NEDO PROJECT COURSE 50. Development of High Throughput and Energy Efficient Technologies for Carbon Capture in the Integrated Steelmaking Process

Transcription

1 NEDO PROJECT COURSE 50 Development of High Throughput and Energy Efficient Technologies for Carbon Capture in the Integrated Steelmaking Process CCS Workshop Düsseldorf, Germany November 8-9, 2011 Masao Osame Sub-Project Leader of COURSE50 (JFE Steel Corporation) P 1

2 NEDO PROJECT COURSE 50 Introduction of COURSE50 Project P 2

3 Member of COURSE50* Project *CO2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50 New Energy and Industrial Technology Development Organization P 3

4 Cool Earth Innovative Energy Technology Program P 4

5 Time Table of Technology Development Project Targets (1) Development of technologies to reduce CO 2 emissions from blast furnace Develop technologies to control reactions for reducing iron ore with reducing agents such as hydrogen with a view to decreasing coke consumption in blast furnaces. Develop technologies to reform coke oven gas aiming at amplifying its hydrogen content by utilizing unused waste heat with the temperature of 800 generated at coke ovens. Develop technologies to produce high-strength & high reactivity coke for reduction with hydrogen. (2) Development of technologies to capture - separate and recover - CO 2 from blast furnace gas (BFG) Develop techniques for chemical absorption and physical adsorption to capture - separate and recover - CO 2 from blast furnace gas (BFG). Develop technologies contributing to reduction in energy for capture - separation and recovery - of CO 2 through enhanced utilization of unused waste heat from steel plants Phase 1 Phase 1 Step 1 Step 2 (2008~12)( ) Phase 2 Industrialization & Transfer NEDO Project Phase 1 Step 1 (2008~ 12) (billion yen) P 5

6 Project Outline (1) Technologies to reduce CO 2 emissions from blast furnace (2) Technologies for CO 2 capture Iron ore H 2 amplification Shaft furnace COG reformer Coke production technology for BF hydrogen reduction Coking plant High strength & high reactivity coke Reduction of coke Coke BF BFG Chemical absorption Physical adsorption CO-rich gas Regeneration Tower Reboiler CO 2 storage technology Iron ore pre-reduction technology Other project H 2 Sensible heat recovery from slag (example) Waste heat recovery boiler Hot air Slag Coke substitution reducing agent production technology Cold air Reaction control technology for BF hydrogen reduction Kalina cycle Power generation Technology for utilization of unused waste heat COURSE50 / CO 2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50 P 6 Absorption Tower CO2 capture technology Steam Electricity Hot metal BOF

7 Research and Development Organization R&D Organization NEDO Contract research COURSE 50 Committee Kobe Steel, Ltd. JFE Steel Corporation Nippon Steel Corporation Nippon Steel Engineering Co., Ltd. Sumitomo Metal Industries, Ltd. Nisshin Steel Co., Ltd. * COURSE 50 Committee at the Japan Iron and Steel Federation (JISF) supports the 6 companies R&D activities. Sub Projects 1. Development of technologies to utilize hydrogen for iron ore reduction. 2. Development of technologies to reform COG through the amplification of hydrogen. 3. Development of technologies to produce optimum coke for hydrogen reduction of iron ore. 4. Development of technologies to capture separate and recover CO 2 from BFG. 5. Development of technologies to recover unused sensible heat. 6. Holistic evaluation of the total process. P 7

8 NEDO PROJECT COURSE 50 Study of Carbon Capture Technology P 8

9 Carbon Flow in Integrated Steelmaking Process Carbon Flow Input C 100 Coke 5 PC 18 Coke Oven Coal 77 Coke 66 COG 8 Coke 62 Sinter etc 9 BF Dust 1 BOF Pig Iron 9 LDG 8 BFG 70 By-product Gas 87 Furnace, Power Plant etc Waste 1 Air 96 Tar 3 Chemical Prduct 3 Gas CO 2 Emission (1000t/Year) Major Composition(% Vol.) H 2 CO CO 2 N 2 CH 4 P 9 Heat Capacity (kcal/nm 3 ) Coke Oven Gas ,800 Blast Furnace Gas 2, LD(BOF) Gas ,000 Hot Stove Gas 1, Average annual emission from a middle sized blast furnace

10 Property of Blast Furnace Gas (BFG) Blast Furnace gas (BFG) Flue Gas of Thermal Power Plant Operating Ratio (%) 97 (-3~+1) 40 (Average) Load Factor (%) Approx ~100 Pressure(kg/cm 2 ) 2.4 (Outlet) 1.0+α 1.0+α Temperature ( ) 144 (Outlet) Room temp. 50~110 Compo- sition CO 2 (%) 22 (±2) 13 (Coal) 3~9 (LNG) CO (%) 23 (±2) 0 H 2 (%) 4 (-1~+2) 0 Heat Cap. (kcal/m 3 Approx <Key Issues> 1. Small fluctuation of BFG generation and its composition among blast furnaces =>Experimental results of one blast furnace can be applied to other furnaces. 2. Composition difference between BFG and power plant flue gas =>Evaluation of CO 2 capture performance for various technology is necessary. P 10

11 Example of Existing CO 2 Capture Technologies Chemical Absorption Physical Adsorption Membrane Separation Pure Oxygen Combustion Process Outline Feed Gas Off-gas CO 2 Re-boiler Feed Gas Off-gas Vacuum Pump Boiler Rich CO 2,H 2 O,O 2 etc Treatment Cooling Water Absorber Regenerator Fuel SO x,no x etc CO 2 Feature *Well established and commodity technology *Suitable for scale-up *Large energy consumption Gas Holder *Simple structure *Well established technology *Large power consumption required for vacuum pump *Simple structure *Low CO 2 collection efficiency and expensive membrane *Suitable for high pressure gas Pure O 2 *Lower CO2 separation cost *Large energy consumption for O 2 production Further R & D Status *Lower energy consumption *Combination of other tecnologies *Lower energy cost through performance improvement of adsorptive material *Early development stage *Commercial test stage Considering from BFG property and required performance, high throughput and energy efficient technologies will be developed based on the existing chemical absorption and physical adsorption practice. P 11

12 NEDO PROJECT COURSE 50 Chemical Absorption Technology P 12

13 What is the chemical absorption process? Gas other than CO 2 Outline of system Absorbent Features CO 2 recovery rate: 90% or more CO 2 purity: 99% or more Issue: A large amount of heat is required. Absorber Feed Gas CO2 partial pressure in gas 1 Pump Desorption area 3 Pump CO2 loaded absorbent Heat Exchanger Reaction in absorbent 120 Absorption and desorption of CO2 CO2 loading on absorbent 2 Stripper Steam Ambient temperature Absorption area Outline of process 1 In the absorber, the absorbent is in contact with the gas containing CO 2. CO 2 is selectively absorbed. 2 The absorbent is sent to the stripper and is heated to about 120 to release CO 2. 3 The absorbent is cooled to ambient temperature and is fed to the top of the absorber to absorb CO 2 again. P 13

14 Development of Chemical Absorbents (Collaborative Research with RITE) 1.Development of chemical absorbent to reduce energy consumption for CO 2 capture 1 Identification of reaction mechanisms of chemical absorbents using quantum chemistry and molecular dynamics, as well as component designing. 2 Designing of high-performance amine compounds by chemoinformatics (analysis by multivariable regression model) with the existing amine database. 3 Examination of synthesis technologies for mass production of highperformance amines. 4 Exploration of absorbents other than amines. 5 Evaluation of chemical absorbents by laboratory experiments and process models. 2.Testing of new chemical absorbents for industrial application 1 Evaluation of new absorbents in terms of corrosivity and long-term stability. 2 Support for experiments with real gas by model simulations. P 14

15 Collaboration Scheme to Develop New Chemical Absorbents Development of new chemical absorbents (NSC + RITE + Univ. of Tokyo) Quantum chemical calculations Design new amine Compounds. Experiment Synthesize new amines Design absorbents Evaluate the performance Industrial application Chemoinformatics Suggest new amine compounds Evaluation with test plants (NSEC) CAT1 (1t- CO 2 /d) CAT30 (30t-CO 2 /d) Absorber Stripper Reboiler P 15

16 Development of New Absorbents Projects Absorbents Development Status * COCS ( ) COURSE50 ( ) RITE-5C (NO. 1) RN-1 (NO. 2) RN-2 2-component absorbent Under investigation for practical use Single-component absorbent Results evaluation of plant tests at CAT1 & CAT30 2-component absorbent 結合が弱化 Under plant test at CAT1 RN-3 Under exploration スルホラン P 16 * Cost-saving CO2 Capture System

17 Development of Technologies for Chemical Absorbents for CO 2 Capture from BFG Objective Development of new amines / absorbents with the aid of quantum chemical calculations Structural transformation of DMAE Prediction of absorption rate and heat of reaction 10 Energy (kcal/ mol) DMAE New Amine activation energy heat of reaction Experimental confirmation of high performance high absorption rate without increasing heat of reaction Reactant Transition State Product CO 2 HCO 3 - R Designing of absorbents incorporating newly found tertiary amines RN-3 family absorbent P 17

18 Development of the chemical absorption process Test Equipment: Process Evaluation Plant (30t/D) Off gas CO2 Absorber Regenerator Nippon Steel Kimitsu Works No. 4BF Bench Plant(1t/D) Rebolie r Absorber Regenerator P ,17 June

19 CO 2 Separation Cost(JP /t-co2) Development of the chemical absorption process Strategy for Cost Reduction 2004Fy Waste heat recovery 3.0 Present P 19 Development of the chemical absorbent Optimization of the chemical absorption process Optimization of the entire system (with the improvement of steel-making process) Goal Heat Unit Consumption (GJ/t-CO 2 )

20 Performance Evaluation (Energy Consumption) Heat energy consumption (GJ/t- CO2) MEA(conventional absorbent) Absorbent developed by competitors Literature values NO. 1 NO. 1 (estimated value) NO. 2 (estimated value) NO. 2 Project Target ,000 10,000 CAT - 1 CAT - 30 CCS commercial plant Plant scale (ton/day) P 20

21 Evaluation of Chemical Absorbent Degradation 15 :CO2 collection from combustion exhaust gas Amine loss (Wt%) 10 5 MEA (Literature value ) No.2 No ,000 1,500 2,000 2,500 Operation time (hours) P 21

22 Corrosion Test Results Feed Gas Gas after removal of CO 2 (off gas) 1 2 Absorber Pretreat - ment Absorbent 3 Absorbent Containing CO 2 Product gas CO 2 4 Stripper Steam Corrosion level (mm/year) Steel quality grade SS400 MEA (general absorbent) CORTEN SUS304 SS400 CORTEN SUS304 SS400 No.1 CORTEN SUS304 SS400 CORTEN SUS304 1Feed gas 2Off Gas 3Stripper inlet 4Stripper outlet P 22

23 NEDO PROJECT COURSE 50 Physical Adsorption Technology P 23

24 Outline of Physical Adsorption Technology Non combustible gases Outline of technology development Selection of adsorbent PSA lab. tests Operating conditions Design bench scale test equipment Cost reduction Adsorption simulation Establish adsorption model Compare with lab. tests Data matching Combustible gases Conceptual diagram of 2-staged PSA for BF gas Bench scale PSA operation Data accumulation for Scaling up incorporation Utilities simulation Gas flow simulation Concretize industrial process Clarify & reduce recovery cost P 24

25 Cost Reduction Target Recovery cost has come down to near the target level. Operational studies will be made with the bench-scale plant to achieve the target. Index of Recovery Cost ~ Conventional Laboratory Estimation Target P 25

26 Flow Diagram of Bench-scale Plant (ASCOA- 3* ) P 26 *ASCOA: Advanced Separation system by Carbon Oxides Adsorption

27 Bird s-eye View of ASCOA-3 P 27

28 Results of the First Run at ASCOA-3 Maximum CO 2 recovery of 4.3tons/day was reached! (Target:3tons/day) All 3 targets were achieved at the same time. CO2 Recovery(t/ day) Purity target:90% Recovery ratio target 80% Recover target:3t/ day Recovery Purity Recovery Ratio 3 targets achieved Achieve 3 targets Max. Recovery:4.3t/ day CO2 Purity, Recovery Ratio(%) Max. Purity:99.5% / 8 3/ 11 3/ 11 3/ 14 3/ 15 3/ 16 P 28 3/ 17 3/ 18 3/ 22 3/ 23 3/ 24

29 NEDO PROJECT COURSE 50 Utilization of Unused Waste Heat for Energy Supply for CO 2 Capture P 29

30 Unused Thermal Energy in Various Process Model steelworks 8 million ton crude steel per annum Temperature [ ] Calorie (TJ/year) Coke oven flue gas after heat recovery Main exhaust gas after heat recovery Unstable generation rate BF slag sensible heat COG sensible heat Main exhaust gas Cooler exhaust gas COG ammonia water Hot stove gas Steelmaking slag sensible heat BOF gas sensible heat HRM RF CAPL RF Plate Mill RF CAPL NOF Slag granulation tank water HDG RF HDG NOF Sintering process Coking plant BF Steelmaking Rolling exhaust gas Waste heat at medium to low temperatures / molten materials at high temperatures difficult to recover economically currently unused P 30

31 Cascade Use of Unused Thermal Energy Exhaust gas from processes 375 A 133 2nd stage Recovery of waste gas after steam generation by new technologies B Organic Rankine Cycle PCM heat accumulation 105 Heat accumulation with PCM (Phase Change Material) Heat pump Power generation with low boiling point. medium Transport C Thermal catalyst for chemical absorption Direct use of sensible heat Fuel reforming Heat pump for high temperature Rankine cycle for medium temperature 140 steam for chemical absorption 1st stage 133 Generation of saturated steam at 140 to the lower temperature limit P 31 T G Kalina Cycle Power for physical adsorption T G 140 steam for chemical absorption Heat pump D

32 Issues of Unused Thermal Energy Usage Boiler Heat pump PCM Power generation with low boiling point medium Direct use of heat Fuel reforming Common issues Improvement of heat exchanger Increased heat transfer rate Compactification Prevention of corrosion & clogging Thermal insulation technology Reduction in equipment cost Optimization of recovery technologies for various waste heat (including combination with heat accumulation) Scaling up Increase in rate of heat absorption & release Specific issues Enhancement of chemical heat pump reaction Development of catalysts Development of catalysts Improvement of reactors Development of PCM Extension of temperature range Improvement of heat accumulation density Control of expansion Improvement of corrosivity Improvement of system efficiency Technology to prevent thermal decomposition of working medium Technology to prevent leakage Optimal reaction conditions (steam ratio, etc) P 32

33 Technology Development for Sensible Heat Recovery from Steelmaking Slag (1) Development of process for slag product Continuous solidification of slag by water cooling roll (Roll forming process) Applicable composition : CaO/SiO 2 =2.2~3.8 Thickness 5mm Recovery air temperature mm Shape controlling roll Cooling roll trough Conveyor Thickness of slag (mm) Slag A CaO/SiO 2 =3.8 Obs. Ave. Gap 4.55mm 2.17mm 1.46mm Rotating rate of cooling roll (rpm) P 33

34 Technology for sensible heat recovery Heat transfer calculation for packed bed with countercurrent flow in consideration of thermal conductivity of slag Thin-plate-type slag provides higher heat recovery ratio and higher temperature air. 797 Heat-transfer calculation in plates Difference calculus Surface coefficient of heat transfer Sphere:Ranz-Marshall`s formula Plate:Johnson-Rubesin`s formula Technology Development for Sensible Heat Recovery from Steelmaking Slag (2) Slag Slag Top bottom Air Air Z-axis z = 0 z = Z Roll forming of slag (thickness 5mm) = High heat recovery ratio Roll forming process of molten slag & Packed bed heat recovery process P 34 with countercurrent flow Distance from top of tower (m) Gas t emperature Top Average slag temperature Surface temperature of slag Heat recovery ratio :49% 3.0 Bottom ,000 1,200 temperature ( )

35 1.6m copper twin water cooling roll Target production rate:1ton/min Direct pouring from slag ladle heat-resistant conveyor Technology Development for Sensible Heat Recovery from Steelmaking Slag (3) Bench-scale test for sensible heat recovery from slag 2010:Construction of bench-scale test equipment for roll forming 2011:Bench-scale test for roll forming Construction of bench-scale test equipment for sensible heat recovery 2012:Bench-scale test for sensible heat recovery ROCSS:Roll type Continuous Slag Solidification process Conveyer Cooling roll Trough Slag ladle (60t/ch) Ladle tilt machine P 35

36 Technology Development for Sensible Heat Recovery from Steelmaking Slag (4) ROCSS Operating Status Cooling roll Conveyer Slag ladle Trough Target ( after roll forming) Thickness of slag : 5mm Slag temperature : 1000 P 36 Ladle tilt machine

37 NEDO PROJECT COURSE 50 Summary P 37

38 Current Status of Technology Development 1. CO 2 Capture (1)30 t-co 2 / day chemical absorption test plant (CAT30) has been operative since early 2010, generating a world s lowest level of heat consumption. (2) 3t-CO 2 / day physical adsorption test plant (ASCOA3) has been operative since early 2011, achieving expected result. 2. Energy Supply for CO 2 Capture (1) Heat recovery from steelmaking slag has been confirmed through laboratory-scale tests. *Test plant(rocss) has been constructed. P 38

39 Hydrogen reduction Timetable for Industrialization JHFC Project * (2001-) COG H2 enrichment Project ( ) PhaseⅠ (Step 1) Partial substitution of carbon by hydrogen Reduction fundamentals Optimized gas injection Bench-scale H2 enrichment PhaseⅠ PhaseⅡ (Step 2) Mini exp. BF Verification Exp. BF + Partially Industrial Post - COURSE50 Industrialization Development of fundamental Green electricity & Green hydrogen production technologies technologies Establishment of infrastructure CO2 Storage & Monitoring CO2 capture COCS Project ** ( ) Intern l collaboration CO 2 capture from BFG Process evaluation plant Total evaluation incorporating mid - low temperature waste heat recovery ULCOS (2004-) Matching between capture equipment and mini exp. BF P 39 Integrated operation of semiindustrial capture equipment (several hundred t- CO2/D) with exp. BF Hydrogen Steelmaking 1 st industrialization by ca <Prerequisite> CO2 storage available Economic reasonability Industrialization * Japan Hydrogen & Fuel Cell Demo. Project. * *Cost-saving CO2 Capture System