Making Products from CO2 and Olivine (accelerated weathering)
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7th Dutch CCS Symposium Lecture during the Dutch CCS CATO mee4ng Date: 19 June 2014. Loca4on: RAI Amsterdam Title: CO2 re'use with accelerated olivine weathering; making products from olivine and CO2 6/19/14 CATO 2014 1
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A lecture held at the Dutch CCS Symposium. Subject: Using accelerated weathering for producing valuable materials from CO2 and Olivine
Transcript of Making Products from CO2 and Olivine (accelerated weathering)
7th$Dutch$CCS$Symposium!
Lecture!during!the!Dutch!CCS!CATO!mee4ng!
Date:!19!June!2014.!!
Loca4on:!RAI!Amsterdam!
Title:!
CO2$re'use$with$accelerated$olivine$weathering;$making$products$from$olivine$and$CO2$
6/19/14! CATO!2014! 1!
Pol!Knops!
Innova4on!Concepts!B.V.!
Tel:!06M51304842!
CO2 (re-)use CO2 re-use with accelerated olivine weathering;
making products from olivine and CO2
Myself$
• Pol!Knops!• 50!year!• MSc!Physisc!@!Twente!
• Renewable,!energy!projects:!• >!12!years!Gravity!Pressure!Vessel!• 4!years!Mineraliza4on!
• PhDMstudent!@!Leuven!(topic:!Olivine!&!GPV)!
CO2: 322,25 ppm
CO2: 401,85 ppm
Presenta8on$
• Historical!development!
• Current!state!• Our!project!
6/19/14! CATO!2014! 4!
Global$CO2$balance!
6/19/14! 5!CATO!2014!
Carbon$deposits$Amount$(C)$(X$10E15$kg)$
Rela8ve$(%)$
Limestone!(CaCO3)! 35.000! 47%$
Dolomites!(CaCO3MgCO3)! 25.000! 33%$
Sedimentary!carbon! 15.000! 20%!
Recoverable!fossil!fuels! 4! 0,005%!
Oceanic!HCO3M!CO32M! 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”
6/19/14! 6!CATO!2014!
Pre$and$post$Industrial$
Seifritz$1990$
6/19/14! CATO!2014! 8!
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#$Re
ferences$
#$Pu
blica8
ons$
Year$
Keywords:!"Mineral!carbona4on!CO2!sequestra4on"!
Reference!to!Seifritz!"CO2!disposal!by!means!of!silicates"!
Publica8ons$
6/19/14! 9!CATO!2014!
Gaining$more$R&D$aSen8on$
Year Name Description University
1997 Jonckbloedtt The dissolution of olivine in acid Utrecht
1997 Lieftink The preparation of and characterization of silica from acid treatment of olivine Utrecht
2004 Gormley An integrated experimental and first-principle computational study of CO2 mineral carbonation reactions in Olivine and Serpentine
Phoenix
Bearat Mineral sequestration of Carbon Dioxide. Enhancing carbonation reactivity of brucite and forsterite
Phoenix
Nunea Mineral sequestration of CO2 in San Carlos Olivine – An atomic level reaction study Phoenix
2005 Park CARBON DIOXIDE SEQUESTRATION: CHEMICAL AND PHYSICAL ACTIVATION OF AQUEOUS CARBONATION OF Mg-BEARING MINERALS AND pH SWING PROCESS
Ohio
2006 Kim Nanoscale analysis for the San Carlos Olivine Carbonation Reaction Mechanism Phoenix
Huntzinger Carbon Dioxide Sequestration in cement kiln Dust through mineral carbonation Michigan
2007 Olsen FORSTERITE DISSOLUTION KINETICS:APPLICATIONS AND IMPLICATIONS FOR CHEMICAL WEATHERING
Virginia
Huigen Carbon Dioxide Sequestration by Mineral Carbonation Wageningen
Hänchen CO2 storage by aqueous mineral carbonation; olivine dissolution and precipitation of MG-carbonates
Zürich
Uliasz-Bochenczyk
Waste used for CO2 bonding via mineral carbonation Krakow
Gaining$more$R&D$aSen8on$2$Year Name Description University
2008 Van Essendelft
Kinetics of the acid digestion of serpentine with concurrent grinding for the purpose of CO2 sequestration
Pennsylvania
Ramme An investigation of CO2 sequestration through mineralization Milwaukee
Jarvis Reaction mechanisms for enhancing carbon dioxide mineral sequestration Phoenix
Teir FIXATION OF CARBON DIOXIDE BY PRODUCING CARBONATES FROM MINERALS AND STEELMAKING SLAGS
Espoo
Staires Assessing the viability of CO2 sequestration in eastern snake river plains basalts, Southern Idaho
Pocatello
Uibu Abatement of CO2 emissions in Estonian oil shale based power production Tallinn
2009 Flaathen Water rock interaction during CO2 sequestration in Basalt Toulouse
Wilson Mineral traps for greenhouse gases in mine tailings. A protocol for verifying and quantifying CO2 sequestration in ultramafic mines
Vancouver
Daldoul Caracterisation et etude de la performance du Chrysoltile dans la capture du dioxyde de carbone dans les procédés gaz-solide
Quebec
Costa Accelerated carbonation of minerals and industrial residues for carbon dioxide storage Rome
Krevor Mineral carbon dioxide sequestration: Enhancing process kinetics and a resource base assessment for minerals suitable for use in enhanced carbonation processes
Columbia
2010 Stasiulaitiene Binding potential of concentrated carbon dioxide using Lithuanian rocks Kaunas
Eloneva Reduction of CO2 emissions by mineral carbonation; steelmaking slags as a rwa material with a pure Calcium Carbonate end product
Espoo
Piredda Stabilization of MSW combustion residues by accelerated carbonation treatment and their potential carbon dioxide sequestration
Cagliari
Gaining$more$R&D$aSen8on$3$Year Name Description University
2010 Saha Advanced Mineral Sequestration Phoenix
Haug Dissolution and carbonation of mechanically activated olivine Trondheim
Prigiobbe Mineral carbonation for CO2 storage Zürich
2011 Renforth Mineral carbonation in soils Newcastle
Kwon MINERALIZATION FOR CO2 SEQUESTRATION USING OLIVINE SORBENT IN THE PRESENCE OF WATER VAPOR
Georgia
Wang Carbon dioxide Capture and Storage by Mineralisation Using Recyclable Ammonium Salts
Nottingham
2012 Stockmann Experimental Study of Basalt Carbonatization Toulouse
Fagerlund Carbonation of Mg(OH)2 in a pressurized fluidized bed for CO2 sequestration Turku
Nduagu Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration Turku
Mervic Determining Timescales of Natural Carbonation of Peridotite in the Samail Ophiolite (Oman)
Woods Hole
Back Mineral Sequestration of CO2 by reaction with alkaline residues Bayreuth
Hövelmann Carbonation reactions in ultramafic rocks: experimental insights into physicochemical processes, microtexure evolution and reaction mechanisms
Oslo
Beinlich Carbonation reactions in ultramafic rocks Oslo
Bonfils Mechasmes et verrous de la carbonation minerale du CO2 en voie aqueuse Toulouse
Gupta CO2 sequestration through Mineral Carbonation in Alkaline Wastes New Delhi
Gaining$more$R&D$aSen8on$4$
Year Name Description University
Paukert CO2 capture and Storage. Natural and Enhanced Mineralization in Peridotite Aquifiers of the Samail Ophiolite (Oman)
New York
Balucan Thermal studies of Magnesium Silicates from the Great Serpentine Belt in New South Wales
NS Wales
2013 Oskierski Natural carbonation of ultramafic rocks in the Great Serpentine Belt NS Wales
Salek Mineral CO2 Sequestration by Environmental Biotechnological Processes. Delft
Santos Sustainable Materialization of Residues from Thermal Processes into Carbon Sinks Leuven
Roland Evaluation of Mineral Carbonation Potential in Ultramafic Rocks West Scotland
2016 Knops CO2 sequestration with a Gravity Pressure Vessel: “Modeling and Lab results” Leuven
“Dutch”$research$• UU:! ! ! Prof.!Schuiling!! ! ! ! ! ! CO2
• NIOZ:!! ! Francesc!Montserrat! ! ! ! alkalinity!• Amsterdam! Arie!Vonk! ! ! ! ! ! nutrients,!CO2
• CATO!2014:!! Shiva!Salek!! ! ! ! ! ! ! biogas
• WUR:!! ! Hein!ten!Berge,!Rene!Rietra!! Alkalinity
• WUR:! ! Ralph!Lindeboom! ! ! ! ! biogas
• Deltares:! RWS,!greenSand!! ! ! ! ! Civil • Movares:! Inspec4on!path! ! ! ! ! ! Civil • Antwerpen! Barley/Wheat! ! ! ! ! CO2,!nutrient!!• Leuven!! Pol!Knops! ! ! ! ! ! ! ! End!product
Mineraliza8on$reac8on$
Olivine: Mg2SiO4 + 2CO2 => 2MgCO3 + SiO2
[∆H = -239.2 kJ/mol]
6/19/14! 15!CATO!2014!
Exothermic$reac8on$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”
6/19/14! 16!CATO!2014!
Advantages$
• Permanent:!– Geological!4me!scale!
– No!legacy!issue!• Environmental!benign!
• Large!quan44es!available!• Poten;al$use$exothermic$reac;on$
Disadvantages$• Slow!reac4on!speed:!
• Volumes!to!be!handled!
• Costs$• Environmental$applica;ons:$Nickel,$Chromium$
Conditions Focus
ambient CO2 Ambient CO2 + Various product HPHT Products
Natural weathering Combined effects Product replacement Process intensification
Products
IPCC$2005$
6/19/14! CATO!2014! 19!
Process$routes$
6/19/14! CATO!2014! 20!
Academic$groups$• ExXsitu$only:$
– Columbia!University!New!York,!USA!
– Turku,!Finland!– KU$Leuven,$Belgium$
– ETH,!Switzerland!– Heriom!Wam,!Edinburgh,!UK!
– Cambridge,!UK!
– University!of!Newcastle,!Australia!– University!of!Rome,!Italy!
– University!of!Tallin,!Estonia!6/19/14! 21!CATO!2014!
Company$ “Maturity”$ Field$of$opera8on$
Cambridge!Carbon!Capture!! ++! Products,!sec.!CO2!
Calera! ++! Products!
Calix!/!Novacem! +! Products!
Carbon8! +++!(plant)$ Waste!improvement!
Carbon!Cure! +++!(pilot)! Products!
Carbstone! +++!(plant)! Products!
Carbon!Engineering!! +! CO2!reuse!
CO2!Solu4ons! ++! CO2!reuse!
CO2!Transforma4on!! ?! Products!
Global!Thermostate!! +! CO2!reuse!
Greenmag! +++$(pilot$plant)$ Products!
Innova4on!Concepts!! +!(batch!lab)! Products!
ICS! 0! Products!
Kilimanjaro!Energy!! +! CO2!reuse!
Skyonic! ++!(pilot$plant)$ Products!6/19/14! 22!CATO!2014!
Cobouw$yesterday$
6/19/14! CATO!2014! 23!
Our$route$
6/19/14! CATO!2014! 24!
Process$intensifica8on$
• Chemical!process!
• Studied!1990M2005:!• High!Pressure,!High!temperature:!
• Enhanced!reac4on!rate:!185°C,!!40M100!bar!P!CO2,!!1!hour!residence!4me!
• Exothermic!behavior!known,!but!not!used!
6/19/14! 25!CATO!2014!
My$experience$
• Slow!reac4on!rate:!275°C,!!100!bar!P!O2,!!1!hour!residence!4me!
• Exothermic!reac4on:!M!Extremely!low!energy!density:$0,34$MJ/kg$
• Typical!550.000!m3/yr!(100!m3/hr)!
6/19/14! 26!CATO!2014!
E!D!
Reactor!
B!
A:!Incoming!material!B:!DownComer!tube!C:!CO2!injec4on!D:!UpComer!tube!E:!Surrounding!cooling!tube!
C$
A!
E$
E$E$
X1200$meter$6/19/14! 27!CATO!2014!
Well!head!
6/19/14! 28!CATO!2014!
Process$• Comparison!to!VerTech!process!Comparison$ VerTech$ CO2$Energy$reactor$
(pilot$scale)$
Experience!Construc4on!period!
>!10!years!1992!M!1994!
Not!!M!
Throughput! 120!m3/hr!550.000!m3/yr!
100!m3/hr!20!ton!Olivine/hr!
Energy!produc4on!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!injec4on! O2:!2400!kg/hr! CO2:!12!ton/hr!100kton$CO2/yr$
Max.!temp!Depth!
270°C!1200!meter!
190°C!!1200!meter!
Rocking$autoclave$
6/19/14! 30!CATO!2014!
Partners$Consor8um$agreement:$M University!of!Leuven! ! ! (Research,!kine4cs)!
M Sibelco!!! ! ! ! ! ! ! (Olivine)!
M Steel!company!! ! ! ! ! (CO2)!
M ISPT! ! ! ! ! ! ! ! ! (Sustainable!Process)!
M Innova4on!Concepts! ! ! (Patent)!
• Adjacent$research$• University!of!Lorain!!! ! ! (Research,!separa4on)!
• CEA!(marcoule)! ! ! ! ! (Separa4on)!6/19/14! 31!CATO!2014!
Reac8on$products$
6/19/14! 32!CATO!2014!
Reac8on$products$
Sample:!U3$
Sample:!U4$
6/19/14! 33!CATO!2014!
Reac8on$products$
Sample:!U3:$
SiO2!
MgCO3!
6/19/14! 34!CATO!2014!
Reac8on$products$
6/19/14! CATO!2014! 35!
Reac8on!3!
Sample:!U2:!Reacted!Olivine:!3$8mes$reacted$6/19/14! 36!CATO!2014!
Reac8on$2$
6/19/14! 37!CATO!2014!
Dissolving olivine
Par8cle$Size$Distribu8on$
6/19/14! 38!CATO!2014!
Input Output
Sequestered$CO2$
6/19/14! CATO!2014! 39!
50!
55!
60!
65!
70!
75!
80!
85!
90!
95!
100!
100! 200! 300! 400! 500! 600! 700! 800! 900!
Weight$(%)$
Temperature$(Celsius)$
TGA$results$Float!3,3!Sink!2,76!
FLoat!2,76!
MgCO3 ------------> MgO + CO2 "SiO2 ------------> SiO2 Mg2SiO4 -------- Mg2SiO4
Heat (450 C)
Per kg product:
350 gram CO2 sequestered
Mineralogy$• Crystalline!MagnesiumMCarbonate!(Magnesite)!
• Amorphous!Silica!
6/19/14! CATO!2014! 40!
Applica8ons$• Concrete! ! ! ! Silica!(pozzolanic!ac4vity)!.!! ! ! ! ! ! ! Fine!dispersed!par4cles!
• Metals! ! ! ! ! Recovery!Fe,!Ni,!Cr!
• Coa4ngs!/!paints!! “filler”!,addi4onal!advantage!.!! ! ! ! ! ! ! (par4cle!size,!color)!!
• Paper!! ! ! ! ! Silica!+!valued!filler!.!! ! ! ! ! ! ! (par4cle!size,!color)!
6/19/14! CATO!2014! 41!
CO2 “positive” + replacement valuable product
Research$phases$• Slurry$stream:$
– Now:!!Batch!autoclave:!1!liter!per!run!
– Next$phase:!!Con4nuous!autoclave!!100!liter/hr!
– Future$1:!!Pilot!scale:!100!m3/hr!(300!kton!CO2/yr)!≈!40%!solids!w/w!≈!20!bar,!≈!60°C!(can!be!varied)!
– Future$2:!Full!scale:!Mton!CO2/yr!!See!above,!focus!metals.!Less!Silica!!
6/19/14! 42!CATO!2014!
Future$
• Phase!2!Consor4um!
• Valorize!endMproducts!• Horizon!2020!
Questions ?
6/19/14! 43!CATO!2014!
Contact$data:$Innova4on!Concepts!B.V.!Gorinchem,[email protected]
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