By
Joel Edward Schmidt
Dayton, OH
August 2011
ii
ABSTRACT
The specific energy storage capacities of phase change materials (PCMs) increase
with temperature, leading to a lack of thermal management (TM) systems capable of
handling high heat fluxes in the temperature range from 20C to 100C. State of the art
PCMs in this temperature range are usually paraffin waxes with energy densities on the
order of a few hundred kJ/kg or ice slurries with energy densities of the same magnitude.
However, for applications where system weight and size are limited, it is necessary to
improve this energy density by at least an order of magnitude. The compound ammonium
carbamate (AC), [NH4][H2NCOO], is a solid formed from the reaction of ammonia and
carbon dioxide which endothermically decomposes back to ammonia and carbon dioxide
in the temperature range of 20C to 100C with an enthalpy of decomposition of 2,010
kJ/kg. Various methods to use this material for TM of low-grade, high-flux heat have
iii
been evaluated including: bare powder, thermally conductive carbon foams, thermally
conductive metal foams, hydrocarbon based slurries, and a slurry in ethylene glycol or
propylene glycol. A slurry in glycol is a promising system medium for enhancing heat
and mass transfer for TM. Small-scale system level characterizations of AC in glycol
have been performed and results indicate that AC is indeed a promising material for TM
of low-grade heat. It has been shown that pressures on the order of 200 torr will achieve
rapid decomposition and thermal powers of over 300 W at 60C have been found,
demonstrating the capability of AC.
iv
I would like to dedicate my work to my father and mother and thank them for all of the
support they have always given me and for serving as an example to follow. I know that
without them I would not have completed this process.
ACKNOWLEDGEMENTS
I would first like to thank the Air Force Research Laboratory for providing the funding
for this work as well as extensive technical expertise. This work was performed at the
Thermal Sciences and Materials Branch in the Materials and Manufacturing Directorate
of the Air Force Research Laboratory at Wright Patterson Air Force Base. I would
specifically like to thank Dr. Douglas Dudis (AFRL/RXBT) for serving as the research
advisor for the thesis work and Dr. Karla Strong (AFRL/RXBT) for assuring the funding
was in place for the project. Additionally, I would like to thank Dr. Douglas Miller
(AFRL/RXBT) for all of his assistance with the effort. Dr. Soumya Patnaik
(AFRL/RZPS) and Stephen Emo (AFRL/RZPS) provided great collaborations and advice
for the project, especially in scale-up efforts. I would like to thank Dr. Kevin Myers for
serving on my committee as well as for serving as my academic advisor and I would like
to thank Dr. Robert Wilkens for serving on my committee.
vi
TABLE OF CONTENTS
vii
viii
ix
LIST OF FIGURES
Figure 11. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 30C ............................ 44
Figure 12. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 20C ............................ 45
Figure 13. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 10C ............................ 45
Figure 14. Comparison of different initial loadings of ammonium carbamate in ethylene
glycol at 30C ................................................................................................. 47
Figure 15. Rate of thermal power versus conversion for the decomposition of ammonium
carbamate in ethylene glycol at 30C ............................................................. 48
Figure 16. Comparison of ammonium carbamate in ethylene glycol and propylene glycol
at 30C ............................................................................................................ 49
Figure 17. Conversion as a function of time for the hysteresis measurements of
ammonium carbamate in ethylene glycol at 30C .......................................... 52
Figure 18. Heat of solution of ammonium carbamate in ethylene glycol as a function of
molality ........................................................................................................... 55
Figure 19. Born-Harber cycle for the decomposition of ammonium carbamate .............. 57
Figure 20. Temperature dependent specific heat of ammonium carbamate ..................... 59
Figure 21. Experimental decomposition pressure of ammonium carbamate powder ....... 60
Figure 22. Decomposition pressure of ammonium carbamate in ethylene glycol ............ 62
Figure 23. Ammonium carbamate decomposition test system ......................................... 63
Figure 24. Experimental test apparatus ............................................................................. 69
Figure 25. Decomposition of ammonium carbamate in reactor ....................................... 71
xi
Figure 26. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 30C ............................................................................................................ 95
Figure 27. Pressure and T for ammonium carbamate in propylene glycol at 30C ....... 95
Figure 28. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
30C ................................................................................................................ 96
Figure 29. Pressure and T for ammonium carbamate in ethylene glycol at 30C.......... 96
Figure 30. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 45C ............................................................................................................ 97
Figure 31. Pressure and T for ammonium carbamate in propylene glycol at 45C ....... 97
Figure 32. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
45C ................................................................................................................ 98
Figure 33. Pressure and T for ammonium carbamate in ethylene glycol at 45C.......... 98
Figure 34. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 50C ............................................................................................................ 99
Figure 35. Pressure and T for ammonium carbamate in propylene glycol at 50C ....... 99
Figure 36. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 55C .......................................................................................................... 100
Figure 37. Pressure and T for ammonium carbamate in propylene glycol at 55C ..... 100
Figure 38. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C .......................................................................................................... 101
Figure 39. Pressure and T for ammonium carbamate in propylene glycol at 60C ..... 101
Figure 40. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with two pressure settings ................................................................ 102
xii
Figure 41. Pressure and T for ammonium carbamate in propylene glycol at 60C at two
pressures ........................................................................................................ 102
Figure 42. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C .............................................................................................................. 103
Figure 43. Pressure and T for ammonium carbamate in ethylene glycol at 60C........ 103
Figure 44. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at two pressures ................................................................................... 104
Figure 45. Pressure and T for ammonium carbamate in ethylene glycol at 60C at two
pressures ........................................................................................................ 104
Figure 46. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C at three pressures.............................................................................. 105
Figure 47. Pressure and T for ammonium carbamate in propylene glycol at 60C at
three pressures ............................................................................................... 105
Figure 48. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at three pressures ................................................................................. 106
Figure 49. Pressure and T for ammonium carbamate in ethylene glycol at 60C at three
pressures ........................................................................................................ 106
Figure 50. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with double ammonium carbamate loading ..................................... 107
Figure 51. Pressure and T for ammonium carbamate in propylene glycol at 60C with
double ammonium carbamate loading .......................................................... 107
Figure 52. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with reused propylene glycol ........................................................... 108
xiii
Figure 53. Pressure and T for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol ................................................................................ 108
Figure 54. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with twice reused propylene glycol ................................................. 109
Figure 55. Pressure and T for ammonium carbamate in propylene glycol at 60C with
twice reused propylene glycol ...................................................................... 109
xiv
LIST OF TABLES
xv
xvi
Table 31. Experimental data for ammonium carbamate in propylene glycol at 60C at
three pressures ................................................................................................ 105
Table 32. Experimental data for ammonium carbamate in ethylene glycol at 60C at three
pressures ......................................................................................................... 106
Table 33. Experimental data for ammonium carbamate in propylene glycol at 60C with
double AC loading.......................................................................................... 107
Table 34. Experimental data for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol.................................................................................. 108
Table 35. Experimental data for ammonium carbamate in propylene glycol at 60C with
twice used propylene glycol ........................................................................... 109
xvii
AC
CFCs
Cp
EG
HCFCs
k
m
mt
n
P
PCMs
Peq
PG
Q
rnet
T
TES
TM
wx
H
H
m
H
H
T
C
L m
Ammonium carbamate
Chlorofluorocarbons
Specific heat
Ethylene glycol
Hydrochlorofluorocarbons
Reaction rate constant
Mass flow rate
Total mass of solvent
Number of moles
Pressure
Phase change materials
Equilibrium pressure
Propylene glycol
Rate of heat flow
Net rate of reaction
Temperature
Thermal energy storage
Thermal management
Error of a measurement
Change in enthalpy
Heat of solution at a known molality
Standard heat of reaction
Standard heat of solution at infinite dilution
Temperature change
Apparent molal heat capacity of a solute
Correction factor for the heat of solution at infinite dilution
xviii
CHAPTER I: INTRODUCTION
Ever increasing power loads for various electronic devices have created a demand
for novel thermal management (TM) technologies to allow these devices to operate in
their ideal temperature ranges to ensure efficiency and lifetime. Most electronic devices
need to operate between 20C and 100C. Cooling these devices with air or conventional
liquid coolants can be energy intensive, require a large TM system, or even be impossible
with high thermal fluxes.1 One class of materials being explored to stabilize these devices
is graphitic foams impregnated with paraffin wax phase change materials (PCMs).1-6
However, the growth in heat fluxes and thermal loads is outpacing the capability of
conventional cooling systems.7,8 This TM problem becomes further complicated when
these high-flux loads are confined to weight and volume limited environments.
Therefore, the need exists to investigate novel methods for the TM of high heat fluxes
near room temperature.
The TM challenge which will be explored in this thesis, herein referred to as this
work, is one which has the following characteristics. The system of this work will be
capable of maintaining temperature in the range of 30C to 60C and amenable to volume
and weight limited applications. It will also operate on a reasonable time scale, defined
by a high thermal power, and will scale well. For this work all materials and proposed
system architectures will be evaluated based on these benchmark characteristics.
1.1.1.2. Ammonia
Ammonia has been used as a PCM in many industrial refrigeration applications.
Its low boiling point at one atmosphere of pressure of -33.4C makes it suitable for low
temperature refrigeration. It has a high latent heat of vaporization of 1371 kJ/kg or 935
MJ/m3 of liquid, which is an order of magnitude increase over conventional refrigerants,
making it one of the most efficient refrigerants.10,11 The major drawbacks of NH3 for use
in refrigeration are that it is both flammable and toxic in small concentrations. Toxicity is
the primary reason NH3 has not been applied to domestic cooling and only to industrial
and secondary cooling systems where some non-toxic fluid, such as water, serves as a
heat transfer medium between NH3 and the air to be cooled.12,13 However, over 100
years of use have led to numerous strategies and a history of experience in dealing with
NH3. The flammability of NH3 is also of concern, as it has a flammable range of 15% to
28% by volume in air. However, NH3 is not considered highly flammable since its flame
temperature is usually below its ignition temperature, so another fuel source must be
present for any fire to propagate.14
1.1.1.3. Carbon Dioxide
The most common use of CO2 as a phase change material is to use its solid-gas
phase change for portable cooling. The enthalpy of sublimation for CO2 is 512 kJ/kg.15
Additionally, CO2 has a long history as a refrigerant which began in 1930s and 1940s as a
refrigerant on ships. However, it fell out of use with the advent of CFCs
(chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). Carbon dioxide is being
reexamined as a refrigerant now that the detrimental environmental impacts of CFCs and
HCFCs are better understood. It can also be used as a pressurized refrigerant in the
3
However, work has been done with impregnating various types of thermally conductive
graphitic foams with paraffins to increase the thermal conductivity. A study conducted in
2000 found that impregnating compressed expanded natural graphite with paraffin
loadings from 65 wt% to 95 wt% led to thermal conductivities of 4 W/mK to 70 W/mK,
equivalent to those of the foam matrix itself. This tremendous, near two order of
magnitude increase from 0.24 W/mK for the pure material, demonstrates how this
system level approach can make a low thermal conductivity material into a system with a
good thermal power rating by increasing the thermal conductivity, something necessary
for this work.19 Other studies have found similar results, that using thermally conductive
matrices can greatly enhance the thermal conductivity of paraffin PCM systems.1,2,4 A
drawback with using a heat transfer enhancing medium is that it increases system size
and weight, which lowers the system specific properties. Additionally, as the system size
is increased, the system properties will scale linearly as the same amount of thermally
conductive medium must be used, so there is no advantage to make a larger system.
Overall, paraffins are promising PCMs. However, they do suffer from long cycle
times, reversibility issues which lead to long-term performance degradation, the liquid
phase introduces the possibility of a liquid leak in the system and paraffins are not
suitable for applications requiring high energy densities. Therefore, they are not suitable
for this work.
since chemical bonds are being broken and formed. These types of materials generally fit
into two categories: those with a gas-gas reaction and those with a solid-gas reaction.
1.1.2.1. Gas-Gas Reaction Systems
There have been many chemical reaction working pairs suggested which are difficult
to use for this work because of the high operation temperatures, bulky containment
systems required for high pressures, and the corrosive or toxic nature of some of the
species.
One proposed chemical reaction system is the conversion of methane in a steam
reforming plant powered by heat from a nuclear reactor.20 The methane is reacted with
steam at 950C by the endothermic reactions in Equations 1 and 2.
CO
CO
3H
4H
H = 205.2 kJ/mol
(1)
H = 163.3 kJ/mol
(2)
The methane can then be catalytically reformed in an exothermic process by the reverse
reactions which take place at 450C and the heat used to make steam. The purpose of this
process is to react the methane at a central location to store the heat in the reaction
products and then be able to distribute the product gases and reform them in locations
where steam is needed. While impractical for the type of problem which is the focus of
this work, it shows that chemical reaction systems have a very high energy change and
are serious contenders for thermal energy storage (TES).
A similar process is the CO2 reforming-methanation cycle shown in Equation 3.
2
(3)
This process has been proposed to use a catalyzed reaction at 700C to 900C to form
the CO and H2 which are then transported to the place of use where they recombine
6
exothermically at 350C to 450C to form steam.21 The main advantage of this reaction
over methane-steam reformation is that there are no condensable species. This feature
makes the system operation much simpler and does not require the gases to be
transported at high temperature to prevent condensation.
Other possible reaction pairs proposed in the literature are listed in Table 1.22-24
All operate at too high of a temperature to be practical for this work (300C to 700C)
and many are hazardous, but collectively they provide background to the motivation for
using a chemical reaction heat transformer rather than a phase change TES material.
2
2
2
2
Equation
(4)
(5)
(6)
(7)
(8)
This reaction is promising for large scale applications due to the low cost of methanol
and the relatively low temperatures required, which are still much higher than those
required by this work.
In the above reaction pairs all species are gaseous provided that condensation is
prevented. This is ideal for large scale processes since it allows for easy transportation of
the reactants and products over relatively large distances. It also presents difficulties
since the high pressure gases require expensive support equipment. While these systems
are possible for large scale operations, they are not viable for a small system or where the
system energy density needs to be maximized. Additionally, they are not practical for the
temperature range of this work. Overall, these pairs demonstrate the difficulty of
identifying a suitable system for low-grade, high-flux waste heat. The toxicity,
flammability and reactivity of the materials shown attest to the difficulty of finding a
better system and underscore the need for this work.
1.1.2.2. Gas to Solid Reactions
Gas-solid reactions are promising for energy storage and TM because of their
high specific enthalpy changes. In addition to using the high energy change from a
reaction they also benefit from a large entropy change for the solid to gas transformation
which increases their specific properties. However, many have discounted these types of
TES materials because the large change in volume makes them difficult to handle and
also makes cycling problematic.25-27 Three types of solid-gas reactions are considered:
metal hydrides, ammoniates and complete decomposition reactions.
Many solid-gas reactions are of the form of sorption with reaction. Metal hydrides
are one example of this type of system and can have very high gravimetric thermal
energy densities. There are many possible metal-hydrogen storage material systems
which have been reported elsewhere.25,28 These materials are candidates for thermal
energy storage because hydrogen is able to chemically bind to the metal, with a high
binding energy, in a process which is controlled by temperature and pressure. Much of
the research into metal hydrides is being conducted for hydrogen storage for fuel cells,
especially those on vehicles. Hydrogen storage requires minimization of the thermal load
associated with the sorption process; however, metal hydride systems with a high thermal
8
load may be good candidates for TM. The Mg/MgH2 system is well characterized with a
thermal energy storage density of 1850 kJ/kg while LiAlH4 has been reported to have an
extremely high thermal density of 4200 kJ/kg.22,29
Metal hydrides appear to be promising materials for TM applications as well as
other energy applications but they suffer from many shortcomings that need to be
addressed before they can be used. The first is that of safety. Hydrogen is dangerous to
handle because of its extreme flammability and danger of explosions. Additionally, metal
hydrides are often violently reactive to water, including atmospheric water, making their
storage a serious concern. Finally, these materials suffer from slow kinetics, poor
reversibility, a very high desorption temperature and little familiarity outside of
laboratories. For these reasons metal hydrides are still a far off goal for thermal energy
storage.
A second popular class of sorption working pairs is ammoniates which utilize
NH3 and various metal salts such as LiCl, MgCl2, PbCl2, ZnCl2, CuCl2, FeCl2 and other
period 4, 5 and 6 metal chlorides.30-32 These systems take advantage of the exothermic
reaction of the NH3 with metal salts and the endothermic desorption reaction to upgrade
waste heat to usable temperatures. While these can operate at lower temperatures than the
metal hydrides, the systems require high pressures and large masses of adsorbent
materials, which make them impractical for any application requiring a high specific
energy density at the system level. The low thermal conductivity of the sorbent salts also
presents cycling challenges. These systems generally operate above 150C and at high
pressures.32
(9)
This reaction can be controlled by temperature and pressure. The reaction to form AC
and its disassociation are well documented. It is a simple reaction and fairly safe with
10
NH3 gas being the only toxic product. It is even used in a Physical Chemistry laboratory
textbook as an undergraduate student experiment to study the kinetics and
thermodynamics of a heterogeneous gas phase reaction by studying the decomposition
pressure of the material as a function of temperature and is a suggested experiment in the
Journal of Chemical Education.34,37
12
900
800
Pressure (Torr)
700
600
500
400
300
200
100
0
10
20
30
40
Temperature (C)
50
13
60
70
14
Claudel and Boulamri64 reaction mechanism as being implausible since it breaks down
for P > Peq as it predicts that for this case the pressure would increase in time, not
decrease towards Peq. Additionally Ramachandran, Halpern, and Glendening point out
that the correlation between kobs and 1/T was poor. The authors considered two different
scenarios for the kinetic mechanism. The first mechanism involves NH3, CO2 and
carbamic acid in the gas phase. However, they found this type of mechanism to be
improbable and to lack evidence since IR analysis of the gas phase did not show any
evidence of carbamic acid. The second mechanism proposed still involved a carbamic
acid intermediate, but the carbamic acid did not leave the surface of the AC. The authors
found this mechanism to be the most promising for the reaction. In their publication they
alluded to future work on determining rate constants, but that was apparently never
published.
For the purpose of this work, knowing the exact mechanism of reaction is not
critical. Rather, establishing pressure as the primary driving force of the reaction as well
as understanding the impact that surface area will have on reaction rate is key. This
conclusion will need to be considered in any system design since a large pressure
gradient resulting from a low pressure system will be desirable to achieve a maximum
rate of reaction. It will also be desirable to process the AC to a small particle size to
maximize the surface area available for reaction.
CO2 and NH3 separately. These stored gases can then be brought back together to reform
the AC, an exothermic process, to provide heat for space heating and generating steam.
Ammonium carbamate is good for this system since the gases can be stored indefinitely
and then reacted to provide heat as needed, creating an on-demand, regenerable heat
source.
The first system was presented in a patent from 1979 and was intended to use
solar energy to decompose the AC, then reform it later to take advantage of its
exothermic formation.69 The patent presents a few different operation modes. In the first
the carrier fluid is water. However, this is undesirable to the system because of the
formation of urea, which in a mixture of water, is corrosive. In the second operational
method an anhydrous heat transfer medium such as Therminol or Dowtherm is used
instead of water, avoiding urea formation and corrosion problems. The principle of
operation of the system is to dissociate AC at a temperature of 100C to 200C under
pressure using solar energy. The NH3 and CO2 are then used immediately to provide heat
at a different location or are separated using compression and stored indefinitely. The
separation is simple in principle because at a pressure of 10 atmospheres at ambient
temperature the NH3 is a liquid while the CO2 remains a gas. They can be separated
easily, the NH3 stored as a liquid, and the CO2 stored as a compressed gas. When
recombined, the heat can be used for a wide range of purposes. The authors suggest a
radiator, air heater or hot water heater. They also claim this system is advantageous
because of the low operating temperatures and the relatively low hazards associated with
AC as compared with other systems such as phosgene and carbon monoxide. However,
using a system similar to this is not practical for this work because the operating
16
temperatures of 100C to 200C are too high. Importantly, this paper elaborates a simple
method of separating the CO2 and NH3, as the patent suggests a compression to ~10
atmospheres is sufficient to separate the species.
The second system is similar to the first since it uses solar energy but is
specifically designed to use solar energy to disassociate the AC and then store the gases,
and finally use them to provide space and water heating.70 The proposed system was also
very large, enough to provide heating to a Greek settlement of 500 people for 15 winter
days. Such a large system would be used to heat 11,800 kg/hr of water from 20C to
90C by reacting 820 kg/hr of NH3 and 1060 kg/hr of CO2, the water would then be used
as the heat transfer medium. This system runs based on the same principles of the
previous patent but relies totally upon an anhydrous system to avoid urea formation.
Another distinction is that this analysis also included the idea of using CO2 that was
produced as a byproduct of fermentation or combustion processes. In this mode of
operation the NH3 was recycled and was separated using ethanol. This is a simple
separation since the solubility of NH3 in ethanol at 0C is over 20% by weight at 1
atmosphere of pressure. The NH3 can then be reacted with the CO2 in the ethanol
solution, the heat of reaction will cause all components to volatilize, then the ethanol can
be condensed and reused. The study found that using CO2 obtained from fermentation to
be the most practical since it avoided costly compression, the closed loop cycle involving
CO2 compression to be the second most desirable and that obtaining CO2 from
combustion would be the least economical due to the expensive purification required of
the effluent gas. Like the previous patent, the operating temperatures and pressures are
17
well above those required for this work, but the system does suggest an additional
separation method using inexpensive alcohols at ambient pressure.
The two aforementioned systems demonstrate that AC has been considered for
large scale, terrestrial-based thermal energy storage. However, the operating temperatures
are significantly above room temperature. Important insights that can be drawn from
these proposed systems are methods for separating the NH3 as well as the idea of using a
carrier fluid to enhance heat transfer and aid in mass transfer.
they measured the density to be 1.36 g/cm3.74 Bulk AC available from BASF chemicals
in 25 kg bags has a density range of 780-850 kg/m3.75 According to patent 4,567,294 the
bulk density of AC is 780 kg/m3.59 A density of 780 kg/m3 corresponds to a volumetric
energy density 1.57 GJ/m3. A comparison to other commonly used materials for TM is
given in Table 3, all volumetric measurements are based on the solid bulk density. Thus
the energy density of decomposition for the material is quite competitive and at a lower
temperature than the liquid to gas phase change of water but higher than that of NH3.
Even though the phase change of NH3 occurs at a lower temperature, the use of NH3
requires bulky pressure containment systems and presents a significant toxicity risk,
which is not encountered with solid AC.
20
21
t=0s
t = 10 s
t = 20 s
t = 30 s
t = 40 s
22
Measurement
Technique
Hot wire using
pressed sample
pellets 7mm
thick
Hot wire
23
more important since in practice the AC used will be in powder form and will have an
even lower thermal conductivity.
the heat transfer area. Therefore, impregnating a foam with AC would enhance heat
transfer and lead to improved cycling times in a TES system.
The difficulty in impregnating a foam lies in the fact that AC exists only as a
solid. The method used to impregnate carbon foams with paraffin PCMs is to melt them
into the foam in a vacuum oven to degas the foam and draw the wax into the pores. This
method has been shown to fill around 80% of the available pore space.2 A similar method
has been used to impregnate foams with salts such as CaCl22H2O or MnCl2. In this
process the salt is dissolved in water and then put in a vacuum chamber to allow the salt
solution to fill the pores. Finally the water is removed at high temperature, leaving the
salt in the foam.80,81
Based on this previous research, there exists the possibility of dissolving the AC
in a liquid and using a vacuum technique to impregnate it in a foam and then removing
the liquid. The difficulty for doing this with AC is its limited solubility and the fact that it
cannot be taken above ~20C while the liquid is removed. This restriction eliminates
using many liquids, such as water, since they could not be effectively removed without
also decomposing the AC. Liquid NH3 has a good possibility of being used to
impregnate AC by two different methods. One method would be to use a low temperature
vacuum technique to impregnate the foam and then slightly raise the temperature to
remove the NH3 but leave the carbamate in the foam pores. A second method would be to
use the same procedure to impregnate the foam but not remove the NH3. The TES device
could then rely on the heat of vaporization of NH3 and the heat of decomposition of the
AC, possibly enhancing the overall thermal energy density of the system. The second
design would necessitate a pressure containment system to prevent the NH3 from
25
evaporating during storage. It may also be possible to use other solvents in which AC
may be soluble to impregnate the foam.
26
g of AC were
added. The solubility at -78.5C was determined by stirring the mixture with a magnetic
stir bar in a dry ice/acetone bath. From visual observation it did not appear that a
significant amount of the AC went into solution, leading to the conclusion that AC is
virtually insoluble at that temperature in liquid NH3. The solubility at -41C was then
evaluated using an acetonitrile slush bath. Once the NH3/AC mixture was warmed to this
temperature the solubility did not appear to change appreciably.
The room temperature solubility of AC in liquid NH3 was also determined. At this
temperature the vapor pressure of NH3 is ~8 atmospheres. A sealed, flame dried heavy
walled Schlenk tube was filled with ~25 mL of liquid NH3. To this 0.5 g of AC were
added. The tube was allowed to slowly heat to room temperature while stirring using a
magnetic stir bar. As the mixture heated, it first turned a violet color, this color went
27
away after 1 hour. After the mixture reached room temperature (20C) the entire solid
was not dissolved. The source of the violet color is unknown. However, it is known that
when metals dissolve in liquid NH3 they form similar colored solutions as the result of
free electrons, so it is possible that the color came from the metal cannula that was used
to put the NH3 inside the tube.
Since AC was not readily soluble in liquid NH3, additional methods were
explored to increase its solubility. According to a 1935 patent, adding ammonium
chloride (NH4Cl) will increase the solubility of AC in liquid NH3.48 This patent claims
the solubility of ammonium chloride to be 134.0 g/(100 g NH3) at 30C. The solution
made previously to find the solubility of AC in liquid NH3 was used to find the effect on
solubility of adding ammonium chloride. Since there were ~15 g of NH3, it should be
possible to dissolve ~19.5 g NH4Cl. For the first attempt 5 g of NH4Cl were added while
the NH3/AC was in a dry ice/acetone bath to prevent evaporation. Once the solution had
warmed to room temperature all the solids dissolved, confirming the patents assertion
that the NH4Cl would increase the solubility of AC in liquid NH3. To find the maximum
amount of AC that would dissolve with the NH4Cl, additional AC was added in the
following increments: 0.5 g, 0.5 g, 1 g, 1 g, 1 g. The procedure at each addition was to
cool the solution in dry ice/acetone, add the solid and then allow the mixture to heat up to
room temperature slowly. Each time the solution was cooled a good amount of solid
came out of solution and had a fluffy white appearance but when the mixture was
brought up to room temperature all the solid redissolved. Eventually 4.5 g AC were
added to the 5 g NH4Cl and at that point no more AC would go into solution, giving a
mass ratio of AC:NH4Cl of 1:1.1 and a molar ratio of 1:1.6. Although this result shows
28
one way to increase the solubility of AC in liquid NH3, it is not expected to be useful in
an actual system because the melting point of NH4Cl is 340C and the effect of adding
such a large amount of ammonium chloride would lower the energy density by mass of
the system by more than a factor of two and will still require pressure to maintain the
NH3 as a liquid at room temperature.
All of these experiments show that NH3 is impractical in a system involving AC
since the solubility of AC in liquid NH3 is so small that for any practical system it can be
considered negligible.
in a 50 mL Erlenmeyer flask. Methanol was added to a titration burette and slowly added
to the stirring methanol/AC solution until all of the AC had just dissolved. Exact amounts
used in each experimental run are listed in Table 7.
30
Vacuum Vessel
Methanol with
AC
Weight
Carbon Foam
Figure 3. Vessel used to impregnate carbon foam with methanol and ammonium
carbamate
After the liquid evaporated, the carbon foam was removed. It was cut in half using
a razor blade and examined visually under a microscope. No AC was observed in the
pores although the odor of NH3 was noticeable. Because no AC could be seen it was
apparent that most of the AC had been removed along with the methanol. A series of
experiments are subsequently detailed to test this.
Approximately 2 g of AC powder were added to the previously used polymer
reactor. The vessel was immersed in an ice/water bath. The system was connected to the
Schlenk line and the system was exposed to a vacuum of 10 mTorr for three hours. After
this time it did not appear that any significant amount of AC had evaporated. Next a
saturated solution of AC/methanol was placed in the vessel and the same vacuum was
applied with the vessel in ice water. Under these conditions all of the methanol
evaporated and no AC was left in the vessel. These experiments show that it is not
possible to remove the methanol without the AC.
To test if the reason the AC was being removed with the methanol was its
solubility, an experiment was performed with the AC in pentane, in which it is insoluble.
31
The boiling point of pentane at one atmosphere of pressure is 36.1C and that of
methanol is 64.7C, so the pentane should be much easier to remove using vacuum. A
slurry of pentane and AC was placed in the previously used vessel and immersed in ice
water. When the vessel was evacuated the pentane was removed, leaving the AC behind.
This experiment demonstrates that using a liquid medium in which the AC is insoluble
will not cause the AC to decompose while the liquid evaporates, but one in which it is
soluble will cause the AC to decompose as the liquid evaporates. The practical
implication is that using a solvent will not allow the impregnation of foams followed by
solvent removal in which the AC is left in the foams. Additionally, a liquid in which AC
is insoluble will not allow the pores to be infiltrated with AC, so the foams cannot be
impregnated with this type of fluid either. These limitations show that it will not be
possible to impregnate a foam with AC through a vacuum technique.
conductivity will have to be evaluated for any use of a foam to maximize energy density
and minimize cycling time. Surface area increases with both increasing density and pores
per inch. The amount of surface area will be the amount of heat transfer area for the AC,
so increasing surface area will increase the rate of heat transfer, and this will lead to a
tradeoff similar to that for thermal conductivity.
33
show that it is possible to pack the AC inside metal foam close to its bulk powder density
of approximately 780 kg/m3.
Sample
10 PPI
20 PPI
40 PPI
To quickly examine the effect that AC would have on the heat transfer in an
aluminum foam, a simple experiment was run with the foam on a hot plate. The 10 PPI
foam was filled with 26.784 g of AC powder and placed on a hot plate. The 20 PPI foam
had no AC in it and served as the control for temperature. A thermocouple was placed
inside each foam sample as well as on the surface of the hot plate. The experimental
setup is shown in Figure 5. The temperatures of the hot plate surface, bare metal foam
and impregnated metal foam are given in Table 9. The experiment clearly demonstrates
that the AC is effective at removing heat from the foam through its decomposition. It is
apparent from this that a thermally conductive open celled foam would be able to
enhance the heat transfer to the AC.
34
Weight to ensure
good contact
Foam with AC
Thermocouple
wires
Control Foam
35
37
The schematic of the experimental apparatus used to measure the maximum rate
of decomposition of AC as a function of temperature is shown in Figure 6. The lowest
pressure that the system could achieve was lower than the gauge resolution of 1 x 10-5
torr. However, given that the gauge was located much closer to the diffusion pump than
the reaction vessel, it is likely that the pressure was higher at the reaction vessel. For the
temperature range for the experiment the water bath could be regulated between 5 and
50C.
AC was added to the flask, its mass determined, and then the Schlenk flask was
immersed in the temperature controlled water bath for at least twenty minutes to allow
thermal equilibrium. The air was then evacuated from the system to a pressure no greater
than 5 x 10-4 Torr on the pressure transducer. Next the valve between the liquid nitrogen
trap and the vacuum pump was closed. In this way the liquid nitrogen worked to keep the
pressure low in the vacuum manifold as well as to trap any decomposed AC. This setup
prevented AC from being pulled through the system into the pump. The valve on the
reaction vessel was opened and the AC was allowed to decompose for five minutes. After
this time the vessel was backfilled with nitrogen and weighed to find the mass change.
The procedure to evacuate the system, allow it to come to thermal equilibrium and then
run the decomposition for five minutes was repeated for a total decomposition time of at
least thirty minutes. At each temperature an initial run with just EG was conducted to find
its baseline rate of evaporation and loss.
2.3.6.2. Heat Transfer Fluid Analysis
The first experiment which was conducted was to determine whether EG, in which
AC is soluble, or a heat transfer fluid in which it is insoluble, would lead to a greater rate
of decomposition. Tetraglyme (boiling point at one atmosphere pressure is 275C) was
selected as the heat transfer fluid in which AC is insoluble due to its high boiling point.
Both tetraglyme and EG were evaluated at 30C using equal fluid volumes and amounts
of AC using the aforementioned experimental procedure. They are also compared to the
bare powder at twice the solubility multiple in Figure 7 and at four times the solubility
multiple in Figure 8. The amounts used are shown in Table 11 and the solubility
multiples correspond to the solubility of AC in EG.
39
Conversion
1.00
0.90
Ethylene Glycol
0.80
Tetraglyme
0.70
Bare Powder
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0
10
20
30
40
50
60
Time (min)
1.00
Ethylene
Glycol
Tetraglyme
0.90
0.80
Conversion
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0
10
20
30
40
50
Time (min)
40
Table 11. Amounts of ammonium carbamate and tetraglyme added for decomposition
studies
Solubility Multiple Tetraglyme (mL) AC (g)
2x
49.8
18.79
4x
51.1
37.51
As these profiles show, the reaction rate is greatly depressed in tetraglyme at the
same experimental conditions of temperature, pressure, amount of solvent and amount of
carbamate. Additionally, the conversion rate is nearly identical in tetraglyme as it is in
bare powder showing that merely having a heat transfer fluid is not sufficient to increase
the conversion rate. This leads to the conclusion that the fact that AC is soluble in EG
must play a role in the rapid decomposition under vacuum conditions. This was suspected
with the initial experiments in methanol where the AC was removed when methanol was
the fluid but not when pentane was used. Therefore, EG will be further evaluated and the
study of heat transfer fluids in which AC is insoluble will be discontinued.
Since EG was demonstrated to be the superior heat transfer fluid, the experiment
in EG was repeated at 50C, 40C, 30C, 20C and 10C, and the results are shown in
Figure 9. For a first run at each temperature, the AC was added to the vessel at twice its
solubility limit at room temperature (18.5g/100mL EG). As expected, as temperature
increased the rate of reaction increased as well. The 40C and 50C conversion profiles
are nearly identical. This is most likely because the rate of reaction was limited in these
cases by how quickly the gases could be removed. The rapid rate of decomposition
limited how far the valve on the Schlenk tube could be opened because with the valve
fully open, the rapid gas removal rate led to liquid entrainment into the vacuum system.
This meant the rate of decomposition was effectively throttled to keep the EG inside
the tube. At lower temperatures this problem was not as pronounced since the
41
decomposition was slower. Because the 40C and 50C profiles were nearly identical it
was decided to not run further trials at 50C on this system. A limitation of the system is
the inherently low rate of mass transfer found in high vacuum systems, which are
designed to achieve low pressure but not high flow rates. This means that the rate of
reaction may have been limited at all temperatures by mass transfer.
1
0.9
0.8
Conversion
0.7
0.6
0.5
0.4
0.3
50
40
30
20
10
0.2
0.1
0
0
10
15
20
25
30
35
40
Time (min)
42
averaged at each temperature and the results are shown in Table 12 and are reflected as
the error bars on the plots.
43
1.00
Run 1 Powder
0.90
Run 2 Powder
Conversion
0.80
Run 3 Powder
0.70
Run 1 Slurry
0.60
Run 2 Slurry
0.50
Run 3 Slurry
0.40
0.30
0.20
0.10
0.00
0
10
15
20
25
30
35
40
Time (min)
Figure 10. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 40C
1.00
0.90
0.80
Conversion
0.70
0.60
Run 1 Powder
0.50
Run 2 Powder
0.40
Run 3 Powder
0.30
Run 1 Slurry
0.20
Run 2 Slurry
0.10
Run 3 Slurry
0.00
0
10
20
30
40
50
Time (min)
Figure 11. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 30C
44
1.00
0.90
0.80
Conversion
0.70
0.60
0.50
Run 1 Slurry
0.40
Run 2 Slurry
0.30
Run 3 Slurry
Run 1 Powder
0.20
Run 2 Powder
0.10
Run 3 Powder
0.00
0
10
15
20
25
30
35
40
45
Time (min)
Figure 12. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 20C
1.00
Run 1 Slurry
Run 2 Slurry
Run 3 Slurry
Run 1 Powder
Run 2 Powder
Run 3 Powder
0.90
0.80
Conversion
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0
10
15
20
25
30
Time (min)
Figure 13. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 10C
As this work developed, it was determined that the optimum desired operating
temperature for the system is ~30C. Therefore, attempts were undertaken to run
45
additional trials at 30C with different loadings of AC in the EG. Trials were run at 2, 3,
4, 5 and 6 times the solubility limit of AC in EG. A larger Schlenk tube had to be used for
these trials because the decomposition was so rapid. Use of the smaller tube resulted in
material being pulled out of the small tube. Because of this, the valve could not be fully
opened, which would lower the reaction rate, forcing a change to a larger tube. The
conversion as a function of time is shown in Figure 14 and the bare powder conversion is
included for comparison. Table 13 shows the initial amounts of solvent and AC.
1.00
2x Solubility
3x Solubility
4x Solubility
5x Solubility
6x Solubility
Powder
0.90
0.80
Conversion
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0
10
15
Time (min)
46
20
25
30
1.00
2x Solubility
0.90
3x solubility
0.80
4x solubility
Conversion
0.70
5x Solubility
6x Solubility
0.60
Powder
0.50
0.40
0.30
0.20
0.10
0.00
0
10
15
20
25
30
Time (min)
Table 13. Initial amounts of ethylene glycol and ammonium carbamate to test rate of
reaction at different initial loadings of ammonium carbamate in ethylene glycol
Solubility Multiple EG (mL) AC (g)
2x
50.3
19.45
3x
51.0
28.17
4x
49.2
35.25
5x
49.3
46.18
6x
49.2
54.27
In each trial approximately the same amount of solvent was used, but as the
amount of AC was increased the conversion as a function of time decreased only slightly,
meaning a greater rate of decomposition occurred at increasing solubility multiples. The
amounts of AC were increased to determine the maximum rate of decomposition that
47
could be accomplished in this system. In order to determine this, a plot of the average
thermal energy consumed in the decomposition (in kW) was plotted as a function of
conversion. The power needed was determined from the reaction enthalpy change. The
plot is shown in Figure 15 which shows that a maximum rate of ~0.065 kW is reached for
the three systems with 4x, 5x and 6x loadings of AC.
0.07
0.06
0.05
0.04
0.03
2x Solubility
3x solubility
0.02
4x solubility
5x Solubility
0.01
6x Solubility
0
0.00
0.20
0.40
0.60
0.80
1.00
Conversion
Figure 15. Rate of thermal power versus conversion for the decomposition of ammonium
carbamate in ethylene glycol at 30C
Propylene glycol (PG) was evaluated as an alternative heat transfer fluid in which
AC is soluble. This is because EG is toxic and bad for the environment while PG is foodsafe and considered to be environmentally friendly. Propylene glycol was tested with AC
at 30C with 18.58 g of AC in 50 mL of PG and is graphically compared to AC in EG at
30C with 19.45 g of AC in 50 mL of EG in Figure 16. In the figure the run in PG shows
a conversion of greater than 1 which occurred since a larger amount of PG was entrained
than with EG. The experiment was also repeated with the same result. While it is not
48
possible to find the amount of PG entrained the fact that conversion as a function of time
is comparable to that of AC in EG lends support to using PG instead of EG. The greater
amount of liquid entrainment can be explained by comparing the viscosity of the two
liquids. The viscosity of PG at room temperature is 50 centipoise and the viscosity of EG
at room temperature is 11 centipoise.89,90 The greater viscosity would lead to a greater
amount of PG being entrained which explains a conversion greater than one.
1.20
1.00
Conversion
0.80
0.60
0.40
PG
0.20
EG
0.00
0
10
15
20
25
30
35
40
45
Time (min)
Figure 16. Comparison of ammonium carbamate in ethylene glycol and propylene glycol
at 30C
2.3.7. Ammonium Carbamate Materials Compatibility
No data on corrosion specific to AC exists, so corrosion considerations will focus
on issues arising from CO2 and NH3. The Handbook of Corrosion Data presents
information on the corrosion of a wide variety of compounds with many metals.91 Only
NH3 is considered since it is generally more corrosive than CO2 or the heat transfer fluids
used in this work. Metals suitable for use with NH3 are stainless steels, aluminum and
titanium. Copper and copper alloys must be avoided when working with NH3 as NH3 and
49
2.3.8. Hysteresis
As this has been envisioned as a system where AC could be continuously loaded
into a glycol slurry and the glycol not recycled or treated in any way, it is desirable to
have an idea of the effect of reusing the glycol. The solubility of CO2 in EG has been
reported to be 39.4 mmol/L at 25C and a partial pressure of 760 Torr.92 However, the
solubility of CO2 in EG increases with increasing pressure, so at the vacuum conditions of
the system the solubility will be lower.93 The solubility of NH3 in EG has been reported
in terms of mole fraction to be very high. At atmospheric pressure and 25C it has been
reported to be a mole fraction of 0.406.94 It is been conjectured that this extremely high
solubility is due to a reversible chemical reaction between the NH3 gas and solvent
forming ammonium radicals at the hydroxyl groups.94 It is possible that this high
solubility of NH3 will affect the system of AC and EG. However, under lower pressure
50
the solubility will decrease which should help avoid any effects due to a large amount of
dissolved NH3 on the reaction equilibrium.
The possibility of hysteresis on the EG was tested by repeating the previous
experiment to remove the AC from the EG at 30C under vacuum. The same EG was
used for four consecutive experimental runs. Initially, 50.0 mL of EG were loaded into
the Schlenk tube. For each run ~28 g of AC was added. Table 14 shows the initial and
final amounts of solvent for reach run and how much AC was added. The amount of
solvent was found using the baseline solvent evaporation rate of 0.05 g/min, which was
found by subjecting the Schlenk tube with only EG to vaccum to find its rate of
evaporation. It should be noted that the mass of material remaining in the flask after the
final run was 55.21 g. This can be attributed to NH3 or CO2 dissolved in the EG.
However, even though the reaction products are soluble in the EG it is evident from the
conversion time profiles in Figure 17 that the rate of decomposition is relatively
unaffected by the reuse of EG, so the EG could be successfully reused in a system level
application.
51
1.00
0.90
0.80
Conversion
0.70
0.60
0.50
0.40
0.30
Run 1
Run 2
0.20
Run 3
0.10
Run 4
0.00
0
10
15
20
25
30
Time (min)
(13)
52
where
is a correction for
the heat of dilution to infinite dilution. It is also necessary to know the apparent molal
heat capacity of the solute,
. In the
to extrapolate to
and
at a
. The value of
(14)
where mt is the mass of solvent and solute, Cp is the specific heat, T is the temperature
change, and n is the moles of solute added. This value is determined experimentally by
adding a known quantity of solute to a known amount of solvent and finding the
maximum temperature change in an adiabatic vessel.
The experimental methodology was validated by finding the heat of solution of
NH4Cl in water. Data were collected for three trials of NH4Cl in water and the
experimental details and results are shown in Table 15. The heat of solution must be
adjusted for the dilution using Equation 13 where
Table 15. Experimental details and results for the heat of solution of ammonium chloride
in water
Mass H2O (g) Mass NH4Cl (g) T(C) Heat of Solution (kJ/mol)
103.73
8.47
-5.2
15.4
Trial 1
103.79
8.35
-5.1
15.3
Trial 2
104.97
8.49
-5.2
15.2
Trial 3
53
The experimental uncertainty was evaluated using the method in Equation 15 and
the variables are defined along with their values in Table 16. All error values are from the
instrument manufacturers.
(15)
54
can be found in Table 17. The heat of solution of AC in EG was determined to be 9,700
J/mol. This value is lower than that of ammonium chloride in water and quantifies the
cooling effect observed when the AC was dissolved in EG; it also shows that merely
adding AC to EG will lower the system temperature.
12000
10000
8000
6000
4000
2000
y = -2379.3x + 9686.4
R = 0.9647
0
0
0.2
0.4
0.6
0.8
1.2
1.4
1.6
Molality
55
CO g
2NH g
NH COONH solid
NH COONH solution
NH COONH solid
NH COONH solid
9.7 kJ
157 kJ
NH COONH solution
147.3 kJ
157 kJ
CO g
CO g
2NH g
2NH g
(16)
(17)
(18)
(19)
58
(20)
2.5
1.5
y = 0.0069x + 1.5018
R = 0.9937
0.5
0
0
20
40
60
80
100
120
Temperature (C)
vessel was immersed in a thermostated water bath and the material in the vessel was
allowed to equilibrate for at least 30 minutes at each temperature before a reading was
taken.
The first experiment conducted was to measure the decomposition pressure of the
neat powder to compare to published results. The results of the experiment are shown in
Figure 21. The black squares are experimental data and all other points are from literature
sources. As the data shows the experimental setup gives accurate data so it can be used
for decomposition pressure experiments.
1000
Egan, Potts, Potts (62)
900
800
Pressure (Torr)
700
600
500
400
300
200
100
0
10
20
30
40
50
60
70
Temperature (C)
60
solvent is well below the decomposition pressure of the solid, so it should not play a
significant role in the experiment.
The vapor pressure of the AC in EG was measured by making a slurry of AC in
EG. The same experimental procedure was used as with the neat powder. The results are
shown in Figure 22, the literature references in this figure are the same as in Figure 21.
Up to 40C, the results for the slurry are identical to the bare power and show a slightly
higher pressure above 40C. This can be explained by examining the components that
contribute to the total pressure in the vessel. Equation 21 shows that the total pressure in
the vessel will be a combination of the partial pressures of the EG, CO2 and NH3. It is
likely that the sum of these terms will be greater than the sum of the partial pressures of
CO2 and NH3 above the neat solid for two reasons. The first is that the partial pressures
above the solution will likely be higher due to the entropy dependence of the
decomposition pressure which will show a dependence on concentration and temperature.
This will not exist for the neat powder and the temperature dependence explains why the
deviation was only noticed at higher temperatures. The second reason is that the addition
of the EG term should also slightly raise the equilibrium pressure. Although the
experiment shows a slight elevation in the decomposition pressure for the EG slurry, it is
unlikely that this small deviation explains the markedly different decomposition rates
observed.
(21)
61
1000
Literature Bare Powder
900
800
AC in EG
Pressure (Torr)
700
600
500
400
300
200
100
0
10
20
30
40
Temperature (C)
50
60
70
62
64
Table 19. Test matrix for ammonium carbamate system (see key and text for explanation)
Solubility
Multiple
0.5
1:1
Scale
11.1
120
240
11.1
60
120
11.1
30
60
11.1
20
40
11.1
15
30
11.1
12
24
11.1
10
20
1:5
Scale
2.22
24
48
2.22
12
24
2.22
6
12
2.22
4
8
2.22
3
6
2.22
2.4
4.8
2.22
2
4
1:10
Scale
1.11
12
24
1.11
6
12
1.11
3
6
1.11
2
4
1.11
1.5
3
1.11
1.2
2.4
1.11
1
2
1:25
Scale
0.444
4.8
9.6
0.444
2.4
4.8
0.444
1.2
2.4
0.444
0.8
1.6
0.444
0.6
1.2
0.444
0.48
0.96
0.444
0.4
0.8
Key
1:50
1:100
1:200
Scale
Scale
Scale
0.222
0.111
0.0555
2.4
1.2
0.6
4.8
2.4
1.2
0.222
0.111
0.0555
1.2
0.6
0.3
2.4
1.2
0.6
0.222
0.111
0.0555
0.6
0.3
0.15
1.2
0.6
0.3
0.222
0.111
0.0555
0.4
0.2
0.1
0.8
0.4
0.2
0.222
0.111
0.0555
0.3
0.15
0.075
0.6
0.3
0.15
0.222
0.111
0.0555
0.24
0.12
0.06
0.48
0.24
0.12
0.222
0.111
0.0555
0.2
0.1
0.05
0.4
0.2
0.1
AC Needed (kg)
Liquid Volume (liters)
System Size (liters)
Vacuubrand CVC 3000 vacuum controller was selected for the process. The controller
measures pressure using an external vacuum gauge on the reaction vessel and regulates
the vacuum through the Vacuubrand VV-B 6C solenoid vacuum valve. The valve is made
with a corrosion resistant flowpath which prevents the NH3 from causing any problems to
the valve.
67
The data logger is capable of up to 8 temperature input channels and can store up to
512,000 temperature points.
68
necessary. The entire system was assembled according to the schematic in Figure 23. The
exhaust from the diaphragm pump was vented into a laboratory hood.
Pressure
Transducer
Solenoid valve
Reaction vessel
Diaphragm
vacuum pump
Temperature
logger
Pressure controller
Thermal load
Work
The decomposition system allows for the thermal power rating to be calculated
for the system by using the time dependent temperature data. This is a measurement
based on an energy balance around a recirculator and is different than the earlier
measurements which calculated the energy based on the amount of AC decomposed. For
each experiment conducted with the system, 650 mL of heat transfer fluid was used as it
was determined that this was the amount necessary to cover the heat transfer coils.
Although it was initially planned to use less heat transfer fluid in the system design
process, it was necessary to use this amount of fluid to completely cover the heat transfer
69
coils. The fluid was brought into thermal equilibrium at the test temperature before the
addition of the AC. Before the AC was added the temperature logger was started. The
amount of AC that was added was recorded as well as the time when the AC was added
and the time when the vacuum pump was started. The overhead pressure could be
controlled for each experiment. By using the time dependent temperature data, circulator
flow rate and the specific heat of water, the thermal power for the system could be found
by Equation 22.
(22)
where
specific heat of water, and T is the water temperature change between the inlet and
outlet of the reactor. The time dependent power rating was then integrated with respect to
time using the trapezoid rule to find the total amount of energy consumed by the AC
decomposition. This result was compared with the amount of energy consumed by the
decomposition and the amount of energy necessary to heat the AC to the reactor
temperature. The amount of energy consumed by the decomposition was determined
from the mass of the AC added and the literature value of the heat of decomposition of
2.01 kJ/g. The amount of energy necessary to bring the AC from room temperature to the
reactor temperature was calculated using the heat capacity of the AC, which was assumed
to be constant. The heat loss through the reactor walls was neglected and a vacuum
insulated reactor was used to assure that this was a reasonable assumption.
Both EG and PG were used as heat transfer fluids in the decomposition
experiments so that their performance could be compared to give a recommendation of
the optimal heat transfer fluid for the system. Tests were conducted at the following
70
temperatures: 30C, 45C, 50C, 55C and 60C. The greatest number of experiments
was conducted at 60C since this is the highest temperature that would be of practical
value for this work and as the highest temperature should give the best thermal power
rating by providing the most rapid decomposition. For an initial run at each temperature,
the pressure controller was set to 0 torr so that the vacuum pump would run continuously
and result in the maximum rate of decomposition available from the system. At 60C
higher pressures of 200 and 400 torr were tested as well. A representative picture of the
decomposition reaction occurring is shown in Figure 25. Bubbles of the product gases
can be seen in the image.
temperature as measured by the reactor thermistor probe. The vacuum pump to the
reactor jacket was turned on. The approximate amount of AC was measured; the exact
amount added for the reaction was determined by weighing the jar with the AC and then
the empty jar after addition. The temperature logger was started at least one minute prior
to the test so that the initial temperatures could be recorded. The pressure controller was
set to the appropriate pressure for the test. Next, the AC was quickly added to the reactor,
the reactor was closed and the vacuum pump was turned on using the pressure controller.
The time when the AC was added to the reactor and the time when the vacuum pump was
started were recorded. The pressure displayed on the vacuum controller was manually
recorded at appropriate intervals throughout the experiment. The decomposition was
allowed to continue until the reactor contents, water inlet and water outlet were at steady
state.
The bounds of integration are shown for each run in the form of vertical lines on the
graphs which can be found in the appendix. For each run the percent difference between
energy found from the integration and AC mass value is shown. The T shown is that
between the reactor inlet and outlet for the circulator. Each experimental run is
summarized in Table 20. In this table the difference is negative when the predicted
energy value is higher than amount of energy found using numerical integration.
Solvent
AC
(g)
Decomp.
(kJ)
Cp (kJ)
Integration
(kJ)
Difference
Peak
Power (W)
105.2
Set
Pressure
(torr)
0
30
PG
211.53
1.88
161.32
-24.4%
39.3
30
EG
104.0
208.95
1.86
107.99
-48.8%
52.2
45
PG
104.6
210.31
6.01
255.98
18.3%
138
45
EG
104.3
209.59
5.92
225.05
4.4%
145.5
50
PG
102.4
205.73
7.40
190.67
-10.5%
144.7
55
PG
101.4
203.76
6.96
206.31
-2.1%
203.8
60
PG
100.9
202.89
7.05
186.82
-11.0%
223.9
60
PG
102.6
200, 0
206.27
7.18
195.37
-8.5%
223.3, 42.0
60
EG
102.0
204.99
6.58
206.64
-2.3%
241.5
60
EG
101.7
200, 0
204.34
6.30
219.50
4.2%
238.8, 74.2
60
PG
102.2
205.39
7.38
236.12
11.0%
60
EG
103.0
207.02
7.41
208.73
-2.7%
60
PG
204.4
400, 200,
0
400, 200,
0
0
410.75
14.77
530.85
24.8%
174.2,
101.3, 44.0
159.4,
134.1, 87.7
319.2
60
PG, reused
100.3
201.53
7.16
248.90
19.3%
266.9
60
PG, reused
102.3
205.59
7.27
256.73
20.6%
269.8
73
be discussed are the effect of temperature, pressure, solvent, and the amount of AC added
on the amount of heat removed by the AC and the peak power rating that was achieved.
The early decomposition experiments conducted for this work indicated that
temperature would have a strong effect on the rate of decomposition and therefore on the
thermal power achieved. This trend is clearly demonstrated since the peak power
increases as the temperature increases from a minimum of 39.3 W at 30C to a maximum
319.2 W at 60C. Hence, for situations in which it is desired to have a high thermal
power rating, it is shown that the decomposition reaction vessel should operate at the
highest possible temperature. The current system has mass transfer limitations because
the vacuum pump being used limits mass transfer capability. Therefore, one way to
overcome the temperature limitation would be to install a more powerful vacuum pump,
or multiple pumps, to achieve a greater rate of mass transfer.
The pressure set by the vacuum pump also has an effect on the peak power
achieved by the system. The data collected only allows analysis at 60C, but it is
expected that similar trends would also be found at other temperatures. At 60C, setting
the pressure controller to either 200 torr or 0 torr did not have an appreciable effect on the
peak power. With EG the peak powers were observed to be 241.5 and 238.8 W at 0 and
200 torr, respectively, and with PG the peak powers were 223.9 and 223.3 W at 0 and
200 torr respectively. A way to explain this observation is that the equilibrium pressure of
AC at 60C is approximately 850 torr which is considerably higher than 200 torr.
Additionally, examining the pressure data for the experiments in Figure 39 and Figure 43
shows that even when the pressure controller was set to 0 torr it remained considerably
above this pressure for much of the experiment. This means that while the controller was
74
set low, the pressure in the reactor was much higher due to rapid decomposition.
However, a more marked difference is noted when the pressure was set to 400 torr. With
EG the peak power was 159.4 and 241.5 W for 400 torr and 0 torr, respectively, and for
PG the peak power was 174.2 W and 223.9 W for 400 torr and 0 torr respectively. The
difference observed in changing the set overhead pressure from 200 to 400 torr shows
that the pressure certainly has a strong effect on the system thermal power and therefore
must be considered in any system design.
An important result of the pressure tests is that while it is necessary to lower the
pressure of the system for high power ratings a high vacuum will not be needed. In the
early decomposition testing, all runs were conducted with a high vacuum system. It was
suspected that a system capable of that level of vacuum was not needed for rapid
decomposition. The fact that there was no difference in peak power at both a system set
to 0 and 200 torr makes the idea of using a system at reduced pressure more realistic. In
an application, it is foreseeable to lower system pressure to this level, but it would be in
no way reasonable to lower the system pressure to 1 x 10-5 torr as was used in the early
decomposition experiments.
It was noted when the system was set to different pressures that the amount of AC
which decomposed until the system reached steady state changed. This is evaluated using
numerical integration to find the amount of heat rejected to the thermal load. For the case
of AC in PG at 400 torr, 200 torr and 0 torr, as seen in Figure 47 and Table 31, the
amount of energy that was rejected to the AC at each pressure was 173 kJ, 44.6 kJ and
18.4 kJ, respectively, for a total of 236.1 kJ, compared to a predicted total of 212.8 kJ.
The reason that steady state was reached at each pressure is that some amount of AC, or
75
its decomposition products, will be soluble in the PG at each pressure. This is evident
since as the pressure was reduced from a value where the system was at steady state, the
vessel temperature fell as the AC decomposed and caused the system to reject more heat
to the simulated thermal load. Visually, it was evident in the system since when the set
pressure was changed from 400 torr to 200 torr or from 200 torr to 0 torr, the heat transfer
fluid began to bubble. The source of this bubbling could either be dissolved AC
decomposing or decomposition products being removed from solution in an endothermic
process which lowered the vessel temperature. It is likely that ammonia could be the
decomposition product removed since it is extremely soluble in EG, and presumably in
PG, as discussed in Section 2.3.8. Therefore, it is plausible that once the pressure was
lowered, additional ammonia was removed from the solution, lowering the temperature.
On a full scale system this steady state limitation can be overcome by continuously
adding AC to the decomposition system to keep the reactor contents far from equilibrium
conditions to maintain a high power rating.
Early experiments showed that using a heat transfer fluid in which AC is soluble
showed a drastic increase in the rate of decomposition as compared to a heat transfer
fluid in which it is insoluble. Ethylene glycol was the first heat transfer fluid which was
found to satisfy both the solubility criteria and have a very high boiling point so that it
would not be consumed during the process. Propylene glycol was also considered since it
is similar to EG but is much less toxic, to the point where it is considered to be food safe.
Both EG and PG were considered in testing to determine if EG had an appreciable
advantage over the preferred PG. It was found at each temperature that EG had a slightly
higher peak power than PG. The comparisons can be found in Table 20 and showed
76
percent differences of 28%, 5% and 8% for 30C, 45C and 60C, respectively. The
larger percent difference at 30C can be explained since the peak powers were relatively
low so a small difference of only 12.9 W leads to a difference of 28% while at 60C a
difference of 17.6 W leads to a difference of 8%. Since, especially at higher temperatures,
the two solvents offer comparable performance it can be concluded that using nontoxic
PG should not lead to performance degradation compared to EG.
The amount of AC initially added to the system has an effect on the peak power.
This can be shown by comparing the experiments conducted in PG at 60C where initial
charges of 100.9 g and 204.4 g of AC were added. The peak power found at 100.9 g was
223.9 W, while that for the 204.4 g charge was 319.2 W. Part of this increase in peak
power arises from the heat capacity of the AC. Adding more AC will cause a greater
initial temperature depression in the reactor contents since it is at a lower temperature
than the PG and a greater amount of AC will further lower the temperature of the PG.
The heat capacity of AC at 60C is 1.92 kJ/kgC and the heat capacity of PG at 60C is
2.73 kJ/kgC.90,96,97 Therefore, adding 100.0 g of AC at 20C to 650 mL PG at 60C
should cause the temperatures to stabilize at approximately 56C while adding 204.4 g of
AC at 20C should cause the temperature to stabilize at 53C. It was observed that adding
100.9 g of AC caused the reactor contents to reach a temperature minimum of 47.6C,
while adding 204.4 g of AC caused the reactor contents to reach a minimum of 45.6C.
These temperature differences are approximately the same as would be expected from the
specific heats alone. However, this is not sufficient to account for a peak power
difference of 35%. A second explanation for the marked increase in peak power is that
adding a greater amount of AC kept the reactor contents farther from equilibrium
77
conditions and therefore increased the rate of decomposition which increases the power
rating. This makes sense in light of the aforementioned discussion of the effect of
equilibrium in the system. For system design recommendations this shows that keeping a
greater amount of AC in the slurry will increase the system power rating by maximizing
the rate of decomposition.
The conclusion from the pressure effect is positive from a real system perspective since it
is much more realistic to obtain a pressure on the order of 200 torr than 10-5 torr. The
choice of either EG or PG led to comparable results, so PG seems preferable as the
system heat transfer medium, since it is non-toxic and environmentally friendly. Finally,
the amount of AC in the reactor does have an effect on the thermal power and adding a
greater amount of AC to the system should function to increase the thermal power rating.
This can be tested by using a method to continuously add AC to the system and then
evaluate the optimal amount of AC to maintain in the reactor.
79
80
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92
APPENDIX
The data presented in the appendix has a data table and two graphs for each
experimental run. In the data tables the initial bulk temperature is the temperature of the
heat transfer fluid prior to the addition of the AC. The initial AC temperature is the room
temperature, which is assumed to be the AC temperature since it was stored on the
laboratory bench. The heat from decomposition is the amount of energy required to
completely decompose the mass of AC added. The heat from the temperature change of
the AC accounts for the temperature change of the AC using the heat capacity. The
bounds of integration were chosen based on the time when the AC was added or the
pressure changed and the time when steady state was reached. The percent difference is
negative when the energy from the integration is less than that from the calculated energy
based on the AC mass. In the first figure for each run the bulk temperature is the
temperature of the heat transfer fluid. The temperature in is the water temperature
measured from the recirculator immediately before it enters the heat transfer coil into the
reactor. The temperature out is the water temperature measured from the recirculator
immediately after its leaves the heat transfer coil in the reactor. The heat rejected is the
thermal power calculated from the energy balance around the recirculator heat exchanger
in the reactor. In the second figure the pressure was manually recorded as displayed on
the pressure controller. The T is the reactor inlet and outlet recirculator water
temperature difference. The vertical lines on each graph represent the bounds of
93
integration. Where there is more than one area of integration different colors were used
for each zone of integration.
94
Table 21. Experimental data for ammonium carbamate in propylene glycol at 30C
300
30.0
19.3
105.241
12.00
211.5
1.88
100
9500
161.3
-24.41%
PG
Heat Rejected
Bulk Temperature
Temp In
Temp Out
250
200
150
100
50
0
0
2000
4000
6000
35
34
33
32
31
30
29
28
27
26
25
Temperature (C)
8000
Time (s)
50
45
40
35
30
25
20
15
10
5
0
2.00
1.80
1.60
1.40
1.20
1.00
0.80
0.60
0.40
0.20
0.00
10000
Pressure
T
2000
4000
6000
8000
T (C)
Pressure (torr)
Figure 26. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 30C
Time (s)
Figure 27. Pressure and T for ammonium carbamate in propylene glycol at 30C
95
Table 22. Experimental data for ammonium carbamate in ethylene glycol at 30C
30.0
19.3
103.957
12.00
208.9
1.86
180
10000
108.0
-48.77%
EG
300.00
Heat Rejected
Bulk Temperature
Temp In
Temp Out
250.00
200.00
150.00
100.00
50.00
0.00
0
2000
4000
6000
8000
35
34
33
32
31
30
29
28
27
26
25
10000
Temp (C)
Time (s)
Figure 28. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
30C
40
30
25
20
15
10
5
0
0
2000
4000
6000
8000
T (C)
35
Pressure (torr)
2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
10000
Pressure
Time (s)
Figure 29. Pressure and T for ammonium carbamate in ethylene glycol at 30C
96
Table 23. Experimental data for ammonium carbamate in propylene glycol at 45C
200
180
160
140
120
100
80
60
40
20
0
0
1000
2000
3000
45.2
28.2
104.632
12.79
210.3
6.00
60
3700
256.0
18.34%
PG
50
48
46
44
42
Heat Rejected
40
Bulk Temperature
38
Temp In
36
Temp Out
34
32
30
4000
5000
6000
Temperature (C)
Time (s)
140
Pressure (torr)
120
100
80
60
40
20
0
0
1000
2000
3000
4000
5000
5
4.5
Pressure
4
T
3.5
3
2.5
2
1.5
1
0.5
0
6000 7000
T (C)
Figure 30. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 45C
Time (s)
Figure 31. Pressure and T for ammonium carbamate in propylene glycol at 45C
97
Table 24. Experimental data for ammonium carbamate in ethylene glycol at 45C
200
180
160
140
120
100
80
60
40
20
0
0
1000
2000
3000
45.3
28.6
104.274
12.79
209.6
5.92
20
5500
225.1
4.43%
EG
50
48
46
44
42
Heat Rejected
40
Bulk Temperature
38
Temp In
36
Temp Out
34
32
30
4000
5000
6000
Temperature (C)
Time (s)
Figure 32. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
45C
120
T
80
60
40
20
0
0
1000
2000
3000
4000
5000
6000
T (C)
100
Pressure (torr)
5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
7000
Pressure
Time (s)
Figure 33. Pressure and T for ammonium carbamate in ethylene glycol at 45C
98
Table 25. Experimental data for ammonium carbamate in propylene glycol at 50C
49.8
19.3
102.353
12.71
205.7
7.40
50
2500
190.7
-10.54%
PG
300
55
250
50
200
Heat Rejected
Bulk Temperature
Temp In
Temp Out
150
100
45
40
50
35
30
4000
1000
2000
3000
Temperature (C)
Time (s)
Pressure (torr)
160
140
Pressure
120
100
80
60
40
20
0
0
1000
2000
3000
5.00
4.50
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
T (C)
Figure 34. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 50C
4000
Time (s)
Figure 35. Pressure and T for ammonium carbamate in propylene glycol at 50C
99
Table 26. Experimental data for ammonium carbamate in propylene glycol at 55C
300
250
200
150
100
50
0
0
500
1000
1500
55.2
21.5
101.372
12.18
203.8
6.95
90
2200
206.3
-2.09%
PG
60
58
56
54
52
Heat Rejected
50
Bulk Temperature
48
Temp In
46
Temp Out
44
42
40
2000
2500
3000
Temperature (C)
Time (s)
300
Pressure (torr)
250
200
150
100
50
0
0
500
1000
1500
2000
5.00
Pressure
4.50
4.00
T
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
2500
3000
T (C)
Figure 36. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 55C
Time (s)
Figure 37. Pressure and T for ammonium carbamate in propylene glycol at 55C
100
Table 27. Experimental data for ammonium carbamate in propylene glycol at 60C
60.1
20.8
100.94
11.57
202.9
7.05
39
2000
186.8
-11.01%
PG
300
70
250
65
200
60
150
Heat Rejected
Bulk Temperature
Temp In
Temp Out
100
50
0
0
500
1000
1500
55
50
45
2500
2000
Temperature (C)
Time (s)
Figure 38. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C
300
7
Pressure
T
200
6
5
4
150
100
T (C)
Pressure (torr)
250
50
0
0
500
1000
1500
2000
0
2500
Time (s)
Figure 39. Pressure and T for ammonium carbamate in propylene glycol at 60C
101
Table 28. Experimental data for ammonium carbamate in propylene glycol at 60C with
two pressure settings
300
60.2
20.7
102.624
11.57
206.3
7.18
60
1700
195.4
-8.47%
PG
Heat Rejected
Bulk Temperature
Temp In
Temp Out
250
200
70
65
60
150
55
100
50
50
45
0
1000
2000
Temperature (C)
3000
Time (s)
Figure 40. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with two pressure settings
7
Pressure
Pressure (torr)
300
250
6
5
200
150
100
50
0
0
1000
2000
T (C)
350
3000
Time (s)
Figure 41. Pressure and T for ammonium carbamate in propylene glycol at 60C at two
pressures
102
Table 29. Experimental data for ammonium carbamate in ethylene glycol at 60C
60.3
24
101.986
11.57
205.0
6.58
50
1900
206.6
-2.33%
EG
300
70
250
65
200
60
150
Heat Rejected
Bulk Temperature
Temp In
Temp Out
100
50
0
0
500
1000
1500
2000
2500
55
Temperature (C)
50
45
3000
Time (s)
300
Pressure (torr)
250
200
150
100
50
0
0
500
1000
1500
2000
10
9
Pressure
8
T
7
6
5
4
3
2
1
0
2500
3000
T (C)
Figure 42. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C
Time (s)
Figure 43. Pressure and T for ammonium carbamate in ethylene glycol at 60C
103
Table 30. Experimental data for ammonium carbamate in ethylene glycol at 60C at two
pressures
Initial Bulk Temperature (C)
Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration 1 (s)
Upper Bound of Integration 1 (s)
Lower Bound of Integration 2 (s)
Upper Bound of Integration 2 (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent
Heat Rejected
Bulk Temperature
Temp In
Temp Out
250
200
70
65
60
150
55
100
50
50
45
5000
1000
2000
3000
4000
Temperature (C)
300
60.3
22
101.661
11.57
204.3
6.30
121
2200
2800
4200
219.5
4.21%
EG
Time (s)
300
Pressure (torr)
250
200
150
100
50
0
0
1000
2000
3000
10
Pressure
9
8
T
7
6
5
4
3
2
1
0
4000
5000
T (C)
Figure 44. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at two pressures
Time (s)
Figure 45. Pressure and T for ammonium carbamate in ethylene glycol at 60C at two
pressures
104
Table 31. Experimental data for ammonium carbamate in propylene glycol at 60C at
three pressures
300
59.7
19.3
102.184
11.57
205.4
7.38
60
2300
2380
3200
3580
4100
236.1
10.97%
PG
Heat Rejected
Bulk Temperature
Temp In
Temp Out
250
200
70
65
60
150
55
100
50
50
45
5000
1000
2000
3000
4000
Temperature (C)
Time (s)
450
400
350
300
250
200
150
100
50
0
Pressure
T
4.00
3.50
3.00
2.50
2.00
1.50
T (C)
Pressure (Torr)
Figure 46. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C at three pressures
1.00
0.50
0
1000
2000
3000
4000
0.00
5000
Time (s)
Figure 47. Pressure and T for ammonium carbamate in propylene glycol at 60C at
three pressures
105
Table 32. Experimental data for ammonium carbamate in ethylene glycol at 60C at three
pressures
300
59.7
19.5
102.997
11.57
207.0
7.41
60
900
1400
2500
3150
3900
208.7
-2.66%
EG
Heat Rejected
Bulk Temperature
Temp In
Temp Out
250
200
64
62
60
58
150
56
100
54
50
52
50
5000
1000
2000
3000
4000
Temperature (C)
Time (s)
450
400
350
300
250
200
150
100
50
0
Pressure
T
3.5
3
2.5
2
1.5
T (C)
Pressure (Torr)
Figure 48. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at three pressures
1
0.5
0
500
1000
1500
2000
2500
3000
0
3500
Time (s)
Figure 49. Pressure and T for ammonium carbamate in ethylene glycol at 60C at three
pressures
106
Table 33. Experimental data for ammonium carbamate in propylene glycol at 60C with
double AC loading
500
450
400
350
300
250
200
150
100
50
0
0
1000
2000
59.8
19.1
204.355
11.57
410.7
14.8
110
2700
530.8
24.75%
PG
65
63
61
59
57
55
Heat Rejected
Bulk Temperature
53
Temp In
51
Temp Out
49
47
45
3000
4000
Temperature (C)
Time (s)
Figure 50. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with double ammonium carbamate loading
300
T
200
150
100
50
0
0
500
1000
1500
2000
2500
3000
T (C)
250
Pressure (torr)
10
9
8
7
6
5
4
3
2
1
0
3500
Pressure
Time (s)
Figure 51. Pressure and T for ammonium carbamate in propylene glycol at 60C with
double ammonium carbamate loading
107
Table 34. Experimental data for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol
300
250
200
150
100
50
0
0
500
1000
1500
59.8
19.6
100.264
11.57
201.5
7.16
70
1500
248.9
19.27%
PG Reused
65
63
61
59
57
Heat Rejected
55
Bulk Temperature
53
Temp In
51
Temp Out
49
47
45
2000
2500
3000
Temperature (C)
Time (s)
Figure 52. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with reused propylene glycol
300
T
200
150
100
50
0
0
500
1000
1500
2000
2500
T (C)
250
Pressure (torr)
10
9
8
7
6
5
4
3
2
1
0
3000
Pressure
Time (s)
Figure 53. Pressure and T for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol
108
Table 35. Experimental data for ammonium carbamate in propylene glycol at 60C with
twice used propylene glycol
300
250
200
150
100
50
0
0
500
1000
1500
59.9
19.9
102.285
11.57
205.6
7.27
100
1600
256.7
20.61%
PG Reused
65
63
61
59
57
Heat Rejected
55
Bulk Temperature
53
Temp In
51
Temp Out
49
47
45
2000
2500
3000
Temperature (C)
Time (s)
300
Pressure
Pressure (torr)
250
200
150
100
50
0
0
500
1000
1500
2000
2500
10
9
8
7
6
5
4
3
2
1
0
3000
T(C)
Figure 54. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with twice reused propylene glycol
Time (s)
Figure 55. Pressure and T for ammonium carbamate in propylene glycol at 60C with
twice reused propylene glycol
109