Chapter 9: Carbon Dioxide (R744) - The New

Refrigerant
Introduction and Discussion

In the early days of refrigeration the two refrigerants in common use were
ammonia and carbon dioxide. Both were problematic - ammonia is toxic and
carbon dioxide requires extremely high presures (from around 30 to 200
atmospheres!) to operate in a refrigeration cycle, and since it operates on a
transcritical cycle the compressor outlet temperature is extremely high
(around 160°C). When Freon 12 (dichloro-diflouro-methane) was
discovered it totally took over as the refrigerant of choice. It is an extremely
stable, non toxic fluid, which does not interact with the compressor lubricant,
and operates at pressures always somewhat higher than atmospheric, so that if
any leakage occured, air would not leak into the system, thus one could
recharge without having to apply vacuum.

Unfortunately when the refrigerant does ultimately leak and make its way up
to the ozone layer the ultraviolet radiation breaks up the molecule releasing
the highly active chlorine radicals, which help to deplete the ozone layer.
Freon 12 has since been banned from usage on a global scale, and has been
essentially replaced by chlorine free R134a (tetraflouro-ethane) - not as stable
as Freon 12, however it does not have ozone depletion characteristics.

Recently, however, the international scientific consensus is that Global

Warming is caused by human energy related activity, and various man made
substances are defined on the basis of a Global Warming Potential (GWP)
with reference to carbon dioxide (GWP = 1). R134a has been found to have a
GWP of 1300 and in Europe, within a few years, automobile air conditioning
systems will be barred from using R134a as a refrigerant.

The new hot topic is a return to carbon dioxide as a refrigerant. The previous
two major problems of high pressure and high compressor temperature are
found in fact to be advantageous. The very high cycle pressure results in a
high fluid density throughout the cycle, allowing miniturization of the systems
for the same heat pumping power requirements. Furthermore the high outlet
temperature will allow instant defrosting of automobile windshields (we don't
have to wait until the car engine warms up) and can be used for combined
space heating and hot water heating in home usage (refer for example:
Norwegian IEA Heatpump Program Annex28).
Recent update March 2013 - Volkswagen, Daimler, Audi, BMW and
Porsche have announced plans to develop CO2 MAC (Mobile Air
Conditioning) systems (refer: Environmental Leader)

Property Tables for Carbon Dioxide (R744)

We were not able to find any published tables for Carbon Dioxide (R744)
refrigerant, hence decided to create our own. The following set of tables was
developed using software from the NIST (National Institute for Standards and
Technology) and has been organized in a format suitable for evaluating
refrigeration and heat pump systems

Thermodynamic Properties of Carbon Dioxide R744

The P-h diagram for Carbon Dioxide (R744)

The h-s Diagram for Carbon Dioxide (R744)

A Heat Pump System using Carbon Dioxide
Refrigerant (R744)
In addition to being a environmentally benign fluid, there can be significant
advantages to using carbon dioxide in a home air-conditioning/heat-pump
system environment. Consider the following system diagram:
Notice that in addition to serving as an air conditioner/space heater, the high
compressor outlet temperature can be used to provide hot water at a
significant economy over the regular gas or electric hot water heater. Thus the
heat flow to the hot water heater cools the gas from 160°C to 70°C, and the
heat flow to the space heater further reduces the gas temperature to 45°C.

In order to determine the enthalpy at outlet station (4) we need to consider the
energy equation applied to the internal heat exchanger. Since we assume that
it is externally adiabatic, all the heat transfer is internal, as shown in the
following:

Drawing all the processes of the above scheme on a P-h diagram we obtain
the following diagram. Notice the sketches on the diagram of the various
components as well as the internal heat exchanger indicating the heat flow
from the gas cooler outlet (3) - (4) to the compressor inlet (6) - (1).
Problem 9.1 - Use the R744 refrigerant property tables in order to
evaluate the following:

 Determine the work done on the compressor [97 kJ/kg].

 Determine the heat rejected to the hot water heater [164 kJ/kg], and that
rejected to the space heater [97 kJ/kg].
 Determine the Coefficient of Performance of the hot water heater
[COPhw=1.7] and that of the space heater [COPspace=1] (Recall that
COP is defined as the desired heat transferred divided by the work done
on the compressor).
 Determine the Coefficient of Performance of the air conditioner
[COPa/c=1.7]. (Notice from the P-h diagram that the internal heat
exchanger significantly increases the capacity of the air conditioner.)

Problem 9.2 - For the following additional questions we can assume that
the compressor power is 1kW. (Note - we can use the COP values to answer
these questions - we do not need to evaluate the mass flow rate of the
refrigerant ):
  Determine how long it will take to heat 100 liters of water in the tank
from 30°C to 60°C [2 hours]
 During the summer months when the air conditioner is operating,
determine the volumetric flow rate of the air [5.1 m3/min] flowing
through the evaporator cooling duct in order to reduce the air
temperature from 30°C to 13°C. (Note - assume a pressure of 100kPa
and temperature of 25°C to evaluate the specific volume of the air)
 During the winter months when the heat pump is operating, and using
the same fan as above determine increase in temperature of the air
[10°C] flowing through the space heating duct.

Problem 9.3 - Notice that the compressor does not follow an isentropic
process. This is a practical system with data adapted from an actual
automobile a/c design. In this exercise you should do the following:

 Plot the compressor process (1)-(2) on the enthalpy-entropy (h-s)

diagram provided above. Plot also the isentropic compressor process
and (using the Property Tables) determine the compressor isentropic
efficiency ηC. Recall that the compressor isentropic efficiency ηC is
defined as the isentropic work done on the compressor divided by the
actual work done. Indicate both the isentropic work done and the actual
work done on the h-s diagram. [ηC=74%]

Problem 9.4 - A R744 (CO2) Home Geothermal Heat-Pump - It is a

well known fact that there is a year round constant temperature only a few
meters below the earths surface. In this problem we wish to evaluate a system
which is designed to use this underground thermal source to advantage.

Introduction and Description

With the global quest for energy efficiency, there is renewed interest in
Geothermal Heat Pumps which were have been in limited use for more than
60 years. Essentially this technology relies on the fact that a few meters below
the surface of the earth the temperature remains relatively constant throughout
the year (around 55°F (13°C)), warmer than the air above it during winter, and
cooler during summer. This means that we can design a heat pump which can
combine hot water and space heating in winter in which the earth is used as a
heat source (rather than the outside air) at a considerable increase in
coefficient of performance COP. Similarly, with suitable valving, we can use
the same system in summer for hot water heating and air conditioning in
which the earth is used as a heat sink, rather than the outside air. This is
achieved by using a Ground Loop in order to enable heat transfer with the
earth, as decribed in the USDOE website: Geothermal Heat Pumps. Another
description of geothermal heat pumps has been provided by David White
Services of Southeastern Ohio and includes a youtube video by
WaterFurnace: GEOTHERMAL How does it work.

Problem 9.4 - We wish to do a preliminary thermodynamic analysis

of the following CO2 home geothermal heat pump system designed for
wintertime hot water and space heating. Notice that with suitable valving this
system can be used both in winter for space heating and in summer for air
conditioning, with hot water heating throughout the year.

Notice that the gas cooler section includes both the hot water and space heater.
We assume that 50°C is a reasonable maximum hot water temperature for
home usage.
Using the conditions shown on the diagram:

 On the P-h diagram provided below carefully plot the five processes of
the heat pump together with the following constant temperature lines:
50°C (hot water), 13°C (ground loop), and -10°C (outside air
temperature)
 Using the R744 property tables determine the enthalpies at all five
stations and verify and indicate their values on the P-h diagram.
 Determine the mass flow rate of the refrigerant R44. [0.0167 kg/s]
 Determine the power absorbed by the hot water heater [2.42 kW] and
that absorbed by the space heater [1.5 kW].
 Determine the time taken for 100 liters of water at an initial
temperature of 20°C to reach the required hot water temperature of
50°C [1 hr 26 minutes].
 Determine the Coefficient of Performance of the hot water heater
(COPHW) (defined as the heat absorbed by the hot water divided by the
work done on the compressor) [2.42]
 Determine the Coefficient of Performance of the heat pump (COPHP)
(defined as the total heat absorbed by the hot water and space heaters
divided by the work done on the compressor) [3.92]
 What changes would be required of the system parameters if no
geothermal water loop was used, and the evaporator was required to
absorb its heat from the outside air at -10°C. Plot the new system
processes required on the P-h diagram and discuss the advantages of
using the geothermal ground loop heat pump system.