A NEW METHOD FOR CO2 CAPTURE: FROSTING CO2 AT ATMOSPHERIC PRESSURE

D. Clodic, M. Younes Ecole des Mines de Paris – Center for Energy Studies 60, boulevard Saint-Michel – F 75272 Paris Cedex 06

ABSTRACT

CO2 capture in the flue gas of energy production facilities shows a great advantage providing that it is performed at atmospheric pressure. Taking into account that the triple point of CO2 is at 520 kPa and –56°C, the only possibility to capture CO2 at atmospheric pressure is to freeze it on cold surface. This frosting is performed with a system consisting in an integrated cascade, which is a vapor compressor system using progressive distillation of a refrigerant blend in order to evaporate at low temperature (between –130 and –110°C) and at sufficient high pressure to keep an acceptable pressure ratio for a single stage compressor. The design and control of the frosting/defrosting on the heat exchanger surface permits to recover fusion heat when CO2 is changing from solid to liquid phase. This latent heat of fusion is used to cool down the liquid blend of refrigerants just before evaporation. The paper presents the global design of the system, the energy consumption and the coefficient of performance of this low temperature refrigerating system.

INTRODUCTION

To capture CO2 a number of processes have been proposed : Pressure Swing Adsorption (PSA) [6], membranes [8], water injection [5], MonoEthnaolAmine (MEA) or DiMethylFormamide (DMF) [4] absorption, absorption + membrane [3], Oxy-combustion and CO2 removal by compression and liquefaction [1, 9]. Some are under field tests, others are at laboratory development. In order to realize balanced comparisons between those different processes, the CO2 frosting / defrosting process at atmospheric pressure presented in this paper (and in [2]) follows a format permitting to evaluate advantages and drawbacks of each technical option. Comparisons need to address: ! energy consumption referred to the captured mass flow rates (water, CO2, other species), ! type of energy used by the process (thermal or electric power), ! level of temperature and availability of thermal energy for flue gases of power generation plants, ! direct and indirect energy consumption depending on the "accessories" and on transport and use of CO2, ! sensitivity of energy efficiency referred to the temperature sink, ! sensitivity to the CO2 concentration in the flue gas, ! capture efficiency depending on the final CO2 concentration and on the difference of initial and final CO2 concentrations,

the lower the level of freezing temperature .3 2 -116.5°C permits to freeze the CO2 at an average temperature of –110. The ABC line in Figure 1 indicates the thermal and energy evolutions associated with the CO2 cooling in gas phase until 194.65K (-78. capability to capture other minor species). (% V/V) Freezing temp.5 15 -99. (°C) 100 -78. temperature and pressure of the captured CO2. TABLE 1 VARIATION OF THE FREEZING POINT TEMPERATURE DEPENDING ON THE CO2 CONCENTRATION Concen. Table 1 indicates the variation of the freezing temperature depending on the concentration. whereas the reverse phase change from gas to solid has no well defined designation .5°C.8 As it can be seen the lower the residual concentration. In order to limit the difference of temperature between the refrigerant and the frosting CO2.5°C) which is the freezing point at atmospheric pressure. it will be called "anti-sublimation" in this paper. Between –99 and –122°C.1 -136. more than 93% of a 15% CO2 concentration are captured by this process. 1.002 -155.7 1 -121.1 5 -109. This paper will focus mainly on energy consumption referred to the flue gas mass flow rate and on the sensitivity of energy efficiency associated with initial CO2 concentration. CO2 is frosted on the external surface of an evaporator (see figure 2) at temperatures varying between -99 et -122°C.! ! pre and post processing of the flue gas (required purity. . for –122°C the residual concentration is of 1%. A D E B C Figure1: Temperature – Entropy diagram of pure CO2 [7] The partial pressure is directly related to the volumetric concentration of CO2 in the flue gas and so is the freezing temperature. The refrigerant blend will typically evaporates between –125 an –102°C and so an average evaporating temperature of –113. CO2 CAPTURE BY "ANTI-SUBLIMATION" Sublimation is the phase change from solid to gas. the choice of a refrigerant blend with nearly the same glide of temperature permits to limit exergy losses. then the CO2 freezes at constant pressure and temperature.3 10 -103.7 0.9 0.

Then the solid CO2 begins to melt and is recovered in liquid phase by the pump. The 2 first evaporation levels are realized in evaporatorcondensers where the "heavy" components of refrigerant blend evaporates to condense on the other side of the heat-exchanger wall a fraction or the remaining fraction of "lighter" components of the refrigerant blend. to prevent plugging. THE INTEGRATED CASCADE The refrigerating system permitting the low temperature CO2 frosting consists in an Integrated Cascade (IC). the blend will contain typically 5 refrigerants with progressively low normal boiling points. like water at 0°C and some trace gases as hydrocarbons or SO2.1 and no. Figure 2: Low temperature evaporators The frosting/defrosting process is performed alternatively on evaporators no. Figure 3: Integrated Cascade for CO2 frosting Figure 3 shows an embodiment of the system. as shown in figure 1 by the segment C-D-E. A CO2 capture system is set at the exhaust of a gas turbine coupled to a combined cycle. The staged cooling is used to separate the components in the flue gases that can freeze at temperatures above –90°C. The IC concept is defined by the use of a single compression stage with 3 or 4 levels of evaporating temperature (3 are shown on figure 3).2 permitting to save up to 35% energy by defrosting capacity recovery. Figure 2 illustrates how the "hot" refrigerant blend enters in evaporator no.The frosting/defrosting process is organized in order that the refrigerant mass flow rate recovers the defrosting latent heat when solid CO2 melts.2 is shut). taking the halocarbon series the higher could be R-152a and the lower R-14. For a final average evaporation level of –113°C. .2 at a typical temperature of –50°C (the volume containing evaporator no. Thus during the defrosting process. Taking the hydrocarbon series the higher could be butane and the lower methane. 2. the temperature and the pressure raise up to –56°C and 520 kPa.

TABLE 2 BOILER FLUE GAS COMPOSITION %mass % vol N2 70. The energy required to cool the exhaust gas and capture the carbon dioxide depends on the concentration of H2O and CO2 and depends also on the ambient temperature. ! The flue gases pass through an adsorption matrix (dehydrator. ! The remaining gases at the exit of the evaporators (nitrogen. and are first cooled in an air or water heat exchanger (HX. The plate heat exchangers used in the integrated cascade may have an area density of about 400 m2/m3. ! The flue gas is then routed to the evaporators to freeze CO2 at an average temperature of about -110°C. ENERGY CONSUMPTION The flue gas temperature considered for the calculations is 5K above the sink temperature (20°C in the following calculations).Process steps ! Flue gases exit the heat recovery steam generator at a temperature of about 85°C.7% (boiler) CO2 concentration stream. finned heat exchangers for the partial condenser and the evaporators. copper and aluminum for finned H_Ex. Taking into account that the frosting temperature of the CO2 depends on the partial pressure of the CO2.1 H2O 3. The different heat exchangers used in the integrated cascade system are typically plate heat exchangers for the evapo-condensers. The considered frosting period is of 10 minutes.…) exchange counter-currently with the initial flue gases to cool them and thus the hotter flue gases recover the energy from the cooled gas exiting the evaporators.5 TABLE 3 COMPOSITION AFTER WATER REMOVAL % vol N2 79. Nitrogen is thereby almost cooled by nitrogen minus the heat transfer efficiency.45kg/s per m3 for a 18.9 CO2 14. CLASSICAL TECHNOLOGIES FOR A NEW PROCESS One key point of this deep cooling process is the use of available technologies to capture the CO2 from the flue gases. ! Then flue gases enter a first cascade heat exchanger and are cooled down to a temperature slightly above 0°C to condense the water from the stream. The available heat-exchanger technologies offer a compactness of about 800 m2/m3 for the gas heat exchangers.4 H2O 0 . which is equivalent to a flue gas stream of 8. After removal of water performed in the first cooling stage. Figure 3) in order to adsorb the remaining water vapor. The working temperatures of these heat exchangers are in the range of usual materials : stainless steel for plate heat exchangers. However corrosion of trace gases shall be taken into account depending on the flue gas composition. ! A second cascade heat exchanger operating at a temperature around –40°C to –50°C permits to cool the flue gases and condense trace gases or unburned HCs.4 5. Figure 3) down to a temperature depending on the ambient temperature (ambient air or ambient water).9 O2 5.5 CO2 20. 4. the energy necessary to the capture of 90% of the CO2 from a boiler exhaust gas is calculated here below.7 O2 5. A typical boiler flue gases composition is shown in table 2.8 75.3 5. the volumetric flue gas composition is indicated in table 3. so the compressor is a usual compressor for refrigerant mixtures. argon.5 13. The refrigerant mixture used for the integrated cascade is composed of refrigerants available for refrigeration. 3.35kg/s per m3 for a 5% (m/m) (gas turbine) CO2 concentration and 3. permitting a CO2 capture capacity of about 250kg/m3.

The total energy required by the system to capture the CO2 and compress it to 15MPa will be 1224kJ/kg CO2.8kJ/kg of flue gas which is equivalent in this case to 1297kJ/kg CO2. (which is the partial pressure of nitrogen and remaining trace gases) to the ambient pressure. Impact of higher condensing temperatures Taking into account a sink temperature of about 35°C and an average refrigerant condensing temperature of 40°C. ! to transfer the remaining CO2 vapor from the evaporators to the first tank by a volumetric pump. the energy required to compress the CO2 is 15 kJ/kg CO2.0147 MPa to end at 154K (-119°C). the evaporation temperature begins at about 150K (-123°C) and finishes at about 180K (-93°C). are based on a condensing temperature of 20°C and a compressor COP of 0. about 220kJ/kg CO2 have to be subtracted. which is equivalent to about 121kJ/kg CO2.56 to 15 MPa . For those conditions. the maximum work required to transfer the CO2 vapor is about 11kJ/kg CO2.41 and 1584 kJ/kg CO2 if the COP is of 0. the average evaporating temperature is about 164 K (-109°C) since the refrigerant blend evaporates with a temperature glide. the total amount of energy required to capture the CO2 is about 1077kJ/kg CO2 and the energy efficiency of the power generation is lowered by 10. the temperature corresponding to a partial pressure of the CO2 of 0. Table 4 shows the energy required to cool the flue gases as well as the energy required by the IC compressors. For an average temperature of 164K. Since the defrosting energy of the CO2 is recovered. The required energy is about 25kJ/kg gas.So the CO2 will begin to freeze at 174K (-99°C).8% due to the power consumption of the compressors.08 MPa abs. . the temperature corresponding to a 90% of the CO2 removal. taking into account typical compressor global efficiencies in the range of 70%. ! to compress the liquid CO2 captured in the tank from 0.108 The total amount of energy required by the integrated cascade compressor to cool and freeze the CO2 is about 265. This range corresponds to the average level of actual screw compressor technology used for industrial processes. Different systems or ways to minimize this energy can be applicable according to each system.55.45. COP values have been calculated based on simulations of the cascading system. TABLE 4 ENERGY REQUIRED FOR THE LIQUEFACTION OF CO2 Energy required by CO2 capture (kJ/kg of CO2) Energy required including auxiliaries (kJ/kg of CO2) Change in energy efficiency of power conversion 1077 1224 0. Much higher efficiencies can be reached by centrifugal compressors. Results summarized in table 4. The system needs auxiliaries requiring energy : ! to compress the exhaust gases from 0. The multiple staged cooling of integrated cascade permits to extract heat from the flue gases at different temperatures. the total amount of energy required to capture the CO2 and compress it to 15MPa will be 1708kJ/kg CO2 considering a COP for the 164K (-109°C) cascade level of about 0.

6. 7. “Hydrocarbon combustion power generation system with CO2 sequestration”. 2000.A (US).C. 2001. 1979. Nilsen E. 1999.I. Falk-Pedersen O. 2. “Installation for separation of CO2 from gas turbine flue gas”. 4. 9.E. Report T2002262. Nilsen Finn P. 8. . Younes M. Mock-up of this system is under realization in order to verify the level of energy efficiency and the effectiveness of CO2 capture.. Separation and compression of CO2 in an O2/CO2-fired power plant. “Process for separation of CO2 from CO2 containing gases”. Reddy S by Fluor Corp. Birkestad. US 4528002. REFERENCES 1. Torkildsen B. Taylor J. “Recovery of carbon dioxide plant vent gas using membranes”. The use of multi components blends in an integrated cascade leads to simple compression design and permits to take advantage of the temperature glide during evaporation. 1985. 1991. Reynolds W. “CO2 frosting/defrosting process at atmospheric pressure”. Linde G.H. WO 00/27505.. Standford University. Ravikumar R.CONCLUSIONS The capture of CO2 at atmospheric pressure avoids modifications of the power generation process. 1999. Thermodynamic properties in S. Progresses have also been made to improve efficiency of heat transfer for plate heat exchangers as well as for fin-tube heat exchangers. Sauer R. Dannstrom H. Clodic D. “Recovery of CO2 and H2 from PSA offgas in a H2 plant”. 1999. by Norske Stats Oljeselskap. Brandt H. by Clean energy systems inc.. which limits exergy losses for the low temperature evaporators. Linga H. FR 01 01 232. WO 99/13967. by LINDE AG. WO 994190. Refrigerating compression system is a well established technology where a number of progresses have been performed in order to reach high energy efficiency. Paganessi J E (FR) by Air Liquide. “a gas liquid membrane contactor for natural gas treatment”. Sigmundstad M. Typically centrigufal water chillers show coefficient of performance of the equipment referred to the ideal Carnot efficiency ranging from 75 to 85%. Chalmers University of Technology. H. The process described in this paper includes original concepts for the frosting/defrosting control and for the lay out of heat exchangers. The use of those technologies in adapted embodiment for CO2 capture permits to develop efficient CO2 capture systems. Anderson R. Sweden. 5. EP 0410845 B1. Refrigerating systems are clearly mature technologies where energy efficiency constraints have permitted to develop high efficiency equipment. 3. and so it can be used on existing systems as well as on new designs. Viteri F.

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