ULCOS Development of ULCORED Technology
ULCORED
Direct Reduction Concept for ULCOS
a brief intoduction
Peter Sikström LKAB
11th November 2013
OUTLINE • Introduction • Todays dominating processes • Potential for new DR-process • Proposal for new processes – Natural gas based – Coal based • Summary INTRODUCTION Requirements for a new DR-Process proposed 2006:
1. Different from existing processes like Midrex or HYL.
2. The Plant should only have one source where CO2 leave the process.
3. The Energy consumption has to be less than 8,4 GJ / t DRI.
4. Equipment and operation has to be simple.
5. Potential for use of fuels other than natural gas.
6. Investment costs has to be comparable to existing plants / plant concepts.
7. There must be good reasons for tests – technically and economic. TODAYS DOMINATING PROCESSES
Midrex HYL
Midrex process configuration
5 HYL PROCESS CONFIGURATION
6 • Introduction • Todays dominating processes • Potential for new DR-process • Proposal for new processes – Natural gas based – Coal based • Summing-up Dominating CO2 emissions from DR – EAF route arises from the DR-plant.
The main features for ULCORED :
• Use of oxygen instead of air in DR-plants results in
an off gas of 100 % CO2, which needs only to be compressed. • There should be possibilities to reduce the need of natural gas in DR-processes by 15 – 20 %. • Coal-, biomass-, bio waste gasification and hydrogen can be an alternatives to natural gas.
8 REACTIONS STARTING FROM METHANE
Endothermic
CO2 reforming CH4 + CO2 ↔ 2 CO + 2 H2 Ht = 247 kJ/mol Midrex
Steam Reforming CH4 + H2O ↔ CO + 3 H2 Ht = 206 kJ/mol HYL
Thermal cracking CH4 ↔ C + 2 H2 Ht = 75 kJ/mol
Partial oxidation CH4 + ½ O2 → CO + 2 H2 Ht = -36 kJ/mol Ulcored
Water gas shift CO + H2O ↔ CO2 + H2 Ht = -41 kJ/mol
Boudouards reaction 2 CO ↔ C + CO2 Ht = -173 kJ/mol
Complete combustion CH4 + 2 O2 → CO2 + 2 H2O Ht = -803 kJ/mol Exothermic
Source:9 TUDelft SYNGAS PRODUCTION TECHNIQUES
Feed (CnHm, …)
Steam Methane Reforming (SMR) Auto-Thermal Reforming (ATR): Partial Oxidation (POx). Endothermic: heating necessary Combined oxidation and steam Steam used for enhancing CH4 reforming heat is balanced conversion and avoid soots SMR ATR Pox reactants CH4 + steam CH4 + O2 + steam CH4+O2 +steam NG 450°C inlet T° 500-600 °C 750 °C O2 200°C outlet T° 870 °C 900-1000 °C 1300-1400 °C H/C in syngas 3 - 6 1,8 – 3,7 1,6 – 1,9
H2O content 5 % 18 % 10-13 % estimated cost without piping, 20 M€ 10 M€ 20 M€ ? 10 for ~ 40 000 Nm3/h (POx without shift)
MIDREX HYL ZR Iron Ore T= 420°C
T= 780°C T= 1085°C
CO2 reforming Steam reforming DRI CH + CO + Heat ↔ 2 CO + 2 H 4 2 2 CH4 + H2O + Heat ↔ CO + 3 H2 CO + N in off gas 2 2 CO2 + (N2) in off gas
POX pilot Partial oxidation
CH4 + ½ O2 ↔ CO + 2 H2 + Heat
CO2 in off gas
11 POX PILOT AT LINDE
• Tested in two campaigns
• New designed burner for H2 rich feed gas • Tube reactor with preheated gas
- 60% H2 - 40% CH4
ERPOX, Linde LE
TI Data registration 902 FIR TIR PIR O2 101 101 101
HH TI TIRS Local measurement 901 QE 1, Feed 803a HH TIRS N2, T ca. 25 °C, ca. 3 TIR 803b FIR TIR PIR 802 Nm³/h LNG 201 201 201 B 02
DN 80 CH4,LNG,C3H8,H2 DN 800 FI SG 608 607 V611 DN 1400 FI R 01 602 V602 QE 2, Combustion Probe distance to burner: N2 FI 609 chamber 90/150/210/270 cm HH_P HH_P H H FIR SG TIRS TIRS 901 608 701/1 701/2
TI HH_P H 901 TIRS 702/1 PI HH_P 902 H TIRS TI 703/1 504 H2- D Cooling water, T=15 °C, HH_P HH_P FI Trailer H H 502 ca. 3 m³/h TIRS TIRS V512 704/1 704/2
HH DN 800 H PI TIRS 401 401 flare
E 01
0
0
1
1
5
N V D QE 3, Product gas
LI 501
TIR 502 TI
503
0
9
1
0
N
5
D V
DN25 DN 25 H AT (°C) V503 AD (barü) zum Siphon Piping and Instrument Diagram Proj.- Nr.: 2471 2972 23.9.08 Tautz ERPOX ERPOX _ H2 rich feed gas Datum Ausgabe PFP01 12Y : / EFV / !Projekte/ 2471_XL-ATR / Umbau / Zeichnungen /Fließschema14.vsd CONCLUSIONS BY LINDE • The burner and reactor could be operated without problems.
• A stable flame without significant noise production could be demonstrated.
• The soot production is expected lower than 300-460 mg/Nm³ wet gas volume.
• Due to the atm pressure, the CO2 and CH4 content will be higher than the pre-calculations on the basis of assumed equilibrium.
• A higher operation pressure up to 7 bar(a) will reduce this contents
13 • Introduction • Todays dominating processes • Potential new DR-process • Proposal for new processes – Natural gas based – Coal based • Summary ULCORED • No reformer • No heater • High pressure
Less gas velocity in the shaft, gives less fluidisation, less fines leaving the shaft
CO2-removal and POx units are smaller than Midrex/HYL shifter/reformer
Less electric power need for recycle compressor
PSA instead of VPSA can be used
15 ULCORED
16 In depth studies of ULCORED
Fundamental modeling – Pellet scale models • LSG2M and NTNU – Reduction models – reduction kinetics – Shaft models • LSG2M, NTNU and SSSA – Process models by flow sheet simulations • MEFOS developed an HSC-model in SP 12 • IRMA developed in SP 2 by Corus • ASPEN developed by LSG2M in SP 9
17 Achievements from modeling Fundamental reduction modelling – Fundamental understanding of the DR process including dissemination of knowledge to the Universities
Flow sheet modelling – Optimisation of the process layout to fit the ULCORED process in steel plant environment – Process understanding including dynamics
Different approaches - similar results – Create credible basis for evaluation of the concept in different scenarios
18 Natural gas ULCORED
Useful fuel for complete plant Concept details
Full CO2 capture in the process
CO2 storage potential
O2 instead of air (low N2 in system) Reforming by a POX reactor
High H2 content in reduction shaft by water-gas shifter
(CO + H2O = H2 + CO2)
Bleed of H2 containing N2
19 Natural gas ULCORED H2 rich gas H rich 2 Bleeding N2 and for use in the steel plant
CO2 removal Gas cleaning CO2 storage
Shifter CO+H2O=CO2+H2
DRI reactor
Feed to the cooling Oxygen zone to re-heat the gas to the POX DRI cooler POX Natural gas
GREEN FIELD DRI
20 Coal based ULCORED
Excess gas for Concept details external users
CO removal 2 Reducing gas from coal in a Gas cleaning CO2 storage
Shifter gasifier, e.g. Shell gasifier
CO2 storage DRI reactor O2 instead of air
Coal gasification High H2 content in reduction DRI cooler Coal shaft by WGS water-gas shifter
Dust and sulphur removal GREEN FIELD DRI BROWN FIELD Hot or cold H2 excess gas for external
Oxygen users
21 Coal based ULCORED
Excess gas for external users
CO2 removal Gas cleaning CO2 storage Shifter
DRI reactor 22 Coal gasification
DRI cooler Coal
Dust and sulphur GREEN FIELD DRI BROWN FIELD removal Hot or cold
Oxygen Integration into a steel plant
The purpose of an integration of ULCORED into the existing steelmaking system is to
utilise the possibility to have one CO2 emission point from the system, instead of having one per heating gas consumer CO2 Gas holder H2 rich gas, in plant usage Natural gas / Coal Power station ULCORED DRI Oxygen 92% Met.
Electric power
Electric Hot Ladle arc Casting rolling furnace HRC furnace mill
23 Material-Balance related to 1 t DRI (cold) (Metallization 92%, Carbon 2,76 %)
0 0
*Remark 24 Mass-Balance for new DR-Concept (cold DRI)
25 Energy-Balance for new DR-Concept (cold DRI)
26 Energy consumption and CO2 emissions
27 Capex & Opex
28 SUMMARY
• Can be ”quick-fix” for a brown field improvement of CO2 emissions, especially where natural gas is relatively cheap.
• By integration in a steel plant, LRI can be a choice considering the successful tests made in the LKAB Experimental BF.
– The LRI-tests with a DR-product reduced to only 65% metallization degree respond very positive in the BF with stable operation and coke consumption at 200 kg/tHM.
• Tests has to be done to prove the concept. EXPERIMENTAL DR PLANT
• Production: 1 ton Fe/h
• Recirculation of top gas
• Working pressure (shaft) 0-8 bar (g)
• Gas flow: ~1700-3100 Nm3/h
• Temp to shaft: 900-1050 ºC
30 EXPERIMENTAL DR PLANT
31 WE STRIVING FOR A SUSTAINABLE FUTURE
THANK YOU
32 CHARGING A PRE-REDUCED BURDEN INTO EBF
Trials during 2 campaigns in the Experimental BF
DRI at 15, 30 and 60 % of the burden LRI at 50 and 100 % of the burden
Reductant rate decrease up to 26 % Reductant rate decrease up to 33 % Emission of CO decreased up to 37% Emission of CO2 decreased up to 24% 2
DRI metallisation degree over 90 %. LRI metallization degree about 65%
Significant productivity increase with increasing amount of pre-reduced iron ore