1. Introduction - Firenze University Press

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[17] Lei Wanga, Yiying Jin, Yongfeng Nie, An investigation of accelerated and natural carbonation of MSWI fly ash with a high content of Ca, Journal of Hazardous Materials 2010;174:334–343 [18] Frederic Clarens, Fidel Grandia, Sandra Meca, Lara Duro, Joan de Pablo. Determination of CO2 sequestration capacity and stabilization of MSWI fly ash through accelerated carbonation. Proceedings of the third international conference on Accelerated Carbonation for Environmental and Materials Engineering, Turku (Finland), 29 November - 1 December 2010 [19] A. Gustavo Gonzalez, M. Angeles Herrador, A practical guide to analytical method validation, including measurement uncertainty and accuracy profiles, Trends in Analytical Chemistry 2007;26(3):227-238. [20] Renato Baciocchi, Alessandra Polettini, Raffaella Pomi, Valentina Prigiobbe, Viktoria Nikulshina Von Zedwitz and Aldo Steinfeld (2006). CO2 Sequestration by Direct Gas-Solid Carbonation of Air Pollution Control (APC) Residues. Energy & Fuels; 2006(20):1933-1940. 217
Abstract: PROCEEDINGS OF ECOS 2012 - THE 25 TH INTERNATIONAL CONFERENCE ON EFFICIENCY, COST, OPTIMIZATION, SIMULATION AND ENVIRONMENTAL IMPACT OF ENERGY SYSTEMS JUNE 26-29, 2012, PERUGIA, ITALY Process efficiency and optimisation of precipitated calcium carbonate (PCC) production from steel converter slag Hannu-Petteri Mattila a , Inga Grigalinait b , Arshe Said c , Sami Filppula d , Carl-Johan Fogelholm e and Ron Zevenhoven f a Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland, hmattila@abo.fi, CA b Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland, currently at Feyecon, Weesp, The Netherlands, ingagrigaliunaite@feyecon.com c Department of Energy Technology, School of Engineering, Aalto University, Espoo, Finland, arshe.said@aalto.fi d Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland, sfilppul@abo.fi e Department of Energy Technology, School of Engineering, Aalto University, Espoo, Finland, carl-johan.fogelholm@aalto.fi f Thermal and Flow Engineering Laboratory, Åbo Akademi University, Turku, Finland, rzevenho@abo.fi CO2 emissions could be reduced with capture and storage (CCS) methods. CCS causes costs for the industry, creating an extra barrier for implementation of these techniques. A recently developed mineral carbonation process producing a valuable product covering process implementation costs is advanced towards commercial scale. In this two-step process, calcium-rich steel converter slag is treated with an aqueous ammonium salt solution to selectively extract the calcium. Then the dissolved calcium is removed from the process liquid as pure precipitated calcium carbonate (PCC) by introducing gaseous CO2 to the system. This concept would utilise waste material from steel industry, and spare the natural resources used for conventional PCC production. Experimental results have shown that papermaking grade PCC can be produced with ammonium nitrate, chloride or acetate solvents. The used solvent has also been regenerated and recycled between the process stages, which reduces the need for fresh solvent and lowers the process costs. To maximise the PCC production in a continuous process, a thermodynamic process model in Aspen Plus is now constructed. The modelling results are validated with a series of semi-continuous experiments. It is found that by using staged carbonate precipitation the yield of pure product is increased. Ammonium nitrate is observed to enable the highest conversion of calcium from steel slag to calcium carbonate also in continuous operation. At ambient conditions the process steps generate heat but this low temperature heat cannot be utilised. The mixing and pumping energies for process operation are small in comparison to the heat duties in chemical reactors. Preliminary results on solid-liquid separation studies, on washing of the solid outlet streams, as well as on recovery and make-up needs of process chemicals are discussed. The work is a continuation of work presented by Said et al. at 22 nd ECOS in Brazil 2009. Keywords: Ammonium salt solution, Chemical thermodynamics, Mineral carbonation, pH swing process, Steel converter slag. 1. Introduction It is a widely accepted fact that the climate on Earth is changing because of human activities. One major factor causing global warming is the high emission rate of so-called greenhouse gases. Of these, carbon dioxide is an especially problematic one, since modern economies are based on combustion of fossil, carbon-based fuels. Thus the amount of CO2 emissions is also high compared to other greenhouse gas emissions like N2O that are possibly more harmful to the climate calculated per mass only [1]. Various methods have been proposed to diminish CO2 emissions. Apart from improving the efficiencies of existing combustion processes, choosing CO2 neutral fuels and decreasing the need 218
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Proceedings e report 90
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ECOS 2012 : the 25 th International
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Advisory Committee (Track Organizer
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The 25 th ECOS Conference 1987-2012
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VOLUME VI CONTENT VI. 1 CARBON CAPT
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-----------------------------------
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» Personal transportation energy c
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» Excess enthalpies of second gene
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VOLUME IV IV . 1 - FLUID DYNAMICS A
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» Exergy analysis and genetic algo
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» Optimal lighting control strateg
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» Stability and limit cycles in an
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PROCEEDINGS OF ECOS 2012 - THE 25 T
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Fig. 2. The exergy destruction of M
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ineffectiveness of the catalyst, in
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[ P EXmth EX SNG] ESR F where EXm
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Fuel inputkW 728221 203771 237719 3
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Not only at desined Rc (the ratio o
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4. DISCUSSION The graphic exergy an
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Figure 9(a) illustrates the energy
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Engineering Technical Conferences &
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generally there are four kinds of m
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However, even under the off-design
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Fig. 3. 600MW supercritical coal-fi
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CO2 rich loading(molCO2/molMEA) 0.4
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Net efficiency (%) 40.28 30.29 26.4
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Fig. 11. Schematic diagram of heat
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28.67%. In addition, through heat i
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Applied Thermal Engineering 2010;30
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Abstract: PROCEEDINGS OF ECOS 2012
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Fig. 1. Solution diagram of „four
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K ~ K 1 eK 1a p K 1a iK mK
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Oxygen recovery rate, % 105 95 85 7
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Calculated optimal compressor press
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The net amount of the flue gas leav
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Figure 3. Idea for lignite drying b
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Energy efficiency, % 34,00 33,00 32
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points efficiency increase related
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Figure A1b. Thermoflex flow sheet o
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Figure A3a. Thermoflex flow sheet o
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Figure A4. Thermoflex flow sheet of
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2.1. Life Cycle Assessment 2.1.1. G
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these factors. A sensitivity analys
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methane slip contributes to 13% of
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As can be seen in Fig. 5 the impact
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References [1] Eurobserv’er, The
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in which CO2 is separated from H2,
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dimensions of water droplets and wa
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Temperature (°C) 8 7 6 5 4 3 2 1 0
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4. Conclusions In the present paper
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penalty, but without separate captu
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0.5 - 0.7 kg/kg, resulting typicall
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3.3 - Utilising waste heat All exis
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4.5 - Suomusjärvi olivine deposits
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material will change from a few % t
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Fig. 5 Schematic diagram of the PFB
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8. Combined SO2 capture and CO2 min
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Fig. 10 Carbonate- (left) and sulph
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[13] Ekdahl, E., Idman, H. Statemen
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HEAT Fig. 1. Scheme and main reacti
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(raw) materials pre-heating and AS
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Fig 3- Aspen Plus® model 110
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Table 4. Elemental and XRD analysis
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the ÅA CSM route. The content of M
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moisture - 0,2237 ash - 0,0876 LHV
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2.2 CFB plant For the current momen
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The CO2 emission factor which indic
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The CO2 emission factor calculated
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Appendix A Fig A.1. Simulation mode
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(b) Fig. A.2. Simulation model of C
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Table A.1. Calculated parameters at
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References [1] Pfaff I., Oexmann J.
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with a CC installation could be avo
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2.3. Basic CHP plant indices. The b
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3. Off-design calculations The main
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Fig. 6. CHP plant efficiency Fig. 7
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amount of steam delivered to the he
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[5] Lukowicz H., Mroncz M.: Analysi
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water removal is feasible by coolin
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Figure 2. Sketch of the suggested P
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a b Figure 5. a) Exergy balance of
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The basis of comparison of each met
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Figure 7a. Impact of S/CATR on PCU
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However, more energy duty is requir
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3.1. JACOBIAN-ASPEN Interface ASPEN
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Fig. 3. Triple Pressure Bottoming S
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As seen from Table 1, the mass flow
Page 193 and 194: 4. Conclusion Fig. 5. Partial Emiss
Page 195 and 196: [19] Yantovski E., Shokotov M., Sho
Page 197 and 198: investigation and the developing of
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Page 201 and 202: hydrogen combustion technology at d
Page 203 and 204: eversibility of a pre-treated synth
Page 205 and 206: Fig. 1. TG curves collected for spe
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Page 211 and 212: CO2 capture capacity up to 150 th c
Page 213 and 214: the way for biogas utilisation is t
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Page 217 and 218: 4. Pilot plant tests In order to de
Page 219 and 220: Concerning the absorption reaction,
Page 221 and 222: with Regeneration (AwR), consists i
Page 223 and 224: [25] Aspen Plus 2004.1. Cambridge,
Page 225 and 226: systems for fuel drying waste strea
Page 227 and 228: heated in a heat exchanger placed i
Page 229 and 230: Fig. 2. Lower heating value of fuel
Page 231 and 232: Acknowledgements The results presen
Page 233 and 234: large amount of CO2 [1,5-7]. APCr a
Page 235 and 236: N 1 i ( x x i n 1 m ) 2.3. Carbon
Page 237 and 238: DTA analysis of the untreated APCrs
Page 239 and 240: Table 4. Relative Error (%) of the
Page 241 and 242: CaO HCl CaCl H O 193kJ / mol (
Page 243: [1] M. Fernández Bertos, S.J.R. Si
Page 247 and 248: 2. Process development 2.1. Backgro
Page 249 and 250: to dissolve the chloride salts prec
Page 251 and 252: The remaining 25% (5 ml/min) of the
Page 253 and 254: Table 6. Experimental conversions o
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Page 257 and 258: Calculating from the Aspen Plus mod
Page 259 and 260: [11] Mattila, H.-P., Experimental s
Page 261 and 262: Mg2SiO4(s) + 2CO2(g) →2MgCO3(s) +
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Page 265 and 266: Figure 2. Effect of Mg/Fe ratio of
Page 267 and 268: Figure 4 shows that an increase in
Page 269 and 270: Figure 5. Process flow diagram of M
Page 271 and 272: 2. Only cold utility is needed belo
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Page 275 and 276: Table A2. Extraction equations and
Page 277 and 278: [13] Teir S, Kuusik R, Fogelholm CJ
Page 279 and 280: In the area of coal technologies al
Page 281 and 282: Tabel 1. Characteristics quantities
Page 283 and 284: N m eT 4a ~ T cp T4a 1 ( K
Page 285 and 286: Auxiliary power rate of ASU, % 40 4
Page 287 and 288: [8] Buhre B.J.P., Elliott L.K., She
Page 289 and 290: 1.1 - Cement Manufacturing The ceme
Page 291 and 292: 2. Numerical model The purpose of t
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Table 4 - Results of the optimizati
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1. Define the studied system (in th
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cycle) or a lignin extraction plant
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limiting factor for the maximum siz
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Table 5. Key data for the four ener
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Global CO 2 emissions [ktonnes/yr]
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for biofuels and the investment cos
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The possibility to capture CO2 from
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[17] Berglin N, Andersson L. Proces
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Therefore NL Agency (an agency of t
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2.2.2. Pinch analysis Pinch analysi
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3. Case study 3.1. Plant and proces
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Te 1000 mp era 900 tur 800 e [°C 7
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Application of the approach led to
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The advantage of dynamic models is
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e equal at both time intervals and
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2.5. Selecting the number of TSs Se
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A) Time Slices for solar thermal en
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The first step of procedure is to p
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cTSs demand TS solar TSs 0 2 4 6 8
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In the presented paper a framework
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[5] Erdil E, Ilkan M, Egelioglu F.
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district energy network simulation
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were decreased by 10°C.All scenari
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Site 3 Heat sources Heat load Site
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3.2.2. Input data and assumptions A
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Fig.7 shows the operation forecast
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[13] TERMIS Operation User Guide, 7
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Polygeneration is a term used to de
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The increase in energy utilization
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are available for an entire year, 8
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6. Extensions to core methodology 6
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thermal storage and possible suppor
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laterites. Ore Geology Reviews, v.
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gasification [15], hybrid biomass g
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the second reactor. In this unit, s
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The variables effect was evaluated
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atio, as well as the shift-syngas f
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Fig. 4. Effect of operating tempera
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SDG has slight effect on the syngas
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[26.] Castle WF. Air separation and
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1. Introduction - Firenze University Press

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