrial
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13. CO2 emissions
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14. Solutions
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15. Solutions
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16. CCS / CCU
CCS CCU
Waste Business case
Mton kton
Energy Steel, cement, Fertiliser
CCS è CCUS
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17. CO2
• Climate Change
• Circulair economy
• CO2: Circular
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18. CO2
• CO2 emissions to 0 (even negative)
• CO2 waste ? => CO2 as feedstock
• Circular:
• Parallel CO2-Based <–> Bio-based
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19. CO2 energy levels
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20. CO2 re-use
• CO2 to chemicals
• CO2 to fuels
• CO2 to minerals
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21. CO2 re-use
• CO2 to chemicals Covestro
• CO2 to fuels
• CO2 to minerals
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22. CO2 re-use
• CO2 to chemicals
• CO2 to fuels Audi
• CO2 to minerals
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23. CO2 re-use Mineralisation
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24. CO2 re-use
• CO2 to chemicals
• CO2 to fuels
• CO2 to minerals Carbon8, Ruwbouwgroep
Green Minerals
Mineral Carbonation Int
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25. Process
Olivine Green MineralsCO2
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26. Mineralization reaction
Olivine:
Mg2SiO4 + 2CO2 + 2H2O => 2MgCO3 + Si(OH)4
Mg2SiO4 + 4CO2 + 4H2O => 2Mg2+ + 4HCO3
- + Si(OH)4
[∆H = -239.2 kJ/mol]
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27. Advantages
• Permanent:
– Geological time scale
– No legacy issue
• Environmental benign
• Large quantities available
• Potential use exothermic reaction
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28. Exothermic reaction
Coal
Gaseous CO2
Solid Carbonate
ΔH = 11,1 MJ/kg CO2
80%
ΔH = 2,7 MJ/kg CO2
20%
“The ground energy state
of carbon is a mineral
carbonate”
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29. Occurence
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30. Disadvantages
• Slow reaction speed:
– Natural weathering
– Enhanced weathering
– Product replacement
– Process intensification
• Volumes to be handled
• Nickel, Chromium
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31. Volume
• To compensate GLOBAL CO2 emissions:
– 7 km3 per year (25 Gton)
– Comparable biggest mine
• Lignite: 1 Gton/yr
• Coal: 4 Gton/yr
Overburder factor: 5
• Oil sand: >1 Mton/day
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32. Mineralization reaction
3 routes:
conditions focus
natural weathering ambient CO2
Product replacement various Replacement
Process intensification HPHT End Products
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33. Natural weathering
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34. Olivine solution
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35. -Natural weathering:
Reaction rate Geological time scale
-Enhance weathering:
milling,
organic acids, lychens,
erosion sensitive places
Natural & enhanced weathering
On tidal flats
Lichens secrete oxalic acid Constant abrasion Lugworm eats top layerMycorrhizal fungi secrete a
range of organic acids
In soils In surf zoneOn bare rocks
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36. Product replacement
• Use Olivine:
– As pebbles, sand, etc.
– Fertilizer:
pH stabilizing,
Magnesium release,
CO2 binding
• Lifetime of the product
= weathering rate
• Nickel
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37. Process intensification
• Chemical process
• High Pressure, High temperature:
• Enhanced reaction rate:
185 C,
40-100 bar P CO2,
1 hour residence time
• Exothermic behavior known, but not used
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38. My experience
• Slow reaction rate:
275 C,
100 bar P O2,
1 hour residence time
• Exothermic reaction:
- Extremely low energy density: 0,34 MJ/kg
• Typical 550.000 m3/yr (100 m3/hr)
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39. ED
Reactor 5
B
A: Incoming material
B: DownComer tube
C: CO2 injection
D: UpComer tube
E: Surrounding cooling tube
C
C
C
A
C
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- The Olivine (or Serpentine) is grinded outside the
reactor and fed into the reactor.
- CO2 is injected into the DownComer tube
- Effluent material further to be degassed, dewatered
and land filled/applied
- Energy recovery (depending on exothermic reaction)
2018 Geleen
E
E E

40. Construction
• Conventional drilling:
Straight, 30”
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41. Well head
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42. Process
• Comparison to VerTech process
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Comparison VerTech CO2 Energy reactor
(pilot scale)
Experience
Construction period
> 10 years
1992 - 1994
Not
-
Throughput 120 m3/hr
550.000 m3/hr
100 m3/hr
20 ton Olivine/hr
Energy production
Recovery
9.5 MW(th)
50% @ 260 C
9.8 MW(th)
50% @ 180 C
Energy density 0.34 MJ/kg 0.42 MJ/kg
Gas injection O2: 2400 kg/hr CO2: 12 ton/hr
100kton CO2/yr
Max. temp
Depth
270 C
1200 meter
190 C
1200 meter

43. Status
• Test equipment:
Rocking Batch autoclave 120 bar, 300 C
• Research:
RWTH (Uni Aachen)
HeidelbergCement
IASS Potsdamm
Green Minerals
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44. Product
- 1/3 CO2
- Exothermic reaction
Very small particles:
-1/3 Amorphous Silica
- 2/3 Magnesite
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45. Particles
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46. - Concrete
- Paper
- Polymer
Applications
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47. - CO2MIN
RWTH / HeidelbergCement/IASS Potsdamm
- 3 year Research
Budget € 2.8M
TRL3 -> TRL5
Concrete
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48. ● Replacement “PCC”
● CO2 negative paper
● In addition to “bio-based” also
“CO2 based”
Paper
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49. • Replacement grounded lime
“functional fillers”
• 1st Prototype 3D printing
• Biobased polymers +
CO2 based fillers
Polymer
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50. • Partners:
- CHILL
- Hogeschool Zuyd
- Topologx
- Brightlands Innovation Factory
CO2 for 3D printing
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51. Business Case
Olivine Green MineralsCO2
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52. Next steps
• 1. Batch autoclave
CO2MIN (RWTH/HeidelbergCement)
CO2 for 3D printing
? Paper application
• 2. Design continuous autoclave
• 3. Scale up research, process
• 4. Co-development applications
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53. Summary
• Circular economy:
Bio-based
CO2-based
• CO2 from waste to beneficial product
• Business cases (with clients)
(and mean time ”save the world” !)
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54. Questions ..
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