Paper ID: 7, Page 1

THERMO-ECONOMIC ANALYSIS OF ZEOTROPIC MIXTURES

AND PURE WORKING FLUIDS IN ORGANIC RANINKE CYCLES
FOR WASTE HEAT RECOVERY

Florian Heberle* and Dieter Brggemann

University of Bayreuth, Center of Energy Technology (ZET),

Lehrstuhl fr Technische Thermodynamik und Transportprozesse (LTTT),
Universittsstrae 30, 95447 Bayreuth, Germany
e-mail: [email protected]
Web page: http://www.zet.uni-bayreuth.de

* Corresponding Author

ABSTRACT

We present a thermo-economic analysis of an Organic Rankine Cycle (ORC) for waste heat recovery.
A case study for a heat source temperature of 150 C and a subcritical, saturated cycle is performed.
As working fluids R245fa, isobutane, isopentane and the mixture of isobutane and isopentane are
considered. The minimal temperature difference in the evaporator and condenser as well as the
mixture composition are chosen as variables in order to identify the most suitable working fluid in
combination with optimal process parameters under thermo-economic criteria.
In general, cost-effective systems show a high minimal temperature difference TPP,C at the pinch-
point of the condenser and a low minimal temperature difference TPP,E at the pinch-point of the
evaporator. In case of R245fa, the design parameters TPP,E = 1 K and TPP,C = 13 K lead to minimal
costs of 56.8 /GJ. Choosing isobutane as working fluid leads to the lowest costs per unit exergy with
52.0 /GJ (TPP,E = 1.2 K; TPP,C = 14 K). Considering the major components of the ORC, specific
costs range between 1150 /kWel and 2250 /kWel. For the mixture isobutane/isopentane, a mole
fraction of 90 % isobutane leads to lowest specific costs per unit exergy. Despite an increased
efficiency an overcompensation of the additional expenses for the heat exchange equipment is not
achieved compared to isobutane. The pure working fluid is 3.3 % more cost-effective. A sensitivity
analysis for the ORC system using isobutane as working fluid shows high sensitivity of the costs per
unit exergy to the costs of process integration and the isentropic efficiency of the turbine.

1. INTRODUCTION

Organic Rankine Cycle (ORC) systems for waste heat recovery have a high growth potential
(Tchanche et al., 2011). Numerous investigations are performed in order to maximize the efficiency
of such power plants by working fluid selection with respect to the heat source temperature.
Particularly, the use of zeotropic fluid mixtures is a promising optimisation approach due to a good
glide match of the temperature profiles at phase change. In this context, Angelino and Colonna di
Paliano (1998) show for a low-temperature application that mixtures of natural hydrocarbons (n-
butane/n-hexane) lead to an efficiency increase of 6.8 % compared to the pure working fluid n-
pentane. Other case studies for geothermal heat sources prove the potential of zeotropic mixtures as
working fluids in ORC systems (Demuth, 1981; Iqbal et al., 1976). For subcritical cycles an increase
in efficiency by up to 16 % is obtained compared to pure working fluids, like isobutane or isopentane.
More recent investigations include sensitivity analyses for crucial parameters (Borsukiewicz-Gozdur
and Nowak, 2007; Wang and Zhao, 2009; Chen et al., 2011; Garg et al., 2013; Dong et al., 2014;
Lecompte et al., 2014; Shu et al., 2014). In addition, Heberle et al. (2012b) show high second law
efficiencies for mixture compositions which lead to an good match of the temperature profiles at

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 Paper ID: 7, Page 2

condensation. However, these concentrations show a significant increase in heat exchange capacity.
Similar results are obtained by Andreasen et al. (2014) considering pure components and their
zeotropic mixtures as working fluids for subcritical and transcritical cycles in case of a low-
temperature heat source. For a heat source temperature of 120 C, mixtures of propane and higher
boiling natural hydrocarbons as well as isobutane/isopentane show high first law efficiency for the
subcritical cycle. At the same time, an increase of the heat exchange capacity for the condenser is
presented, which is an indicator for the requirement of high heat transfer areas. Angelino and Colonna
di Paliano (2000) compare an equimolar mixture of n-butane/n-hexane and pure n-pentane as ORC
working fluids in a case study for waste heat recovery. Fan power savings of the air-cooling system of
49 % by using the zeotropic mixture are determined. However, an additional heat transfer area of 73
% is required. Weith et al. (2014) have recently shown for a waste heat recovery unit that the use of a
siloxane mixture leads to an efficiency increase of 3 % compared to the most efficient pure
component. In consequence, a 14 % higher heat transfer area of the evaporator is determined for the
zeotropic mixture.
The described dependence suggests a thermo- or exergo-economic analysis of ORC systems in order
to evaluate the increased power output and the additionally required heat exchange area for fluid
mixtures. Existing thermo-economic analyses of ORC systems are focused on pure working fluids
(Tempesti and Fiaschi, 2013; Astolfi et al., 2014; Heberle and Brggemann, 2014). Regarding small-
scale waste heat recovery ORC units, Quoilin et al. (2011) determine specific investment costs for 8
working fluids in the range of 2136 /kW and 4260 /kW. For an electric capacity between 30 kW
and 120 kW, Imran et al. (2014) considered different plant schemes and working fluids. In this
context, specific investment costs in the range of 3556 /kW and 4960 /kW are obtained. Quoilin et
al. (2013) indicate specific investment costs between 8000 /kW and 1000 /kW for an ORC waste
heat recovery module in the range of 10 kW and 7500 kW electrical power output. In case of an
geothermal resource, Heberle et al. (2012a) identify isobutane as a cost-efficient working-fluid
compared to isopentane. The lowest specific costs are obtained for a minimal temperature difference
of 3 K in the evaporator and 7 K in the condenser.
Under the consideration of zeotropic mixtures as potential ORC working fluids, we provide a thermo-
economic analysis of waste heat recovery ORCs. In order to clarify if an efficiency increase
overcompensates the additional heat transfer requirements. A case study is performed for a heat
source temperature of 150 C. In this context, a second law analysis for the ORC working fluids
R245fa, isobutane and isopentane as well as for the zeotropic mixture isobutane/isopentane is
conducted. Based on processes parameters the required heat exchange equipment is designed. Finally,
the specific costs for the generated electricity are calculated. Depending on the working fluid
composition and the minimal temperature difference in the condenser and evaporator, the most cost-
efficient system is identified.

2. METHODS

2.1 Exergy analysis

For the exergy analysis, steady-state simulations are performed using the software Cycle Tempo
(Woudstra, N. and van der Stelt, T.P., 2002). Fluid properties are calculated by RefProp Version 9.1
(Lemmon, E.W. et al., 2013). Process simulations are conducted for a subcritical and saturated cycle.
The scheme of the module and the corresponding T,s-diagram in case of a pure working fluid is
illustrated in Figure 1.
The present case study is conducted for a low-temperature waste heat source of 150 C. As a heat
transfer medium pressurized water is assumed (pHS = 6 bar). The mass flow and the outlet temperature
of the heat source are chosen according to a thermal heat input of 3 MW. For the analysis, an air-
cooled system is considered. R245fa, isobutane and isopentane as well as the zeotropic mixture
isobutane/isopentane are examined as ORC working fluids. For the considered mixture, the
composition is varied in discrete steps of 10 mole-%. The temperature difference in the evaporator
and condenser is chosen as independent design variables in order to identify the most cost-efficient

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 Paper ID: 7, Page 3

process parameters. The analysis is conducted neglecting pressure and heat losses in the pipes and
components. In Table 1 the boundary conditions for the cycle simulations are shown.
injection production
preheater evaporator 200
drill hole drill hole
heat transfer
geothermal 175
H H medium
water

temperature ( C )
150
2 3 4
125
turbine
generator 100

5 75 3 4
50 5
1,2
25
pump cooling 0
condenser cooling water
1 medium -0.5 0.0 0.5 1.0 1.5
ORC - working fluid entropy (kJ/kg K)
Figure 1: Scheme of ORC system and corresponding T,s-diagram for the working fluid isopentane

Table 1. Boundary conditions assumed for the second law analysis

parameter
mass flow rate of heat source HS 10 kg/s
outlet temperature of heat source THS,in 80 C
inlet temperature of cooling medium TCM,in 15 C
temperature difference of cooling medium TCM 15 C
maximal ORC process pressure p2 0.8pcrit
isentropic efficiency of feed pump i,P 75 %
isentropic efficiency of turbine is,T 80 %
efficiency of generator G 98 %

To evaluate the cycle efficiency, the net second law efficiency II of the ORC is calculated by

PG + PPump + PFans Pnet

II = = (1)

EHS m HS eHS

where PG and PPump correspond to the power of the generator and the pump. PFans is related to the
power of the air cooler fans. The exergy flow of the heat source HS is obtained by multiplying the
specific exergy eHS with the mass flow rate HS. The specific exergy could be calculated by

eHS = h h0 T0 (s s0 ) (2)

where the subscript 0 corresponds to the reference state (T0 = 15 C and p0 = 1 bar). Corresponding to
(Bejan et al., 1996), the exergy analysis is extended by an exergy balance for each component k of the
system

E F ,k = E P ,k + E L ,k + E D ,k (3)

where F and P describe the exergy flow rate of the fuel and the product. The exergy flow rate L
includes heat losses to the surrounding or exergy that leaves the system in a physical way, like
exhaust gases. Here L = 0, due to neglected heat losses. The exergy flow rate D represents the
exergy destruction rate associated to irreversibilities. Exemplarily, the exergy destruction rate of the
preheater can be calculated as

3rd International Seminar on ORC Power Systems, October 12-14, 2015, Brussels, Belgium
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h h2
E D , PH = m ORC T0 ( s 3 s 2 ) 3 (4)
Tm, PH

where Tm,PH corresponds to the thermodynamic mean temperature of the heat source in the preheater.

2.2 Component design and economic analysis

For the major components of the ORC module, the purchased equipment costs (PEC) are estimated
based on cost data of Turton et al. (2003). Purchased equipment costs C0 based on ambient operating
conditions and a carbon steel construction are calculated in US $ depending on parameter Y:

log10C0 = K1 + K 2log10 (Y) + K3 ( log10 (Y))

2
(5)

where Y represents the capacity or size of a component. The parameters K1, K2 and K3 are listed in
Table 2. To convert the PEC in Euro a conversion ratio of 0.815 is considered. Due to maximal ORC
pressures below 35 bar, additional cost factors depending on system pressure are not considered.

Table 2.Equipment cost data used for Equation (5) according to Turton et al. (2003)
component Y; unit K1 K2 K3
Pump (centrifugal) kW 3.3892 0.0536 0.1538
2
Heat exchanger (floating head) m 4.8306 -0.8509 0.3187
Heat exchanger (air cooler) m2 4.0336 0.2341 0.0497
Turbine (axial) kW 2.7051 1.4398 -0.1776

By setting the corresponding Chemical Engineering Plant Cost Index (CEPCI2001) of 397 into relation
to the value of 2014 with 575, the inflation and the development of raw material prices are taken into
account Turton et al. (2003). For the costs Ctot,ORC of the major components of the ORC power plant
the PEC are summarized. The total investment costs of the power plant are calculated by multiplying
Ctot,ORC by the factor Fcosts = 6.32. According to Bejan et al. (1996) this parameter represents additional
costs like installation, piping, controls, basic engineering and others. The heat exchange area A is
determined for the shell and tube heat exchanger in counter flow. Therefore, the overall heat transfer
coefficient Utot of each heat exchanger is calculated by

1 1 1 ro ro ln ( ro / ri )
= + + (6)
U tot o i ri t

where o represents the heat transfer coefficient at the outside of the tube, respectively, the shell side
and i corresponds to the heat transfer coefficient at the inside of the tube. The inner and outer radius
of the tube are represented by ri and ro. The thermal conductivity of the tube corresponds to t. The
outer diameter of the tubes is 20 mm and the wall thickness of the tube is 2 mm. In order to calculate
the required diameter of the shell and the number of tubes, the maximal flow velocities of 1.5 m/s for
liquid flows and 20 m/s for gaseous flows are assumed according to chapter O1 of the VDI Heat Atlas
(VDI-GVC, 2010). In general, the ORC working fluid is led inside the tubes. Regarding the tube
layout, a squared pitch and a pitch to diameter ratio of 1.22 are assumed. The considered heat transfer
correlations for the calculation of i, depending on phase state and flow configuration are listed in
Table 3. In case of the preheater and the evaporator, the method of Kern (1950) is applied for the shell
side (o). For the air-cooled condenser a tube bank staggered arrangement is applied. In this context, a
cross-flow heat exchanger with finned tubes is considered and the following design parameters are
assumed: fin height of 3 mm, a fin thickness of 0.3 mm, a fin spacing of 2 mm and a transversal tube
pitch of 60 mm. The air-side heat transfer coefficient is determined by the method of Shah et al.
(2003). For all considered heat exchangers, the heat transfer surface is finally calculated by

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 Paper ID: 7, Page 5

Q = U tot AFLMTD Tlog (7)

where Tlog is the logarithmic mean temperature difference. In general, the logarithmic mean
temperature difference correction factor FLMTD is equal 1 for condensation and boiling heat transfer. In
this study, the simplifying assumption of FLMTD = 1 is also met for single phase heat transfer.

Table 3. References for the considered heat transfer correlations

heat exchanger tube side
preheater (Sieder and Tate, 1936)
evaporator (pure working fluid) (Steiner, 2006)
evaporator (zeotropic mixture) (Schlnder, 1983)
condenser (pure working fluid) (Shah, 1979)
condenser (zeotropic mixture) (Bell and Ghaly, 1973; Silver, 1964)

2.3 Exergy costing

The thermo-economic analysis combines thermodynamic and economic aspects. In this context, the
product of the energy conversion as well as each component can be evaluated according to the cost
formation process. For the presented analysis, the method by Tsatsaronis and Winhold (1985), also
known as exergo-economic method, is used. The exergy costing converts an exergy stream to a cost
stream , by multiplying the exergy with corresponding average costs per unit of exergy, respectively,
specific costs c. In this context, a system of equations is set up consisting of the cost balance for each
component k of system (Bejan et al., 1996), (Heberle et al., 2012a):

C P ,k = C F ,k C D ,k + Z k (8)

The cost streams k describe the costs of the k-th component depending on operation and maintenance
O&M and capital investment CI. In order to calculate the described cost streams the economic
boundary conditions listed in Table 4 are assumed.

Table 4. Economic parameters for the calculation of the cost streams k

parameter
lifetime 20 years
interest rate ir 4.0 %
annual operation hours 7500 h/year
Cost rate for operation and maintenance 0.02CI
Costs for process integration CPI 0.2Ctot,ORC
Power requirements of the air-cooling system 5 kWe/MWth
Electricity price /kWh 0.08 /kWh

The selected optimization criteria for the system is the minimization of the costs per unit exergy of the
total system cP,tot. In this study, the generated electricity is considered as the product of the system and
the P,tot correspond to the power output of the generator. In this context, the auxiliary power
requirements are covered by electricity from the grid. Alternatively, the net power output of the
system can be considered in the denominator of Equation (9). The exergy rate of the fuel F,tot
represents the exergy rate of the waste heat source transferred to the ORC system.

( cF ,tot E F ,tot + Z k )
C P,tot
cP ,tot = = k (9)
E P,tot E P,tot

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In addition, the specific investment costs SIC are calculated:

Ctot ,ORC
SIC = (10)
Pnet

3. RESULTS AND DISCUSSION

3.1 Identification of cost-efficient design parameters

For each working fluid the minimal costs per unit exergy cp,tot are identified depending on the minimal
temperature difference TPP in the evaporator and condenser. In order to vary the minimal
temperature difference, the corresponding upper and lower ORC pressure is adapted. In Figure 2, the
resulting specific costs of the product are shown exemplarily for R245fa. The most cost-efficient
design parameters for this ORC working fluid are TPP,E = 1 K and TPP,C = 13 K. For these
parameters, costs per unit exergy of 56.8 /GJ are obtained. Considering a minimal temperature
difference between 0.5 K and 6 K for the evaporator and 8 K and 14 K for the condenser, the
maximum costs per unit exergy of 60.0 /GJ are calculated (TPP,E = 6 K; TPP,C = 8 K). In general,
the cost minimum is a compromise between rising power output and increasing costs with decreasing
minimal temperature difference in the heat exchangers. The results show that the condenser is crucial
for the total PEC. Due to the highest amount of transferred thermal energy combined with the lowest
logarithmic mean temperature difference, the highest heat transfer areas and component costs are
obtained for the condenser. Therefore, the most cost-effective parameters show a low TPP for the
evaporator and a high value in case of the condenser.

60
J)
costs per unit exergy (/G

59

58

9
57
(K)

10

11
P,C

12
P

56
6

13
5

TP (K
2

14
1

P,E )
0

Figure 2: Costs per unit exergy for R245fa as ORC working fluid depending on minimum temperature
difference in the evaporator and condenser

3.2 Comparison of ORC working fluids

Power output, heat transfer area and, therefore, capital investment costs for the ORC modules may
considerably vary due to the working fluid selection and the corresponding fluid properties. In this
context, Figure 3a illustrates the costs per unit exergy for the pure ORC working fluids isopentane,
isobutane and R245fa as function of the minimum temperature difference in the condenser. For

3rd International Seminar on ORC Power Systems, October 12-14, 2015, Brussels, Belgium
 Paper ID: 7, Page 7

TPP,E, always the most cost-effective parameter is shown. In Figure 3b specific costs of the product
are shown for selected mole fractions of the zeotropic mixture isobutane/isopentane.
Isobutane is identified as the most cost-effective working fluid for the considered case study with
costs per unit exergy of 52.0 /GJ. The corresponding design parameters are TPP,E = 1.2 K and
TPP,C = 14 K. R245fa and isopentane lead to 9.2 % and 15.0 % higher costs per unit exergy (see
Table 4). Although, these alternative pure working fluids show optimal design parameters with a
lower minimum temperature difference, the power output is 10.8 % and 14.6 % lower. Net second law
efficiency is between 1.0 % and 3.0 % lower compared to isobutane. The total heat exchange area
differs only slightly and is 0.3 % lower for R245fa and 2.1 % higher for isopentane.

62 62
isobutane/isopentane
isopentane 10/90
costs per unit exergy (/GJ)

costs per unit exergy (/GJ)

60 60
30/70
58 58
R245fa
50/50
56 56
70/30
54 54
90/10
isobutane
52 52

50 50
7 8 9 10 11 12 13 14 15 16 11 12 13 14 15 16 17 18 19
TPP,C (K) TPP,C (K)
Figure 3: Costs per unit exergy for the pure ORC working fluids (3a) and for the zeotropic mixture
isobutane/isopentane (3b) depending on the minimum temperature difference in the condenser

Regarding the mixture isobutane/isopentane, a mole fraction of 90 % isobutane leads to the lowest
costs. In case of TPP,E = 2 K and TPP,C = 15 K specific costs of 53.8 /GJ are obtained. However, the
costs per unit exergy are 3.5 % higher compared to the most efficient component isobutane. This is
due to a 5.5 % lower power output. At same time the total heat exchange area is only 3.6 % lower for
90/10 compared to isobutane.

Table 4. Selected ORC parameters for the most-effective cycles depending on fluid selection
parameter isobutane R245fa isopentane isobutane/isopentane
APH (m2) 173.2 100.0 90.8 108.1
AE (m2) 123.1 118.1 118.6 112.8
AC (m2) 747.1 821.7 856.0 785.0
PG (kW) 387.8 345.9 331.0 366.4
PPump (kW) 60.1 21.6 12.1 41.4
TPP,E (K) 1.2 1.0 1.0 2.0
TPP,C (K) 14.0 13.0 13.0 15.0
II (%) 30.3 30.0 29.4 30.0
SIC (/kW) 1161.9 1270.1 1336.23 1203.0
cp,tot (/GJ) 52.0 56.8 59.8 53.8

3.3 Sensitivity analysis for selected boundary conditions

In order to identify the most cost-important parameters of the estimated boundary conditions, Figure 4
illustrates the costs per unit exergy as function of interest rate, turbine efficiency, costs for process

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 Paper ID: 7, Page 8

integration, costs for operation and maintenance and F-factor. The specific costs per unit exergy show
the highest sensitivity for the isentropic efficiency of the turbine and the costs for process integration.

65.0
isentropic efficiency costs for
62.5
of turbine
costs per unit exergy (/GJ) process
60.0 integration

57.5

55.0

52.5 costs for

interest rate O&M
50.0
F factor
47.5

45.0
-20 -10 0 10 20
deviation from standard boundary conditions (%)

Figure 4: Cost per unit exergy as function of selected parameters for the working fluid isobutane

4. CONCLUSIONS

A thermo-economic case study for waste heat recovery by ORC is conducted. Cost-efficient design
parameters concerning the temperature difference at the pinch point are identified in the case of pure
working fluids and mixtures. In general, low minimum temperature differences in the evaporator and
high values in the condenser are suitable for a cost-efficient ORC system. Isobutane as a working
fluid leads to the most cost-effective ORC (TPP,E = 1.2 K; TPP,C = 14 K). Regarding the considered
mixture isobutane/isopentane, a mole fraction of 90 % isobutane leads to the lowest costs per unit
exergy. The economic parameters show a high sensitivity with respect to the estimated isentropic
efficiency of the turbine and the costs for process integration. For further work, a variation of the heat
source temperature and the heat exchanger design will be considered. In the context of a reliable
estimation of the turbine efficiency, a detailed turbine model will be implemented in the analysis.

NOMENCLATURE

A heat transfer area (m2)

c costs per unit exergy (/GJ)
C costs ()
cost rate (/h)
e specific exergy (kJ/kg)
exergy flow (kW)
F cost factor (-)
h specific enthalpy (kJ/kg)
K constant (-)
mass flow (kg/s)
p pressure (bar)
P power (kW)
r radius (m)
s specific entropy (kJ/(kgK))
SIC specific investment costs (/kW)
T temperature (C)
U overall heat transfer coeff. (W/(m2K))

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Y capacity/size parameter (kW) or (m2)

cost rate (/h)
heat transfer coefficient (W/(m2K))
T temperature difference (K)
efficiency (%)

Subscript
C condenser log logarithmic
CI capital investment m mean
CM cooling medium net net
D destruction o outer
E evaporator out outlet
F fuel O&M operation and
G generator maintenance
HS heat source P product
i inner PH preheater
is isentropic PP pinch point
II second law Pump pump
K k-th component t tube
L loss tot total
LMTD logarithmic mean 0 reference state
temperature difference

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ACKNOWLEDGEMENT

The work was funded by the Deutsche Forschungsgemeinschaft (DFG) with project No. BR 1713/12.
The authors gratefully acknowledge this support.

3rd International Seminar on ORC Power Systems, October 12-14, 2015, Brussels, Belgium