Chromium research at SINTEF and NTNU Eli Ringdalen, SINTEF

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1 Chromium research at SINTEF and NTNU Eli Ringdalen, SINTEF

2 SINTEF - Who we are Our vision -Technology for a better society Independent non-profit research institute >90 % of income from contract R&D, Turnover 400 mill 2000 employees 75 % researchers 55 % of researchers with PhD SINTEF Materials and Chemistry One of 7 Institutes in Sintef, Turnover 100 mill 400 employees 5 departments Materials and Nanotechnology Oil and gas process technology Sustainable energy technology Biotechnology and nano medicine Industrial process technology 2

3 Industrial process technology (Metallurgy) 3 Industrial research within metal production Ferroalloys (mainly Mn alloys, but also Cr) Silicon, Ferrosilicon and some SiC Aluminum and electrolysis Main expertise areas: Minerals and raw materials Metal production process metallurgy and electrolysis Recycling Casting and casting technology Metal forming and preparing Emission and environmental monitoring Thermodynamics and kinetics Process modelling

4 NTNU- Norwegian University of Science and Technology Dep. Materials Science and Engineering registered students 240 doctoral degrees awarded/year 550 professors Light metals (Al, Mg) Ferroalloys & silicon Ceramic materials Energy Technology 21 professors 190 1st 5th grade students (MSc) 10 exchange students 70 Ph.D. students 20 post doc. 4 International 2 year Master program available

5 SINTEF - NTNU strategic and operational cooperation Strategic coordination NTNU personnel work on SINTEF projects SINTEF staff teach at NTNU Joint use of laboratories and equipment 5 Cooperation between SINTEF and NTNU has developed over 65 years

6 Chromium research at Sintef-NTNU Determining thermodynamic data for chromium (1995) Included in Fact Sage data base Used in calculation in chromium projects Reaction mechanisms and kinetics PhD E Ringdalen 1999 Excavations of industrial furnaces Ore properties and slag chemistry (2011) Ferbasa Energy consumption and pretreatment (2013- ) Ferbasa Utilising of Mn-competence Use of natural gas in chromium reduction ( ) Effect of ore properties, temperature and gas In cooperation with Oleg Ostrovski Road map for use of gas in metal production

7 Zones in HC FeCr furnaces Drying, heating, Loose charge A + B C Loose charge LEVEL OF TAPHOLE Solid materials: Ore Coke Fluxes 6,1 m Slag + metal+ ore+ Slag + metal coke Porous Metal Metal Cokebed Slag + metal+ ore+ coke Slag + metal Coke bed Liquid slag + coke 10,0 m From excavation at Elkem Rana

8 Most Cr 2 O 3 in slag is found as undissolved chromite % Cr 2 O 3 in sample % Cr 2 O 3 in liquid slag % Chromite in sample Slag C Slag A Dissolution and chromium content lost to slag is most likely determined by a combination of ore and slag properties This is indicated by a rim of Al 2 O 3 around some undissolved chromite Slag D Slag E Slag B Chromite Slag C: 14.1 % Cr 2 O 3 Slag B: 6.95 % Cr 2 O 3 Al 2 O 3 Slag Dissolution of CrO x CrO x Cr Exchange Chromite Slag Alloy reaction SiO 2 Si Chromite From investigations at Ferbasa

9 Ore properties vary considerably - example from Ferbasa Comisa High amount of gangue minerals Chromite grains have Outer Fe rich rim with cracks Jaccurici Low SiO 2 in ore in concentrate Highest melting temperature Slag with lowest Cr content Alloy with highest Si content Jaccurici ores with highest melting temperatures must be used to produce alloy with highest % Si Comisa ores will give lowest Cr-losses to slag Probably due to Fe-rich rim with cracks From investigations at Ferbasa

10 Energy requirement for main HCFeCr- reactions H 2 O(l) = H 2 O(g) Fe 2 O 3 + 3CO(g) = 2Fe + 3CO 2 (g) FeO + CO = Fe + CO 2 (g) ΔH 298 = 44.0 kj ΔH 298 = kj ΔH 298 = kj With CO gas in prereduction zone or unit H 2 O(g) + CO = H 2 (g) + CO 2 (g) CO 2 + C = 2CO Fe 2 O 3 + 3C = 2Fe + 3CO (g) FeO + C = Fe + CO (g) FeCr 2 O 4 + 3C = Fe + Cr 2 O 3 +CO (g) Cr 2 O 3 + 3C = 2Cr + 3CO (g) Coke bed ΔH 298 = kj ΔH 298 = 114 kj ΔH 298 = kj ΔH 298 = kj ΔH 298 = kj ΔH 298 = kj With solid C in prereduction zone or unit Solid materials: Ore, Coke Flux, Quartz Slag + coke MgCr 2 O 4 + 3C = 2Cr + MgO + 3CO (g) SiO 2 + 2C = Si + 2CO ΔH 298 = kj ΔH 298 = kj

11 Staged heat and material balance HCFeCr Ferbasa February 2011 Charge in 25 o C 3,39 H 2 O(l) = 3,39 H 2 O(g) 1.55CO +0,78 O 2 =1.55CO o C 2,7 H 2 O + 2,7 C = 2,7 H 2 + 2,7 CO 1000 o C 1200 o C 1400 o C 1700 o C 778 kwh 0,32FeO + 0,32C = 0,32 Fe + 0,32CO 169 kwh 5,33 FeCr 2 O 4 +5,33 C=5,33 Cr 2 O 3 +5,33 Fe+5,33 CO 530 kwh 5,33 Cr 2 O 3 +16C =10,66 Cr+ 16 CO 1,31SiO 2 +2,62C=1,31Si+2,62 CO 6,31 C= 6,31 C 8,8 SiO 2 =8,8 SiO 2 (l) 9,5MgO=9,5MgO(l) 3,26 Al 2 O 3 =3,26 Al 2 O 3 (l) 0,42CaO = 0,42 CaO (l) 2108 kwh Total 3585 kwh Gas out 450 o C 25.5 CO 1000 o C 27,0 CO 1200 o C 24,3 CO 1400 o C 24,0 CO 1700 o C 18,62 CO Drying Energy from CO-gas Reduction of bound water Reduction of FeO not bound in chromite Reduction of FeO in chromite Reduction of oxides to alloy Melting of fluxes to slag Energy from electrical current Coke bed 4217 kwh/ton alloy Incl. losses

12 kwh/ton Energy consumption vary with raw material and product temperatures Off gas temperature Increasing raw material temperature from 25 o C to 600 o C, decrease energy consumption by 488 kwh/ton Slag temperature Base case Raw material temperature Base case Temperature C Example from Ferbasa

13 kwh/ton Energy consumption vary with compositions % H 2 O in raw materials Energy consumption increases with 22 kwh/ ton alloy for each % increase in H 2 O in raw materials % Si in alloy % Cr 2 O 3 in slag Base case % Si in alloy, %Cr 2 O 3 in slag, % H 2 O in raw materials Example from Ferbasa

14 kwh/ ton of alloy Reduction in energy consumption by pretreatment Increasing temperature Base case Removal of H 2 O + removal of crystalline H 2 O + Preheating to 600 o C + prereduction of all FeO + prereduction of 75 % Cr 2 O 3 Example from Ferbasa

15 Temperature C CO (ion intensity) Temperature C CO (ion intensity) Reduction of chromite with CH 4 or H 2 gas - NatGasMetal Cr 2 O 3 is reduced with methane CH 4 while chromite ores are only partly reduced Exp. Max reduction Conversion rate rate Temperature C % F4 Cr 2 O ,8 F5 Cr 2 O ,2 F6 Comisa ,9 F7 Comisa , F5 Cr 2 O F7 Chromite Temperature C CO 0 Temperature CO 0 00:00:00 01:12:00 02:24:00 03:36:00 04:48:00 06:00:00 07:12:00 00:00 01:12 02:24 03:36 04:48 06:00 07:12 Time (hh:mm) Time (hh:mm) Planned to be published at INFACON 2018

16 Coralsea - Chrome Oxide Reduction an Atomic Level modelling and Spectrographic Experimental Approach Pure chrome oxide is reduced by methane, but real ores are not: Cr 2 O 3 + CH 4 ->Cr 3 C 2 Why? Experimental Chrome ore synthesis Vary levels of Mg, Al Carburization experiments Computational Atomistic description of pure chrome oxide Interaction with CH4 (adsorption, decomposition) Influence of other elements Two PhD-students:.

17 Road map for use of gas in metal production - Increased value creation and reduced emissions Vision Sustainable and CO 2 neutral Norwegian metal industry Use of gas in metal production will contribute to this The roadmap will be used in discussions with authorities as goverment, financing institutions and for own strategies The road map is based on goverments CO 2 strategies Content of the roadmap Alternative technologies Prerequisites for technology development Competence R&D, Short and long term Research infra structure Financing technology development Prerequisites for industrial use A living industry Profitable, sustainable technology Availability of raw materials including gases Availability of Electrical energy Risk capital Made by SINTEF and NTNU in cooperation with the industry

18 Relevant technologies, examples Pretreatment and pre-reduction Pretreatment of Mn-ores with gas Pre-reduction of ilmenite with gas Reduction to metal in solid phase DRI Direct reduced iron with syn-gas or H 2 (learn from technologies) Reduction by methane, CH 4 to alloy Gas as carbon source Composite raw materials with carbon black from gas Densifying bio based charcoal Carbon black from gas in electrode production New Mn-process Gas in liquid melt Gas refining New processes Liquid metal as a reductant, new Mn-process Reduction with solid carbon in gas mixtures with H 2 or CH 4 SiC from SiO and CH4 Gas anodes in Al-electrolysis Co-location of different industries in industrial clusters Densifying bio carbon with gas

19 Effect on CO 2 emission of reductant and of pre treatment Prereduction unit Energy production for SAF Fossile fuel Renewable energy sources - oil, gas, coal, coke, - hydropower, sun, wind,. Fossile fuel - Natural gas, oil, coal Fossile fuel Biocarbon, off-gas, - Natural gas Fossile fuel Biocarbon, off-gas Renewable sources

20 Thanks for your attention

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