Heat Recovery Systems & CHP Vol. 14, No. 4, pp.

437-446, 1994
Elsevier Science Lid
Pergamon Printed in Great Britain
0890-4332/94 $7.00 + .00

EXPERIMENTAL ASSESSMENT OF AN
AMMONIA/LITHIUM NITRATE ABSORPTION COOLER
OPERATED ON LOW TEMPERATURE GEOTHERMAL
ENERGY

R. AYALA, J. L. FRiAS, L. LAM, C. L. HEARD* and F. A. HOLLAND,"

Centro Cerro Prieto, Instituto de Investigaciones E16ctricas, M6xico; *Departamento de Geotermia,
Divis6n Fuentes de Energia, Instituto de Investigaciones El6ctricas, M6xico; and tOverseas Educational
Development Office, University of Salford, Lancashire M5 4WT, U.K.

(Received 28 August 1993)

A~traet--An attractive way to directly exploit low temperature geothermal energy is to produce
refrigeration using heat-driven absorption coolers. In Mexico this would contribute to the cold chain in
areas of agricultural production and transshipment. An experimental 10.5 kW cooling capacity ammo-
nia/water absorption cooler, that had been evaluated in the Cerro Prieto geothermal field, was modified
to use ammonia/lithium nitrate (NH3/LiNO3). This prototype was successfully operated with generator
temperatures from 90 to 145°C and with cold chamber temperatures from 0 to -10°C.

NOMENCLATURE
CR compression ratio Pco/P=, [dimensionless]
COP coefficient of performance [dimensionless]
F flow rate [m3s -I (10-s)]
FR flow ratio [dimensionless]
M mass flow rate [kg s - t ]
N efficiency [%]
P pressure [bar]
Q heat duty [kW]
T temperature [°C]
Subscripts
a actual
AB absorber
eel Carnot for cooling
CO condenser
ecl enthalpy based for cooling
EV evaporator
GE generation
m mixture
r refrigerant
rec recuperator
s solution
v geothermal steam

INTRODUCTION

In previous experimental work it was demonstrated that the experimental ammonia/water

absorption cooler system has a high performance using low temperature geothermal energy [!, 2, 3].
It was observed that evaporating temperatures of -10°C can be reached with generation
temperatures of 125°C. Lower evaporating temperatures down to -20°C would require generation
temperatures above 140°C.
Since most of the geothermal resources in Mexico have a temperature between 90 and 115°C,
an alternative option to take advantage of these sources of geothermal heat with absorption cooling
systems, is to use ammonia/lithium nitrate (NH3 LiNO3) as the working fluid. These systems attain
an optimum coefficient of performance (COP) at generation temperatures of 90°C (for -10°C
evaporating temperatures) [4].
437
438 R. AYALAet al.

The ammonia/water (NH3H20) absorption systems use a rectifier and a rectification column,
making these systems relatively complicated and expensive. Using an alternative non-volatile
absorbent would make it possible to dispense with the rectification system.
The NHflLiNO 3 solution as a working fluid for cooling systems is a very promising alternative
for the utilization of waste heat and solar energy as heat sources for cooling applications. Most
NH3/LiNO 3 absorption cooling system studies have been theoretical. Therefore, there is a good
deal of experimental work which needs to be done in order to better understand this kind of system.
This paper describes the experimental studies carried out with the experimental absorption
system using NH3/LiNO 3 as a working fluid, in order to reduce the amount of equipment required
and to use a wider range of generation temperatures.

THE NH 3/LiNO3 ABSORPTION R E F R I G E R A T I O N CYCLE

A schematic diagram of the relationship between pressure and temperature in a conventional

heat driven absorption cooler is shown in Fig. 1. This system uses heat energy instead of mechanical
energy to make the necessary change of the conditions to complete a refrigeration cycle. The
condensation, expansion and evaporation processes are the same as in a conventional compressor
driven system. However, in the absorption cycle the compressor is replaced by a secondary circuit
in which a solution (NH3/LiNO3, refrigerant/absorbent) is circulated by a pump. The evaporated
refrigerant is absorbed by the circulating liquid and the pressure is increased by the pump prior
to entering the generator. An amount of high grade heat QGEis added at an absolute temperature
TeE in the generator to produce the high pressure refrigerant vapour required to feed the
condenser.
The NH3/LiNO 3 absorption system technique is a specific example in which the vaporizing
r e f r i g e r a n t is ammonia and the absorbent solid is lithium nitrate, in a dilute solution of ammonia
(weak solution). The absorber produces a concentrated solution of ammonia in lithium nitrate
( s t r o n g solution). This rich solution is separated, by boiling, into two streams, an ammonia vapour
overhead product (recycled as refrigerant) and the lithium nitrate-rich stream (weak solution) used
as the absorbent. Figure 2 shows the basic flow diagram for the NH 3/LiNO3 absorption system
installed at the Cerro Prieto geothermal field.
This working fluid pair was studied by Infante Ferreira [4]. An experimental study of the
thermodynamic and physical properties data equations for NH3/LiNO3 and ammonia/sodium
thiocyanate (NH3/NaSCN) solutions was undertaken. The purpose of that work was to provide
equations for the thermodynamic and physical property data for the NH 3/LiNO3 and NH3/NaSCN
systems in a form readily adaptable to a computer programme.

~E

O.
%0-
i i0oo0.n-i Ooo
E

o, l
-- I I

Fig. 1. Plot of temperature against pressure for an absorption cooler.

 Assessment of an absorption cooler 439

aoolln9 water aeparotor/naoumulator

eondanaar
13 10 ~11
evaporator praooolar

generator
O0011flgwatar
19 roauporstor

mixer [-~

absorber ?I' ~ak aoluUan

strong aolUtlOn
$
wltar
geothermal
staam
pump

'- aaoumulator )
I

Fig. 2. Schematicdiagram of the ammonia/lithium nitrate absorption cooler.

T H E R M O D Y N A M I C CONSIDERATIONS

The main parameters that define the performance of an NH3/LiNO 3 absorption cooling system
are as follows. From thermodynamic analysis and from mass and heat balance considerations, with
reference to Fig. 2, and using the above defined nomenclature, the actual coefficient of performance
is given by the following equation:
QEv
C O P , = QGE" (1)

The actual coefficient of performance, already defined by equation (1), can also be written as:
M,(H. - Hl~)
C O P , = MA" ( H 8 _ 1t7)' (2)
where H8 is the enthalpy per unit mass of the vapour/liquid mixture leaving the generator.
The Carnot coefficient of performance is given by the equation

TGE _lL T c o - TEV (3)

and the theoretical coefficient of performance based on the corresponding enthalpy is given by the
equation
(H,7 - H,s)
COPe~l = Hie - H u + ( S u - H T ) F R , ' (4)
where F R , is the actual flow ratio, which is defined as the ratio of the mass flow rate of solution
from the absorber to the generator, to the mass flow rate of refrigerant from the condenser to the
evaporator.
Mm
F R . -.-- - - (5)
M,
Alternatively, the flow ratio can be rewritten in terms of concentration as
X,- X~E
F R = X m - XGE" (6)
440 R. AYALA et al.

The efficiency of the recuperator is given by the equation

H 5 H+ - -

Nre c - - - - (7)
H + - H+3'
where /-/+3 is the enthalpy of the NH3/H20 solution with concentration .1"+but at the solution
temperature entering the recuperator, T3.
The efficiency of the generator is defined as
//7-//+
NGE = H7 -- Hvs' (8)
where Hv8 is the enthalpy of the vapour/liquid mixture leaving the generator at the geothermal
vapour temperature Tv.

EXPERIMENTAL

The main modification made to the experimental NH3/H20 absorption system was the
replacement of the solution accumulator tanks, in order to replace the rectifier and to reduce the
solution inventory. Figure 3 shows the modified process diagram after the modifications made in
order to use NH3/LiNO3.
Figures 4 and 5 show the new accumulator tanks for weak and strong solutions respectively. The
weak solution tank is also a liquid/vapour separator. These tanks have a volume of 55.61 and they
were made with nominal 12 in. (30.48 cm) tubes, and have a height of 30 inches (76.2 cm).
Both tanks were installed as follows. The strong solution tank was installed, bypassing the old
strong solution accumulator, and the weak solution accumulator/separator was installed replacing
the rectifier and the old weak solution accumulator.
These changes were made in the context of the original process flow diagram, with NH3/H20
as the working fluid, just closing and opening the correct valves without removing any equipment.
The experimental absorption system was filled with 45.5 kg of industrial grade (99.9%) lithium
nitrate (LiNO3), approximately 35kg of agricultural grade ammonia and 0.3kg of sodium
dichromate (Na2Cr207" 2H20), as ~ corrosion inhibitor.

It . . . . .

? ....
p. . . . . .

+ , ........
+......
+++++
+ ~)~A'~Ito~rilt°r

g l n l P l t o p+.....
l111flClP
+
2 leplrl~Orl . . . . . . 1atop

h
+ + +..+

NOTES:

............... oeothermll fLu£d IDIOPDIP

- - worklfl O flu£d
,+s
expenelon 1
oheok valve ValVO

~- needle vllve strong

l O l U t Lon
Dell valve
Oltl VllVl
.,--)

| 0 1 u t 1on
heat
additLonel nxohonOer
oooler.

F- J

Fig. 3. Diagram of the experimental NH3/LiNO 3 absorption cooler system.

442 R. AYALA et al.

Table 1. NH3/LiNO 3 tests experimental main thermodynamic parameters

Date TeE COPa COPc~I COP~I FR FR= Nr¢¢ Not QEV CR
160992 135,0 0.43 1,68 0.54 5.39 10,44 0.43 0.84 5.21 4.0
170992 135.2 0.41 1.73 0.54 5.23 10,41 0,44 0.85 5.20 3.8
290992 132.9 0,45 1.77 0,54 4.99 9.28 0.44 0,85 5.29 3.2
300992 134,6 0,50 1.73 0.52 5,10 7.78 0.48 0.87 5.24 3.1
011092 135,2 0.63 2.00 0,58 4.23 5.92 0.55 0.88 5,42 2.9
051092 133.2 0.39 1.92 0.56 4.75 10.84 0.43 0.85 5.31 3.1
061092 118,8 0,39 2.39 0.69 3.66 14.37 0.27 0.80 3.63 2.3
081092 119.0 0.54 1.96 0.61 4.49 8.38 0.52 0.84 5.35 2.8
091092 119,5 0.50 2.11 0.67 3.92 9.86 0.64 0.82 2,95 2.5
121092 118~7 0.42 1.68 0.55 5.79 10.69 0.32 0.83 5,29 3.0
131092 104.5 0.55 1.46 0.54 6.93 8,39 0.48 0.83 5,11 2.9
141092 108.9 0.45 1.58 0.55 6.46 10.56 0,36 0.86 5.24 2.8
151092 96.4 0.47 1.69 0.65 5.89 10.64 0.31 0.84 5.31 2.5
161092 135,0 0.43 1.61 0.54 5.39 10.44 0.43 0,84 5.21 4.0
191092 93.3 0.63 1.77 0.70 5.42 5.91 0.43 0.90 5.30 2.9
201092 131,7 0.35 1,50 0,45 7.54 12.70 0.38 0.85 5.18 3.8
220193 113.0 0.42 1.71 0.51 6.23 10.88 0.40 0.86 5.32 3.1
250193 112,2 0.47 2.49 0.63 3.78 8.91 0.53 0.88 5.43 2.6
260193 111,8 0.56 8.84 0,76 2,23 6.13 0.80 0,92 5.73 1.3
270193 100.8 0.41 2.03 0,65 4.61 11.17 0.33 0,86 5,37 2.4
280193 90.7 0.38 2.36 0.74 3.66 14,28 0.38 0.81 3,19 2.0
020293 108.2 0.29 4.12 0.69 3.26 16.23 0.27 0,86 5.37 1.7
030293 103.5 0.30 3.96 0.71 3.31 16.81 0.25 0.85 5,39 1.6
040293 109.5 0.34 1,73 0.53 6.36 13.67 0.31 0.87 5.36 3.0

The system was manually operated and it was controlled by fixing the weak solution flow rate
and the generation temperature, according to the test plan. This was accomplished by manipulating
the NH3/LiNOa solution valve, between the additional cooler and the mixer, and the geothermal
steam valve at the generator inlet, respectively.
During each one of the 24 experimental test runs, 45 readings of temperatures, pressure and flow
were manually recorded every 30 min, in English units.

RESULTS AND DISCUSSION

Table 1 shows the results of the analysis performed using a computer programme developed for
this purpose [5]. Using the values of this table and plotting them in order to better understand the
system performance, a series of diagrams were prepared. These diagrams illustrate the performance
of the NH3/LiNO3 prototype absorption cooling system operated with geothermal energy.
Figure 6 is a plot of the thermodynamic flow ratio against the actual flow ratio. In this plot it
can be observed that the thermodynamic flow ratio does not vary for a range of actual flow ratios

30

25-

t-
.- 20-
r-
E
15-
n"
LL
0

I 0 1 ~ [] oD
5

OF"
0
, 10
, 20 30
Actual flow ratio FRa (dimensionless)

Fig. 6. Plot of thermodynamic flow ratio against actual flow ratio.

 Assessment of an absorption cooler 443

1-

0.9-

0.8"

_•0.7-
.~_ 0.6-
4--
.~ 0.5- [] O
"10
0.4-
0..
O 0.3-

0.2-

0,1"

0
0 1'o 2'0 30
Actual flow raUo Fl~\(dimensionless)

Fig. 7. Plot of actual coefficientof performance against actual flow ratio.

from 6 to 15. The fact that the concentration based thermodynamic flow ratio does not increase
with increasing actual flow ratio is due to limitations of mass and heat transfer in the experimental
unit. Increasing flow ratios were for a nearly constant evaporator heat load. The heat load in the
generator, absorber and recuperator would have to increase greatly to allow the thermodynamic
flow ratio to approach the actual flow ratio at high flow ratios.
Figure 7 is a plot of the actual coefficient of performance against the actual flow ratio. It can
be observed that the actual coefficient of performance increases with decreasing actual flow ratio.
Figure 8 is a plot of the evaporator heat load against the actual flow ratio. It can be observed
that the heat load was practically constant for the range of actual flow ratios.
Figure 9 is a plot of the generator and recuperator efficiency against the actual flow ratio (FR=).
It can be observed that the generator efficiency is almost constant with the variation of the FR=
and the rceuperator efficiency increases with the decrease of FR,. The reduction in recuperator
efficiency is to be expected as the flow ratio increases, since the potential for heat recovery in the
absorbent circuit increases. This reduction in recuperator efficiency has a direct impact on the
overall efficiency of the cycle (Fig. 10). In a commercial or industrial design the approach

10-

9-

8-

7-

O
6- D

s-
t,,.
D
[]
3- D

2-
1

0
0 lO 2o 30
Actual flow ratio FRa (dimensionless)

Fig. 8. Plot of evaporator heat load against actual flow ratio.

444 R. AYALA el al.

100"
90"
80" +

70"

+ ++
++
'B + +
4- 4- -F
4-
:~+ +
30- '4- +.4.

20-
10-
0
0 1'o 2b 30
Actual flow ratio FRI (dimensionless)
o Generator + Rocuperator

Fig. 9. Plot of efficiency against actual flow ratio.

temperature of the recuperator is a key parameter in optimizing the design with respect to energy
and capital costs.
Figure 11 is a plot of the coefficients of performance against the generator temperature. With
this working pair the efficiency of the refrigeration cycle is practically independent of generator
temperature from 90 to 135°C.
Figure 12 is a plot of the LiNO3 weight concentration in the strong and weak NH3/LiNO3
solution against the generator temperature. It can be seen in the trends that the difference of the
concentration is almost constant for the strong and weak solutions at the operation conditions of
90 to 140°C, generator temperatures.
Figure 13 is a plot of the evaporation and condensation pressure against the generator
temperature. This plot shows the typical operating pressures for a NH3/LiNO3 absorption system
at generator temperatures from 90 to 140°C.
Figure 14 is a plot of the compression ratio against generator temperature. It can be observed
that the compression ratio increases with the increasing generator temperature.

2.5
+ +

+
4-
2- + + +

+ +
8 1.5- + +

|
_E
o.
8
0.5
r~

0
o ~ ~ eo 100
R~Ul:~'mor ~ Nreo (%)
D COP. + COP~ ~ COP~

Fig. 10. Plot of coefficient of performance against recuperator efficiency.

 Assessment of an absorption cooler 445

2.5 +

+
-b
+ +

.4_
4- "t- -I- -'b
÷ ~"4-
£; -)-
+
0 1.5'
C
®
.E_
O.
0
o
0.5
[] o°

°o loo ' 12o 14o

Generator temperature TGE (°C)
o COPa + COPed )~ COP~

Fig. 11. Plot of coefficient of performance against generator temperature.

IO0

[]

.•
.~
50-
40-
[] [] D

30-
8z 20-
10-
0
9O 16o ' lio 12o 13o 140
Generator temperature TeE ( ~ )
[] Strong solution + Weak solution

Fig. 12. Plot of LiNO3 concentration against generator temperature.

16

14
[]

12 [] [] 0

10 0[3 []
[]
"~ 8 []

0. -4- + "4-
"4-
4.'1" ,q-

0
9O 100 li0 t20 140
Generator temperature TaE (=C)
o Condensation + Evaporation

Fig. 13. Plot of solution vapour pressure against generator temperature.

446 R. AYALAel al.

5"

4.5-

[::
e"
.o F.7 121

3.5-

3' []
[] F] []
n"
O 2.5
° E3

N 2"

[]

E '
8

9o ' ' lao 14o

Generator temperature TGE (~C)

Fig. 14. Plot of compression ratio against generator temperature.

CONCLUSIONS

The NHa/LiNO3 absorption system was successfully operated at generator temperatures from
90 to 145°C, using geothermal steam as the heat resource.
The operating conditions for the NH3/LiNO3 concentration vary due to the generation
temperature but the concentration difference between the strong and weak solutions was nearly
constant.

REFERENCES

1. R. Best, C. L. Heard, H. Fernandez and J. Siqueiros, Developments in geothermal energy in Mexico--Part five: The
commissioning of an ammonia/water absorption cooler operating on low enthalpy geothermal energy. Heat Recovery
Systems & CHP 6(3), 209-216 (1986).
2. R. Best, C. L. Heard, P. Pefia, H. Fernandez and F. A. Holland, Developments in geothermal energy in Mexico--Part
twenty-six: experimental assessment of an ammonia/water absorption cooler operating on low enthalpy geothermal
energy. Heat Recovery Systems & CHP 10(1), 61-70 (1990).
3. R. Ayala, An experimental study of heat driven absorption cooling systems, M.Sc. thesis, University of Salford, U.K.
0992).
4. C. A. Infante Ferreira, Thermodynamic and physical property equations for ammonia/lithium nitrate and ammo-
nia/sodium thiocyanate solutions. Solar Energy 32, 231-236 (1984).
5. E. Rodarte, Programa para ealculo del propiedades termodiwlmicas de la soluci6n NH3/LiNO3, tesis licenciatura, para
obtener el titulo de Ingeniero Mec~nico, CETYS, Mexicali, B.C., M~xico, (1992).