Nano-particle products from new mineral resources in Europe: EU FP7 Project … · 2010-10-15 · Nano-particle products from new mineral resources in Europe: EU FP7 Project “ProMine”

Nano-particle products from new mineral resources in Europe: EU FP7 Project “ProMine” Juha Sarlin, Ali Harlin, Sebastian Teir, Lea Räsänen, John Kettle

VTT Technical Research Centre of Finland, Biologinkuja 7, FIN-02150 Espoo, Finland

Extended Abstract ProMine is the acronym for an EU FP7 four year long research project entitled “Nano-particle products from new mineral resources in Europe” which started in May 2009. The ProMine consortium led by Geological Survey of Finland (GTK) includes 27 partners from 11 EU member states. The philosophy behind ProMine is to stimulate the extractive industry to deliver new products to the manufacturing industries. In particular, the project aims to develop five new, high value mineral-based nano products, two of which can be directly related to the forest industries. Firstly there is the generation of nano particles for coating paper for inkjet printing and secondly, precipitation of metals onto cellulose fibre templates.

Nanomaterials for paper coating Since the 90’s, various processes have been studied for converting silicate minerals to carbonate for CO2 capture and storage purposes. So far, no economic process has been found. Although vast amounts of silica would be produced as a by-product from the process, very little attention has been given to this topic. The work focuses on the development of processes mainly for magnesium- and calcium silicate raw material production [1-3]. Experimental research has been initiated studying two different main routes: one using pressurized CO2 as a solvent and another one using other acidic solvents. Calcium or magnesium silicate-containing rocks are first disintegrated for releasing calcium, magnesium and silica oxides. Nano silica particles are subsequently produced in an aqueous suspension under controlled process conditions for application to a paper web by either a foam application or curtain coating application technique.

Figure 1: Experiments for studying silica production by direct carbonation (1)

Figure 2: Experiments for studying silica production by indirect carbonation (2)

Promising results have been obtained with wollastonite and production route (2) and this can be quickly scaled-up. The estimated operating costs (based on first test): ~1200 €/t PCC (the cost for CO2 is not included – flue gas could possibly be used). Similar experiments with serpentine under way.

The considered application is inkjet printing. High speed inkjet web printing is a printing technology that has been developed over the recent decades and is expected to continue growing rapidly in response to the increased need for personalized editions and mail. To be commercially viable cheaper pigment formulations are required that still meet the requirements of offset printing. The paper web faces huge challenges for use in high speed inkjet printing. Poor image quality issues such as “ink bleed” coupled with poor optical density are amongst the main problems encountered. Other problems include “image strike through” when double sided printing due to uncontrolled penetration into the sheet and this also leads to extended drying time and this in turn limits the printing speed. The generated sustainable material is to be used as the top coating layer of inkjet papers for high speed printing. The technical concept is to replace the expensive, relatively thick top coating layer of multiple coated premium inkjet paper with a thin top coating of nano silica particles applied directly onto the paper printing surface using either a foam or curtain coating technique.

Precipitation of metals onto cellulose fibre templates The production of metal nano-particles using mine drainage water includes pre-treatment by filtration, subsequent sorting of the metals and finally production of metallised fibres by precipitation of a metal or metal compound, such as copper, onto cellulose fines. These metallised cellulose fibres so formed will be used as an electrically conductive material in an ink which can be used in industrial inkjet applications to form the conductive element in a semi-conductive or dissipative ink for abrasive paper. The density of these particles on surface should be sufficient to realize a semi-conductive or a dissipative surface. The density of the metal particles on the fibre surface should enable semi-conductivity about 10 -6 10 -8 S cm-1.

Experimental mine water titrations were modelled with ChemSheet (Gibbs energy minimisation of a system with ~150 components) and a procedure was developed to separate the metals in the complex mining water system.

Table 1

The first test of precipitation of the mine waters from Pyhäsalmi mines has been completed, where the main cations known to be present were Cu, Zn, Cd, Ba, K, Ca, Al, Mg, and Na, sulphate as the dominant counter-ion, pH around 2.8 and electrical conductivity ca. 600 mS/m

Figure 3: Experimental mine water titrations were modelled with ChemSheet

References 1. O’CONNOR, W.K., DAHLIN, RUSH, G.E., GERDEMANN, S.J., PENNER, L.R., NILSEN, D.N., 2005. Aqueous Mineral Carbonation, Final Report, DOE/ARC‐TR‐04‐002, 15 March 2005.

2. HUIJGEN, W.J.J., WITKAMP, G.‐J., COMANS, R.N.J, 2006. Mechanisms of aqueous wollastonite carbonation as a possible CO2 sequestration process. Chemical Engineering Science, 61, 4242–4251.

3. JIA, L., ANTHOY, E.J., LIN, W., RUAN, Y., GORA, D. 2004 Carbonation of Magnesium Silicate MInerals: an Experimental Study. Canadian Journal of Chemical Engineering, 82(6), 1289–1295.

Nano-particle products from new mineral resources in Europe

EU FP7 Project

Presented by:

John KettleInternational Development ManagerVTT Technical Research Centre of Finland

OverviewOverview

What is ProMine?What are the goals of this project?Part 1 Nano-materials for paper coatingPart 2 Precipitation of metals onto cellulose fibre

templatesConclusionsAcknowledgements

http://promine.gtk.fi

EU FP7 ProMineEU FP7 ProMine““

ProMine is an EU FP7-NMP-2008-LARGE project1. Started in May 2009, duration 48 months.

The ProMine consortium led by Geological Survey of Finland (GTK)

1. Includes 27 partners from 11 EU member states.

The philosophy behind ProMine is to stimulate the extractive industry to deliver new products to the manufacturing industries.

Nano-particle products from new mineral resources in Europe


EU FP7 ProMineEU FP7 ProMine

The project aims to develop five new, high value mineral-based nano products, two of which can be directly related to the forest industries.

1.1. The generation of nano particles for coating paper for The generation of nano particles for coating paper for inkjet printing inkjet printing

2.2. The precipitation of metals onto cellulose fibre The precipitation of metals onto cellulose fibre templates. templates.


Part IPart INanoNano--materials for paper coatingmaterials for paper coating


Goal of the nanoGoal of the nano--particle generationparticle generation

Can nano-scale silica particles be produced from magnesium and calcium silicate minerals using pressurized CO2?Application: paper coating using VTT technology

1. Aqueous suspension of hydrophobic/cationic nanosilica (or nanocalcite) particles

2. Particle size range < 100 nm3. Cost ~< 1200 €/t4. High purity (”paper white”)


Basic extraction experiments performed Basic extraction experiments performed for the following materials:for the following materials:

1. Wollastonite, CaSiO3 (concentrate product), 75 – 125 µm

2. Serpentine, Mg3Si2O5(OH)4 (ground mine tailings), 75 – 125 µm

3. Greek Olivine (ground mine tailings), < 100 μm

Norwegian Olivine, Mg2SiO4 (ground mine tailings)


Chemical extraction routeChemical extraction route

A multi-step process for selective extraction and precipitation

purer materialsallows for better control of the particle shape and size

Development of a multi-step process for carbonate production published in literature (Teir et al., 2007-2009)

Summary of wollastonite experimentsSummary of wollastonite experiments

Wollastonite 100 g

Solvent

Additive Additive CO2

Residue 15 g Gel 9 g Neutralisation precipitate 48-51 g

Carbonation precipitate 31-37 g

Spent solvent

Amorphoussilica

(80% SiO210% H2O)

Amorphoussilica

(80% SiO210% H2O)

Amorphoussilica

(86% SiO214% H2O)

Amorphoussilica

(86% SiO214% H2O)

Amorphoussilica and calcium

compounds

Amorphoussilica and calcium

compounds

99% CaCO31: Calcite2: Mostly vaterite

99% CaCO31: Calcite2: Mostly vaterite

Nanoparticle AnalysisNanoparticle Analysis

Mineral and water

CO2

Liquid ICP-AES-analysis

reactor

pH pH

Solid residue SEM,TGA, XRD & XRF-analysis

Turbiscan -optical instrumentfor measuring back-scatteringand transmission particle size

Turbiscan -optical instrumentfor measuring back-scatteringand transmission particle size

Nanosight - tracks the movement of individual nanoparticle undergoing Brownian motion to establish particle size,

Nanosight - tracks the movement of individual nanoparticle undergoing Brownian motion to establish particle size,

Summary of wollastonite experiments

Possible to produce pure amorphous silica from wollastonite using the chemical route

Floating gel purer (impurities <1 %) than sediment (impurities <11 %)• Brightness might still be enough

Floating gel smaller particle size than sediment particlesSize reduction verified with SEM: 75-125 μm tens of μm Part of the silicate dissolved into solution weaker solvent could possibly be used?

Wollastonite, 75-125 μm Leached residue (sediment) Leached residue (gel)

Types of PapersTypes of Papers

Coated paper has1. Increased smoothness of the printing surface2. Improved printed gloss3. Uniform ink absorption

For inkjet printing the coated surface needs 1. chemical groups that can form hydrogen bonds

and/orionic bonds with ink colorants, or

1. promote bonding with ink binders to provide adhesion for the pigmented layer.

Coated paper –v-Uncoated paper

Aim of inkjet ink setting processAim of inkjet ink setting process

To provide a dried ink surfaceTo fix the colorant part of ink at or in the uppermost layer of the coating

1. To produce high optical print density, bright colour tones, high sharpness, low bleeding, low print-through, and high rub and wet resistance

Allow the diluent/solvent part of ink to penetrate deeper into the structure.


Some terms in print quality of ink jetSome terms in print quality of ink jet

Feathering - WickingLarge scale,up to several mm

Small scale< 0.4 mm

Bleeding

colours mix together


Coating testing lineCoating testing line

Roll coating operated as 2- or 3-roll configurationSpray coatingCurtain coatingAir drying units 5 piecesUV-unit Egde guidance PLC-guidanceCorona-unitOffline calender*

•Velocity range 3…90 m/min•Substrates 40…300 g/m2

•Coating weight 0.1…400 g/m2

•Viscosities 1…15 000 mPas•Online monitoring


Part IIPart IIPrecipitation of metals onto Precipitation of metals onto

cellulose fibre templatescellulose fibre templates


Stages involvedStages involved

Extraction of copper and zinc from mine-tailingsGeneration of a conductive graphene coated copper nanoparticle inkjet fluidJetting ink to substrate


Mine tailing water analysis

The first test of precipitation of the mine waters from Pyhäsalmi mines has been completed, where the main cations known to be present were Cu, Zn, Cd, Ba, K, Ca, Al, Mg, and Na, sulphate as the dominant counter-ion, pH around 2.8 and electrical conductivity ca. 600 mS/m

Experimental mine water titrations were Experimental mine water titrations were modelled with ChemSheetmodelled with ChemSheet

Ink manufactureInk manufacture

Early stages of formulationultrasonic bath dispersionmicrotip sonication

no conductivity detected


ConclusionsConclusions

Nanoparticles can be generated from wollasonite for application to paper for inkjet printingMine tailings analysed, copper & zinc extracted for treatment of fibreWork continues….

ProMine Stakeholder workshop 30th September 2010


AcknowledgementsAcknowledgements

European Commision, FP7, NMP Grant agreement 228559Promine Project Consortia PartnersVTT colleagues:

1. Juha Sarlin, Prof. Ali Harlin, Sebastian Teir, Lea Räsänen


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Thank youPRESENTED BY

John Kettle

International Development Manager

VTT Technical Research Centre of Finland


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Nano-particle products from new mineral resources in Europe: EU FP7 Project … · 2010-10-15 · Nano-particle products from new mineral resources in Europe: EU FP7 Project “ProMine”