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International Journal of Refrigeration 27 (2004) 604–611

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Pervaporation membrane process for vapour absorption system


S.B. Riffat, S. Wu*, B. Bol
School of Built Environment, The University of Nottingham, University Park, Nottingham NG7 2RD, UK
Received 23 March 2003; received in revised form 4 March 2004; accepted 10 March 2004

Abstract
This paper describes a novel vapour absorption refrigeration system in which a pervaporation membrane replaces the
conventional generator for the concentration of working fluids. The use of a pervaporation membrane gives two potential
advantages to the vapour absorption system; i.e. enhanced selectivity of the components to be separated from the working fluids
and a lower space requirement. Issues related to integration of a pervaporation membrane into a vapour absorption system and
the performances of such a system have been investigated. The results indicate that the pervaporation membrane process could
be an alternative to the distillation process that is widely used in vapour absorption systems.
q 2004 Published by Elsevier Ltd and IIR.
Keywords: Design; Absorbtion system; Absorber; Membrane; Mass transfer; COP; experiment

Système à absorption de vapeur: procédé à membrane


Mots-clés: Conception; Système à absorbtion; Absorbeur; Membrane; Transfert de masse; COP; expérimentation

1. Introduction rejected for use owing to the property of forming an


azeotropic solution.
The concentration process of vapour absorption systems Effort has been made to improve the performance of
has a strong influence on system efficiency and volume. vapour absorption systems in many ways, including the
Distillation has been the usual choice for the concentration design of the thermodynamic cycle, choice of working fluids
process owing to its simplicity and low cost. However, and system components [1 –4]. However, few investigations
distillation does have some drawbacks that it does not work have been carried out on alternative methods for concen-
efficiently when both refrigerant and absorbent of a working tration. Zerweck [5] patented a system using semi-
fluid are volatile; it cannot work with azeotropic solutions in permeable membrane (not clear what type of membrane)
which the components comprising the working fluid have to separate the refrigerant (NH3) from the solution (NH3 þ
the same boiling point; and it requires a large space for LiNO3) but no further development was carried out. Reverse
interfacing the liquid and vapour. These problems have a osmosis technology was also considered and tested for
negative impact on the system performance. For example, concentration but this required a very high mechanical
rectifying devices are needed when both refrigerant and pressure. More recently, tests on new separation processes,
absorbent are volatile. This not only increases the cost and taking advantage of mass transfer through dense mem-
volume of the system but also reduces energy efficiency. branes, have already shown that very significant energy
Furthermore, potentially excellent working fluids could be saving could be made compared to traditional technologies
(e.g. distillation, etc.) when used in some industrial
* Corresponding author. Tel.: þ 44-1158467875; fax: þ 44- separation processes. Among these separation processes,
1159513159. pervaporation is one of the most promising [6]. Pervapora-
E-mail address: shenyi.wu@nottingham.ac.uk (S. Wu). tion is a membrane separation process involving the partial
0140-7007/$ - see front matter q 2004 Published by Elsevier Ltd and IIR.
doi:10.1016/j.ijrefrig.2004.03.005
S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611 605

solutions, or reverse. Components being separated from the


Nomenclature solution experience dissolution, diffusion and evaporation in
the pervaporation process. The processes are clearly shown
A surface area of membrane, m2
in Fig. 1. With reference to Fig. 1, a solution comprising
CA;f concentration at feed side, mol m23
components A and B flows parallel to the membrane at a
CA;p concentration at permeate side, mol m23
pressure high enough to maintain it as the liquid mixture and
COP coefficient of performance
in contact with the dense, thin membrane film where the
D diffusion coefficient, m2 s21
components are dissolved and permeated. Normally,
d hydraulic diameter, m
components A and B permeate through the membrane at
h enthalpy, J kg21
different speeds that depend on the structure and material of
Ji flux of pervaporation membrane, kg m22
the membrane. As a result, the concentrations of the
L length of flow path, m
components at both sides of the membrane are changed.
kov overall coefficient of mass transfer,
The faster permeating component A becomes concentrated
kg m mol21
in permeating side while the slower component B becomes
km coefficient of mass transfer through mem-
concentrated in the feed side. In the separation process, the
brane, kg m mol21
difference in speed is so large that one of the components is
kbl coefficient of mass transfer through bound-
virtually unable to pass through the membrane. The driving
ary layer, kg m mol21
force behind pervaporation separation is chemical potential.
m
_r mass flow rate of refrigerant, kg s21
The difference in chemical potential between the two sides
m
_d mass flow rate of weak solution, kg s21
of the membrane is normally maintained by adding heat to
m
_c mass flow rate of weak solution, kg s21
the feed solution. It should be noted that the pervaporation
pm permeability, kg m2 mol21
_e separation process is sometimes confused with the mem-
Q cooling capacity, W
_ in brane distillation process although they are different in
Q heat input, W
principle. In pervaporation separation process, the com-
Re Reynolds number
ponents diffuse through the membrane in the liquid phase
Sh Sherwood number
while in membrane distillation, the permeate components
Sc Schmidt number
pass through the membrane in the vapour phase. Definitions
x hydraulic diameter, m
for these two processes can be found in Ref. [8]. More
xd concentration of dilute solution, % w/w
information about pervaporation membranes can be found
xc concentration of concentrated solution, %
in Refs. [9,10].
w/w
The pervaporation membrane is highly suited to
d thickness of membrane, m
integration into vapour absorption systems. This can be
l circulation factor
achieved by choosing a pervaporation membrane and
working fluid so that only the refrigerant is able to pass
through the membrane. The suitability of a pervaporation
vaporisation of a liquid mixture through a dense membrane membrane for a vapour absorption system can be assessed
whose downstream side is usually kept under vacuum [7]. by several criteria. Among them, the selectivity and
The nature of pervaporation process makes it very suitable
for integration into vapour absorption systems for concen-
trating the working fluid. A system with pervaporation
process for the concentration is likely to provide some
advantages over those using the distillation process. The
system with the pervaporation membrane could be more
compact, as the membrane confines the working fluid in a
small space, so that large vapour space is not necessary. The
system could work efficiently when both refrigerant and
absorbent are volatile because of the selectivity of the
membrane. The selectivity of the pervaporation membrane
expands the choice for working fluid and enables azeotropic
solutions to be used.

2. Pervaporation and vapour absorption cycle

Pervaporation is a thermal separation process originally


used in industries for removal of water from organic Fig. 1. Concentration process in the membrane module.
606 S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611

permeability of the membrane are the most important. follows:


Selectivity is a quantitative measure of the difference in
Ji ¼ kov ðCA;f 2 CA;p Þ ð2Þ
permeation speed of the components in terms of a
concentration ratio at the permeate side to the feed side. The coefficient of mass transfer kbl is a parameter that is
For vapour absorption systems, this ratio is the concen- linked with fluid flow patterns in the feed side of the
tration of the refrigerant. High selectivity is desirable to membrane. Typical mass-transfer coefficients for channel
increase the efficiency of the system. Permeability measures flow are obtained from general empirical film-model
the capability of the pervaporation membranes to allow the correlation:
selected components to pass through. Again, high per-  k
k x d
meability is important, as this would allow the system to be Sh ¼ bl ¼ aRem Scn ð3Þ
more compact. The selectivity and permeability of a D L
pervaporation membrane are affected by the solution, The values of a; m; n and k in the above equation change
membrane materials and operating conditions. considerably from the laminar to turbulent regime. For the
It should be noted that there are some differences laminar regime, corresponding to a Reynolds number lower
between the pervaporation membrane for vapour absorption than 2300 for flow inside a tube, the most commonly used
systems and for its traditional applications. These differ- correlation is the Lévêque correlation [11]:
ences can be addressed as follows. In vapour absorption   0:33
systems, a large concentration change is normally required d
Sh ¼ 1:62 ReSc ð4Þ
in order to avoid heat loss in the circulating solution. In an L
aqueous lithium bromide absorption system, for example, For turbulent regimes, one of the most widely used
the concentration change is normally in a range 5– 10%, correlations is [12]:
while the required concentration change in its traditional
purification applications could be much less than 1%. Low Sh ¼ 0:026Re0:8 Sc0:33 ð5Þ
circulation flow rate is crucial to vapour absorption systems
The coefficient of mass transfer kbl can be determined from
to reduce heat loss (this may not be so important in its
Eqs. (3)– (5) depending on the flow patterns and structure of
traditional application). The operation conditions for vapour
the flow channels. The membrane mass transfer coefficient
absorption systems are strictly determined by the surround-
km is determined from the following equation:
ing temperature but this may not be the case in its traditional
applications. Low cost and high efficiency are always p
km ¼ m ð6Þ
primary objectives for vapour absorption systems. While d
these are important in its traditional applications, these are Here pm and d are the permeability and thickness of
not always primary target. To summarise, membrane pervaporation membrane, respectively. The permeability
modules with high selectivity, high permeability and low can be determined theoretically or experimentally. The total
cost are most suitable for application in vapour absorption resistance for the mass transfer is
systems.
1 1 1 d x
¼ þ ¼ þ ð7Þ
kov km kbl pm aRem Scn D
3. Mass transfer of the pervaporation membrane Here D is diffusion coefficient of the permeated components
in the solution and x is the hydraulic diameter of the flow
The transport of components through the pervaporation channel. From Eq. (7), the overall coefficient of mass
membrane from the feed side to the permeate side consists transfer can be determined by the permeability and thick-
of five steps, each with its own resistance: (a) diffusion ness of pervaporation membrane, the properties of the
through solution boundary layer, (b) sorption to membrane working fluid and the flow patterns at the feed side.
top layer, (c) diffusion through the top layer, (d) de-sorption The variation of the coefficient of mass transfer by
out of the top layer and (e) diffusion through porous support diffusion, kbl ; for water in aqueous potassium formate
layer. Since steps (d) and (e) have much less resistance solution with the feed flow rate, is shown in Fig. 2. The
compared with the other steps, the analysis can be simplified hydraulic diameters were taken from two membrane
by omitting them. The total resistance can then be written as modules supplied by Sulzer Chemtech. PERVAP@2201C
follows according to the resistances-in series model: is a dense membrane while silicon membrane system (SMS)
membrane is a porous membrane. As shown in Fig. 2, the
1 1 1 diffusion of water through the solution toward the
¼ þ ð1Þ
kov km kbl membrane increases with the feed flow rate. The overall
coefficient mass transfer, kov ; also increases with the feed
Here km is the mass transfer coefficient for steps (b), (c) and flow rate and there is a jump between 0.5 and 1 l min21 as
kbl is the mass transfer coefficient for step (a). The flux of the shown in Fig. 3. The jump is the result of a transition from
components through the membrane can be written as boundary layer dominated to membrane dominated mass
S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611 607

a pervaporation membrane is used for the solution


concentration. For this system, COP can be expressed as
follows; this is exactly the same as it is for conventional
single-effect systems
_e
Q h5 2 h9
COP ¼ ¼ ð9Þ
_
Qin h8 2 h6 þ lðh10 2 h6 Þ
Here pump work is neglected. l is the circulation factor
[13], which can be calculated from solution concentrations
m
_c
l¼ ð10Þ
m
_r
_ r ; in Eq. (10) depends on the flux
The refrigerant flow rate, m
and surface area of the membrane, and it can be calculated
from below:
Fig. 2. Effect of the flow rate of the feed solution on mass diffusion
in the boundary layer (feed solution, potassium formate at 70 8C, _ r ¼ J_ A A
m ð11Þ
and 73% mass fraction).
where J_ A is the flux of refrigerant per second, and A is the
surface area of the membrane. The circulation factor
transfers. Figs. 2 and 3 suggest that the mass transfer could
therefore becomes:
be improved by increasing the feed flow rate. However, it
may be more sensible to increase the flow rate to avoid m
_
l¼ _ c ð12Þ
diffusion-dominated region, because the improvement in the JA A
overall mass transfer gained by increasing the feed flow rate In order to achieve high COP from the system, the circulation
may not compensate the increase in the heat loss in factor should be maintained as low as possible. This requires
circulation. This will be discussed later in more detail. the mass flow rate, m_ d to be as low as possible while the flux of
Substituting Eq. (7) into Eq. (2), allows the flux of mass the membrane, J_ A ; should be as high as possible according to
transfer to be determined from the following equation: Eq. (12). When the pervaporation membrane is connected in
ðCA;f 2 CA;p Þ series into the circulation loop, the permeate flux J_A becomes
JA ¼ ð8Þ
d d dependent on the circulation flow rate m _ d and the link between
þ them could restrict adjustment of the circulation factor l in
pm aRem Scn D
order to achieve high COP.
COP of the pervaporation absorption system was
simulated using a computer model based on above analysis.
4. Efficiency of pervaporation absorption system When evaporating temperature is 10 8C, condensing and
absorber temperatures is 30 8C and solution temperature
An example of a pervaporation absorption system is
shown schematically in Fig. 5. This system is similar to
conventional single-effect vapour absorption system except

Fig. 4. COP of the pervaporation membrane vapour absorption


Fig. 3. Effect of the flow rate of the feed solution on the overall cycle as a function of circulation factor and effectiveness of solution
coefficient of mass transfer of the pervaporation membrane (feed heat exchanger (aqueous potassium formate solution as working
solution, potassium formate at 70 8C, and 73% mass fraction). fluid).
608 S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611

entering the membrane module is 75 8C, the simulation


results show that the COP of the pervaporation absorption
system decreases with increasing feed flow rate m _ d (Fig. 4).
This is because, although the flow rate increase can boost the
mass transfer in the pervaporation process as shown in Figs.
2 and 3, the heat loss in the heat transfer by circulation is
much higher than the gain from the increase in the mass
transfer.

5. Prototype of pervaporation absorption refrigerator

A prototype system of vapour absorption system using a


pervaporation membrane for concentration was built for
investigation. The schematic diagram of the system is as
shown in Fig. 5. A photo of the prototype system is shown in Fig. 6. Prototype of the pervaporation absorption system.
Fig. 6. This prototype system employed two pilot membrane
modules supplied by Sulzer Chemtech. One of them is fitted permeate pressure and solution concentration played an
with sheet polymer membranes (PERVAP@2201C), and the important role in determining the permeate flux. The
other is fitted with tubular silicon membranes (SMS). The permeate flux decreases with the solution temperature but
feed sides of the two modules were connected in series into increases with decreasing concentration or permeate
the system to form a circulation loop between concentration pressure (Figs. 7 and 8). In Fig. 7, a dashed line is used to
and absorption. For this connection, the circulation flow rate show the flux change for 76% concentration because only
m_ d is the feed flow rate of the membrane modules. two points was available. This line serves for indication
purpose only. If Fig. 8 is compared with Fig. 7, we find that
the decrease in permeate flux with increasing permeate
6. Experimental results pressure is smaller at high solution temperature (70 8C) than
at low solution temperature (55 8C). The smaller effect of
6.1. Permeate flux of the membranes the permeate pressure when the solution temperature is high
is because the chemical potential at the feed side is so high
The experiment showed that the solution temperature, that the difference in chemical potential between two sides
of membrane does not change significantly with increase in
the permeate pressure. The permeate flux of the silicon
membrane module has a similar response to the temperature,
pressure and concentration changes, however, the permeate
flux of this module is much high. The high permeate flux of
the silicon membrane is due to its porous structure of the
membrane layer, which enables the components with small
diameter to pass through easily (Fig. 9).

Fig. 7. Permeate flux as a function of concentration and pressure


(solution temperature ¼ 55 8C, solution concentration in mass
Fig. 5. Diagram of the pervaporation vapour absorption system. fractions).
S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611 609

Fig. 10. The permeate rate for mixture solution on silicon membrane
(55% potassium formate þ 25% caesium formate, solution
Fig. 8. Permeate flux as a function of concentration and pressure temperature ¼ 70 8C).
(solution temperature ¼ 70 8C, solution concentration in mass
fraction). the polymer membrane module and 44% was contributed by
6.2. Effect of working fluid the silicon membrane module. In terms of the cooling
capacity per m2 of membrane surface under the working
The experimental results also show that the mixture of conditions described above, the polymer membrane module
working fluids could improve permeate rate. With 75% and the ceramic membrane module delivered 39 and
concentration of a mixture of working fluid (55% potassium 256 W m22, respectively.
formate and 25% caesium formate), the silicon membrane Under the same working conditions, the measured power
module can deliver permeate flux above 580 g h21 m22 in input to the system was 2545 W excluding the power
the same permeate pressure range, which is approximately consumption of the circulation pump which was measured
five times that of the potassium only solution (Fig. 10). approximately 10% of the input heat. This gives a COP of
0.06 to the prototype system for cooling. Compared with
6.3. Cooling capacity and COP of the prototype system conventional absorption systems, the COP of the prototype
system is very low. However, it should be noted that the low
The cooling capacity and COP of the prototype system COP is the result of the high circulation factor used in
were tested under the following conditions: 30 8C for the system, which is necessary because these pilot membrane
absorber and condenser temperatures (corresponding to modules require high feed flow rate to operate. The COP of
42 mbar of permeate pressure); 75 8C for the feed solution the system could be improved significantly, if the structure
temperature; the concentration change was within 0.1%. of the membrane modules were properly designed to suit the
The very small concentration change in this case was due to application for vapour absorption heat pump systems.
the large feed flow rate required by the pilot membrane
modules. Under these conditions, 10 8C evaporating tem- 6.4. Pore blockage
perature was achieved from the prototype system experi-
mentally and the cooling capacity of 140 W was measured It was noticed that the permeate rate of the silicon
for the prototype system, in which 56% was contributed by membrane module decreased with running time. Further
experiment showed the relationship between the falling
permeate flux and time in Fig. 11. As it can be seen from

Fig. 9. Permeate flux varied with back pressure (solution


temperature ¼ 70 8C, potassium formate concentration ¼ 78% in Fig. 11. Permeate flux of the silicon membrane decreases with usage
mass fraction, porous membrane). time.
610 S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611

Fig. 11, the fall in the permeate flux occurred at every operation conditions is 8.41. It is obvious that if the
permeate pressures investigated. The permeate flux could be prototype system had been operated between 73.3 and 80%
restored to the original value, if the membrane module was concentrations, the COP of the system would have been
washed with fresh water. In contrast to the silicon somewhere around 0.5. Clearly, the COP of the prototype
membrane, the dense membrane (PERVAP@2201C) did system has been severely affected by the high circulation
not show a fall in permeate flux with time. The polymer factor. It is therefore crucial to keep the solution flow rate in
membrane module (PERVAP@2201C) worked well with the membrane module as low as possible for this
aqueous potassium formate solution throughout the experi- application. The requirement for the solution velocity in
mental period. It is therefore believed that the fall in the membrane module could be met by reducing the cross-
permeate flux was due to salt gradually blocking the pores of sectional area of the flow path. Use of high permeability
the membrane. This finding suggests that the porous membrane could also effectively reduce the circulation
membrane may not be suitable for salt-based working fluids. factor. This problem could also be eliminated by separating
the circulation for the concentration process from the main
solution circulation of the system at the cost of an extra
7. Discussion pump. Nevertheless, this is not a major issue for the
pervaportion membrane to be used in vapour absorption
7.1. Low COP from the prototype system systems.

As indicated in previous sections, the low COP of the


prototype system was due to a very high circulation factor 8. Conclusion
which was necessary because the pilot membrane modules
required the feed flow rate to be above 2 l min21. In the This paper reports the investigation of a pervaporation
experiment, the actual feed flow rate was measured at membrane for vapour absorption systems. The investigation
2.2 l min21. Water removed from the working fluid by shows that the pervaporation could be used in vapour
pervaporation was at a rate of 202 g h21. Under this absorption heat pump systems for the purpose of concen-
condition, we have a circulation factor: trating the working fluid. A cooling temperature of 10 8C
m
_c 2:2 £ 1023 £ 1538 £ 60 2 0:202 was achieved from a prototype system driven by 80 8C hot
l¼ ¼ ¼ 1004 water, while the absorber and condenser temperatures were
m
_r 0:202
30 8C. Although the COP of the prototype system from the
where density of the solution used here is 1538 kg m23. experiment was low, this could be improved if the prototype
Compared with a normal circulation factor, ranging from 5 system operated at a lower circulation rate.
to 20 in conventional vapour absorption systems, this value The potential COP of a pervaporation absorption
is very high. The high circulation factor increases the heat refrigeration system depends on the development of
loss significantly in the solution heat exchanger. As a result, pervaporation membrane technology and should be as
deterioration of energy efficiency is inevitable. The impact good as the conventional single-effect systems, if suitable
of the high circulation factor on COP can be estimated from membrane modules are available. The use of pervaporation
Eq. (9). To simplify, the equation is rewritten as follows: membranes could expand the choice of working fluids,
a allowing the use of new working fluids with better
COPl ¼
b þ cl performance. For the pervaporation process to be suitable
for vapour absorption systems, high permeate flux is crucial.
where a ¼ h5 2 h9 ; b ¼ h8 2 h6 and c ¼ h10 2 h6 : COPl
However, the match between the membrane and the
denotes the efficiency varied with the circulation factor l:
working fluid is equally important.
The enthalpy change a normally does not vary with the
circulation factor if the system operates at same conditions
except the solution concentration. Therefore, the ratio of
COPl at different circulation factor is as follows: Acknowledgements
COPl1 b þ c2 l2
¼ 2 The authors would like to thank EPSRC UK for funding
COPl2 b1 þ c1 l1
this research project.
We choose l1 ¼ 10:94 (the corresponding concentration
changes from 73.3 to 80%) and l2 ¼ 1004 (from the
experimental condition) for comparison and assume the References
weak solution entering the membrane modules is 10 8C
lower than the exiting solution. For aqueous potassium [1] Riffat SB, Shankland N. Integartion of absorption and vapour-
formate working fluid, when the solution temperature in the compression system. Appl Energy 1993;46(4):303–16.
membrane module is 75 8C, the ratio of COPl s for the two [2] Riffat SB, Wong CW, James S. Absorption-re-compression
S.B. Riffat et al. / International Journal of Refrigeration 27 (2004) 604–611 611

chiller using a new working fluid. Int J Ambient Energy 1999; [7] Neel J. Introduction to pervaporation. In: Huang RYM, editor.
20:31–8. Pervaporation membrane separation processes. Amsterdam:
[3] Riffat SB, Su YH. Analysis of a novel absorption refrigeration Elsevier; 1991. Chapter 1.
cycle using centrifugal separation. Energy 2001;26(2): [8] Lawson KW, Lloyd DR. Membrane distillation. J Membr Sci
115–219. 1997;124:1–5.
[4] Wu S, Eames IW. Innovations in vapour absorption cycles, [9] Seader JD, Henley EJ. Separation process principles. New
recent developments in refrigerator and heat pumps. Proceed- York: Wiley; 1998.
ings of ImechE Conference. Professional Engineering Publi- [10] Humphrey JL, Keller G, II. Separation process technology.
cations, 1999;113 –27. 1 86058 238 9. New York: McGraw-Hill; 1997.
[5] Zerweck G. Ein-oder mehrstufige Absorptionswarmepumpe. [11] Lévêque MA. Kles lois de transmission de chaleur par
German Patent No DE 30 09 820 A1; 1980. convection. Ann Mines 1928;13:201.
[6] Jonquières A, Clément R, Lochon P, Néel J, Dresch M, Bruno [12] Cussler EI. Diffusion: mass transfer in fluid systems, 2nd ed.
C. Industrial state-of-the-art of pervaporation and vapour Cambridge: Cambridge University Press; 1997.
permeation in the western countries. J Membr Sci 2002; [13] Gosney WB. Principles of refrigeration. Cambridge: Cam-
206(1–2):87– 117. bridge University Press; 1982. ISBN 0521236711.

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