research on co2 condensation technologygcep.stanford.edu/pdfs/wr5mezrj2sj6nffl5sb5jg/17_china... ·...
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Research on CO2Condensation Technology
Prof. Zhongyang Luo
State Key Laboratory of Clean Energy UtilizationZhejiang University
Global CO2 Emission
8512
334
825
1109
1800
2010
6522
316
654
832
1559
200119971990
61755836World297274Japan
6461034Former USSR
822620China14801345USA
CO2 Emission
(Mtc)
Country
Source: Energy Information Administration/International Energy Outlook 2001
CO2 Emission in China
1.8615.518.215180.36688322001
65
12
11
8
Mtc
4.461927776.51,1151,1092010
1.461814880.46618221997
1.3717.213881.46258011996
1.2915.89882.95146201990
%%Mtc%MtcMtcNatural GasPetroleumCoalTotal
CO2 CaptureAdsorption of the gas by use of molecular sieves Physical absorptionChemical absorptionlow temperature (cryogenic) processes Membranes
Physical absorption
Physical absorption using Selexol is the most appropriate technique to remove CO2 –CO2 Wheel
Removal CO2 by NH3 Scrubbing for Urea Production
US DOE– Win-WIN Scheme for CO2 Sequestration via Aqua Ammonia Scrubbing—28% Amonia capture 97% CO2SETRC of China and Tsinghua University make experimental research.
Cryogenic Processes--Frosting
Cryogenic methods for CO2 capture options –Ecole de Mine de Paris, France
Scheme of CO2 Sequestration by Membrane Contactor
Pumps
FGD Membrane Contactor
Heater
Flue Gas
StorageTank
Regenerator
CO2
AbsorptionLiquid
Cooler
Heater
Supplement liquid
Characteristics of MembraneAverage diameter of micropores: 0.02 ×0.2µmPorosity: 35-50%Longitudinal tensile strength: > 120MPaRapture strength: > 1.0MPaGas permeation rate:
2.0 × 10-2cm3(STP)/cm2⋅ s⋅ cmHg
CO2 Sequestration Process
Gas AbsorptionLiquid
Hollow Fiber Membrane Contactor
Flue Gas
Absorption
Liquid
Effect of Absorption Liquid Temp. on CO2 Sequestration Eff.
0
10
20
30
40
50
60
70
80
90
100
25 30 35 40 45 50 55
Absorption Liquid Temp.(℃)
Rem
oval
Eff
.(%)
MEA
MDEA
氨基酸盐
Effect of Absorption Liquid Concentration on CO2 Sequestration Eff.
0
10
20
30
40
50
60
70
80
90
100
0 0.5 1 1.5 2 2.5 3 3.5
Absorption Liquid Concentration(mol/L)
Rem
oval
Eff
.(%)
MEA
MDEA
氨基酸盐
Effect of Flue Gas Velocity on CO2 Sequestration Eff.
0
10
20
30
40
50
60
70
80
90
0.2 0.3 0.4 0.5 0.6
Flue Gas Velocity(m/s)
Rem
oval
Eff
.(%)
1mol/L的MEA
2mol/L的MEA
BoilerAshRemoval
FGD
Coal
Air
COMembraneScrubbing
2 CORecovery
2
CO Removal From Conventional PCF Power Plant2
Advantages of Oxygen Rich Combustion
Using O2/CO2 mixture in combustion system, raising CO2 content to 95%Not necessary to separate CO2 from flue gasImprovement in boiler efficiencyReduction SOx, NOx emission Simplification of flue gas treatment
CORecovery
2
Pulverized Coal
Air
O
Flue Gas Recycling
O /CO Combustion Process2 2
AshRemoval
Boiler
AirSeparation
O /CO2 2
2
O2/CO2 CombustionCombustion
SO2 Emission
0
20
40
60
80
0 1 2 3 4 5 6 7 8u (m/s)
SO2 R
emov
al E
ff. (
%)
Air-FB
O2/CO2-FB
Air-CFB
流化床
0
20
40
60
80
100
0 1 2 3 4 5
Ca/S molar rate
SO2 R
emov
al E
ff. (
%)
Air-FB
O2/CO2-FB
Air-CFB
Nox Emission
200
250
300
350
400
1050 1100 1150 1200 1250
Bed Temperature (K)
NOx (ppm)
Air-FB
O2/CO2-FB
Air-CFB
100
150
200
250
300
350
0.7 0.8 0.9 1 1.1Primary/Total Flow Rate
NOx (ppm)
Air-FB
O2/CO2-FB
Air-CFB
流化床
IGCC1
WasteWaterTreatment
GasCleanupGasifier
Expander
AirSeparationUnit
CombustionChamber
HeatRecoverySteamGeneration
SteamTurbine
GasTurbineCompressor
G
G
GMoisturewater
Air
Nitrogen
Oxygen
Slag
RawFuelGas Clean Fuel Gas
To SulphurRecovery
WaterCoal
Waste WaterStack Gas
IGCC2
WasteWaterTreatment
GasCleanupGasifier
Expander
AirSeparationUnit
CombustionChamber
HeatRecoverySteamGeneration
SteamTurbine
GasTurbineCompressor
G
G
GMoisturewater
Air
Nitrogen
Oxygen
Slag
RawFuelGas Clean Fuel Gas
To SulphurRecovery
WaterCoal
Waste WaterStack Gas
Oxygen
CO2
IGCC3
WasteWaterTreatment
Shift/CleanupGasifier
AirSeparationUnit
CombustionChamber
HeatRecoverySteamGeneration
SteamTurbine
GasTurbineCompressor
GGMoisture
waterAir
NitrogenOxygen
Slag
RawFuelGas
To SulphurRecovery
WaterCoal
Waste WaterStack Gas
Separator
CO2
H2
Gasifior
Heat Exchanger,
Clean SystemGas Turbine
Boiler
Combustor
Steam Turbine
Generator
Generator
Coal
Semicoke
Hot Gas Clear Gas
Flue Gas
Steam
Oxygen
PGCC
Clear System
Near zero emissions coal utilization technology with combined gasification and
combustion
Chemical Looping Gasification (CLG)
Near zero emissions coal utilization technology with combined gasification and combustion
CoalBiomass
Steam
Char¡¢ash¡¢ CaCO
CaO¡¢ash
Limestone
CO
Pressure or atmosphereCFBcombustor
PressureCFBGasifier
User
SOFCpower
Dust removal
Steam turbine
HRSG CondensationCO disposal
Ash drain
Water
Gas turbine
DustRemovalH2
2
3
H2
H2
2
H2
H2OO2
Air
Gas turbine
AirAirHeater
Exit
AirAir separation
CFB Gasifier:CO2 acceptor gasification process (~25bar)
Main reactions in gasifier:C+H2O=CO+H2-131.6kJ/mol
CH4+H2O=CO+3H2-206.3kJ/mol
CO+H2O=CO2+H2+41.5kJ/mol
CaO+CO2=CaCO3+178.1kJ/molH2S+CaO=CaS+H2O Coal
Biomass
Steam
Char¡¢ash¡¢ CaCO
CaO¡¢ash
Limestone
CO
Pressure or atmosphereCFBcombustor
PressureCFBGasifier
Ash drain
H2
2
3
O2
CFB CombustorChar combustion CaCO3 calcinationHydrogen combustion
Main reactions in CFB combustor:
CaCO3=CaO+CO2-178.1kJ/mol
C+O2=CO2+393.791kJ/mol
H2+1/2O2=H2O+286kj/mol
CoalBiomass
Steam
Char¡¢ash¡¢ CaCO
CaO¡¢ash
Limestone
CO
Pressure or atmosphereCFBcombustor
PressureCFBGasifier
Ash drain
H2
2
3
O2
H2 from SOFC
Advances:
Reduce the requirements on gasification. Only part of coal with high activity is gasified and the char with lower activity is burned in CFB combustor.
Realize Anaerobic Hydrogen Production with CO2 acceptor gasification and high concentration CO2for disposal in combustor
Realize near zero emission: few NH3 generating during gasification may be removed easily, H2S is captured by CaO in gasifier and transformed into CaSO4 in the combustor. Other pollution gas may be disposal together with CO2 gas stream.
Advances:
System is simplified by applying two circulating fluidized bed reactors.
Lower operation pressure (20~30bar) reduce the difficulties and cost.
High efficiency with applying SOFC
Efficiency calculation for a samplePower generation:400MWCoal gasification ratio: 0.7Operation Pressure: 25bar
Proximate analysis/w%, ar
Ultimate analysis/w%, ar Heat value/MJ/kg,
arM V A C H O N S Qdw
2.7 25.17
21.62 63.39
3.88 6.51 0.78
1.13
23.143
66.52System efficiency(%)
413538.88Net Power generation(kW)
99821.12Power consumption of the air compressor, kw
25955Power consumption of the air separation(kW)
3956.7Power generation from the steam turbine cycle,kw28Efficiency of steam turbine cycle (%)
152115.31Power generation from the gas turbine(KW)
59Efficiency of gas turbine cycle(%)
269208.48Power generation from the SOFC(kW)
51Oxygen utilization ratio in the SOFC(%)
85Fuel utilization ratio in the SOFC(%)
4.25Limestone supplement(kg/s)
1.1Excess oxygen ratio
1482.44Heat loss of the combustor(kJ/s)
1135Temperature in the combustor(K)
25Pressure in combustor(bar)1.42Hydrogen production rate(kmol/s)
0.7Coal gasification ratio3120.93Heat loss of the gasifier (kJ/s)
1205Temperature in the gasifier(K)
25Operation Pressure(bar)18.35Coal feed rate(kg/s)
CalculationItem
Effect of gasification ratio and operation pressure
0.55 0.6 0.65 0.7 0.75 0.8Gasification ratio
64
65
66
67
68
69
70
Syst
em e
ffici
ency
(£¥)
10 15 20 25 30Operation pressure£¨bar£©
60
61
62
63
64
65
66
67
68
69
70
Effic
ienc
y£¨£
¥£©
0.60.70.8
Experiments on char combustion in an atmosphere Fluidized bed combustor
出口气体
气体采样分析
压强机
N2O2CO2
气体混合器
流量计
反应器
气体预热器
Char combustion in different reaction atmosphere
0 50 100 150 200 250 300time (s)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8ca
rbon
con
vers
ion
rate
O2/CO2=61/39%O2/CO2=45/55O2/CO2=31/69AirO2/CO2=11/89
GE Current Options
3.944.22¢/kWHrCOE(1st Year)
Low sulfur (compliance) coals favored
All Coals plus liq. &solid opportunity fuels
FeedstocksFuel Flexibility40%40%%HHVEfficiency0.010.005lb/MMBtu- PM0.040.01lb/MMBtu- SO20.020.02lb/MMBtu-NO
Emissions$1,225$1,450$/KWCapitalSCPCIGCC
1. Pure Oxigen Combustion
2. O2 /CO2 Combustion---- Combustor need to be change
3. Shift Syngas to H2+CO2, Then Separate CO2 with MEA or Frosting
4. Separation of Flue Gas
5. Similar with Version 21
IGCC -- CO2 Condensation
1. Retrofit of IGCC
2. O2 /CO2 Combustion
3. Separation of Flue Gas
Compare of IGCC, SCPC +Seperation and O2 /CO2 Combustion
1. Capacity: 2×1000 MW2. Capital: 8388.05Million RMB3. Capital per KW:508 $/KW4. Coal:Shenfu Dongshen Coal5. Boiler:520 Million/Unit6. Efficiency: 45.16 %7. Coal Consumption:272 g/kW·h8. Ratio of Electricity used by Plant:6.5%9. COE:0.392RMB/kW·h
Compare of IGCC, SCPC +Separation and O2 /CO2 Combustion
With Membrane for CO2 Separation1 Velocity in the Membrane 0.2m/s,2. Size of Absorber 90M*90m*90m3. Price of Membrane: 20yuan/m2,4. Total area of Membrane:: 0.58 Million m2
5. Cost of 2 Seperator: 240 Million RMB6. Cost of the Total System: 600 Millions7. Separation Efficiency: 90%8. Capital per KW: 72.7 $/KW9. COE: increased 0.165 RMB/Kwh10. Total COE: increased 0.172RMB/Kwh
Compare of IGCC, SCPC +Seperation and O2 /CO2 Combustion
With CO2/O2 Combustion for CO2 Condensation
1 System for Oxygen 1760 Million RMB2. Total Cost of Retrofit: 2000 Millions RMB3. Cost per ton CO2 RMB/ton CO24.. Capital per KW: 242 $/KW5. COE: increased 0.108 RMB/Kwh6. Total COE: increased 0.131 RMB/Kwh
Compare of IGCC, SCPC +Seperation and O2 /CO2 Combustion
• Condensation technology for the CO2need to be evaluated,
• Utilization of CO2 is a best way for CO2control, need to be form the cycle–- Cycle Economy
Conclusion