Applied Energy 119 (2014) 204217

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Alkanes as working uids for high-temperature exhaust heat recovery

of diesel engine using organic Rankine cycle
Gequn Shu a, Xiaoning Li a, Hua Tian a, Xingyu Liang a, Haiqiao Wei a,, Xu Wang b
a
b

State Key Laboratory of Engines, Tianjin University, Weijin Road 92, Nankai District, Tianjin 300072, China
School of Aerospace, Mechanical and Manufacturing Engineering, RMIT University, Australia

h i g h l i g h t s
 Less complex uids are preferred due to their excellent performances.
 The cyclic Alkanes are considered as the most promising candidate.
 Maximum improvement of 10% in BSFC is obtained by DE-ORC combined systems.
 Alkane-based ORCs may be more attractive than steam cycle for exhaust heat recovery.

a r t i c l e

i n f o

Article history:
Received 19 August 2013
Received in revised form 26 December 2013
Accepted 29 December 2013
Available online 25 January 2014
Keywords:
Waste heat recovery (WHR)
High-temperature exhaust gas
Alkanes
Working uids
Organic Rankine cycle (ORC)

a b s t r a c t
Study on recovering waste heat of engine exhaust gas using organic Rankine cycle (ORC) has continuously
increased in recent years. However, it is difcult to nd out appropriate working uids to match with
exhaust gas waste heat due to high temperature. In this work, several tentative attempts and explorations are made in selecting Alkanes as working uid owing to their excellent thermo-physical and environmental characteristics. Parameters optimization of the combined system of diesel engine with
bottoming ORC (DE-ORC) is performed on Alkane-based working uids with six indicators, including
thermal efciency (g), exergy destruction factor (EDF), turbine size parameter (SP), total exergy destruction rate (IORC), turbine volume ow ratio (VFR) and net power output per unit mass ow rate of exhaust
(Pnet). Afterwards, the impact of molecular complexity on the indicators of VFR and SP is analyzed. Furthermore, the energy distribution of engine exhaust gases and the improvement of fuel economy, after
integrating the bottoming ORC with diesel engine, are also discussed. Finally, the performance comparison between Cyclohexane-based ORC and steam cycle with relative pressure is carried out. The results
show that optimized working uids are not always constant subject to different indicators and operation
parameters. However, cyclic Alkanes, Cyclohexane and Cyclopentane are considered as the most suitable
working uids when taking into account of all comprehensive indicators. The maximum improvement of
10% in brake specic fuel consumption (BSFC) is obtained for DE-ORC combined systems with Cyclohexane used as working uid. In addition, although steam has more advantages in thermal efciency in the
current conditions, from a technical and economic point of view, Alkane-based ORCs may be more attractive than conventional steam cycles, specically for DE waste gas heat recovery.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The primary driving force in seeking sustainable and economically viable technologies is escalating fuel prices, national energy
security and stringent regulations for environmental emissions.
Clean and effective ways for energy conversion and utilization
have to be found in order to tackle these situations. Diesel engine
(DE) is the prime mover often chosen for its reliability, exible

Corresponding author. Tel./fax: +86 22 27891285.

E-mail address: whq@tju.edu.cn (H. Wei).
0306-2619/$ - see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.12.056

layout, high power density and efciency and low specic cost.
Although DE efciency can be improved by such advanced technologies as electronic control high-pressure common rail fuel
injection, homogeneous charge compression ignition (HCCI) or exhaust-gas turbocharging, it is difcult to achieve a peak efciency
of DE higher than 45% [1]. Except for energy conversion to power,
in regard to the balance of DE energy, exhaust energy accounts for
about one-thirds of fuel chemical energy, which is exhausted to the
environment by engine in several forms.
Recently, researches on heat recovery from engine exhaust
gases have become hot topics in waste heat recovery (WHR)

G. Shu et al. / Applied Energy 119 (2014) 204217

205

Nomenclature
Cp
cp
E_
h
I_
_
m
n
M
P
Q_
R
s
T
V_
_
W

DHis

isobaric ideal gas heat capacity (J/(mol K))

mean specic heat at constant pressure (J/(mol K))
exergy ow rate (kW)
specic enthalpy (kJ/kg)
irreversibility (kW)
mass ow rate (kg/s)
number of carbon atoms
molecular weight (g/mol)
pressure (kPa)
heat ow rate (kW)
universal gas constant (J/(mol K))
specic entropy (kJ/(kg K))
temperature (C)
volumetric ow rate (m3/s)
power (kW)
isentropic enthalpy difference (kW)

Greek symbols
n
inverse of slope of saturated vapor curve
g
thermal efciency
r
molecular complexity
Subscripts and superscripts
c
condenser
cond
condensing
crit
critical
cw
cooling water
e
evaporator
evap
evaporating
f
working uid
fuel
diesel fuel
g
exhaust gas
i
each state point

[26]. For example, Horst et al. [2] developed a dynamic model of

evaporator used in Rankine cycle for exhaust WHR in passenger
car. Yun et al. [3] established a power generation and heat recovery
model for internal combustion engines (ICEs). Fu et al. [4] obtained
the mapping characteristics of naturally aspirated engine by experiments, and the characteristics of exhaust waste heat energy were
analyzed using energy and exergy analysis method. Love et al. [5]
investigated thermoelectric devices as a means of improving fuel
economy for engines through converting exhaust waste heat to
usable electricity. Pandiyarajan et al. [6] investigated in detail the
integration of a n-tube heat exchanger with an IC engine setup
to extract exhaust gas heat energy, and excessive energy was
stored in a thermal energy storage tank.
ORC processes, with similar structure as typical Rankine cycle,
use organic uids instead of water as working uids. In ORC process, turbines are usually less complex as the organic uids have
the relatively lower enthalpy drop, and higher efciencies can be
obtained at part loads as well [7]. In addition, a number of advantages can be attributed to ORC systems, such as simple structure,
component availability, and the ease of application to local
small-scale power generation systems. ORC as bottoming cycle to
couple with engines to recover waste heat energy results in combined power unit with enhanced overall system efciency, and is
considered as one of the most promising technologies. ORC systems consume no additional fuel for extra power. Moreover, compared with the original engine, the combined system has the
potential to greatly reduce specic pollutant emissions.
Many researchers have performed studies on this subject from
the perspectives of both theoretical analysis and experimental

in
inlet
loss
loss
max
maximal
min
minimal
net
net
out
outlet
p
pump
s
ideal state
sv
saturated vapor
t
turbine
0
standard condition
14
state points
2s, 4s, 4s0 stat points for the ideal case
Abbreviations
BSFC
brake specic fuel consumption
DE
diesel engine
DE-ORC diesel engine-organic Rankine cycle
EDF
exergy destruction factor
est
estimated value
GWP
global warming potential
HCCI
homogeneous charge compression ignition
ICE
internal combustion engine
ODP
ozone depletion potential
ORC
organic Rankine cycle
PPTD
pinch point temperature difference
RD
relative deviation
ref
reference value
SP
size parameter
VFR
volumetric ow ratio
WHR
waste heat recovery

investigation [813]. Zhang et al. [8] analyzed the characteristics

of a dual loop ORC, in which the coolant, intake air and engine exhaust was used as waste heat source, integrated with a light-duty
diesel vehicle engine using R245fa and R134a as working uids.
The optimization of the system by combining a heavy duty diesel
(HDD) engine with a bottoming cycle that was presented (Ref.
[9]) where R245fa and water were used as working uids to recovers waste heat energy from the sources. Based on various refrigerant-based uids, Tian et al. [10] performed a study on uids and
parameters optimization of ORCs integrated with stationary ICEs
where the engine exhaust gases were proposed to be a thermal
source and used in their solutions. Yu et al. [11] presented an
ORC simulation model, which had similar structure to actual bottoming system, using R245fa as working uid to recover waste
heat energy of cooling water and engine exhaust gas. Wang et al.
[12] performed a study of working uid selection of ORCs for engine WHR, and the refrigerants were used as working uids. Vaja
and Gambarotta [13] coupled ORCs with a stationary ICE to establish a combined power generation model, in which the overall efciency was improved by 12% compared with the original engine,
and three different working uids including benzene, R11 and
R134a were employed for three different cycle setups.
Based upon the above-mentioned researches, it is found that
refrigerants are most selected as working uid candidates in previous studies, while critical temperature and thermal decomposition
temperature are relatively low for most refrigerants. A great temperature difference occurs in heat transfer between high-temperature exhaust gases and uids, which inevitably results in high
irreversible rate. Furthermore, there are some environmental

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G. Shu et al. / Applied Energy 119 (2014) 204217

issues for the applications of some refrigerants; so it is imperative

to nd appropriate uids to match with engine high-temperature
exhaust gases to obtain the best performance.
The availability of waste heat energy at different temperature
levels is important to choose a suitable organic uid for the application of ORCs. Roy et al. [14] presented performance analysis of an
ORC, in which four refrigerant-based uids were used as working
uids, using the heat source at different temperature levels under
superheated conditions. A detailed analysis was performed to
investigate CO2-based transcritical power cycle in which low-grade
waste gases from industrial process were used as a heat source
[15]. Performance was compared for both transcritical power cycle
and subcritical ORC using various kinds of refrigerant-based uids
to exploit low-temperature geothermal energy [16]. Wang et al.
[17] conducted an experimental study on recuperative Rankine cycle system in order to exploit low-temperature solar energy using
R245fa as working uid. Generally, low-temperature heat sources
have a temperature lower than 230 C, and different working uids
can be used in ORC power generation systems to achieve output
power.
However, high-temperature applications have attracted
intensive interests in recent years. In contrast, there is less knowledge about high-temperature applications, in which parameters
and working uids are greatly different from the low-temperature applications. Typical uses include the combined cycles for
biomass applications [7], combustion fuel gas WHR [19], bottoming cycle for molten carbonate fuel cells [20], among others. Nowadays, Alkane-based working uids have been employed by ORC
manufacturers in order to achieve better system performance in
some high-temperature applications as higher working temperatures can be reached by these compounds.
High-temperature ORCs based on Alkane-based working uids
are available in the open literature [2024]. Algieri and Morrone
[21] evaluated cyclic Alkanes and linear Alkanes as working
uids in a biomass application. Lai et al. [22] proposed Alkanebased high-temperature ORCs in which thermodynamic properties were obtained through computational program based on
the law of corresponding states. Siddiqi and Atakan [23]
conducted a detailed performance comparison analysis and discussion between Alkanes and other uids used in Rankine cycles
for the waste heat sources with different temperature ranges.
Linear Alkanes were adopted in a bottoming ORC in order to enhance the micro-gas turbine performances [24]. From the above
literatures, it is evident that only few Alkane-based working
uids have been investigated. Moreover, most of the abovementioned researches were performed based on the rst law of
thermodynamics and thermal efciency was assigned as the only
performance indicator. Up to now, however, there are few papers
in which a systematic study was carried out on the application
of Alkane-based working uids based on various indicators for
WHR from DE exhaust gases.
The present paper focuses on evaluating the improvement of
BSFC by using DE exhaust gases as a heat source for saturated vapor power cycle, thus with a rather simplied design of heat
recovering unit, under the hypothesis of operating the engine at
full load while considering the cycles using Alkane-based uids
where there are no more than 10 carbon atoms in the carbon
backbone. The aim is to investigate the performances of the
Alkane-based working uids used in ORCs to recover engine
exhaust gases with a high thermal level. Here, the exhaust gases
of DE with an outlet temperature of 519 C under a rated operating condition are used as a heat source. A thermodynamic model
is established and six indicators, including thermal efciency (g),
net power output per unit mass ow rate of hot exhaust (Pnet),
total exergy destruction rate (IORC), exergy destruction factor

(EDF), turbine volume ow ratio (VFR) and turbine size parameter

(SP), are proposed and analyzed. In addition, the inuence of
molecular complexity on the indicators of VFR and SP is analyzed.
Energy distribution of engine exhaust gases, as well as the BSFC
improvement after the integration of the bottoming ORC with
the DE, is discussed. The optimal value of each performance
indicator for different Alkane-based working uids is also been
compared respectively. Finally, the performance comparison
is made between Cyclohexane-based ORC and steam cycle with
relative pressure.

2. Alkanes
2.1. Nomenclature and taxonomy
Alkanes are one kind of simple chemical compounds only composed of hydrogen and carbon atoms. Since only single bonds are
contained in the compounds, they are often known as saturated
hydrocarbons. The saturated hydrocarbons can be categorized on
the basis of their molecular structure:
 Linear Alkanes, having a general formula CnH2n+2, such as Pentane and Hexane.
 Branched Alkanes, having a general formula CnH2n+2 (n > 3),
such as Isopentane and Isohexane.
 Cyclic Alkanes, having a general formula CnH2n (n > 2), such as
Cyclopentane and Cyclohexane.
Following standard rules, saturated straight-chain Alkanes
take the sufx -ane, and the rst portion of the name is derived
from the Greek numeric prex that cites the number of carbons in
the Alkane, with the exceptions of Nonane, which has a Latin prex. Straight-chain Alkanes are sometimes indicated by the prex
n- (for normal) where a non-linear isomer exists. While cyclic
Alkanes are simply prexed with cyclo- before the corresponding straight-chain hydrocarbons. For example, C5H10 is Cyclopentane and C6H12 is Cyclohexane. The name rules of branched
Alkanes become relatively complex compared with straight-chain
and cyclic Akanes, which are named as a straight-chain Alkane
with attached alkyl groups. Simple branched Alkanes, however,
often have a common name using a prex iso- to distinguish
them from linear Alkanes. For example, C5H12 is Isopentane and
C6H14 is Isohexane.
The thermodynamic characteristics of some selected Alkanes
are shown in Table 1. These hydrocarbons are attractive since
some of them have near-ambient boiling points to enable condensation near atmospheric pressure. For the high-temperature
ORC, Alkanes are selected as working uids because of their
appropriate critical temperature and pressure. In addition,
Alkanes are also environmentally friendly working uids with a
zero ozone depletion potential (ODP) and a relatively low global
warming potential (GWP) value [25]. Moreover, Alkanes have
been widely used in ORC process, in which good performance
can be achieved.
The positive slope of the saturated vapor entropy line in Ts
diagram is one of the main advantages of using organic uid as
working uid of Rankine cycle. The water steam cycles will be in
the two-phase region at the outlet of the turbine if a saturated cycle is performed, while organic uids are used instead of water
steam, with regard to the majority of the organic uids, the outlet
of the turbine will be in the superheated vapor region, which depends on the shape of the saturated vapor curve. The organic working uids can be classied according to the shape of the saturated
vapor curves, which can be characterized by the slope of the

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G. Shu et al. / Applied Energy 119 (2014) 204217

Table 1
Thermodynamic characteristics of Alkanes.
Name

Tcrit (C)

Pcrit (kPa)

n (J/kg K2)

Type

M (g/mol)

ODP

GWP

Pentane
Hexane
Heptane
Octane
Nonane
Decane
Isopentane
Isohexane
Cyclopentane
Cyclohexane

5
6
7
8
9
10
5
6
5
6

196.55
234.67
266.98
296.17
321.4
344.55
187.2
224.55
238.54
280.49

3370
3034
2736
2497
2281
2103
3378
3040
4515
4075

1.7151
1.9675
2.1141
2.1943
2.2500
2.2765
1.8098
2.1227
0.1902
0.7740

Dry
Dry
Dry
Dry
Dry
Dry
Dry
Dry
Isentropic
Isentropic

72.149
86.175
100.2
114.23
128.26
142.28
72.149
86.175
70.133
84.161

0
0
0
0
0
0
0
0
0
0

Very
Very
Very
Very
Very
Very
Very
Very
Very
Very

saturated vapor curve on a Ts diagram. The inverse of slope of the

saturated vapor curve can be expressed as


n

ds
dT


1
sv

Eq. (1) can be used to predict the types of working uids, that is, a
wet uid (n < 0), an isentropic uid (n  0) and a dry uid (n > 0). For
a non-regenerative cycle, in order to achieve the highest efciency,
the uid should be expanded directly from saturated vapor line to
avoid unnecessary superheating [7]. For a wet uid (e.g. water),
liquid droplets may be formed during expansion in turbine if the
uid is expanded directly from saturated vapor line [14]. Dry and
isentropic uids, however, which take the vast majority of organic
uids used in ORCs, may remain in the state of saturated or superheated vapor even after the expansion from the turbine [16]. Thus,
dry and isentropic uids exhibit better thermodynamic efciencies
of expansion devices, as there are no liquid droplets in the turbine,
contrary to wet uids.
Fig. 1 presents the inverse of the slope of the saturated vapor
curve (n) determined by Eq. (1) with different induced temperatures, and the reference temperature is set as 60 C (the condensation temperature of ORC) for the working uids considered. As
seen in Fig. 1, the values of n are all higher than zero for the
investigated working uids at reference temperatures, and the
uids with this behavior are known as dry uids or isentropic
uids according to the aforementioned classication. The category results for the selected working uids can be seen in
Table 1.

Fig. 1. The inverse of slope of the saturated vapor curve as a function of reduced
temperature.

low
low
low
low
low
low
low
low
low
low

In subcritical cycles, the evaporation temperature is limited by

the critical temperature, and the uids can be divided into three
categories based on the critical temperature [18]:
 High temperature uids, wherein the critical temperatures are
above 250 C.
 Medium temperature uids, wherein the critical temperatures
are in the range 150250 C.
 Low temperature uids, wherein the critical temperatures are
below 150 C.
According to the critical temperatures as displayed in Table 1,
the selected working uids belong to the category of medium-high
temperature.
2.2. Molecular complexity
Molecular structures have great inuence on thermo-physical
properties of uids. The difference in molecular structure of different uids can be characterized as molecular complexity. Harinck
et al. [26] dened the complexity of the uids as follows:

2  M  C p T crit  R
R

wherein Tcrit means the critical temperature of the uid (K), Cp is the
heat capacity under constant pressure (J/mol/K), and R denotes the
universal gas constant (J/mol/K).
Molecular complexity has positive inuence on the specic
isentropic work in accordance with the literature [26]. For a
dense-gas, the more complex the molecular structure is, the closer

Fig. 2. Molecular complexity of selected working uids.

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G. Shu et al. / Applied Energy 119 (2014) 204217

complexity and only minor performance improvement [16]. Also,

it has been certied that signicant increase in system irreversibility will be achieved if superheating and subcooling of the working
uids are employed [27].
Fig. 4 shows Ts process diagrams of ORC for engine exhaust
gases heat recovery. After condensation, the saturated working
uid is pressurized through pump to the set-pressure in the ORC
process (12). Saturated vapor is generated in the evaporator, in
which the heat from engine exhaust gas is absorbed by the cold
working uid (23). And then expansion work is produced by turbine after the saturated vapor produced in the evaporation process
enters the turbine (34). After leaving the turbine, the exhausted
working uid vapor enters the condenser, in which saturated liquid is generated after condensation process, and then a cycle
completes (41). The energy and exergy analysis will be performed
in the following section after choosing each system or component
in Fig. 3 at control volume. In addition, proper simplication is
made to simplify computing and complexity without losing computational accuracy. The cycle is assumed to work in steady state
in this work, and the heat loss by radiation and pressure drop in
the pipes, condenser and evaporator can be neglected.
Fig. 3. Schematic diagram of DE-ORC combined system.

3.2. Initial conditions and boundary conditions

to an ideal gas behavior, which results in higher specic isentropic
work output. The molecular complexity of selected working uids
can be seen in Fig. 2.
3. System modeling
3.1. Description of ORC system
As shown in Fig. 3, the combined system is composed of DE and
its bottoming cycle. Here, only subcritical saturation steam cycle is
employed in the proposed solutions. A regenerator is recommended to be added to improve ORC performance in some cases.
In the present work, a regenerator will not be included as it will
lead to considerable increase of heat exchanger cost and system

In the present study, a commercial 6-cylinder, 4-stroke supercharged diesel generator set is employed as topping system, and
the main parameters of the DE are listed in Table 2. Among them,
the available exhaust gas temperature is obtained after the turbocharger of the DE. ORC will be employed in the study as bottoming
cycle to recover the engine exhaust waste heat. The gas properties
can be evaluated by the composition of the exhaust gases, including N2 = 73.04%, H2O = 5.37%, O2 = 6.49%, CO2 = 15.10% based on
mass. In this work, the rated operating conditions are assumed
for the adopted engine, and the most appropriate organic working
uids that would better t the given heat source conditions will be
determined.
As shown in Fig. 4, evaporators used in the ORCs are usually
simple components designed as heat exchanger to directly use
hot gases released from the thermal source, and intermediary uids (e.g. heat conducting oil) can be excluded [13]. The typical range of the efciencies of turbine and pump are from 75 % to 85 %
according to literature [8,16,2729]. For this study, the efciencies
of turbine and pump have been imposed as 0.8, which is reasonable and close to the actual value for ORC applications [7,15,21].
The pinch-point temperature difference (PPTD) is the smallest
temperature difference in the ORC heat exchanger, establishing
the maximum allowable evaporation pressure and, thus, limiting
the ORC performance. For the evaporator, the PPTD (DTg) at pinch
point, to meet the gas-uid heat exchanger performance, is considered to be 30 C [10,13]. Note that the outlet exhaust temperature
(Tg,out) depends on the characteristics of ORC heat exchanger. The
minimum exhaust gas temperature at the evaporator outlet should
be above 90 C. Otherwise, low temperature corrosion will occur if

Table 2
The main parameters of the diesel engine under rated conditions.

Fig. 4. Ts diagram of the ORC process.

Parameter

Values

Units

Power output
Torque
Exhaust temperature
Rotate speed
Fuel consumption
Brake fuel consumption rate
Exhaust mass ow
Smoke intensity

235.8
1500
519
1500
47.79
202.7
990.79
0.55

kW
Nm
C
rpm
kg/h
g/kW h
kg/h
FSN

G. Shu et al. / Applied Energy 119 (2014) 204217

209

Fig. 5. The cycle upper limit of the selected working uids.

Table 3
Parameters and boundary conditions of the ORC model.
Parameter

Value

Units

Inlet temperature of exhaust gases

Inlet temperature of cooling water
PPTD (condensation)
PPTD (evaporation)
Condensation temperature
Isentropic efciency (turbine/pump)
Generator efciency

519
25
10
30
60
0.8
1

C
C
C
C
C

the temperature is below this threshold [27]. Condensing temperature has been set to 60 C in this study. The corresponding condenser pressures are above 5 kPa, as suggested in literature [19],
but a lower condensing pressure will be chosen for Decane and
Nonane (1.52 kPa and 3.98 kPa respectively) in order to keep condensing temperature consistent with that of other working uids.
The lower pressure and temperature limit of the cycle can be seen
in Fig. 5 for the selected working uids. A water-cooled condenser
will be adopted in this study. And it is very easy to replace the
water cooling type condenser with an air-cooled type condenser
for WHR application at the condensing temperature considered
above. Other parameters and boundary conditions of the ORC model can be seen in Table 3.
The actual temperature and pressure limits of the adopted cycle
will be determined in the next step according to cycle characteristics of each working uid. Generally speaking, the higher the pressure ratio it has, the more mechanical energy will be extracted
from a given mass of working uid due to its higher thermal efciency. However, some practical restrictions have to be taken into
account when attempting to increase operation pressure toward
the critical pressure.
The system may become unsteady near the critical region as the
pressure has a high sensitivity to minor temperature change at this time. Namely, great change in pressure will take place when
temperature varies within a very small range. Hence, an appropriate higher limit of the cycle should be considered based on the critical point of the uid. However, there is no uniform view on
choosing a rational gap between the cycle upper limit and the critical point of the uid.
Schuster and Heberle [28,29] suggested setting critical pressure
multiplied by a certain coefcient (e.g. 0.7) as the pressure upper
limit of the cycle. Since the differences of critical properties among
different working uids are evident, a xed ratio used to determine

the pressure limit may not be a very unanimous way to identify

pressure interval between the pressure upper limit and the critical
pressure.
In the present work, the upper limit of the adopted cycle will be
determined with the slope of the saturated vapor entropy line in
the Ts diagram. Maximum live vapor pressure of the turbine
should not exceed the pressure upper limit to eliminate the
impingement of liquid droplets on turbine blades. The pressure
upper limit can be determined with the point (point 3 in
Fig. 4) at which the slope of the saturated vapor entropy line in
the Ts diagram is equal to innity, and beyond which condensation will take place within the turbine (point "300 " in Fig. 4). The
upper cycle limits have been calculated based on this criterion,
as shown in Fig. 5.
3.3. Mathematical model
3.3.1. Energy analysis
An evaluation model based on the rst and the second laws of
thermodynamics is introduced to describe the energy behavior of
different working uids under different working conditions. These
formulas introduce the equations to perform the thermodynamic
comparative analysis.
For the pump:

_ pW
_ p;s =g m
_ f h2s  h1 =gp
W
p

For the evaporator:

_ g hg;in  hg;out m
_ f h4  h2
Q_ e m

For the turbine:

_ tW
_ t;s g m
_ f h3  h3s gt
W
t

For the condenser:

_ cw hc;out  hc;in m
_ f h4  h1
Q_ c m

For the net output:

_ net W
_ tW
_ p
W

Thermal efciency of the cycle can be calculated as:

g W_ net =Q e W_ t  W_ p =Q e

The net power output per unit mass ow rate of exhaust is given by

_ net =m
_g
Pnet W

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G. Shu et al. / Applied Energy 119 (2014) 204217

The BSFC of the engine and the DE-ORC conguration can be

estimated as:

_ DE
_ fuel =W
BSFCDE m
BSFCDE-ORC

_ DE W
_ net
_ fuel =W
m

E_ in 

_i
E_ out  W

Source
Benezene
R11
R134a

11

12

The 0 subscripts are used to denote the specied dead reference

state under ambient pressure and temperature conditions. In the
present work, the dead state is specied by T0 = 25 C and
P0 = 1 atm. The irreversibility of each component can be expressed as

I_i

Parameter

10

3.3.2. Exergy analysis

The thermodynamic irreversibility, occurring generally on each
component, can be determined with exergy analysis method. At
any point of the ORC, the exergy ow rate of working uid can
be calculated as:

_ f hi  h0  T 0 si  s0 
E_ i m

Table 4
The results have been compared for the present work and reference [13].

13

Wnet (kW)
Ref. [13]
349.3
290.3
147.5

Mass ow rate (kg/s)

Present
351.2
292.4
148.7

RD
0.54%
0.72%
0.81%

Ref. [13]
2.737
7.487
8.9667

Present
2.743
7.514
9.013

RDa
0.22%
0.36%
0.52%

RD: relative difference, see Eq. (19).

wherein ref denotes the reference value, est means the estimated
value.
According to the developed model, a simulation program in
which the process units are modeled is developed using Matlab
language. Under the conditions of the same operation, the obtained
results have been compared with those of Vaja and Gambarotta
[13] to validate the present model. The results of the mass ow
rate and net power output have been compared between this work
and the reference as shown in Table 4. A corresponding result with
reference is obtained by the developed model and the relative difference is less than 1%. Therefore, the model has been validated.

The total irreversibility of the cycle can be calculated as:

I_ORC

I_i

14

The exergy loss of the exhaust gases leaving the ORC can be calculated as:

_ g cp;g T g;out  T 0  T 0 logT g;out =T 0 

I_loss m

15

Exergy destruction factor (EDF) can be determined as:

_ net
EDF I_ORC =W

16

3.3.3. Turbine design

Volumetric ow ratio (VFR), accounting for the compressibility
effect through the expansion, is dened as:

VFR V_ 4 =V_ 3

17

wherein V_ 3 and V_ 4 are the volume ows at inlet and outlet of the
turbine respectively.
According to Ref. [30], lower values of VFR deliver higher
turbine efciency. In addition, according to the viewpoint in Ref.
[24] the turbine efciency over 80% can be achieved only when
VFR is below 50.
Turbine size parameter (SP), taking volumetric ow in turbines
outlet and isentropic enthalpy difference throughout the turbine
into account, is expressed as

SP

q
V_ 4 =DH1=4
is

4. Results and discussion

The calculated conditions of the present system are given in
Table 3 along with the characteristics of the turbine, pump, etc.,
and the main parameters of an actual DE are expressed in Table 2,
which provides the heat source (exhaust gases) conditions of the
developed model. The thermodynamic properties of uids are
calculated with REFPROP 8.0 software [31]. The results of a comparative study for different working uid-based ORC systems will
be presented in the following paragraphs, and different working
uids can be equally evaluated. Based on six different indicators
considered in this analysis, including g, Pnet, IORC, EDF, VFR and
SP, the performances of different working uids investigated for
the bottoming ORC system are shown in Figs. 612. For the convenience of description, relative pressure, which is the ratio of
evaporating pressure (Pevap) and the maximum allowable
evaporating pressure (Pmax), is introduced.
4.1. The inuence of evaporating pressure
Volume ow ratio (VFR) is the ratio between outgoing isentropic and incoming volumetric ows, showing how much the uid
volume increases through expansion. VFR is a particularly

18

wherein V_ 4 stands for volumetric ow in the turbines outlet, DHis is

the isentropic enthalpy difference throughout the turbine. The
parameter of turbine size is shown as SP here with meter as unit.
Since there is certain proportion between the SP and the actual
turbine size, SP, being regarded as an indicator of turbine dimensions, given by Eq. (18), can be used to evaluate the actual turbine
size in place of a detailed design calculation [24,30]. This can be
used to compare different turbine sizes and is an appropriate indicator of its relative cost. Larger size parameter means bulkier and
more expensive turbines.
3.4. Validation of the model
The RD (relative deviation) is given by

RD

ref -est
 100%
ref

19
Fig. 6. Turbine volume ow ratio (VFR) with relative pressure.

G. Shu et al. / Applied Energy 119 (2014) 204217

Fig. 7. The turbine size parameter (SP) with relative pressure.

Fig. 8. Thermal efciency with relative pressure.

Fig. 9. Net power output per unit mass ow rate of hot exhaust with relative
pressure.

signicant parameter since it is related to turbine efciency and

whether a single stage expander could be employed. According
to Invernizzi et al. [24] a VFR of above 50 is not considered, since

211

Fig. 10. Total exergy destruction rate with relative pressure.

Fig. 11. Exergy destruction factor (EDF) with relative pressure.

Fig. 12. Turbine size parameter (SP) and turbine volume ow ratio (VFR) with
molecular complexity.

in this case turbine efciency will be less than 80%. This is mainly
true for axial single-stage turbines. As shown in Fig. 6, the curves
ascend with the increase of evaporating pressures for all uids.

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G. Shu et al. / Applied Energy 119 (2014) 204217

VFR values increase with the increase of the numbers of carbon

atom in chain for the three Alkane categories considered under
the same relative pressure. Cyclic Alkanes show higher values than
corresponding linear Akanes with the same number of carbon
atom numbers in chain, whereas branched Alkanes present lower
values than corresponding linear Akanes. Based on the demarcation line of VFR = 50, the VFR values of the working uids, including Isopentane, Pentane, Cyclopentane and Isohexane are below 50
under all evaporating pressures, and the VFR values of the rest are
below 50 but only under a portion of evaporating pressures. Specifically, in addition to the aforementioned four working uids, single-stage turbines cannot be adopted for the rest working uids
under some evaporation pressures due to relatively low turbine
efciency. For the working uids with high carbon atom numbers
in chain, taking Decane as an example, VFR value is close to 1200
under the maximum evaporating pressure, so multi-stage turbines
have to be adopted, which increases turbine size and relative cost.
Turbine size parameter (SP) given by Eq. (18) is an indicator of
turbine size. SP is proportional to actual turbine size, which can be
used to compare different turbine sizes, thus is an appropriate indicator of its relative cost. Larger size parameters mean that bulkier
and more expensive turbines will be employed. As shown in Fig. 7,
it is evident that SP initially drops rapidly with the increase of
evaporating pressure, and then decreases more slowly under higher evaporating pressures for all considered working uids. SP values increase with the increase of the numbers of carbon atom in
chain under certain relative pressures for the considered three categories of working uids. There is a similar trend of the working
uids with the same carbon atom number in chain. SP values of linear Alkanes are between that of corresponding cyclic Alkanes and
branched Alkanes with the same numbers of carbon atom under
high relative pressure. Curve intersections appear only under very
low relative pressure. It is evident that a larger turbine size will be
required for the working uids with more numbers of carbon
atoms in chain. It can be observed that a maximum SP value of
1.168 m is achieved by Decane under the maximum evaporating
pressure, while Isopentane achieves the minimum value of
0.128 m among all working uids. The working uids including
Isopentane (SP = 0.128 m), Pentane (SP = 0.142 m), Cyclopentane
(SP = 0.165 m) and Isohexane (SP = 0.189 m) require lower SP values, which is in agreement with the above-mentioned observations
regarding the inuence of the volumetric ow rate on the cost and
size of the system. In addition, for some uids with high molecular
complexity r, the demarcation points of VFR = 50 have been
marked in Fig. 7. For these uids, the minimum values of SP have
been extended in different degrees (e.g. SP = 1.257 m for Decane)
according to this constraint condition. For the uids considered
in this paper, the optimal values of SP have been listed in Table 6
after the isentropic turbine efciencies are conned to an acceptable range.
Fig. 8 shows the variation of thermal efciency with relative
pressure for Alkane-based working uids considered. Although linear Alkanes and branched Alkanes have similar variation with relative pressure, branched Alkanes have a lower thermal efciency
than corresponding linear Alkanes containing the same carbon atom number. The thermal efciency increases with the numbers of carbon atom in chain for linear Alkanes and branched
Alkanes. However, a rapid increasing trend can be found for cyclic
Alkanes, which is obviously different from linear Alkanes and
branched Alkanes. This is mainly due to the facts that higher evaporation pressures can be obtained by cyclic Alkanes under the
same relative pressure, which contribute to achieving a higher
compression ratio compared to other uids. In addition, the cyclic
Alkanes also have relatively high levels of evaporation temperature, which will contribute to achieving better temperature matching between heat carrier (exhaust gas) and uids to reduce the loss

caused by heat transfer between them. The highest thermal efciency of about 19.3% is achieved by Cyclohexane among all uids
considered under maximum relative pressure. Cyclohexane is followed by Decane. Decane exhibits a thermal efciency about
18.1% that is about 6% lower than Cyclohexane. Moreover, Cyclopentane also shows high thermal efciency of about 17.8%, which
is about 8% lower than Cyclohexane. For some uids with high
molecular complexity r, however, the thermal efciencies have
been diminished to various extents by conning the isentropic turbine efciencies within a limited range. Taking Cyclohexane as an
example, the thermal efciency is reduced from 19.3% to 18.2%.
The maximum thermal efciencies of uids considered within an
acceptable isentropic turbine efciencies range have been shown
in Table 6.
Net power output per unit mass ow rate of hot exhaust can be
used to denote the power output performance of the exhaust gases.
Fig. 9 presents variation of Pnet values for various working uids
under different relative pressures. Higher Pnet value means that
more power output can be obtained with the same heat source
mass ow rate. As shown in Fig. 9, Pnet value increases with the relative pressures. The increase trend of various working uids is
obvious under low relative pressures, and becomes smooth near
maximum live vapor pressure. In addition, Pnet values ascend with
the increase of the numbers of carbon atom in chain under any relative pressure for linear Alkanes, and branched Alkanes show a
similar trend as the linear Alkanes do. However, cyclic Alkanes
show different trends, and Pnet values are signicantly higher than
that of the corresponding linear Alkanes and branched Alkanes
containing the same number of carbon atom for all admissible live
vapor pressures. For cyclic Alkanes, the variation trends of Pnet are
similar to that of thermal efciency (g) in Fig. 8, which are caused
by the same reasons as mentioned above. Among all the considered
working uids, Cyclohexane shows the highest Pnet value of about
91.7 kJ/kg under maximum allowable evaporating pressure
3529.8 kPa. Decane also presents higher Pnet value of about
86.2 kJ/kg under maximum allowable evaporating pressure
1898.3 kPa, which is approximately 6% lower than Cyclohexane.
Moreover, Cyclopentane also presents high Pnet value of about
84.3 kJ/kg (at 3313.6 kPa), which is 8% lower than that of Cyclohexane. However, for some uids with high molecular complexity r,
the maximum Pnet values have been decreased at different levels
within the scope of the isentropic turbine efciencies restriction,
among which the Pnet value of Cyclohexane has fallen to
86.47 kJ/kg from 91.7 kJ/kg. The maximum Pnet values for the uids
considered within an acceptable isentropic turbine efciencies
range have been presented in Table 6.
The behavior of the exergy destruction rate is opposite. It decreases with relative pressure until a minimum value is obtained,
as shown in Fig. 10. This is mainly due to the entropy generation
decrease in evaporation process-the main contribution to the exergy destruction rate due to a great temperature difference existing
between the heat sources and the working uids considered in
the systems. As shown in Fig. 10, for linear Alkanes, exergy
destruction rate decreases with both the increase of the numbers
of carbon atom in chain and the rise of relative pressure, which
is also applicable to branched Alkanes and cyclic Alkanes. Different
from branched Alkanes, cyclic Alkanes present lower IORC value of
29.5 kW (at 3529.8 kPa) and 32.3 kW (at 2379.5 kPa) for Cyclohexane and Cyclopentane, which are 4.6% and 14.5% higher than that
of Decane respectively. Decane presents the lowest value of
28.2 kW (at 1898.3 kPa) among all the working uids considered.
However, the cases are quite different after the constraint is given
to limit the isentropic turbine efciencies to an acceptable range.
The minimum IORC values for some uids with high molecular complexity r have been increased to different extents. Although the
minimum IORC value is also achieved by Cyclohexane after the

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G. Shu et al. / Applied Energy 119 (2014) 204217

isentropic turbine efciencies are conned within an acceptable

range, it has increased from 29.5 kW to 31.11 kW. The minimum
values of IORC for uids considered within an acceptable isentropic
turbine efciencies range have been summarized in Table 6.
The exergy destruction rate reects, to a certain extent, energy
conversion performance for the systems considered, but the power
output performance cannot be covered. Exergy destruction factor
(EDF) is proposed in order to evaluate the energy conversion and
power output performance of the systems considered comprehensively. As shown in Fig. 11, EDF decreases with both the increase of
the numbers of carbon atom in chain and the rise of relative pressure for the considered three categories of working uids. The decrease trend of various working uids is obvious under low relative
pressures and becomes smooth near maximum live vapor pressure. There are only minor differences among them when the minimum values are reached for the majority of the working uids.
Cyclohexane presents the lowest EDF value of 1.16 (at
3529.8 kPa), owing to a relatively high power output performance
and low exergy destruction rate. In addition, Decane and Nonane
also present lower EDF values of 1.18 (at 1898.3 kPa) and 1.22
(at 2041.6 kPa), which are 1.7% and 5.2% higher than that of Cyclohexane respectively. In addition, after conning the isentropic turbine efciencies to an acceptable range, the distributions of EDF
are similar to that of IORC in Fig 10. The minimum EDF value is still
achieved by Cyclohexane, but it has been increased from 1.16 to 1.296. The optimal values of EDF for uids considered within
acceptable isentropic turbine efciencies range have been given
in Table 6.
Through the above analysis, it is evident that the maximum value of Pnet and VFR, and the minimum value of IORC, EDF and SP appear when evaporating pressures reach the maximum values
(Pevap/Pmax = 1) for selected working uids. Table 5 reports the
main performance sequence of the uids under maximum relative
pressure (Pevap/Pmax = 1). It can be observed that the maximum
thermal efciency (g) of 19.32% and Pnet value of 91.68 kJ/kg and
the minimum EDF value of 1.157 are achieved by Cyclohexane,
while the maximum thermal efciency (g) and Pnet value decrease
to 18.13% and 86.17 kJ/kg respectively for Decane. From Table 5 it
can also be observed that minimum values are obtained by Decane
in the case of IORC = 28.24 kW. However, it should be noted
that Decane reaches the maximum values in the cases of
VFR = 2590.73 and SP = 1.168 m respectively. The minimum values
(the optimal value in these cases) of 14.55 for VFR and 0.128 m for
SP are achieved by Isopentane. Simultaneously, a large deviation
can be observed in VFR and SP among different working uids.
Whether a working uid is the optimized one or not depends on
the trade-off between different indicators.
In practice, the optimal value under the maximum relative
pressure Pevap/Pmax = 1 may fail to realize for some uids as the
VFR values are more than 50 under this pressure. The isentropic
turbine efciencies will be lower than 80% at this time if a single
stage expander is employed. So it is more rational and practical

to discuss the performances when the values of VFR are no more

than 50. Performance sequence of the working uids at VFR = 50
has been given in Table 6. Compared with linear Alkanes and
branched Alkanes, cyclic Alkanes have obvious advantage in thermal efciency (g), Pnet, IORC and EDF. The maximum thermal efciency (g) and Pnet value are 18.20% and 86.47 kJ/kg respectively
for Cyclohexane. And the minimum IORC value of 31.11 kW and
EDF value of 1.296 are also obtained by Cyclohexane. However,
the performances of linear Alkanes, especially for the uids of high
molecular complexity r, have been signicantly degraded when
the isentropic turbine efciencies are conned to the acceptable range. For SP, cyclic Alkanes are wholly at medium or lower
level while linear Alkanes reach the medium and even high level
for some uids with high molecular complexity r. On the whole,
cyclic Alkanes have more outstanding performance than other uids after the isentropic turbine efciencies are limited to an acceptable range.
4.2. The inuence of molecular complexity
Fig. 12 shows SP and VFR of the ORC with molecular complexity
of working uids considered, where Tevap = 170 C and Tcond = 60 C
are assumed for WHR cycle. Working uids are arranged in the
transverse coordinate axis in ascending order of r in the gure. It
can be seen that SP and VFR are quite variable and strictly dependent on the working uids considered. In the cases analyzed here,
SP varies from a minimum of about 0.13, in correspondence with
higher values of r, to about 1.3 and the variety of VFR takes place
within a wide range from about 13 for Cyclopentane to about 58
for Decane. Based on all performance factors discussed in this section, higher r results in higher SP and VFR values. The two exceptions to this rule are Cyclohexane and Cyclopentane. This means
that large turbine size and volume ow ratio will be required in
ORC system employing the working uids of high r if the working
uids are not cyclic Alkanes.
It has been made clear from above-mentioned standpoint that
efciencies higher than 80% can only be achieved when VFR is less
than 50 for single stage axial turbines. For given Fig. 12, from the
VFR respect, target efciency (higher than 80%) of turbine can only
be realized when r is below 92. Among the working uids given in
Table 1, only Decane (VFR = 58) dissatises this limit under the
aforementioned conditions. Summarizing the impact of r on SP
and VFR, less complex uids are preferred, since such uids result
in acceptable turbine efciency and low SP and VFR values, so that
the use of simple expanders such as single-stage turbines will be
allowed.
4.3. The energy and exergy distributions
The major purpose to investigate the energy distribution of engine exhaust gases is to determine energy grade and energy distribution. Energy grade, on which energy conversion performance

Table 5
Performance sequence of the working uids under the maximum relative pressure Pevap/Pmax = 1.
Working uids

g (%)

Pnet (kJ/kg)

IORC (kW)

EDF ()

VFR ()

SP (m)

Pevap (kPa)

Tevap (C)

Pcond (kPa)

Decane
Nonane
Octane
Heptane
Cyclohexane
Hexane
Isohexane
Cyclopentane
Pentane
Isopentane

18.13
17.95
17.67
17.10
19.32
16.09
15.31
17.78
14.08
13.32

86.17
85.34
83.97
81.22
91.68
76.38
72.68
84.34
66.82
63.22

28.24
29.01
30.01
31.40
29.46
33.38
34.33
32.30
36.64
37.60

1.180
1.224
1.287
1.392
1.157
1.574
1.701
1.379
1.974
2.142

2590.73
1012.62
404.61
157.44
122.46
54.18
42.95
32.76
17.98
14.55

1.168
0.761
0.497
0.325
0.250
0.213
0.189
0.165
0.142
0.128

1898.3
2041.6
2200.3
2379.5
3529.8
2499.0
2526.7
3313.6
2581.4
2632.8

337.1
313.4
287.0
257.1
269.0
221.3
212.0
215.3
179.3
171.1

1.52
3.98
10.45
28.04
51.90
76.42
100.64
142.44
214.54
273.13

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G. Shu et al. / Applied Energy 119 (2014) 204217

Table 6
Performance sequence of the working uids at VFR = 50.

Working uids

g (%)

Pnet (kJ/kg)

IORC (kW)

EDF ()

VFR ()

SP (m)

Pevap (kPa)

Tevap (C)

Pcond (kPa)

Decane
Nonane
Octane
Heptane
Cyclohexane
Hexane
Isohexaneb
Cyclopentaneb
Pentaneb
Isopentaneb

13.73
14.49
15.28
15.87
18.20
16.00
15.31
17.78
14.08
13.32

65.36
68.97
72.70
75.29
86.47
75.99
72.68
84.34
66.82
63.22

36.6
35.45
34.26
33.47
31.11
33.49
34.33
32.30
36.64
37.60

2.017
1.851
1.700
1.600
1.296
1.587
1.701
1.379
1.974
2.142

50
50
50
50
50
50
42.95
32.76
17.98
14.55

1.257
0.806
0.518
0.332
0.255
0.214
0.189
0.165
0.142
0.128

80.0
199.0
492.6
1142.8
2389.1
2045.6
2526.7
3313.6
2581.4
2632.8

165.1
178.2
194.0
209.1
228.0
218.3
212.0
215.3
179.3
171.1

1.52
3.98
10.45
28.04
51.90
76.42
100.64
142.44
214.54
273.13

VFR < 50, performance sequence of the working uid at maximum achievable value of VFR.

depends, is determined by exergy content in the energy with the

above analysis. Fig. 13 reveals the energy distribution of the hot
source (engine exhaust gases) and the improvement of BSFC before
and after the integration of the bottoming ORC with the DE for the
working uids considered. It is evident that the heat energy absorbed by the ORC system accounts for about 73.5% from exhaust
gases and, in which, the exergy occupies about 46.2% of this part
of the energy. The above data indicate that the energy absorbed
by an ORC system takes on a high energy grade. The recovery system converts a part of this exergy into turbine work, with conversion quantity depending on the adopted working uids. The
conversion capacities (the ratio of turbine work to the exergy in exhaust gases) of cyclic Alkanes (43.8% for Cyclohexane, 40.7% for
Cyclopentane) are higher than that of linear Alkanes (40.1% for
Decane, 39.9% for Nonane) and branched Alkanes (35% for Isohexane, 31.2% for Isopentane). The pump power occupies only a small
portion of turbine work depending on the adopted working uids.
It is evident that high pump work will be required for the working
uids with less numbers of carbon atoms. After the heat is absorbed by the ORC system, exhaust gases still contained a portion
of available energy, accounting for about 25% of the total energy.
However, this part of the energy represents a very low energy

grade since the exergy occupies only about 4% of the energy, and
its utilization value is still low at present.
As shown in Fig. 13, the BSFC improvement for DE-ORC combined systems is signicant compared with the original engine,
and there are different improvement degrees depending on the
adopted working uids. Cyclohexane presents the greatest BSFC
improvement, about 10%, due to high power output. In addition,
due to relatively high power output and low pump power consumption, Decane and Nonane also present higher BSFC improvement, about 9.2% for Decane and 9.1% for Nonane. Isopentane
shows the lowest BSFC improvement, about 6.9%, because of low
power output and high pump power consumption. However, the
cases are quite different after the limited condition is given to limit
the isentropic turbine efciencies to an acceptable range. The maximum BSFC improvements of DE-ORC combined systems for some
uids with high molecular complexity r have been decreased at
different levels, among which the maximum BSFC improvement
of Cyclohexane has fallen to 9.3% from 10%. This is mainly due to
the facts that the rapid decrease of pressure ratios will be observed
with the sharp drop from the peak of evaporation pressures, especially for some uids with high molecular complexity r, after the
isentropic turbine efciencies are conned to an acceptable range.
The performance sequence of different working uids considered in the present paper based on four different screening criteria
are shown in Table 7. The four different screening criteria are
dened as follows:

RD1 Pnet;max  Pnet =Pnet;max  100%

RD2 IORC;min  IORC =IORC;min  100%
RD3 EDFmin  EDF=EDFmin  100%

20

RD4 SPmin  SP=SPmin  100%

Fig. 13. The energy ow distribution and BSFC with different working uids where
Pevap/Pmax = 1.

As shown in Table 7, each uid has great discrepancies in the four

screening criteria. There is relatively minor deviation for net power
output per unit mass ow rate of hot exhaust for the working uids
under each optimized operating condition. The greatest deviation
value is 31%. Cyclohexane performs best among all the uids
according to the rst screening criterion. Moreover, the greatest
deviation value of EDF value of the working uids under each optimized operation condition is 85.1%, and Cyclohexane shows better
performance than the other uids. With regard to the second
screening criterion, the greatest deviation is 33.1% in terms of the
total exergy destruction rate of uids under each optimized operating condition, and Decane shows better performance than the other
uids in this case. However, Decane shows the worst performance
in terms of SP under optimized operating condition, and the greatest deviation value is as high as 812.2%. Furthermore, the condensing pressures are less than 5 kPa for Decane and Nonane at the
corresponding condensing temperature of 60 C. Based on the
fourth screening criterion, Isopentane, which contains the least
numbers of carbon atoms in chain, presents the optimized value

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G. Shu et al. / Applied Energy 119 (2014) 204217

Table 7
Performance sequence of different working uids according to four different screening criteria.
Pnet

Pe (kPa)

RD1

IORC

Pe (kPa)

RD2

EDF

Pe (kPa)

RD3

SP

Pe (kPa)

RD4

Cyclohexane
Decane
Nonane
Cyclopentane
Octane
Heptane
Hexane
Isohexane
Pentane
Isopentane

3529.8
1898.3
2041.6
3313.6
2200.3
2379.5
2499
2526.7
2581.4
2632.8

0.0
6.0
6.9
8.0
8.4
11.4
16.7
20.7
27.1
31.0

Decane
Nonane
Cyclohexane
Octane
Heptane
Cyclopentane
Hexane
Isohexane
Pentane
Isopentane

1898.3
2041.6
3529.8
2200.3
2379.5
3313.6
2499
2526.7
2581.4
2632.8

0.0
2.7
4.3
6.3
11.2
14.4
18.2
21.6
29.7
33.1

Cyclohexane
Decane
Nonane
Octane
Cyclopentane
Heptane
Hexane
Isohexane
Pentane
Isopentane

3529.8
1898.3
2041.6
2200.3
3313.6
2379.5
2499
2526.7
2581.4
2632.8

0
2.0
5.8
11.2
19.2
20.3
36.0
47.0
70.6
85.1

Isopentane
Pentane
Cyclopentane
Isohexane
Hexane
Cyclohexane
Heptane
Octane
Nonane
Decane

2632.8
2581.4
3313.6
2526.7
2499
3529.8
2379.5
2200.3
2041.6
1898.3

0
10.5
28.7
48.0
66.6
95.3
153.5
288.1
494.1
812.2

in this case. But Isopentane shows the worst performance in other

situations. Although the optimized uids are not the same according to different screening criteria, the cyclic Alkanes Cyclohexane
and Cyclopentane are considered the most suitable working uids
due to relatively high power output, reasonable condensing
pressure, relatively low irreversibility and SP based on the aforementioned results. Also, Heptane and Hexane can be considered
as the suitable working uids when considering all indicators
comprehensively.

4.4. Comparison of ORC and steam cycle

Water is a typical wet uid that is characterized by a negative
slope of the saturated vapor curve on a Ts diagram. This implies
that the superheating of the vapor is required in a steam cycle to
avoid moisture formation in the steam turbine. Therefore, a much
higher evaporation temperature must be achieved in a conventional steam cycle. Much higher requirements are imposed to temperature level of the waste heat source that limits the maximum
superheating temperature and the evaporation pressure of the
steam cycle. In this study, the waste heat temperature (exhaust
temperature) is over 500 C. Thus the steam cycle is available
in a certain range. A contrastive analysis of ORC and steam cycle is made under the same initial and boundary conditions (same
heat source/sink temperatures and other setting conditions). The
difference is that the essential condition of the superheating must
be achieved to keep the steam in the superheated vapor region
after expansion. The Cyclohexane is selected from Alkane-based

working uids to be compared with water owing to its good overall performance.
As shown in Fig. 14, the steam offers better efciency than that of
Cyclohexane over the whole relative pressure range. This is mainly because the higher level of temperature (highest temperature of
482 C for steam compared to 269 C for Cyclohexane) can be
achieved by steam due to superheating. The total irreversibility of
steam has a similar variation trend to that of Cyclohexane with the
increase of relative pressure. But the steam can provide less total
irreversibility than that of Cyclohexane under higher relative pressure. With the increasing of superheating temperature, better
temperature matching between heat carrier (exhaust gas) and steam
can be achieved. There is a very similar trend of SP between Cyclohexane and steam with relative pressure. However, the SP of steam
is about two times higher than that of the Cyclohexane. This means
a larger turbine will be required for steam cycle.
The above analysis indicates that steam has more advantages in
thermal efciency than Cyclohexane in the current conditions, but
bulkier and more expensive turbines must be employed for steam
at the same time. The higher thermal efciency of steam is mainly caused by the higher superheating temperature. So it has a high
demand for the quantity and quality of energy, which makes it
more suitable for high-temperature large-scale applications. However, since the superheated vapor has the low heat exchange coefcients, very large and expensive heat exchangers must be
employed in this case [28]. Furthermore, the rated operating conditions are assumed for the adopted engine in this work, but the
diesel engine more often operates in transient and variable
working conditions. At some engine operating points, the exhaust

Fig. 14. Performance comparison between Cyclohexane and water with relative pressure.

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G. Shu et al. / Applied Energy 119 (2014) 204217

temperature is below 500 C, or even lower than 300 C. Under this

situation, the waste heat (exhaust gas) temperature is not suitable for operating the steam cycle. For Alkane-based ORCs, however, good performances still can be achieved by them. From a
technical and economic point of view, Alkane-based ORCs may
be more attractive than conventional steam cycles, specically
for DE waste gas heat recovery.

follow if heat conduction oil is introduced. The entity of these

losses will be numerically quantied by a detailed exergy analysis.
A detailed economy analysis model for Alkane-based power generation system will be established in future work. In summary, discussions and conclusions of this paper are helpful in selecting
proper working uids for the DE-ORC system and in determining
optimal system operation conditions.
Acknowledgements

5. Conclusions
In this study, Alkane-based working uids are employed for the
ORC processes. The processes operate at different evaporating temperatures and under different pressures to recover waste heat energy from high-temperature exhaust gases where a commercial
diesel generator is operated under a rating condition. The system
parameters of the ORC using different working uids are optimized
with six indicators in this paper. Moreover, the inuence of molecular complexity on VFR and SP are analyzed. And the energy distributions of engine exhaust gases and BSFC improvement after
combining a DE with a bottoming ORC are also discussed. The
following conclusions can be drawn based on the performance
investigation and parametric analysis carried out in the present
work:
1. The optimized uids are not the same in terms of different indicators. However, on the whole, the uids with more number of
carbon atoms in chain (e.g., Decane or Nonane) have better
thermal efciency, power output performance and lower exergy
destruction rate. The exceptions to this rule are cyclic Alkanes.
They show good performance in thermal efciency, power output performance and exergy destruction rate, while requiring
small turbine sizes.
2. Molecular complexity has signicant and positive impact on SP
and VFR. That is, greater molecular complexity results in higher
values of SP and VFR if they are not cyclic Alkanes. Less complex
uids are preferred in this case, since they result in acceptable
turbine efciency with relatively low values of SP and VFR.
Therefore, using simple expanders such as single-stage turbines
is allowed.
3. Heat energy absorbed by the ORC system from exhaust gases
has a high energy grade because of its high content of exergy.
The highest power output is obtained by Cyclohexane, which
results in prominent BSFC improvement, about 10% for DEORC combined systems, compared with the original engine.
4. In comprehensive consideration, cyclic Alkanes Cyclohexane
and Cyclopentane are considered as the most suitable working
uids due to relatively high power output, reasonable condensing pressure, relatively low irreversibility and SP values.
5. Although steam has more advantages in thermal efciency in
the current conditions, from a technical and economic point
of view, Alkane-based ORCs may be more attractive than conventional steam cycles, specically for DE waste gas heat
recovery.
Alkanes show favorable performance based on the above analysis. However, such drawbacks as higher ammability of the uids
and their toxicity also have to be taken into account when Alkanebased working uids are used. The two necessary conditions of
good sealing and excellent ventilation must be satised in order
to ensure safe operation for Alkane-based WHR systems if the proposed plants are applied in practical engineering. In future works,
heat transfer oil may be used to operate between engine exhaust
gases and Alkane-based working uids in order to improve system
stability and security. However, additional irreversibility of heat
exchange process, which makes inferior system efciency, will

The authors would like to acknowledge the National Natural

Science Foundation of China (No. 51206117), the National Basic Research Program of China (973 Program) (No. 2011CB707201), and
the Natural Science Foundation of Tianjin (No. 12JCQNJC04400)
for Grants and supports.
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