Dynamic simulation of an ammonia-water absorption refrigeration system

Weihua Cai1 , Mihir Sen2 and Samuel Paolucci3 Department of Aerospace and Mechanical Engineering University of Notre Dame, Notre Dame, IN 46556 July 1, 2010

Abstract A dynamic model of a single-eect absorption refrigeration cycle has been developed. Modeling of the cycle performance requires thermodynamic properties which are obtained from equations of state for refrigerant-absorbent mixtures. The transient response of the absorption refrigeration cycle is investigated using mass, momentum and energy balances for the dierent parts of the system. Some design and operation parameters that aect the cycle performance are identied. Keywords: absorption-refrigeration, ammonia-water, dynamics, equation of state

Introduction

A typical single-eect absorption refrigeration cycle consists of four basic components, an evaporator, an absorber, a generator and a condenser, as shown in the schematic of Fig. 1. The cooling cycle starts at the evaporator, where liqueed refrigerant boils and takes some heat away with it from the evaporator, which produces the cold desired in the refrigerated space. The refrigerant vapor releases its latent heat as it is absorbed by an liquid absorbent in the absorber. It is necessary to separate the refrigerant from the absorbent, and this is done in the generator. A pump drives the solution into the generator which is heated by a heat source (e.g. steam, hot water, direct ring, solar cell). The solution is heated and the refrigerant vapor driven out of it. Part of the solution is throttled back into the absorber.
1 2

Currently at Caterpiller, e-mail: wcai123@gmail.com Corresponding author, e-mail: Mihir.Sen.1@nd.edu 3 E-mail: Samuel.Paolucci.1@nd.edu

A solution heat exchanger, normally located between the absorber and the generator, makes the process more ecient without changing its basic operation. Subsequently, the condenser cools the refrigerant vapor back into the liquid state. The cycle continues after the refrigerant goes through an expansion valve. There have been some papers published on the steady-state and dynamic simulations of absorption refrigeration systems. A computer code ABSIM has been developed for steadystate simulation of absorption systems in a exible and modular form (Grossman and Zaltash, 2001). It has been employed by many users for performing cycle evaluations, testing control strategies, and preliminary design optimization. Detailed distributed models of absorption heat pumps using H2 O/NH3 have been developed (Butz, 1989). Step change response of the system has been investigated. In an advanced energy storage system using H2 O/LiBr as the working uid (Xu et al., 2007b,a), dynamic models of the operation have been developed, and the simulation results predicted the dynamic characteristics and performance of the system. An object-oriented dynamic modeling library named ABSML has been designed (Fu et al., 2006). Dierent absorption chiller models, including single-eect, double-eect, LiBr/H2 O and H2 O/NH3 systems, have been successfully developed in the library. Simulation results on transient behavior and during startup and shutdown show good match between experimental data and simulations. Numerical simulation have been carried out to predict the transient operating characteristics and performance of an absorption heat pump using H2 O/LiBr to recover waste heat (Jeonga et al., 1998). The simulation of absorption and refrigeration systems is very helpful for understanding and evaluating the system as well as for system design, operation and control, and device design or selection in detail (Lucas et al., 2007; Sohel and Dawoud, 2006; Donate et al., 2006; Lucas et al., 2004; Atmaca et al., 2002; Vargas et al., 1998; Yang and Guo, 1987). Modeling the cycle performance requires thermodynamic properties. However, very

few papers utilize equations of state to obtain the thermodynamic properties. Yokozeki 2

(Yokozeki, 2005) is the rst to perform the steady state modeling of an absorption-refrigeration cycle using equations of state to calculate thermodynamic properties. In the present work we develop a dynamical model for a single-stage absorption refrigeration cycle, where all thermodynamic properties have been consistently obtained from equations of state for mixtures. The aim of this work is to study the eects of thermodynamic properties on the steady state performance and dynamic response of an absorption refrigeration cycle. The modeling and calculations are carried out for an ammonia-water system for which good data are available. 2 Dynamic modeling

2.1 Governing equations Fig. 1 shows a schematic of the absorption refrigeration cycle. The principal components of a conventional absorption refrigeration system are generator, condenser, evaporator, and absorber. In the present study, some assumptions are made in developing the dynamic modeling. In the lumped-parameter approach, each component is characterized by a single temperature, pressure, and concentration. The ow in the pipes is assumed to be onedimensional, and no diusion of heat occurs in the ow direction. In addition, there is no heat loss from generator to the surroundings nor heat gain by the evaporator from the surroundings, and the expansion process in the valve is assumed to occur at constant enthalpy. We write the coupled governing equations for the complete absorption refrigeration cycle by examining the balances of mass, energy, and momentum for the dierent components in the cycle. We take Mi (t) to correspond to the mass within component i, and mi (t) the mass ow rate between components, as labeled in Fig. 1. Subsequently, the overall mass balances for each component are given by dMC = m1 m2 , dt dME = m3 m4 , dt 3 (1) (2)

dMA = m4 + m10 m5 , dt dMG = m7 m8 m1 dt m2 = m3 , m5 = m6 = m7 , m8 = m9 = m10 .

(3) (4) (5) (6) (7)

Here we take Ci (t) to be the mass fraction of the absorbent coming out of a component. Subsequently, we have the following absorbent mass balances d (MA CA ) = m10 C10 m5 C5 , dt d (MG CG ) = m7 C7 m8 C8 , dt C5 = C6 = C7 = CA , C8 = C9 = C10 = CG . The momentum equations between the components are given by dm1 1 m1 |m1 | A1 + f1 = (PG PC ) dt 2 1 A1 D1 L1 A2 dm2 1 m2 |m2 | i PC PV1 + f2 = dt 2 2 A2 D2 L2 1 1 i o 1 m2 |m2 | = PV1 PV1 , 2 2 A2 1 V A3 dm3 1 m3 |m3 | o = PV1 PE + f3 dt 2 3 A3 D3 L3 A4 dm4 1 m4 |m4 | = (PE PA ) + f4 dt 2 4 A4 D4 L4 dm5 1 m5 |m5 | A5 i = PA PP + f5 dt 2 5 A5 D5 L5
o i P = PP PP ,

(8) (9) (10) (11)

, ,

(12) (13) (14) , (15) (16) (17) (18) (19) (20)

, ,

A6 o dm6 1 m6 |m6 | + f6 = (P PG ) , dt 2 6 A6 D6 L6 P A9 dm9 1 m9 |m9 | i PG PV2 , + f9 = dt 2 9 A9 D9 L9 4

1 1 i o 2 m9 |m9 | = PV2 PV2 , 2 9 A2 2 V dm10 1 m10 |m10 | A10 P o PA , + f10 = dt 2 10 A10 D10 L10 V2

(21) (22)

where fi is the pipe friction factor (a single correlation relating pipe friction loss to Reynolds number and surface roughness for laminar, transitional and turbulent ow alike is used (Churchill, 1977)), i is the expansion valve friction factor, Li and Di are pipe length and diameter respectively, Ai is the pipe cross-sectional area, and AVi is the smallest crosssectional area of the expansion valve, i is the density, and Pi is the pressure. The superscripts i and o stand for the inlet and outlet of a component, respectively. The performance of a pump, which is the prime mover that increases the pressure of the solution, is given by empirically-determined characteristic curves. This can be conveniently represented as a low order polynomial
o i P = PP PP = a1 + a2 m5 + a3 m2 , 5

(23)

where a1 , a2 and a3 are parameters determined from the manufacturers technical data. For the current study, we assume that they are constant. Letting hi (t) be the specic enthalpy, the energy balances for the components are given by d (MC hC ) = m1 h1 m2 h2 QC , dt d (ME hE ) = m3 h3 m4 h4 + QE , dt d (MA hA ) = m4 h4 + m10 h10 m5 h5 QA , dt d (MG hG ) = m7 h7 m8 h8 m1 h1 + QG , dt Qx = m7 h7 m6 h6 = m8 h8 m9 h9 , m6 h6 = m5 h5 + WP , h2 = h3 , 5 (24) (25) (26) (27) (28) (29) (30)

h9 = h10 ,

(31)

where Qi = Fi Ui Ti , Fi the total heat transfer area, Ui is the overall heat transfer coecient, Ti = Ti Ti, , Ti is the temperature of the component, Ti, is the temperature surrounding the component, and WP is from Eq. (73). Note that convective heat losses have been neglected in the above model. The above equations are complemented by an equation of state (EOS) P = P (T, V , x) , (32)

where V = V /n is the molar volume, V is the total volume, x xr = nr /n is the mole fraction of the refrigerant, n = nr + na is the total number of moles, and nr and na are the number of moles of the refrigerant and absorbent respectively. In addition, we note that the total mass M is given by M = V , where is the total density given by = 1 [xMr + (1 x)Ma ] , V (34) (33)

where Mr and Ma are the molecular masses of the refrigerant and absorbent respectively. Lastly, the mass fraction y of the absorbent is given by y= Note that x= Ma (1 y) . yMr + (1 y)Ma (36) Ma (1 x) . xMr + (1 x)Ma (35)

2.2 Equation of state The theoretical performance of a vapor-absorption refrigeration cycle can be determined once the equation of state is given. A generic Redlich-Kwong (RK) EOS (Yokozeki, 2005) for the mixture is P = where R is the universal gas constant. For a pure specie i, parameters ai and bi are given as
2 R2Tci i , ai = 0.42748 Pci

a RT , V b V (V + b)

(37)

bi = 0.08664

RTci , Pci

(38)

where Tci and Pci are the critical temperature and pressure, and
3

i =
j=0

Tci T T Tci

(39)

The subscripts are 1 for NH3 and 2 for H2 O. The critical parameters and EOS constants of the pure refrigerant and absorbent are shown in Table 1. For the mixture, the following rules are used a=
i j

xi xj ai aj [1 gij (T )kij ] , xi xj bi + bj (1 nij ) , 2

(40) (41)

b=
i j

where gij = 1 + cij T , cij = cji, cii = 0 , kij = lij lji (xi + xj ) , kii = 0 , lji xi + lij xj (42) (43) (44)

and where cij = cji, lij = lji , and nij = nji are empirical interaction parameters given in Table 2. 7

The enthalpy h is a thermodynamically derived variable given by h=

k 0 Cpk xk dT h ,

(45)

where
V

h = RT and

Z T

dV RT (Z 1) , V

(46)

Z = P V /RT

(47)

is the compressibility. The ideal gas heat capacity at constant pressure for each component is modeled as a polynomial
0 Cp = C0 + C1 T + C2 T 2 + C3 T 3 ,

(48)

where the coecients are given in Table 3. 3 Results and discussion

3.1 Steady state Let mr denote the refrigerant mass ow rate, and ms the solution mass ow rate, and r the mass ow rate recirculation factor. After a suciently long time the system relaxes to the following steady state m1 = m2 = m3 = m4 = mr , m5 = m6 = m7 = ms , m8 = m9 = m10 = ms mr , (49) (50) (51) (52) (53)

yG ms = , mr yG yA 1 A2 D1 1 (PG PC ) , mr |mr | = 2 f1 L1 r 8

2 A2 D2 2 i (PC PV1 ) , f2 L2 2 A2 1 i V o (PV1 PV1 ) , =2 1 3 A2 D3 o 3 (PV1 PE ) , =2 f3 L3 4 A2 D4 4 =2 (PE PA ) , f4 L4 5 A2 D5 5 i ms |ms | = 2 (PA PP ) , f5 L5 6 A2 D6 o 6 (PP PG ) , =2 f6 L6 =2

o i P = PP PP ,

(54) (55) (56) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (67) (68) (69) (70) (71)

ms mr = 2

9 A2 D9 9 i (PG PV2 ) , f9 L9 9 A2 2 i V o =2 (PV2 PV2 ) , 2 10 A2 D10 o 10 (PV2 PA ) , =2 f10 L10

QC /mr = (h1 h2 ) , QE /mr = (h4 h3 ) , QA /mr = h4 + (r 1)h10 rh5 , QG /mr = h1 rh7 + (r 1)h8 , Qx /mr = r(h7 h6 ) = (r 1)(h8 h9 ) , WP /mr = r(h6 h5 ) , h2 = h3 , h9 = h10 . Substituting Eqs. (68) and (69) into Eq. (67) gives QG /mr = h1 + (r 1)h10 rh5 WP /mr .

(72)

The pump power is given by WP = m5 P/5 . (73)

To calculate the coecient of performance (COP), we make following assumptions: (1) the condition at Point 4 in Fig. 1 (exit of evaporator) is that of a saturated vapor; (2) the condition at Point 2 (exit of condenser) is that of a saturated liquid; (3) the condition at Point 1 (inlet to condenser) is a superheated state; (4) the condition at Point 10 (solution inlet to the absorber) is a solution bubble point. The rst step is to obtain PC and PE as saturated vapor pressures of a pure refrigerant at given temperatures of TC and TE . Then, given the pipe geometry and expansion valve specics, the refrigerant ow rate mr is obtained from Eqs. (54)(56). The pressures PG and PA are obtained from Eqs. (53) and (57). Using a method, such as ash calculation (Yokozeki, 2005; Ness and Abbott, 1982), xG , xA , V G and V A are obtained at the given temperatures TG and TA and pressures PG and PA . Given the constants a1 , a2 and a3 from eq. (23), m5 is rst calculated from Eqs. (58)(60), and then the mass circulation ratio r can be calculated. The thermodynamic properties at point 10 are determined using the bubble-point T-method (Yokozeki, 2005; Ness and Abbott, 1982). Enthalpies at other points are obtained from the equation of state with known T, P, V and x. Now it can be readily shown that the COP for the steady state cycle operation is given by COP = QE h4 h3 = . QG + WP h1 + (r 1)h10 rh5 (74)

To calculate the COP, we make the following assumptions: (1) the condition at Point 4 in Fig. 1 (exit of evaporator) is a pure refrigerant dew point with T = TE ; (2) the condition at Point 2 is a refrigerant bubble point and there is no subcooled (saturated) liquid; (3) the condition at Point 1 (inlet to condenser) is a superheated state of a pure refrigerant with T = TG ; (4) the condition at Point 10 (solution inlet to the absorber) is a solutions bubble 10

point specied with the absorber pressure PA and a solution concentration of the generator CG . Taking TG = 100 C, TC = 40 C, TA = 30 C, TE = 10 C, and assuming mr = 1 kg/s without loss of generality, the performance of the absorption refrigeration cycle is shown in Table 4. For the NH3 /H2 O pair, the calculated performance agrees with that of (Yokozeki, 2005). Keeping other temperatures constant, the COP decreases nearly linearly as the temperature of the generator or absorber increases, as shown in Figs. 2 and 3. The decrease in COP means that, in the present example, the generators heat-input increases while the evaporator heat (at a xed temperature) is constant. However, the mass-ow-rate ratio r behaves in opposite trends between the generator and absorber and in a highly non-linear fashion, as shown in Figs. 4 and 5. The steep increase in r at low TG or high TA can be easily understood. The decrease of temperature dierence between TG and TA results in a smaller solubility dierence between xG and xA . As a result, the mass ow rate ratio r increases steeply, which can be seen in Eq. (52). 3.2 Dynamic response under step change Now we study the dynamics of the NH3 /H2 O pair. Initially, the absorption refrigeration cycle is at steady state operation with TG = 100C, TC = 40 C, TA = 30 C, TE = 10 C. The bulk concentration and temperature of a mixture determine its pressure. A step change is introduced by increasing the pressure rise P across the pump by one percent. As a result, the mass ow rate m5 quickly increases, as shown in Fig. 6. It is seen that the system quickly reaches a new steady state. But as the ow rate increase, the frictional loss also increases. The combined result of pressure force and friction results in an overshoot of the ow rate. When more solution ows into the generator, more heat is gained from the hightemperature source, which explains the evolution of QG in Fig. 7. As more solution ows into the generator, more refrigerant m4 is generated, as shown in Fig. 8. When more refrigerant 11

is generated, more heat is gained from the refrigerated space, which explains the increase of QE in Fig. 9. The evolution of the COP is shown in Fig. 10. This can be explained by the evolution of QE and QG . Both QE and QG increase while more heat goes into the evaporator. 4 Conclusions

A lumped-parameter dynamic model has been developed for a absorption refrigeration cycle. All thermodynamic properties have been consistently calculated based on an equation of state for mixtures. We have successfully demonstrated the usefulness of the EOS model for the absorption refrigeration cycle process. We have shown that the coecient of performance of the cycle increases when the generator temperature or absorber temperature decreases. The dynamical response to a step change is also investigated. The system quickly reaches a steady state given the operation parameters for this specic example. The increase of pump pressure rise results in an increase in the system performance. The instantaneous ow rate, heat rates, and COP are also observed to oscillate in time before reaching steady state. Acknowledgment The authors thank the U.S. Department of Energy for support of this work, and Mr. G. Puliti and Drs. J.F. Brennecke, E.J. Maginn and M. Stadtherr for discussions. References I. Atmaca, A. Yigit, and M. Kilic. The eect of input temperatures on the absorber parameters. International Communications in Heat and Mass Transfer, 29(8):11771186, 2002. D. Butz. Dynamic behaviour of an absorption heat pump. International Journal of Refrigeration, 12(4):204212, 1989. 12

S.W. Churchill. Friction-factor equation spans all uid-ow regimes. Chemical Engineering, 84(24):9192, 1977. M. Donate, L. Rodriguez, A. De Lucas, and J.F. Rodriguez. Thermodynamic evaluation of new absorbent mixtures of lithium bromide and organic salts for absorption refrigeration machines. International journal of refrigeration, 29(1):3035, 2006. D.G. Fu, G. Poncia, and Z. Lu. Implementation of an object-oriented dynamic modeling library for absorption refrigeration systems. Applied Thermal Engineering, 26(2-3):217 225, 2006. G. Grossman and A. Zaltash. ABSIM - modular simulation of advanced absorption systems. International Journal of Refrigeration, 24(6):531543, 2001. S. Jeonga, B.H. Kangb, and S.W. Karngb. Dynamic simulation of an absorption heat pump for recovering low grade waste heat. Applied Thermal Engineering, 18(1-2):112, 1998. A. De Lucas, M. Donate, C. Molero, J. Villasenor, and J.F. Rodriguez. Performance evaluation and simulation of a new absorbent for an absorption refrigeration system. International Journal of Refrigeration, 27(4):324330, 2004. A. De Lucas, M. Donate, and J.F. Rodriguez. Absorption of water vapor into new working uids for absorption refrigeration systems. Industrial & Engineering Chemistry Research, 46:345350, 2007. H.C. Van Ness and M.M. Abbott. Classical Thermodynamics of Non-Electrolyte Solutions with Applications to Phase Equilibria. McGraw-Hill, New York, 1982. Y.U. Paulechka, G.J. Kabo, A.V. Blokhin, O.A. Vydrov, J.W. Magee, and M. Frenkel. Thermodynamic properties of 1-butyl-3-methylimidazolium hexauorophosphate in the ideal gas state. J. Chem. Eng. Data, 48:457462, 2003. 13

R.C. Reid, J. Prausnitz, and B.E. Poling. The Properties of Gases & Liquids. McGraw-Hill, New York, 4 edition, 1987. M.B. Shiett and A. Yokozeki. Absorption cycle utilizing ionic liquid as working uid. In US Patent 20060197053A1. 2006. M.I. Sohel and B. Dawoud. Dynamic modelling and simulation of a gravity-assisted solution pump of a novel ammonia-water absorption refrigeration unit. Applied Thermal Engineering, 26(7):688699, 2006. J.V.C. Vargas, I. Horuz, T.M.S. Callander, J.S. Fleming, and J.A.R. Parise. Simulation of the transient response of heat driven refrigerators with continuous temperature control. International Journal of Refrigeration, 21(8):648660, 1998. S.M. Xu, L. Zhang, C.H. Xu, J. Liang, and R. Du. Numerical simulation of an advanced energy storage system using H2O-LiBr as working uid, Part 1: System design and modeling. International Journal of Refrigeration, 30(2):354363, 2007a. S.M. Xu, L. Zhang, C.H. Xu, J. Liang, and R. Du. Numerical simulation of an advanced energy storage system using H2O-LiBr as working uid, Part 2: System simulation and analysis. International Journal of Refrigeration, 30(2):364376, 2007b. W.-J. Yang and K.H. Guo. Solar-assisted lithium-bromide absorption cooling systems. In Proceedings of the NATO Advanced Study Institute, pages 409423, 1987. A. Yokozeki. Theoretical performances of various refrigerant-absorbent pairs in a vaporabsorption refrigeration cycle by the use of equations of state. Applied Energy, 80:383399, 2005.

14

Compound NH3 H2 O

Tc Pc 0 1 2 3 (K) (bar) 103 405.4 113.33 1.0018 0.46017 0.06185 1.68 647.1 220.64 1.0024 0.54254 0.08667 5.25

Reference (Yokozeki, 2005) (Yokozeki, 2005)

Table 1: Critical paramters and EOS constants of pure refrigerants and absorbents.

Binary system (1)/(2) l12 n12 NH3 /H2 O 0.316 0.013

c12 0

Reference (Yokozeki, 2005)

Table 2: Binary interaction parameters of refrigerant/absorbent pairs determined from experimental PTX data.

Compound NH3 H2 O

C0 C1 27.31 0.02383 32.24 1.924103

C2 1.707105 1.055105

C3 1.185 108 3.596 109

Reference (Reid et al., 1987) (Reid et al., 1987)

Table 3: Coecients for ideal-gas heat capacity (J mol1 K1 ) in Eq. (48). Fitted coecients are based on calculated idea gas heat capacity from (Paulechka et al., 2003).

Binary system NH3 /H2 O NH3 /H2 O

PC,G PA,E (bar) (bar) 15.48 6.15 15.64 6.19

xG (mass%) 2.54 59.3 2.51 59.2

xA (mass%) 35.5 35.7

QE COP Reference (kW) 1111.4 0.645 (Yokozeki, 2005) 1109.9 0.642 this work

Table 4: Theoretical cycle performance. TG = 100C, TC = 40 C, TA = 30 C, TE = 10 C, and mr = 1 kg/s. Ideal gas heat capacity coecients taken from Shiett and Yokozeki (2006).

15

QC 1

Hightemperature source QG

G 8 Qx 9 6 5 A 7 Solution

2 V1 3 4 Refrigerant V2

Heat exchanger P Wp

10 E Q
E

Refrigerated space
C: Condenser V1,2 : Valves A: Absorber P: Pump E: Evaporator

QA

G: Generator

Figure 1: Schematic of absorption refrigeration cycle.

16

0.75

0.7

0.65
COP

0.6

0.55

0.5 340

360

380

TG

400

420

440

Figure 2: COP vs. generator temperature.

17

0.7 0.68 0.66 0.64 0.62 0.6 0.58 290

295

300

305

310

315

320

325

Figure 3: COP vs. absorber temperature.

18

9 8 7 6 5 4 3 2 1 340 360 380 400 420 440

r

TG

Figure 4: Mass ow rate ratio vs. generator temperature.

19

7 6 5 4 3 2 1 290
r

295

300

305

TA

310

315

320

325

Figure 5: Mass ow rate ratio vs. absorber temperature.

20

2.5

Flow rate m5 (kg/s)

1.5

0.5 0

20

40

t (s)

60

80

100

Figure 6: Response of mass ow rate of weak solution for step change.

21

5.0412 5.0412 5.0411

QG (J/s)

x 10

5.0411 5.041 5.0409 5.0409 5.0408 5.0408 1 20 40 60 80 100

t (s)

Figure 7: Heat transfer rate at generator for step change.

22

0.2917

0.2916
Flow rate m1 (kg/s)

0.2915

0.2914

0.2913

0.2912 1

20

40

t (s)

60

80

100

Figure 8: Response of mass ow rate of refrigerant for step change.

23

3.237 3.2365 3.236

QE (J/s)

x 10

3.2355 3.235 3.2345 3.234 1

20

40

t (s)

60

80

100

Figure 9: Heat transfer rate at evaporator for step change.

24

0.6421

0.642

0.6419
COP

0.6418

0.6417

0.6416 1

20

40

t (s)

60

80

100

Figure 10: Coecient of performance for step change.

25