Sixth Annual Conference on Carbon Capture & Sequestration

Capture Advanced Concepts

CO2 CAPTURE IN IGCC PLANTS VIA CRYOGENIC SEPARATION

S. Consonni, F. Vigano - Politecnico di Milano(*) T. Kreutz - Princeton University L. De Lorenzo - BP Alternative Energy
May 7-10, 2007 Sheraton Station Square Pittsburgh, Pennsylvania
(*)

currently visiting the Princeton Environmental Institute, Princeton University

Background and Scope

Technologies of choice for the removal of CO2 from shifted syngas in IGCCs are chemical and physical absorption With high-pressure gasification, Selexol physical absorption is apparently preferable Selexol system is expensive (large absorber vessel, large solvent flow rates, recycle compressor, refrigeration system, etc.) and makes CO2 available at low pressure large power requirements An alternative technology could be cryogenic separation This presentation discusses thermodynamic issues and plant configurations Preliminary performance estimates are presented for a system applicable to the IGCC planned by BP at Carson (California) Work is underway to verify simulation results and estimate costs

Syngas expander

CO2 removal by Selexol

CO2 pump Intercooling Refrigeration

~
Saturator to gas turbine

~
Main CO2 compressor CO2 Absorber Refrigeration Aftercooling

CO2 to storage

CO2 lean solvent

from H2S removal

Aftercooling

Solvent Dehydrator

~
Hydraulic turbine

~
Recycle compressor

H2O

~
Flash drums Intercooling Solvent pump

Aftercooling

Basic assumptions
Refer to conditions expected for BP DF-2: IGCC with CO2 capture fed with pet-coke, to be built in the Carson refinery (California) Entrained-flow, oxygen-blown GE quench gasifier followed by two shifts and cooling to nearly ambient temperature
Mole flow Mol fract Mass flow Mass fract kmol/hr % kg/s % 40.1 0.139 0.201 0.121 343.9 1.193 2.676 1.612 15,719.5 54.530 8.802 5.304 12,315.5 42.722 150.556 90.724 5.9 0.020 0.026 0.016 29.8 0.103 0.331 0.199 100.2 0.348 0.780 0.470 271.9 0.943 2.574 1.551 0.2 0.001 0.003 0.002 28,827.0 100.000 165.949 100.000

H2O CO H2 CO2 CH4 Ar N2 H2S COS Total

Temperature, C Pressure, bar 3 Density, kg/m LHV, MJ/kg

40.0 60.0 48.17 6.77

Basic thermodynamics of cryogenic separation

First liquid forms at about -10C

25 bar 40C

Condensation temperature decreases as a consequence of lower CO2 partial pressure in the gas phase When temperature and pressure reach triple point conditions, a solid phase appears

Gas/liquid mixtures
For mixtures with other species in addition to CO2, thermodynamic properties are estimated by RedlichKwong-Soave (RKS) equation of state. Very similar results would be obtained with the PengRobinson equation of state. To be conservative, weve neglected the depression of the freezing point temperature due to the presence of species other than CO2 Further work is needed to clarify the behaviour of CO2based mixtures at low temperature, particularly the freezing point.

Basic process: cool syngas to the lowest temperature that still prevents freezing

T = - 53C

At 60 bar: Removal of H2S is nearly 85% Removal of CO2 is about 80%

Two-stage scheme

31 bar

58 bar 25C 159.36 kg/s

Two-stage scheme: CO2 and H2S capture

Scheme considered in this work

30 bar

31 bar

60 bar 40C 165.95 kg/s

Assumptions
Turbomachines
Polytropic efficiency of compressors Polytropic efficiency of syngas expander Hydraulic efficiency of CO2 pump Mechanical - electric efficiency of motor drivers 0.82 0.85 0.75 0.90 15.00 10.00 3.00 5.00 1.00 1.50 NH3 3.00 5.00 0.20 1.00 10.20

Heat exchangers
Minimum T of gas/gas exchangers, C Minimum T of liquid/gas exchangers, C Minimum T of CO2 refrigerant/condensing gas exchangers, C Minimum T of ammonia/condensing gas exchangers, C p in main heat exchangers, bar Auxiliary power consumption / heat to environment, % Refrigeration fluid T superheating at evaporator exit, C T subcooling at throttle valves inlet, C p in CO2 refrigerant evaporators/condenser/intercooler, bar T along ammonia evaporator/condenser, C COP of auxiliary chillers (evap. 20C, conden. 35C)

External refrigeration cycle and auxiliary CO2 chiller

Internal refrigeration
30 bar 112C 31 bar 10C 24.03 kg/s 100C 135.4 kg/s

135.4 kg/s

60 bar 40C 165.95 kg/s

-53C

-53C

135.4 kg/s

Internal refrigeration
30 bar 112C 31 bar 10C 24.03 kg/s 135.4 kg/s 100C 135.4 kg/s

60 bar 40C 165.95 kg/s

-53C

-53C

150 bar 25C 135.4 kg/s

+3.8C

-33C -56C

Internal refrigeration
30 bar 112C 31 bar 10C 24.03 kg/s 135.4 kg/s 100C 135.4 kg/s

60 bar 40C 165.95 kg/s

-53C

-53C

150 bar 25C 135.4 kg/s

+3.8C

-33C -56C

External refrigeration
30 bar 112C 31 bar 10C 23.13 kg/s 41.38 kg/s 60 bar 40C 165.95 kg/s 100C 23.13 kg/s

-55C

-55C

136.1 kg/s

External refrigeration
30 bar 112C 31 bar 10C 23.13 kg/s 41.38 kg/s 60 bar 40C 165.95 kg/s 100C 23.13 kg/s

-55C

-55C

136.1 kg/s

-60.0C

-45.6C

External refrigeration
30 bar 112C 31 bar 10C 23.13 kg/s 41.38 kg/s 60 bar 40C 165.95 kg/s 100C 23.13 kg/s

-55C

-55C

136.1 kg/s

-60.0C

-45.6C

Preliminary design of syngas turbo-compressor

COMPRESSOR: centrifugal, 5 stages shaft power 28 MW
1st stage: external diameter 0.25 m blade height at impeller discharge 0.016 m

EXPANDER: axial, 6 stages shaft power 23 MW

single shaft 33,000 rpm

6st stage: external diameter 0.24 m blade height 0.025 m

electric motor 5.5 MWel

5th stage: external diameter 0.22 m blade height at impeller discharge 0.01 m

1st stage: external diameter 0.19 m blade height 0.01 m

Cryogenic system Minimum T of gas being treated Maximum P of gas being treated C bar kg/s LHV, MJ/kg bar C kg/s % mol CO2 % mass CO2 kmol/s % kmol/s % ppmvd ppmvd ppmvd ppmvd MW LHV % MW LHV % MW LHV % internal ref. -53.00 300.00 24.03 44.25 30.00 10.00 135.35 97.92 99.71 3.07 91.94 3.07 89.52 19.34 1.84 4.98 0.06 13.47 1.28 1.67 6.18 15.45 1.43 external ref. -55.00 300.00 23.13 45.78 30.00 10.00 136.13 98.01 99.72 3.08 92.48 3.09 90.04 19.34 1.73 4.98 0.06 12.94 1.23 1.63 6.03 14.88 1.38

Syngas to gas turbine

Flow to carbon storage

Internal vs external refrigeration: mass balances

CO2 captured from syngas Carbon captured from syngas H2S in H2S out (to gas turbine) COS in COS out (to gas turbine) H2 lost in flow to storage CO lost in flow to storage Total LHV lost in flow to storage

Internal vs external refrigeration: energy balance

Syngas in Clean syngas out Main syngas compressor Syngas expander Syngas turbo-compressor CO2 pump LT refrigeration compressor MT refrigeration compressor HT refrigeration compressor CO2 refrigeration after compression Auxiliaries for cooling water Overall power consumption kg/s MW LHV kg/s MW LHV kg/s MW shaft kg/s MW shaft MW el kg/s MW el kg/s MW el kg/s MW el kg/s MW el MW el MW el MW el kJel / kg CO2 captured

Cryogenic system internal ref. 159.36 1078.52 24.03 1063.07 44.26 28.50 23.90 -23.39 5.68 115.11 1.57 131.82 7.29 259.29 18.63 338.29 15.90 2.25 0.72 49.80 368.96 external ref. 159.36 1078.52 23.23 1063.64 41.38 27.96 23.13 -23.04 5.47 117.98 1.38 13.13 1.82 40.51 14.26 49.94 11.24 0.00 1.13 35.29 259.99

Ext. refrigeration vs Selexol: flows and compositions

Selexol + CO2 drying + CO2 compression Syngas in kg/s LHV, MJ/kg kg/s LHV, MJ/kg kg/kmol bar C H2O, % mol Ar, % mol CO, % mol CO2, % mol H2, % mol N2, % mol CH4, ppmv COS, ppmv H2S, ppmv kg/s % mol CO2 % mass CO2 165.95 6.77 26.97 40.07 5.44 30.00 131.30 4.89 0.18 1.96 4.86 92.38 0.59 326.99 n.a. n.a. 140.12 99.97 99.99 Selexol for H2S removal + drying + cryogenic with ext. refrigeration 165.95 6.77 27.59 38.37 5.64 30.00 111.90 5.07 0.15 1.92 5.38 91.96 0.56 294.87 0.06 1.73 136.13 98.01 99.72

Syngas to gas turbine

Composition of syngas to gas turbine, dry basis

Flow to carbon storage

Ext. refrigeration vs Selexol: overall performances

Selexol + CO2 drying + CO2 compression CO2 captured from syngas Carbon captured from syngas H2 lost in H2S removal H2 lost together with CO2 to storage CO lost in H2S removal and in flow to storage H2S removed Total LHV lost (loss of H2 and CO + H2S removal) Selexol pumps (net of hydraulic turbines) Selexol compressors Solvent refrigeration CO2 compressors CO2 refrigeration after compression CO2 pump Syngas turbo-compressor NH3 compressors Auxiliaries for cooling water Syngas expander Overall power consumption kmol/s % kmol/s % MW LHV % MW LHV % MW LHV % MW LHV MW LHV % MW el MW el MW el MW el MW el MW el MW el MW el MW el MW el MW el kJel / kg CO2 captured 3.17 93.00 3.19 90.00 n.a n.a n.a 39.08 42.67 3.80 12.11 6.05 10.38 31.33 3.08 1.91 1.63 -6.01 60.49 431.74 Selexol for H2S removal + drying + cryogenic with ext. refrigeration 3.08 90.17 3.09 87.85 5.81 0.55 12.94 1.23 1.63 6.03 39.08 59.77 5.32 2.9 4.17 1.66 1.38 5.47 27.32 1.68 44.57 328.35

Conclusions
CO2 cryogenic separation appears a viable alternative to conventional absorption techniques Must remove H2S upstream of cryogenic process Two-stage schemes can achieve 90% CO2 removal rates External ammonia refrigeration cycle appears definitely superior to internal refrigeration Compared to Selexol, significant reduction of overall power consumption No new technology, although turbomachinery must be specifically designed for cryogenic plant Further work needed to increase accuracy of these preliminary performance estimates and to assess costs