A presentation of my research topic as given to my fellow PhD-students at the University of Leuven. The monthly section meeting usually ends with a PhD student presenting his work.

1. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 1
Sec$on'mee$ng'Presenta$on'
Presenta(on*at*CIT*Sec(on*Mee(ng**
University*of*Leuven*(Department*Chemical*
Engineering,*Unit*Process*Engineering*for*Sustainable*
Systems*Sec(on,*Group*of*Prof.*Tom*van*Gerven).**
Date:*7th*April*2014*
Public:'PhDLstudents*
Dura(on:*20*minutes**

2. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 2
Mineral'Carbona$on'in'
combina$on'with'a'Gravity'
Pressure'Vessel*
Pol*Knops*
KU*Leuven**Innova(on*Concepts' '
Supervisor:*Tom*van*Gerven*
* Rafael*Santos*

3. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 3
Background'myself*
• Pol*Knops*
• Applied*Physics*(MSc.*Twente)*
• Worked*@*Environmental*projects,**
** * * * renewable*energy*
• Since*5*years*involved*in*Mineraliza(on*
– Own*process*(Gravity*Pressure*Vessel)*
– “Enhancing*mineraliza(on”*+*Valuable*endLproducts*

4. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 4
Presenta$on'
• Lecture:**
– CO2*cycle*
– Mineraliza(on*
• Our*process*
– Gravity*Pressure*Vessel*
– Combina(on*
• Research*
– Batch*autoclave*(Rocking*Autoclave)*

5. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 5
Global'CO2'balance*

6. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 6
Carbon'deposits'
Amount'(C)'
(X'10E15'kg)'
Rela$ve'
(%)'
Limestone*(CaCO3)* 35.000* 47%'
Dolomites*(CaCO3MgCO3)* 25.000* 33%'
Sedimentary*carbon* 15.000* 20%*
Recoverable*fossil*fuels* 4* 0,005%*
Oceanic*HCO3L*CO32L* 42* 0,056%*
Dead*Surficial*Carbon*(humus,*peat)* 3* 0,004%*
Atmospheric*CO2* 0,72* 0,00095%*
Biomass* 0,56* 0,0007%*
Anthropogenic*emissions* 0,008/year*
Natural*(volcanic)* 0,00005*/yr* (1%)*
“Live”
“Dead”

7. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 7
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#'References'
#'Publica$ons'
Year'
Keywords:*"Mineral*carbona(on*CO2*sequestra(on"*
Reference*to*Seifritz*"CO2*disposal*by*means*of*silicates"*
Publica$ons'

8. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 8
Advantages'
• Permanent:*
– Geological*(me*scale*
– No*legacy*issue*
• Environmental*benign*
• Large*quan((es*available*
• Poten&al)use)exothermic)reac&on)

9. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 9
Disadvantages'
• Slow*reac(on*speed:*
– Natural*weathering*
– Enhanced*weathering*
– Product*replacement*
– Process'intensifica$on''
• Volumes*to*be*handled*
• Nickel,(Chromium(
• Costs'

10. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 10
Mineraliza$on'reac$on'
Olivine:
Mg2SiO4 + 2CO2 + 2H2O => 2MgCO3 + Si(OH)4
Mg2SiO4 + 4CO2 + 4H2O => 2Mg2+ + 4HCO3
- + Si(OH)4
[∆H = -239.2 kJ/mol]
Wollastonite:
CaSiO3 + CO2 => CaCO3+SiO2 *

11. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 11
Exothermic'reac$on'
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”

12. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 12
Process'intensifica$on'
• Chemical*process*
• High*Pressure,*High*temperature:*
• Enhanced*reac(on*rate:*
185°C,**
40L100*bar*P*CO2,**
1*hour*residence*(me*
• Exothermic*behavior*known,*but*not*used*
6*March*2012** 12*
Confiden(al*Informa(on**Innova(on*
Concepts*

13. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 13
My'experience'
• Slow*reac(on*rate:*
275°C,**
100*bar*P*O2,**
1*hour*residence*(me*
• Exothermic*reac(on:*
L*Extremely*low*energy*density:'0,34'MJ/kg'
• Typical*550.000*m3/yr*(100*m3/hr)*
6*March*2012*** 13*
Confiden(al*Informa(on**Innova(on*
Concepts*

14. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 14
E*D*
Reactor*4*
B*
A:*Incoming*material*
B:*DownComer*tube*
C:*CO2*injec(on*
D:*UpComer*tube*
E:*Surrounding*cooling*tube*
C'
A*
E'
E'E'
Z1200'meter'

15. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 15
Well*head*

16. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 16
Process'
• Comparison*to*VerTech*process*
Comparison' VerTech' CO2'Energy'reactor'
(pilot'scale)'
Experience*
Construc(on*period*
>*10*years*
1992*L*1994*
Not*
*L*
Throughput* 120*m3/hr*
550.000*m3/yr*
100*m3/hr*
20*ton*Olivine/hr*
Energy*produc(on*
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*injec(on* O2:*2400*kg/hr* CO2:*12*ton/hr*
100kton'CO2/yr'
Max.*temp*
Depth*
270°C*
1200*meter*
190°C**
1200*meter*

17. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 17
ReZcap'
• Drive:*CO2*increase*
• One*contribu(on:*Mineraliza$on'
• Idea*of*using*Gravity*Pressure*Vessel*
• Process*intensifica(on*cri(cal*
• Patent*
• Company*started,*research*driven*

18. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 18
KU'Leuven'
• CIT:'
– Reac(on*kine(cs*
– Dissolu(on,*pH*
• Geology:'
– Minerals*
– Composi(on,*XRD,*TGA,*LDA*
• MTM:'
– Characteriza(on*&*use**end*
products*
– XRF,*SEM*
Process intensification
Geological'process'
Valuable'endZproducts'

19. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 19
Batch'autoclave'

20. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 20
1EL5*
Achieved*dissolu(on*
rate*
1EL4* Required*dissolu(on*
rate*
Conversion'

21. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 21
Shrinking'core'model'
FORSTERITE*DISSOLUTION*KINETICS:APPLICATIONS*AND*
IMPLICATIONS*FOR*CHEMICAL*WEATHERING**
Amanda*Albright*Olsen,*pHD*thesis*
Page:*31*
r*=*kT,R*=*dissolu(on*rate**
* (pH,'ref)*(mol/m2s)****
R*diss*=kT*=*Dissolu(on*rate**
* (pH,'temp)*(mol/m2s)**
d0*=*original*diameter*(um)*
X*olivine*=*frac(on*weathered*(%)***
Ω*=molar*volume*(43,97*cm3/mol)**
t*=*(me*(sec)*
d(t)*=*diameter*over*(me*(um)*
Conversion'

22. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 22
Ambient'Weathering'' '
' Z'Rate' ' ' ' ' ' ≈'0,5'μm/year' ' ' ' 1'
Process'intensifica$on'
– Current'state'' ' ≈'6'μm/6'hours'' ' ' 15.000' '
– Required' ' ' ' ≈'40'μm/hour' ' ' ' 700.000' '
Process Intensification: 44 times
Sec$on'Mee$ng'CIT'*April*7,*2014* *Pol*Knops/*Innova(on*Concept**22*
Conversion'

23. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 23
Reac$on'products'
23*CEP*L*Paris*Sud*5/11/14*

24. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 24
Reac$on'products'
Sample:*U3'
Sample:*U4'
5/11/14* 24*CEP*L*Paris*Sud*

25. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 25
0%
1%
2%
3%
4%
5%
6%
7%
8%
9%
10%
0 1 10 100 1000
Distribution
Diameter (um) (logaritmic)
Run 30 Particle Size Distribution
GL30
Run 30 Hoogte 1
Run 30 Hoogte 2
Run 30 Hoogte 3
Run 30 Hoogte 4
Par$cle'Size'Distribu$on'

26. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 26
Silica'forma$on'
• Literature:*Passiva(ng*silica*boundary*layer*
• Our*case:*MgCO3:*due*to*deLpressuriza(on?*

27. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 27
Research'ques$ons'
• pH*in*reactor:*
– Measurements*(CSTR)*
– Chemical*equilibrium*calcula(ons*
• Magnesium*Carbonate:*
– Controlled*precipita(on*
• Metal*recovery:*
– End*of*pipe*?*
– In*fluid:*ligand?*
• Behavior*silica*
– boundary*layer*
– Concrete*applica(ons*

28. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 28
Other'Processes'
• Asbestos'destruc$on'(not'@'KUL')'
• Steel'slags''
• Oil'Shale'residue'
• Red'mud'treatment'
• Bayer'process'(alumina'produc$on)'
• High'Pressure'Acid'Leaching'
• Wet'Air'Oxida$on:'
'' Oil'Sand'residue'

29. April 7, 2014 Section Meeting CIT Pol Knops/ Innovation Concept 29
KU'Leuven'
• Geology:'
• MTM:'
• CIT:'
Geological'process'
Composi$on*
Valuable'endZproducts'
Characteriza$on'
Process'intensifica$on'