Applied Thermal Engineering 20 (2000) 269284

www.elsevier.com/locate/apthermeng

An experimental integrated absorption heat pump euent

purication system. Part II: operating on water/Carrol
solutions
S. Santoyo-Gutierrez a,*, J. Siqueiros b, C.L. Heard c, E. Santoyo d,
F.A. Holland e
a

Unidad Geotermia, Instituto de Investigaciones Electricas, Av. Reforma 113, Col. Palmira, CP 62490, Temixco, Mor.,
Mexico
b
Centro de Investigacion en Ingeniera y Ciencias Aplicadas, Universidad Autonoma del Estado de Morelos, Av.
Universidad 1001, Col. Chamilpa, CP 62210, Cuernavaca, Mor., Mexico
c
Uso de la Energa Electrica, Instituto de Investigaciones Electricas, Av. Reforma 113, Col. Palmira, CP 62490,
Temixco, Mor., Mexico
d
Centro de Investigacion en Energa, Universidad Nacional Autonoma de Mexico, Apartado Postal 34, CP 62580,
Temixco, Mor., Mexico
e
Overseas Educational Development Oce, University of Salford, Salford, M4 5WT, UK
Received 2 March 1999; accepted 2 March 1999

Abstract
An experimental integrated absorption heat pump euent purication system (IAHPEPS) was built
and originally operated with water-lithium bromide as a working mixture. The experimental results of
IAHPEPS operated with water-Carrol as a working mixture are presented. Tap water was used as
euent and distilled water was obtained after purication. Pure euent production rates ranged
between 1.2 and 4 kg h1. The actual coecient of performance (COP)A varied from 1.35 to 1.55. The
heat pump eectiveness (HPE) varied from 0.74 to 0.82. The results from the small scale system indicate
the likely results from industrial scale units which could be operated with low quality heat such as waste
heat, solar or geothermal resources. # 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Absorption; Heat pumps; Purication systems; Distillation; Water purication; Euent concentration

* Corresponding author. Tel.: +52-7318-3811; fax: +52-7318-2526.

E-mail address: ssantoyo@iie.org.mx (S. Santoyo-Gutierrez)
1359-4311/00/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 4 3 1 1 ( 9 9 ) 0 0 0 2 5 - 3

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Nomenclature
COP
FR
GTL
H
HPE
M
Q
T
X

coecient of performance (dimensionless)

ow ratio (dimensionless)
gross temperature lift (TCOTEV) (K)
enthalpy per unit mass (kJ kg1)
heat pump eectiveness (dimensionless)
mass ow rate (kg s1)
heat duty (kW)
absolute temperature (K)
mass fraction (dimensionless)

Subscripts
A
measured or real
AB
absorber or from absorber to generator
C
Carnot
CO
condenser
EV
evaporator
GE
generator
EH
enthalpy based
R
refrigerant
1
into absorber from evaporator
2
out of generator to absorber
3
into generator from absorber
4
out of generator to condenser
5
into evaporator from condenser
1. Introduction
An experimental integrated absorption heat pump euent purication system (IAHPEPS)
was built and originally operated with water-lithium bromide as a working mixture [1].
Dierent working mixtures and dierent euent types can be studied with the IAHPEPS. In
the present work the IAHPEPS was operated using water-Carrol as a working mixture. Tap
water was used as euent to be puried. Carrol is a mixture of lithium bromide and ethylene
glycol in a 1:4.5 weight mixture [2]. It has a wider solubility range than pure lithium bromide.
It allows higher temperature lifts and better eciencies than pure lithium bromide with water
as an absorbent in absorption heat pumps [3].
2. Absorption heat pump
Absorption heat pumps allow heat to drive a heat recovery process with few moving parts
and a high primary energy ratio [4]. Simple distillation processes for solvent recovery and

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271

water purication are highly eective but also energy intensive [5]. A suitable absorption heat
pump could greatly reduce the energy intensity of such a process [68].
Fig. 1 shows the basic process in two parts. The upper diagram is the absorption heat pump
and the lower part the simple distillation system. The driving heat is supplied to the generator
at the highest temperature in the thermodynamic cycle. Heat from the absorber and the
condenser is supplied to the distillation process and heat is recovered from the distillation
process in the evaporator.
The energy eciency of a heat pump most frequently used is the coecient of performance
(COP). This is dened in dierent ways depending on the type of heat pump and the use to

Fig. 1. Schematic diagram of an absorption heat pump assisted euent purication system.

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which it is put. For example, in the case of a mechanical vapour compression heat pump for
cooling the real COP is the energy extracted from the material to be cooled, via the
evaporator, divided by the work energy input to the compressor [9,10]. However for a given
heat pump the maximum theoretical COP is that of the Carnot cycle. The Carnot cycle COP is
solely dependant on the temperatures of the heat supplied and rejected in each component of
the cycle. Eq. 1 gives the Carnot coecient of performance (COP)C for an absorption heat
pump for heating.


TEV TGE TAB
COPC
1
1
TGE TCO TEV
The Carnot cycle is not a useful yardstick for evaluating real heat pump systems, since it
includes assumptions of reversable isothermal heat transfer with innitesimal temperature
dierences and expansion and compression of wet vapour.
In practice the maximum attainable COP is enthalpy based as described in Eq. 2.
COPEH

H1 FR 1H2 FRH3 H4 H5
H4 FR 1H2 FRH3

The comparison of this with the experimental or real COP is the Heat Pump Eectiveness
(HPE) [Eq. 3].
HPE

COPA
COPEH

One of the other important measures of the performance of an absorption heat pump is the
ow ratio (FR). In a simple single eect absorption heat pump for heating this is the ratio of
the mass ow rate of the solution from the absorber to the mass ow rate of refrigerant into
the evaporator (Eq. 4).
FR

MAB
XGE

MR
XGE XAB

The higher the ow ratio the greater the internal heat transfer necessary in the economiser and
the larger the mass ow rates in the absorber and generator. This will be reected in larger
equipment, higher capital costs, more opportunities for heat losses from the system, a slower
startup and a larger inventory of absorbent. Carrol with its higher solubility should allow
systems to be operated with lower ow ratios than pure lithium bromide.
The application of a heat pump to a simple euent distillation process is attractive because
of the small temperature dierence between the euent and the pure solvent. The impurities in
the euent seldom lower the vapour pressure greatly relative to that of the pure solvent. To
equalise or slightly exceed the vapour pressure of the pure solvent it is only necessary to raise
the euent evaporator temperature a little above that of the solvent condenser. The higher the
temperature dierence, the greater the driving force for the process and the greater capacity for
a given size of heat exchangers. However the energy eciency of the heat pump is adversely
aected by raising this temperature dierence. In practice a balance between thermal energy

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273

eciency and equipment size and sophistication will determine the optimum temperature
dierence for a particular application.
Fig. 2 shows how an absorption heat pump system can be integrated into a simple
distillation system. The auxiliary condenser balances the heat ows in the system. In a large
scale installation this heat might be recovered to preheat the euent entering the system,
increasing the energy eciency. The pressure levels refer to the heat pump working uid.
3. Experimental equipment
The experimental equipment was designed for use with water as a working uid and salt
solutions as an absorbent. Most of the heat exchange surfaces were of stainless steel and the
vessels were made of carbon steel. To simplify the construction the main heat exchangers were
made from identical stainless steel coils from 6.1 m lengths of 19 mm (3/4 in) outside diameter
tubing which were mounted in adapted 20 kg domestic gas cylinders. The economiser was an
available spiral tube heat exchanger. The auxiliary puried euent condenser was made from a
length of 12.7 mm (1/2 in) outside diameter tubing coiled in a small carbon steel shell.
Positive displacement sliding vane pumps were used with inverters to control the pump
motor speeds. This allowed calibration of the pumping rate with respect to motor speed to be

Fig. 2. Pressure and temperature levels for an integrated absorption heat pump euent purication system.

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Fig. 3. Schematic diagram of the experimental integrated absorption heat pump assisted euent purication system
(IAHPEPS).

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275

used to measure ow rates. Other ow rates were measured by rotameters. The production of
distillate and the steam consumption were measured by weighing condensates over time.
Temperatures were measured with type E thermocouples. Pressures were measured with
Validyne dierential pressure transducers with respect to ambient pressure which was measured
in the same laboratory with a mercury column barometer. Solution concentrations were
measured from samples extracted from the generator and absorber solutions exits. The
refractive index was measured in an Abbe refractometer whose heating plate was pre-heated at
408C. The solution concentrations were inferred from a previously established concentration/

Fig. 4. Photograph of the experimental integrated absorption heat pump assisted euent purication system
(IAHPEPS).

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refractive index relationship at a constant temperature of 408C using a numerical correlation

derived from experimental data [11].
Fig. 3 is a schematic diagram of the equipment showing how the heat pump and euent
circuits were integrated. The heat pump circuit is a simple single stage absorption system with
low pressure steam used as the heat source. Fig. 4 is a front view of the experimental
integrated absorption heat pump euent purication system (IAHPEPS) showing the physical
distribution of components.
The euent circuit was a forced circulation system with liquid euent pumped through the
heat pump absorber coil and then through the condenser coil. The resulting two phase mixture
was separated for recirculation of the liquid phase and the vapour phase passed to the heat
pump evaporator for subsequent condensation. To close the heat balance an auxiliary puried
euent condenser was placed in series with the heat pump evaporator. The refrigerant circuit
also used a forced circulation system on the evaporator. Forced circulation for uids boiling
inside tubes with condensation on the shell side was used to improve the heat transfer and thus
the capacity of the equipment.
The equipment was manually controlled through the steam pressure of the heat supply to
the generator and the pump speeds. The cooling water temperature in the auxiliary puried

Fig. 5. Enthalpic coecient of performance (COP)EH and the actual coecient of performance (COP)A against the
gross temperature lift GTL=(TCOTEV).

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277

euent condenser was as supplied from the water main. The equipment took from 3040 min
to reach steady state from startup.
The IAHPEPS can be simply described as follows. The procedure was initiated when the
vacuum requirements were achieved using vacuum pumps connected to the system (Fig. 3).
These conditions had to be obtained in the generator, evaporator, absorber and the auxiliary
condenser. Once the IAHPEPS was under adequate vacuum conditions, steam was supplied to
the generator. Simultaneously the solution circulation system was started. Afterwards the
euent circulation was initiated. The euent circulated inside the absorber and the condenser
(Fig. 3). From these components the euent was fed to a centrifugal separator from where the
vapour phase was sent as a heating medium to the evaporator. The partial euent vapour
condensation provided the heat of vaporization for the liquid refrigerant. The separated liquid
euent was recirculated. The refrigerant from the evaporator was fed to a centrifugal
separator, the vapour phase being fed to the absorber and the liquid phase being recirculated
to the evaporator. The startup procedure terminated in the supply of cooling water to the
auxiliary condenser to complete the euent vapour condensation.
Once the system had been started up, steady state conditions needed to be achieved for each
experimental run. This required that the steam supply to the generator and euent, refrigerant

Fig. 6. Gross temperature lift GTL=(TCOTEV) against the evaporator temperature TEV.

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and auxiliary condenser cooling water ow rates be controlled manually with a frequency
controller. Usually these steady state conditions were obtained when the temperature, pressure
and ow rate variations were very small and maintained for at least 30 min. A detailed
description of the experimental run procedure for the IAHPEPS was presented by SantoyoGutierrez (1997) [11].
4. Results
All the results were obtained under steady state conditions. The steady state was checked
during each test and also from the recorded data series. Tap water, characterised by ion
chromatography technique [12], was used as the euent. Chloride, calcium and sulphate
concentrations were measured (Table 1). The working mixture was made up with distilled
water, lithium bromide and ethylene glycol with sodium dichromate added as a corrosion
inhibitor.
The heat balances were determined from measured temperatures, concentrations and ow
rates. Eq. 5 gives the basic heat balance for the heat pump.
QGE QEV QCO QAB

Eq. 6 gives the heat balance for the euent side, ignoring heat losses.
QCO QAB QEV QAUX

where
QAUX QGE

Table 1
Results of the chemical analyses of the euent supplied, euent treated and euent concentrated to the absorption
heat pump assisted euent purication system
Concentration in mg kg1
Test No.

1
2
3
4
5
6
7
8

Euent supplied

Euent treated

Euent concentrated

Cl

Ca

SO4

Cl

Ca

SO4

Cl

Ca

SO4

134.6
136.7
127.0
128.7
130.0
130.4
128.9
133.7

148.1
150.2
140.5
142.2
143.5
143.9
142.4
147.2

56.5
58.6
48.9
50.6
51.9
52.3
50.8
55.6

0.2
0.2
0.1
0.1
0.2
0.2
0.1
0.2

1.0
1.1
1.0
1.0
1.0
1.0
1.0
1.0

0.4
0.4
0.3
0.4
0.4
0.4
0.4
0.4

193.7
196.7
182.7
185.2
187.0
187.6
185.5
192.4

213.1
216.1
202.1
204.6
206.5
207.0
204.9
211.8

81.3
84.3
70.4
72.8
74.7
75.2
73.1
80.0

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279

The solution enthalpies were determined from numerical polynomial correlations obtained by
Reimann and Biermann [13] and the water enthalpies from numerical polynomial correlations
of the values tabulated by Mayhew and Rogers [14]. The ow ratios were calculated from the
measured concentrations.

5. Discussion
The capacity of the system varied from 1.2 to 4 kg h1 distilled water production. Twenty
three experimental runs were made under dierent operation conditions. Generation
temperatures ranged from 1101208C with heat pump evaporation temperatures from 63768C.
Refrigerant poor solution concentrations (XGE) ranged from 56.559.2%.
Fig. 5 shows the variation of the enthalpic coecient of performance (COP)EH and the
actual coecient of performance (COP)A against the gross temperature lift (TCOTEV).
(COP)EH and (COP)A decreased when the gross temperature lift increased. The dispersion of
the points is due to dierences in the conditions for the experimental test runs. This dispersion

Fig. 7. Enthalpic coecient of performance (COP)EH and the actual coecient of performance (COP)A against the
evaporator temperature TEV.

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was also found for compression heat pumps [10]. The COP values ranged from 1.35 to 1.55.
The majority of the experimental test runs are comprised of gross temperature lifts (TCOTEV)
between 28328C. This range of gross temperature lift was easier to obtain because it is not
near the evaporator and condenser temperature limits (see Fig. 6).
Fig. 7 shows the variation of the enthalpic coecient of performance (COP)EH and the
actual coecient of performance (COP)A against the evaporator temperature. The (COP)EH
and (COP)A increased when the evaporator temperature increased. This behaviour agrees with
theory. Eq. (1) shows that when the evaporator temperature increases the numerator increases
and the denominator decreases thus the COP must increase.
Fig. 6 shows the variation of the gross temperature lift (TCOTEV) against the evaporator
temperature TEV. Small gross temperature lifts corresponded to the highest evaporator
temperatures and the lowest condenser temperatures. High values of gross temperature lift
corresponded to low evaporator temperatures and high condenser temperatures. Operating
near the limits of the range for evaporator and condenser temperatures it was not easy to
maintain at steady state conditions. Small values of gross temperature lift are of more interest
for this system since the COP values are highest for these conditions.

Fig. 8. Heat pump eectiveness HPE against the ow ratio (FR).

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281

Fig. 8 shows the variation of the heat pump eectiveness (HPE) against the ow ratio (FR).
The HPE decreases very slowly when the FR values increase. The values of HPE were between
0.74 and 0.82. These results show that the system is working approximately at 80% of the
maximum possible. That such a high HPE was obtained in a small laboratory sized apparatus
augurs well for an industrial sized unit. An industrial unit should be able to operate at HPEs
well above 80% due to lower heat losses, optimised design of heat and mass transfer
equipment and automated control.
Fig. 9 shows the variation of the enthalpic coecient of performance (COP)EH and the
actual coecient of performance (COP)A against the production rate of pure euent. For the
range shown there was no appreciable trend. It is to be expected that for the highest values of
(COP)A the distilled water production values would also be highest.
Fig. 10 shows the variation of the gross temperature lift (TCOTEV) against the production
rate of pure euent. In this gure it is noted that when the gross temperature lift decreases the
production rate of the distilled water increases.
Fig. 11 shows the variation of the evaporator temperature TEV against the production rate
of distilled water. The production of distilled water increases when the evaporator temperature
also increases. It has been shown that the COP values increase when TEV also increases. This

Fig. 9. Enthalpic coecient of performance (COP)EH and the actual coecient of performance (COP)A against the
production rate of pure euent.

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Fig. 10. Gross temperature lift GTL=(TCOTEV) against the production rate of pure euent.

gure shows less dispersion than Fig. 9 where the variation of COP is shown as a function of
the distilled water production rate.
Table 1 shows the results of the chemical analyses of the tap water, distilled water and
concentrated euent for eight test runs. The quality of the distilled water produced was
comparable or better than distilled water produced by an electric resistance water distiller. The
quality of the distilled water obtained is comparable with distilled water obtained using a
compression heat pump assisted water purication system [9,10] and when operating this
system with a water/LiBr solution [1].

6. Conclusions
The system operated well with the pair water/Carrol. HPE values of 0.74 to 0.82 were
obtained showing that the operation of the experimental equipment was ecient and reliable.
A distilled water production rate from 1.2 to 4 kg h1 showed the exibility of operation and
stability under a range of conditions. The (COP)A ranged from 1.35 to 1.55. This was achieved

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283

Fig. 11. Evaporator temperature TGE against the production rate of pure euent.

in small-scale equipment that had the potential for large heat losses since the design was not at
all compact and had relatively long pipe runs.
These results indicate that industrial sized equipment should be highly ecient even with a
simple single eect heat pump system.
If relatively low grade heat such as solar or waste heat are to be used to drive a simple
euent distillation process a single eect system is a good option. However, if a higher grade
heat source is available and suitable working pair can be found, multiple stage absorption heat
pumps oer the prospect of much higher COPs [15].
References
[1] S. Santoyo-Gutierrez, J. Siqueiros, C.L. Heard, E. Santoyo, F.A. Holland, An experimental integrated absorption heat pump euent purication system. Part I: operating on water/lithium bromide solutions, Applied
Thermal Engineering 19 (5) (1999) 461475.
[2] W. Rivera, M.J. Cardoso, R.J. Romero, Theoretical comparison of single stage and advanced heat transformers operating with water/lithium bromide and water/Carrol mixtures, International Journal of Energy
Research 22 (5) (1998) 427442.
[3] R. Best, W. Rivera, M.J. Cardoso, R.J. Romero, F.A. Holland, Modelling of single-stage and advanced

284

[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]

S. Santoyo-Gutierrez et al. / Applied Thermal Engineering 20 (2000) 269284

absorption heat transformers operating with the water/Carrol mixture, Applied Thermal Engineering 17 (11)
(1997) 11111122.
F.A. Holland, J. Siqueiros, S. Santoyo-Gutierrez S, C.L. Heard, E. Santoyo, Water Purication Using Heat
Pumps. E & FN SPON/Routledge, London, UK, 1999.
S. Supranto, I. Chandra, M.B. Unde, P.J. Diggory, F.A. Holland, Heat pump assisted distillation. I
Alternative ways to minimize energy consumption in fractional distillation, Energy Research 10 (5) (1986) 145
161.
M.A.R. Eisa, R. Best, F.A. Holland, Heat pump assisted water purication systems. 3rd International
Symposium on the large scale applications of heat pumps, 3543, Oxford, UK 1987.
R. Best, C.L. Heard, F.A. Holland, Developments of geothermal energy in Mexicopart 16: the potential for
heat pump technology, Heat Recovery Systems & CHP 8 (3) (1988) 185202.
D.L. Hodgett, Aplicaciones industriales de las bombas de calor por compresion mecanica de vapor, Manual
sobre Tecnologias de Bombas de Calor, Programa de Cooperacion e Investigacion: Instituto de Investigaciones
Electricas, Cuernavaca, Mexico y Universidad de Salford, UK, 1990.
J.L. Frias, J. Siqueiros, H. Fernandez, A. Garcia, F.A. Holland, Developments in geothermal energy in
Mexicopart 36: the commissioning of a heat pump assisted brine purication system, Heat Recovery Systems
& CHP 11 (4) (1991) 297310.
J. Siqueiros, C.L. Heard, F.A. Holland, The commissioning of an integrated heat pump-assisted geothermal
brine purication system, Heat Recovery Systems & CHP 15 (7) (1995) 655664.
S. Santoyo-Gutierrez, Absorption heat pump assisted euent purication. PhD Thesis, University of Salford,
1997.
E. Santoyo, R.M. Barragan, D. Nieva, S.P. Verma, Application of ion chromatography to the chemical characterization of brines produced from wells of the Los Azufres geothermal eld (Mexico), in: Proceedings of the
International Ion Chromatography Symposium, San Diego, CA, USA, Special Issue, 1990, p. 10.
R.C. Reimann, W.J. Biermann, Development of a single family absorption chiller for use in solar heating and
cooling systems, Phase III Final Report, Prepared for the USA Department of Energy under contract EG/77/
C/03/1587, Carrier Corporation, October 1984.
Y.R. Mayhew, G.F.C. Rogers, Thermodynamic and Transport Properties of Fluids (SI Units), Basil Blackwell
Publishers, Oxford, UK, 1976.
F. Ziegler, Absorption refrigeration, heat pump, and heat transformer cycles, Seminario: Recuperacion de
Calor Industrial por Medio de Bombas de Calor, 441468, Cuernavaca, Morelos, Mexico 1993.