Presentation at University of Leuven Section meeting

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**


Mineral'Carbona$on'in'combina$on'with'a'Gravity'

Pressure'Vessel*

Pol*Knops*KU*Leuven*\*Innova(on*Concepts' 'Supervisor:*Tom*van*Gerven** Rafael*Santos*


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*


Presenta$on'• Lecture:**

– CO2*cycle*– Mineraliza(on*

• Our*process*– Gravity*Pressure*Vessel*– Combina(on*

• Research*– Batch*autoclave*(Rocking*Autoclave)*


Global'CO2'balance*


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”


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#'Re

ferences'

#'Pu

blica$

ons'

Year'

Keywords:*"Mineral*carbona(on*CO2*sequestra(on"*

Reference*to*Seifritz*"CO2*disposal*by*means*of*silicates"*

Publica$ons'


Advantages'

• Permanent:*– Geological*(me*scale*

– No*legacy*issue*• Environmental*benign*

• Large*quan((es*available*• Poten&al)use)exothermic)reac&on)


Disadvantages'• Slow*reac(on*speed:*

– Natural*weathering*– Enhanced*weathering*– Product*replacement*

– Process'intensifica$on''• Volumes*to*be*handled*

• Nickel,(Chromium(

• Costs'


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 *


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”


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*


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*


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'


Well*head*


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*


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*


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'


Batch'autoclave'


1EL5*Achieved*dissolu(on*

rate*

1EL4* Required*dissolu(on*rate*

Conversion'


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'


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'


Reac$on'products'

23*CEP*L*Paris*Sud*5/11/14*


Reac$on'products'

Sample:*U3'

Sample:*U4'

5/11/14* 24*CEP*L*Paris*Sud*


0%

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0 1 10 100 1000

Dis

trib

utio

n

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'


Silica'forma$on'• Literature:*Passiva(ng*silica*boundary*layer*• Our*case:*MgCO3:*due*to*deLpressuriza(on?*


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*


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'


KU'Leuven'

• Geology:'

• MTM:'

• CIT:'

Geological'process'Composi$on*

Valuable'endZproducts'

Characteriza$on'

Process'intensifica$on'

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Presentation at University of Leuven Section meeting

Education