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D. Clodic, M. Younes

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


CO 2 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 CO 2 is at 520 kPa and –56°C, the only possibility to capture CO 2 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 CO 2 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.


To capture CO 2 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 CO 2 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 CO 2 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, CO 2 , 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 CO 2 ,

! sensitivity of energy efficiency referred to the temperature sink,

! sensitivity to the CO 2 concentration in the flue gas,

! capture efficiency depending on the final CO 2 concentration and on the difference of initial and final CO 2 concentrations,

! pre and post processing of the flue gas (required purity, capability to capture other minor species),

! temperature and pressure of the captured CO 2 .

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 CO 2 concentration.


Sublimation is the phase change from solid to gas, whereas the reverse phase change from gas to solid has no well defined designation ; it will be called "anti-sublimation" in this paper. The ABC line in Figure 1 indicates the thermal and energy evolutions associated with the CO 2 cooling in gas phase until 194.65K (-78.5°C) which is the freezing point at atmospheric pressure, then the CO 2 freezes at constant pressure and temperature.


CO 2 freezes at constant pressure and temperature. D E C A B Figure1 : Temperature




Figure1: Temperature – Entropy diagram of pure CO 2 [7]

The partial pressure is directly related to the volumetric concentration of CO 2 in the flue gas and so is the freezing temperature. Table 1 indicates the variation of the freezing temperature depending on the concentration.











(% V/V)










temp. (°C)

As it can be seen the lower the residual concentration, the lower the level of freezing temperature ; for –122°C the residual concentration is of 1%. Between –99 and –122°C, more than 93% of a 15% CO 2 concentration are captured by this process.

CO 2 is frosted on the external surface of an evaporator (see figure 2) at temperatures varying between -99 et -122°C. In order to limit the difference of temperature between the refrigerant and the frosting CO 2 , the choice of a refrigerant blend with nearly the same glide of temperature permits to limit exergy losses. The refrigerant blend will typically evaporates between –125 an –102°C and so an average evaporating temperature of –113.5°C permits to freeze the CO 2 at an average temperature of –110.5°C.

Figure 2 : Low temperature evaporators The frosting/defrosting process is organized in order that the

Figure 2: Low temperature evaporators

The frosting/defrosting process is organized in order that the refrigerant mass flow rate recovers the defrosting latent heat when solid CO 2 melts, as shown in figure 1 by the segment C-D-E.

Figure 2 illustrates how the "hot" refrigerant blend enters in evaporator no.2 at a typical temperature of –50°C (the volume containing evaporator no.2 is shut). Thus during the defrosting process, the temperature and the pressure raise up to –56°C and 520 kPa. Then the solid CO 2 begins to melt and is recovered in liquid phase by the pump.

The frosting/defrosting process is performed alternatively on evaporators no.1 and no.2 permitting to save up to 35% energy by defrosting capacity recovery.


The refrigerating system permitting the low temperature CO 2 frosting consists in an Integrated Cascade (IC). 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). The 2 first evaporation levels are realized in evaporator- condensers 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. For a final average evaporation level of –113°C, the blend will contain typically 5 refrigerants with progressively low normal boiling points. Taking the hydrocarbon series the higher could be butane and the lower methane, taking the halocarbon series the higher could be R-152a and the lower R-14.

The staged cooling is used to separate the components in the flue gases that can freeze at temperatures above –90°C, like water at 0°C and some trace gases as hydrocarbons or SO 2 , to prevent plugging.

gases as hydrocarbons or SO 2 , to prevent plugging. Figure 3: Integrated Cascade for CO

Figure 3: Integrated Cascade for CO 2 frosting

Figure 3 shows an embodiment of the system. A CO 2 capture system is set at the exhaust of a gas turbine coupled to a combined cycle.

Process steps

! Flue gases exit the heat recovery steam generator at a temperature of about 85°C, and are first cooled in an air or water heat exchanger (HX, Figure 3) down to a temperature depending on the ambient temperature (ambient air or ambient water).

! 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 flue gases pass through an adsorption matrix (dehydrator, Figure 3) in order to adsorb the remaining water vapor.

! 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.

! The flue gas is then routed to the evaporators to freeze CO 2 at an average temperature of about


! The remaining gases at the exit of the evaporators (nitrogen, argon,…) 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. Nitrogen is thereby almost cooled by nitrogen minus the heat transfer efficiency.


One key point of this deep cooling process is the use of available technologies to capture the CO 2 from the flue gases. The different heat exchangers used in the integrated cascade system are typically plate heat exchangers for the evapo-condensers, finned heat exchangers for the partial condenser and the evaporators. The working temperatures of these heat exchangers are in the range of usual materials :

stainless steel for plate heat exchangers; copper and aluminum for finned H_Ex. However corrosion of trace gases shall be taken into account depending on the flue gas composition.

The refrigerant mixture used for the integrated cascade is composed of refrigerants available for refrigeration, so the compressor is a usual compressor for refrigerant mixtures.

The available heat-exchanger technologies offer a compactness of about 800 m 2 /m 3 for the gas heat exchangers, permitting a CO 2 capture capacity of about 250kg/m 3 , which is equivalent to a flue gas stream of 8.35kg/s per m 3 for a 5% (m/m) (gas turbine) CO 2 concentration and 3.45kg/s per m 3 for a 18.7% (boiler) CO 2 concentration stream. The considered frosting period is of 10 minutes. The plate heat exchangers used in the integrated cascade may have an area density of about 400 m 2 /m 3 .


The flue gas temperature considered for the calculations is 5K above the sink temperature (20°C in the following calculations). The energy required to cool the exhaust gas and capture the carbon dioxide depends on the concentration of H 2 O and CO 2 and depends also on the ambient temperature. Taking into account that the frosting temperature of the CO 2 depends on the partial pressure of the CO 2 , the energy necessary to the capture of 90% of the CO 2 from a boiler exhaust gas is calculated here below.

A typical boiler flue gases composition is shown in table 2. After removal of water performed in the first cooling stage, the volumetric flue gas composition is indicated in table 3.



N 2

CO 2

O 2

H 2 O






% vol







N 2

CO 2

O 2

H 2 O

% vol





So the CO 2 will begin to freeze at 174K (-99°C), the temperature corresponding to a partial pressure of the CO 2 of 0.0147 MPa to end at 154K (-119°C), the temperature corresponding to a 90% of the CO 2 removal. For those conditions, the average evaporating temperature is about 164 K (-109°C) since the refrigerant blend evaporates with a temperature glide. For an average temperature of 164K, the evaporation temperature begins at about 150K (-123°C) and finishes at about 180K (-93°C).

The multiple staged cooling of integrated cascade permits to extract heat from the flue gases at different temperatures. Table 4 shows the energy required to cool the flue gases as well as the energy required by the IC compressors.

COP values have been calculated based on simulations of the cascading system, taking into account typical compressor global efficiencies in the range of 70%. This range corresponds to the average level of actual screw compressor technology used for industrial processes. Much higher efficiencies can be reached by centrifugal compressors. Results summarized in table 4, are based on a condensing temperature of 20°C and a compressor COP of 0.55.


Energy required by CO 2 capture (kJ/kg of CO 2 )


Energy required including auxiliaries (kJ/kg of CO 2 )


Change in energy efficiency of power conversion


The total amount of energy required by the integrated cascade compressor to cool and freeze the CO 2 is about 265.8kJ/kg of flue gas which is equivalent in this case to 1297kJ/kg CO 2 .

Since the defrosting energy of the CO 2 is recovered, about 220kJ/kg CO 2 have to be subtracted, the total amount of energy required to capture the CO 2 is about 1077kJ/kg CO 2 and the energy efficiency of the power generation is lowered by 10.8% due to the power consumption of the compressors.

The system needs auxiliaries requiring energy :

! to compress the exhaust gases from 0.08 MPa abs. (which is the partial pressure of nitrogen and remaining trace gases) to the ambient pressure. The required energy is about 25kJ/kg gas, which is equivalent to about 121kJ/kg CO 2 . Different systems or ways to minimize this energy can be applicable according to each system;

! to transfer the remaining CO 2 vapor from the evaporators to the first tank by a volumetric pump; the maximum work required to transfer the CO 2 vapor is about 11kJ/kg CO 2 ;

! to compress the liquid CO 2 captured in the tank from 0.56 to 15 MPa ; the energy required to compress the CO 2 is 15 kJ/kg CO 2 .

The total energy required by the system to capture the CO 2 and compress it to 15MPa will be 1224kJ/kg CO 2 .

Impact of higher condensing temperatures Taking into account a sink temperature of about 35°C and an average refrigerant condensing temperature of 40°C, the total amount of energy required to capture the CO 2 and compress it to 15MPa will be 1708kJ/kg CO 2 considering a COP for the 164K (-109°C) cascade level of about 0.41 and 1584 kJ/kg CO 2 if the COP is of 0.45.


The capture of CO 2 at atmospheric pressure avoids modifications of the power generation process, and so it can be used on existing systems as well as on new designs.

Refrigerating compression system is a well established technology where a number of progresses have been performed in order to reach high energy efficiency. Typically centrigufal water chillers show coefficient of performance of the equipment referred to the ideal Carnot efficiency ranging from 75 to 85%. Progresses have also been made to improve efficiency of heat transfer for plate heat exchangers as well as for fin-tube heat exchangers.

Refrigerating systems are clearly mature technologies where energy efficiency constraints have permitted to develop high efficiency equipment. The use of those technologies in adapted embodiment for CO 2 capture permits to develop efficient CO 2 capture systems.

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 multi components blends in an integrated cascade leads to simple compression design and permits to take advantage of the temperature glide during evaporation, which limits exergy losses for the low temperature evaporators.

Mock-up of this system is under realization in order to verify the level of energy efficiency and the effectiveness of CO 2 capture.


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