MAN ORC SIVI SEÇİMİ Working - Fluid - Selection - For - The - Organic - Rankine - Cy

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Working fluid selection for the Organic Rankine Cycle (ORC) exhaust heat recovery of an
internal combustion engine power plant
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2016 IOP Conf. Ser.: Mater. Sci. Eng. 161 012087
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IOP Conf. Series: Materials Science and Engineering 161 (2016) 012087 doi:10.1088/1757-899X/161/1/012087
Working fluid selection for the Organic Rankine Cycle (ORC)

exhaust heat recovery of an internal combustion engine power
plant
S Douvartzides and I Karmalis

Laboratory of Internal Combustion Engines, Department of Mechanical and Industrial
Engineering, Technical Education Institute (TEI) of Western Macedonia, Koila-
Kozani, Greece
E-mail: [email protected]; [email protected]
Abstract. Organic Rankine cycle technology is capable to efficiently convert low-grade heat
into useful mechanical power. In the present investigation such a cycle is used for the recovery
of heat from the exhaust gases of a four stroke V18 MAN 51/60DF internal combustion engine
power plant operating with natural gas. Design is focused on the selection of the appropriate
working fluid of the Rankine cycle in terms of thermodynamic, environmental and safety
criteria. 37 candidate fluids have been considered and all Rankine cycles examined were
subcritical. The thermodynamic analysis of all fluids has been comparatively undertaken and
the effect of key operation conditions such as the evaporation pressure and the superheating
temperature was taken into account. By appropriately selecting the working fluid and the
Rankine cycle operation conditions the overall plant efficiency was improved by 5.52% and
fuel consumption was reduced by 12.69%.
1. Introduction
Increased fuel prices and environmental pollution concerns force research interest on the enhancement
of the efficiency of existing power systems and the discovery of solutions leading to rational energy
utilization. For a typical internal combustion engine (ICE), approximately 30% of the chemical energy
of the fuel is brought into the environment by the exhaust gases. This energy can be usefully exploited
by an appropriate waste heat recovery system leading in an overall efficiency improvement.
There are three typical approaches of ICE waste heat recovery including thermoelectric generation
[1, 2], electrical or mechanical turbo compounding [3] and steam or organic Rankine cycles. The
organic Rankine cycle (ORC) is a technology for low-grade heat to power conversion. It is similar to
the conventional steam Rankine cycle used in power generation plants, but steam is replaced by an
appropriate organic fluid. Hence, ORC is capable to realize more efficient expansion at low power and
show better thermodynamic performance at low temperatures. Such cycles have been successfully
applied in waste heat recovery, biomass energy plants and geothermal or solar energy applications [4-
6].
Research on organic Rankine cycles for ICE waste heat recovery has started after the oil crisis of
the '70s. BMW, Honda and Cummins have installed ORC waste heat recovery systems in specific car
or truck models and reported overall efficiency improvements in the range of 4-10% [6-8]. In these
cases water, ethanol and R245fa have been selected as working fluids and heat was recovered from
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both exhaust gas and engine cooling systems. Similar results have been reported in numerous research
studies [9-27] using a large variety of other organic fluids. Hung et al. [24] demonstrated that the
major properties affecting the system performance included latent heat and specific heat of liquid and
vapor. Chen et al. [25] and Maizza and Maizza [26] suggested that fluids with high latent heat and
low specific heat are preferable while Yamamoto et al. [27] suggested that low latent heat fluids are
preferable.
In the present investigation ORC exhaust heat recovery is applied in a large Diesel-natural gas dual
fuel engine typically used for ship propulsion and power plant applications. This is the four stroke
turbocharged V18 MAN 51/60 DF engine with maximum brake power of 17550 kW at 500 rpm [28,
29]. Exhaust combustion gases have been considered as the only heat source of the Rankine cycle and
numerous candidate working fluids were compared upon thermodynamic, environmental and safety
criteria.
2. Engine and fuel characteristics

Exhaust gas ORC heat recovery is considered in a V18 MAN 51/60DF engine, shown in Fig. 1. This is
a natural gas-diesel dual fuel engine equipped with a MAN TCA77 (four stroke version) turbocharger.
Engine and turbocharger characteristics are summarized in Table 1.
Figure 1. The V18 MAN 51/60DF (dual fuel) engine.
Table 1. 18 cylinder MAN 51/60DF engine characteristics [28, 29]

Parameter Value
Number of cylinders 18
Cylinder bore 510 mm
Piston stroke 600 mm
Displacement per cylinder 122.5 lt
Compression ratio 13.3
Vee angle 50o
Turbocharger type MAN TCA 77 (four stroke version)[23]
Turbocharger pressure ratio 5.5
Maximum engine speed 500 rpm
Maximum engine power 17550 kW at 500 rpm
2
The real cycle analysis of the engine has been conducted elsewhere [30] and operation conditions
are summarized in Table 2. The engine is considered to steadily operate with either Diesel or natural
gas fuel at the maximum speed of 500 rpm and at full load. Maximum temperature of the exhaust
gases was estimated about 1128 K for natural gas mode. This value is about 30K higher than the
maximum temperature of the Diesel cycle and for consistency natural gas operation will be
considered. Exhaust gas temperature after the turbocharger is 633K as given by the MAN
manufacturer [28]. Exhaust gas composition is given in Table 3.
Table 2. Calculated operated conditions for the Diesel and Natural Gas operation modes.
Engine speed is at the maximum value of 500 rpm [30].
Parameter Diesel mode NG mode
Ambient temperature, 𝑇0 (K) 293
Ambient pressure, 𝑝0 (MPa) 0.1
Turbocharger outlet temperature, 𝑇𝐶 (K) 517.63
Turbocharger outlet pressure, 𝑝𝐶 (MPa) 0.55
Fuel mass flow rate, 𝑚𝑓 (kg/h) 4030.66 3412.82
Air mass flow rate, 𝑚𝑎 (kg/h) 116332.9 116336.2
Fraction of residual gases, 𝑥𝑟 0.0436 0.0425
Temperature of residual gases, 𝑇𝑟 (K) 825 848
Temperature at the end of intake stroke, 𝑇1 (K) 535.83 536.47
Pressure at the end of intake stroke, 𝑝1 (MPa) 0.522 0.522
Temperature at the beginning of combustion, 𝑇2 (K) 1332.66 1334.09
Pressure at the beginning of combustion, 𝑝2 (MPa) 17.29 17.29
Temperature at the end of combustion, 𝑇3 (K) 2284.35 2430.93
Pressure at the end of combustion, 𝑝3 (MPa) 25.93 26.82
Temperature at the end of expansion, 𝑇3 (K) 1095.54 1128.05
Pressure at the end of expansion, 𝑝3 (MPa) 1.09 1.10
Exhaust gas temperature at the exit of the turbocharger, 𝑇I (K) 631[28] 633[28]
Brake (real) power, 𝑃𝑏 (kW) 17473.91 17923.89
Brake (real) thermal efficiency, 𝜂𝑡𝑕 (%) 39.01 37.96
Table 3. Composition of the engine burned mixture for natural gas mode and λ=2 [30].
Product Molar fraction
CO2 0.050522
H2O(g) 0.098183
CO 0
H2 0
O2 0.099613
N2 0.751682
Moles of product mixture: 𝑁𝑃 1
In the natural gas mode, the engine operates according to a lean-burn Otto combustion cycle.
Natural gas is considered with an approximate composition of 95% mol CH4, 4% mol C2H6, 1% mol
C3H8 and with a lower heating value (LHV) of 49.8MJ/kg. Combustion typically takes place with lean
fuel mixtures and the analysis was conducted assuming a lambda λ ratio equal to 2 [30]. The pre-
mixed lean gas–air mixture is ignited by the compression ignition of a small quantity of marine diesel
pilot fuel injected into the main combustion space. A pilot injection of less than 1% of the normal
liquid fuel quantity ensures very low NOx emissions in gas mode [31].
3
3. Rankine cycle analysis

In the present study, exhaust gas energy is exploited for power generation in a bottoming Rankine
cycle. An ORC system consists of a working fluid pump, an evaporator, an organic turbine or
expander and a condenser, as shown in Figure 2. Such a cycle consists of the following four steady
state processes:
 Process 1-2: compression of liquid fluid in a pump.
 Process 2-3: isobaric heat addition to the fluid in an exhaust gas heat recovery exchanger.
 Process 3-4: expansion in a turbine or expander.
 Process 4-1: isobaric heat rejection in a condenser.
These four processes may form a simple Rankine cycle or a superheated Rankine sycle as shown in
the 𝑇-𝑠 diagrams of the Figure 3. In the former case heat addition process 2-3 evaporates the fluid up
to the condition of saturated vapor while in the latter case heat addition proceeds further to provide
high temperature superheated vapor at 3'.
Figure 2. Schematic diagram of the ORC exhaust heat recovery system.
Figure 3. T-s diagrams of a simple (1-2-3-4-1) and a superheated (1-2-3'-4'-1) Rankine cycle.
4
Process 1-2 is carried out by a pump which receives the working fluid in the state of saturated
liquid at the pressure of the condenser and compress it to the pressure of the isobaric heat recovery
exchanger. Deviation from ideal isentropic compression is taken into account by the pump isentropic
efficiency
𝑤𝑝𝑠 𝑕2𝑠 − 𝑕1
𝜂𝑝 = =
𝑤𝑝𝑎 𝑕2 − 𝑕1
where 𝑤𝑝𝑠 is the ideal isentropic specific pump work, 𝑤𝑝𝑎 is the actual non-isentropic specific pump
work, 𝑕1 is the specific enthalpy of the saturated liquid at the inlet of the pump, 𝑕2 is the specific
enthalpy of the compressed liquid at the exit of the actual pump and 𝑕2𝑠 is the specific enthalpy of the
compressed liquid at the exit of the ideal isentropic pump. The pressure of the condenser has been
considered 0.1MPa and the pressure of the heat exchanger has been considered in all base cases 3MPa.
The isentropic pump efficiency was taken 80%.
Heat is recovered from the engine exhaust gases inside an insulated isobaric heat recovery
exchanger. This results in the evaporation of the organic fluid which is taken at the saturation or
superheated state 3. The rate of heat recovery by the exhaust gases is given by
𝑄𝑟 = 𝑚𝐺 𝑕I − 𝑕II ≈ 𝑚𝐺 𝑐𝑣,𝑇I 𝑇I − 𝑚𝐺 𝑐𝑣,𝑇II 𝑇II
where 𝑚𝐺 is the mass flow rate of the combustion gases. Subscripts "I" and "II" correspond to the
states of the exhaust gases before and after the heat recovery process, respectively. If sulfur is present
in the fuel it transforms into sulfur dioxide during combustion and later into sulfur trioxide through
further oxidation. Suflur trioxide can then combine with steam vapor to form corrosive sulfuric acid if
the temperature of the gas effluents is lower than the sulfuric acid dew point. Thus, 𝑇II at the outlet of
the heat recovery exchanger must be kept above the limiting value of 373.15K. In the present study,
temperature 𝑇I is considered 633K as suggested by the MAN manufacturer [28] and temperature 𝑇II is
assumed 378K. These values are kept invariable to set a constant temperature difference for all
comparative fluid cases. Since the heat exchanger is insulated, heat losses are negligible and all heat
recovered is absorbed by the organic fluid. That is,
𝑄𝑟 = 𝑚𝐹 𝑕3 − 𝑕2
where 𝑚𝐹 is the mass flow rate of the organic fluid.

The superheated organic fluid expands into a turbine to produce work. Expansion takes place in a
single stage from the pressure of the recovery exchanger to the pressure of the condenser. Deviation
from ideal isentropic expansion is taken into account by the turbine isentropic efficiency
𝑤𝑡𝑎 𝑕3 − 𝑕4
𝜂𝑡 = =
𝑤𝑡𝑠 𝑕3 − 𝑕4𝑠
where 𝑤𝑡𝑎 is the actual non-isentropic specific turbine work, 𝑤𝑡𝑠 is the ideal isentropic specific turbine
work, 𝑕3 is the specific enthalpy of the superheated fluid at the inlet of the turbine, 𝑕4 is the specific
enthalpy of the expanded fluid at the exit of the actual turbine and 𝑕4𝑠 is the specific enthalpy of the
expanded fluid at the exit of the ideal isentropic turbine. The turbine isentropic efficiency was
considered 80%. The fluid leaving the turbine may be either superheated or a saturated gas-liquid
mixture. In the latter case, the percentage of gas in the mixture is given by the mixture quality 𝑥 as
5
𝑕4 − 𝑕1
𝑥=
𝑕𝑓𝑔
where 𝑕𝑓𝑔 is the latent heat of evaporation at the pressure of the condenser. Quality 𝑥 varies between 0
and 1. Finally, the expanded fluid returns at the initial state 1 by passing through the condenser. Heat
rejected during condensation is given by
𝑄𝑜𝑢𝑡 = 𝑚𝐹 𝑕4 − 𝑕1
The net power produced by the Rankine cycle is calculated as
𝑃ORC = 𝑚𝐹 𝑤𝑡𝑎 − 𝑤𝑝𝑎 = 𝑄𝑟 − 𝑄𝑜𝑢𝑡
and the thermal efficiency of the Rankine cycle is given as
𝑃ORC 𝑄𝑜𝑢𝑡
𝜂ORC = =1−
𝑄𝑟 𝑄𝑟
The overall efficiency of the ICE-ORC power plant is then calculated as
𝑃𝑏 + 𝑃ORC
𝜂=
𝑚𝑓 LHV
where 𝑃𝑏 is the brake power of the engine taken as 17923.89 kW, 𝑚𝑓 is the mass flow rate of natural
gas calculated as 3412.82 kg/h and LHV = 49.8 MJ/kg is the lower heating value of natural gas.
Efficiency improvement is finally given by
𝛥𝜂 = 𝜂 − 𝜂𝑒
where 𝜂𝑒 is the thermal efficiency of the engine which has been calculated 37.96% [30].
4. Working fluids
The working fluid selection is of key importance on the thermal performance of the ORC recovery
system. Generally, the working fluids can be classified into the following three categories:
 wet fluids,
 dry fluids, and
 isentropic fluids.
This classification is based on the slope 𝑑𝑇/𝑑𝑠 of the saturation vapor curve of each fluid in a 𝑇-𝑠
diagram, as shown in Figure 3. The type of the working fuel can be determined through the following
simplified equation [22]
𝑟𝐻 𝑛𝑇
𝐶𝑝 1−𝑇𝑟𝐻 + 1
𝐸= − ΔΗ𝑣𝑎𝑝
𝑇𝐻 𝑇𝐻2
where 𝐸 is the reciprocal of the saturation vapor curve slope (𝑑𝑠/𝑑𝑇), 𝐶𝑝 is the specific heat of the
fluid at constant pressure, 𝑇𝐻 is the evaporation temperature of the fluid, 𝑛 is suggested to be 0.375 or
0.385 by Poling et. al. [32], 𝑇𝑟𝐻 is the reduced evaporation temperature (𝑇𝑟𝐻 = 𝑇𝐻 /𝑇𝑐𝑟 , where 𝑇𝑐𝑟 is
the critical temperature), and ΔΗ𝑣𝑎𝑝 is the latent heat of vaporization. Fluids having 𝐸 > 0 have a
6
negative saturation vapor curve (𝑑𝑇/𝑑𝑠 < 0) and are classified as wet fluids. Instead, fluids having
𝐸 < 0 have a positive saturation vapor curve (𝑑𝑇/𝑑𝑠 > 0) and are classified as dry fluids. Finally,
fluids having 𝐸 ≈ 0 have an almost vertical saturation vapor curve and are classified as isentropic.
Conventional Rankine power plants usually employ water as working fluid. Water has a small
molecular weight (18 kg/kmol), a high boiling point of 100oC at atmospheric pressure and a critical
temperature of 347oC. It is chemically very stable, cheap, abundant, non-toxic and environmentally
friendly but also has some disadvantages. Water is a typical wet fluid and when it is used in Rankine
cycles requires high superheating to avoid condensation and erosion of the turbine blades due to the
presence of liquid at the final stages of expansion. Steam turbines are also complex and expensive as
they require to handle large steam volumes at the turbine exit. Due to these drawbacks water and other
wet fluids are suitable only in high temperature applications like in plants for central power
generation. In ORC recovery systems capturing heat from low-grade sources dry or isentropic organic
fluids are suggested.
Figure 4.Typical T-s diagrams of dry, wet and isentropic fluids. Classifications is based on the slope
of the saturation vapor curve.
4.1. Thermodynamic selection criteria

In terms of thermodynamics, appropriate fuels are usually those having high latent heats, high density
and low specific heats [25, 26]. Higher latent heats are found to provide higher unit work output
during expansion and higher densities are found to provide the same power outputs with smaller sized
equipment. In the present study the thermodynamic comparison of 37 candidate fluids was conducted
considering the same operation conditions of the V18 MAN 51/60DF exhaust heat recovery Rankine
cycle described earlier. The most important thermodynamic properties of these fluids are summarized
in Table 4. All selected fluids have critical pressure above 3MPa and therefore all Rankine cycles
considered are subcritical.
Table 4. Thermodynamic properties of various fluids [33-37].

Latent heat Critical Critical
ASHRAE MW Type
Substance Name of temperature pressure
Code (kg/kmol) of fluid
evaporation (K) (MPa)
7
at 0.1MPa
(kJ/kg)
R11 Trichloromonofluoromethane 137.37 181.49 471.11 4.4076 Isentropic
R12 Dichlorodifluoromethane 120.91 166.3 385.12 4.1361 Isentropic
R13 Chlorotrifluoromethane 104.46 149.47 302 3.879 Wet
R14 Tetrafluoromethane 88.01 134.54 227.51 3.75 Wet
R21 Dichlorofluoromethane 102.92 217.76 451.48 5.1812 Wet
R22 Chlorodifluoromethane 86.468 233.92 369.295 4.99 Wet
R23 Trifluoromethane 70.01 239.552 299.293 4.832 Wet
R32 Difluoromethane 52.02 382.14 351.255 5.782 Wet
R41 Fluoromethane 34.03 489.164 317.28 5.897 Wet
R113 1,1,2-Trichloro-1,2,2-Trifluoroethane 187.38 144.45 487.21 3.3922 Dry
R114 1,2-Dichloro-1,1,2,2-Tetrafluoroethane 170.92 136.06 418.83 3.257 Dry
R115 Chloropentafluoroethane 154.47 116.49 353.1 3.12 Isentropic
R116 Hexafluoroethane 138.02 117.09 293.03 3.048 Wet
R123 2,2-Dichloro-1,1,1-Trifluoroethane 152.93 170.35 456.831 3.6618 Dry
R124 1-Chloro-1,2,2,2-Tetrafluoroethane 136.5 165.99 395.425 3.6242 Wet
R125 Pentafluoroethane 120 164.25 339.173 3.6177 Isentropic
R134a 1,1,1,2-Tetrafluoroethane 102.03 217.16 374.21 4.0592 Isentropic
R141b 1,1-Dichloro-1-Fluoroethane 116.9 222.88 477.5 4.212 Dry
R142b 1-Chloro-1,1-Difluoroethane 100.5 223.43 410.26 4.055 Isentropic
R143a 1,1,1-Trifluoroethane 84.04 226.82 345.857 3.761 Isentropic
R152a 1,1-Difluoroethane 66.05 330.18 386.411 4.5167 Wet
R236ea 1,1,1,2,3,3-Hexafluoropropane 152 165.32 412.44 3.5019 Dry
R236fa 1,1,1,3,3,3-Hexafluoropropane 152 160.48 398.07 3.2 Dry
R245ca 1,1,2,2,3-Pentafluoropropane 134 201.15 447.57 3.925 Dry
R245fa 1,1,1,3,3-Pentafluoropropane 134 196.88 427.2 3.64 Dry
46.6% R125, 50% R134a, 3.4% R600 (by
R417a 106.75 360.19 4.036
weight) Isentropic
85.1% R125, 11.5 R134a, 3.4% R600a (by
R422a 113.6 344.9 3.747
weight) Isentropic
65.1% R125, 31.5% R134a, 3.4% R600a (by
R422d 109.94 352.71 3.903
weight) Isentropic
52.5% R134a, 47.5% R227ea
R423a 125.96 372.64 3.587
(by weight) Isentropic
R170 Ethane 30.07 489.79 305.33 4.8718 Wet
R290 Propane 44.09 426.232 369.825 4.2476 Isentropic
R600 Butane 58.12 386.01 425.125 3.796 Dry
R601 Pentane 72.1 357.89 469.7 3.37 Dry
Cyclohexane 84.16 356.3 553.64 4.075 Dry
Benzene 78.11 394.96 562.05 4.894 Dry
Toluene 92.14 361.007 591.75 4.1263 Dry
R717 Ammonia 17.02 1370.25 405.4 11.333 Wet
8
4.2. Environmental and safety selection criteria

Organic fluids may also be classified according to their chemical structure into the following groups:
 CFCs: Chlorofluorocarbons (CFCs) are organic compound that contain only carbon, chlorine
and fluorine. They are also known by the DuPont brand name "Freon". Such organic fluids are
R11, R12, R13, R113, R114 and R115.
 HCFCs: Hydrochlorofluorocarbons (HCFCs) contain carbon, chlorine, fluorine and hydrogen
atoms. Such organic fluids are R21, R22, R123, R124.
 HFCs: Hydrofluorocarbons (HFCs) contain carbon, fluorine and hydrogen atoms. Such
organic fluids are R23, R32, R41, R125, R134a, R143a, R152a, R236ea, R236fa, R245ca,
R245fa, R417a, R422a, R422d, R423a.
 PFCs: Perfluorocarbons (PFCs) or just fluorocarbons contain only atoms of carbon and
fluorine. Such organic fluids are R14 and R116.
 HCs: Hydrocarbons (HCs) are known substances containing only carbon and hydrogen atoms.
Such fluids are R170 (ethane), R290 (propane), R600 (butane), R601 (pentane), cyclohexane,
benzene and toluene.
In addition to the criteria for thermodynamic performance, selection criteria must also be considered
on the effect of the fluids to the natural environment and on the safety during handling and operation.
Environmental criteria are of major importance and focus on the effect of each fluid on ozone layer
depletion and global warming. Quantification of these effects takes place using the indices of Ozone
Depletion Potential (ODP) and Global Warming Potential (GWP). The ODP is a relative measure of
the degradation effect of each fluid on the ozone layer on the assumption that the ODP value for R11
is equal to 1. The GWP is a relative measure of how much heat the fluid gases trap in the atmosphere
compared to the heat absorbed by an equal amount of carbon dioxide. It is usually calculated over the
time interval of 100 years. Based on these definitions the higher the value of ODP or GWP the more
detrimental is the effect of the fluid on the ozone layer and global warming respectively. ODP values
are considered medium below about 0.1 and high above 0.1. GWP values are considered low below
150, medium between 150-2500 and high above 2500. ODP and GWP values are summarized for the
majority of the candidate fluids in Table 5.
An indication of the dangerousness of a fluid during handling and operation is provided by the
ASHRAE 34 safety classification standard. Accordingly, fluids are classified into two health effect
groups A and B as well as into three flammability groups 1, 2 and 3. Class A rating indicates no
evidence of toxicity below 400ppm while Class B indicates evidence of toxicity below this
concentration limit. On the other hand, class 1 indicates a fluid which does not propagate a flame in
open air under normal conditions, class 2 indicates a fluid that may propagate a flame in open air
under certain conditions and class 3 indicates a fluid of high flammability. Toxicity and flammability
classifications are jointly providing a fluid index which can be either A1, A2, A3, B1, B2 and B3.
Recently two new safety classes A2L and B2L have been added for fluids that are mildly flammable.
For the majority of the candidate fluids of the present investigation ASHRAE 34 classification is given
also in Table 5.
Table 5. Environmental parameters and safety classification of various fluids.

Global
Ozone ASHRAE
ASHRAE warming
Substance Name depletion 34 Safety
Code potential -
potential Group
100 yr
R11 Trichloromonofluoromethane 1 4750 A1
R12 Dichlorodifluoromethane 1 10900 A1
R13 Chlorotrifluoromethane 1.7 14400 A1
R14 Tetrafluoromethane 0 7390 A1
R21 Dichlorofluorometane 0.04 151 B1
9
R22 Chlorodifluoromethane 0.05 1810 A1

R23 Trifluoromethane 0 14800 A1
R32 Difluoromethane 0 675 A2L
R41 Fluoromethane 0
R113 1,1,2-Trichloro-1,2,2-Trifluoroethane 1 6130 A1
R114 1,2-Dichloro-1,1,2,2-Tetrafluoroethane 1 10000 A1
R115 Chloropentafluoroethane 0.44 7370 A1
R116 Hexafluoroethane 0 12200 A1
R123 2,2-Dichloro-1,1,1-Trifluoroethane 0.02 77 B1
R124 1-Chloro-1,2,2,2-Tetrafluoroethane 0.022 609 A1
R125 Pentafluoroethane 0 3500 A1
R134a 1,1,1,2-Tetrafluoroethane 0.055 1430 A1
R141b 1,1-Dichloro-1-Fluoroethane 0.12 725 A2
R142b 1-Chloro-1,1-Difluoroethane 0.12 2310 A2
R143a 1,1,1-Trifluoroethane 0 4470 A2L
R152a 1,1-Difluoroethane 0 124 A2
R236ea 1,1,1,2,3,3-Hexafluoropropane 0 1370
R236fa 1,1,1,3,3,3-Hexafluoropropane 0 9810 A1
R245ca 1,1,2,2,3-Pentafluoropropane 0 693
R245fa 1,1,1,3,3-Pentafluoropropane 0 1030 B1
R417a 46.6% R125, 50% R134a, 3.4% R600 (by weight) 0 2346 A1
R422a 85.1% R125, 11.5 R134a, 3.4% R600a (by weight) 0 3143 A1
R422d 65.1% R125, 31.5% R134a, 3.4% R600a (by weight) 0 2729 A1
R423a 52.5% R134a, 47.5% R227ea (by weight) 0 2280 A1
R170 Ethane 0 5.5 A3
R290 Propane 0 3.3 A3
R600 Butane 0 4 A3
R601 Pentane 0 4 A3
Cyclohexane A3
Benzene B2
Toluene A3
R717 Ammonia 0 0 B2L
CFCs and later HCFCs have been used extensively as refrigerants during the first part of the last
century. These compounds were found to be relatively safe for handling and operation but their
environmental effect was not addressed until the mid '70s. At the time, the severe consequences of the
continuous utilization of the CFCs became obvious and this led to the international phase out treaty of
1987 which is known as the Montreal Protocol. Under this treaty CFCs are currently banned.
Replacement has taken place mainly by HCFCs which were equally safe but their widespread
utilization eventually became a major global warming source. In view of this threat HCFCs fall also
into phase out plans aiming at a gradual step down of their utilization after 2016. In this category, R22
was the most applicable fluid in residential and commercial air conditioning and refrigeration. It has
10
been already phased out in most developed countries but it is still used as a refrigerant in many other
developing. DuPont suggests R22 substitution by HFC refrigerant blends of similar physical properties
such as R417a, R422a and R422d [34-36]. HFCs are currently adopted in preference to HCFCs since
they don't contain chlorine and they don't harm the ozone layer. However, as can be observed in Table
5, they form greenhouse gases with a high GWP. Due to this effect international discussions are open
on the future reduction of HFCs also. PFCs, finally, were also used as replacement fluids of CFCs.
They are generally very inert and non-toxic but have high GWP values between 6000 and 10000.
To replace the substances mentioned above there exist some interesting hydrocarbon choices.
Propane (R290), butane (R600) and pentane (R601) are commonly used as refrigerants or in ORCs.
They are also mixed in hydrocarbon blends containing also ethane (R170). They have excellent
thermodynamic properties, and in this respect they are as good as or better than HCFs or HCFCs in
most applications. They are environmentally friendly with zero ODP and extremely low GWP values.
However, they are highly flammable and must be handled with care. In order to ensure safety,
hydrocarbon applications are governed by various international, regional and national standards and
regulations. They may pose an explosion risk if the concentration is between the lower and upper
flammability limits but following the safety standards the concentration of any leaked hydrocarbon
will not increase enough even in extreme situations.
The list of the selected fuels concludes with ammonia (R717), the only non-organic fluid candidate.
Ammonia is renowned for its favorable thermodynamic properties, it has zero ODP and zero GWP.
However, it has a number of disadvantages that have so far prevented its use in commercial
applications, e.g. material compatibility, toxicity, and flammability. Even under strict safety
regulations there is pressure on ammonia installations to reduce charge levels, especially when situated
in populated areas.
5. Results and discussion

All 37 selected fluids have been comparatively examined for the ORC exhaust heat recovery of the
V18 MAN 51/60 natural gas engine. Initially, ORC operation conditions were kept similar in all cases
with the pressure of the condenser constant at 0.1MPa and the pressure of the evaporator constant at
3MPa. Since all fluids have critical pressures above 3MPa every Rankine cycle examined was
subcritical. Considering simple non-superheated operation the comparative characteristics of all fluids
are summarized in Table 6. As shown, under these conditions exhaust heat recovery was found
capable to increase power plant efficiency by 3.61-4.93%. These terms are translated into additional
power outputs of 1700-2325kW just by exploiting the otherwise wasted engine gases, and also mean
fuel consumption improvements by 8.68-11.45%. Higher efficiency improvements are taken for R22
(4.93%), ethane (4.82%), R143a (4.71%), R41 (4.64%), R14 (4.53%), propane (4.5%), R13 (4.48%),
R32 (4.42%), ammonia (4.41%), R23 (4.40%), R12 (4.40%), R11 (4.32%), R21 (4.28%), R152a
(4.25%).
Table 6. Comparative characteristics of the simple (non-superheated) exhaust heat recovery

Rankine cycle and overall plant efficiency improvement for all candidate fluids.
Fluid Maximum
Pump Turbine ORC ORC Power plant
ASHRAE mass cycle Expanded Δ𝜂
power power Power efficiency efficiency
Code flow temperature fluid quality (%)
(kW) (kJ/kg) (kW) (%) (%)
(kg/s) (K)
R11 44.18 108.19 2146.99 445.07 Superheated 2038.80 19.65 42.28 4.32
R12 51.21 124.77 2199.50 376.25 0.9748 2074.73 19.99 42.36 4.40
R13 61.64 146.76 2257.97 290.67 0.8972 2111.21 20.35 42.44 4.48
R14 75.31 170.18 2306.90 219.98 0.8133 2136.72 20.59 42.49 4.53
R21 36.72 94.66 2158.96 417.06 0.9446 2064.30 19.89 42.34 4.38
R22 39.94 102.68 2428.86 343.19 0.8962 2326.18 22.42 42.89 4.93
11
R23 41.95 105.13 2179.91 280.11 0.8262 2074.78 19.99 42.36 4.40
R32 26.52 79.21 2163.85 321.17 0.8182 2084.64 20.09 42.38 4.42
R41 21.11 86.82 2272.56 287.94 0.7931 2185.74 21.06 42.60 4.64
R113 47.57 114.26 1921.25 478.88 Superheated 1806.99 17.41 41.79 3.83
R114 53.70 128.14 1963.65 414.01 Superheated 1835.51 17.69 41.85 3.89
R115 65.26 151.71 2003.06 350.69 Superheated 1851.35 17.84 41.89 3.93
R116 76.28 172.18 2018.98 292.4 0.955 1846.79 17.80 41.88 3.92
R123 44.64 111.01 1981.46 444.45 Superheated 1870.45 18.03 41.93 3.97
R124 48.39 118.97 2003.16 385.26 Superheated 1884.19 18.16 41.96 4.00
R125 52.21 124.97 2015.99 330.64 0.9895 1891.02 18.22 41.97 4.01
R134a 40.02 105.32 2007.00 359.35 0.9751 1901.68 18.33 41.99 4.03
R141b 34.14 101.38 2083.23 454.73 Superheated 1981.85 19.10 42.16 4.20
R142b 36.58 111.13 2100.45 393.07 Superheated 1989.32 19.17 42.18 4.22
R143a 35.67 110.79 2334.01 359.35 Superheated 2223.22 21.42 42.67 4.71
R152a 27.44 98.31 2102.53 365.22 0.9241 2004.22 19.31 42.21 4.25
R236ea 43.90 107.26 1856.37 405.98 Superheated 1749.10 16.86 41.67 3.71
R236fa 49.16 123.26 1826.30 394.75 Superheated 1703.04 16.41 41.57 3.61
R245ca 36.50 95.41 1862.00 432.09 Superheated 1766.58 17.02 41.71 3.75
R245fa 38.37 101.78 1876.49 416.57 Superheated 1774.70 17.10 41.72 3.76
R417a 44.29 112.39 2040.08 346.87 0.9801 1927.69 18.58 42.05 4.09
R422a 49.27 125.03 2036.64 334.97 0.9854 1911.60 18.42 42.01 4.05
R422d 46.74 118.59 2047.83 341.07 0.9804 1929.24 18.59 42.05 4.09
R423a 47.13 119.59 1961.77 364.09 Superheated 1842.18 17.75 41.87 3.91
Ethane 19.26 128.30 2401.82 282.89 0.8589 2273.52 21.91 42.78 4.82
Propane 19.78 123.35 2246.60 350.84 0.979 2123.25 20.46 42.46 4.50
Butane 19.08 114.98 2092.89 410.85 Superheated 1977.92 19.06 42.16 4.20
Pentane 18.61 110.60 1902.99 462.13 Superheated 1792.39 17.27 41.76 3.80
Cyclohexane 17.10 86.11 1837.94 529.43 Superheated 1751.82 16.88 41.68 3.72
Benzene 17.66 78.63 2014.62 523.55 0.1294 1935.99 18.66 42.07 4.11
Toluene 17.43 81.07 1826.40 566.22 Superheated 1745.33 16.82 41.66 3.70
Ammonia 7.24 38.45 2118.90 338.87 0.8366 2080.44 20.05 42.37 4.41
The list of thermodynamically favorable fluids which was selected in the previous discussion may
be greatly narrowed on the basis of their environmental footprint. Among these choices R22, R14,
R13, R12 and R11 have already been prohibited as CFCs. R143a is an HFC used mainly as a blend
component in refrigerants. It has zero ODP, high GWP at 4470 and is mildly flammable at the A2L
class. R41 is also an HFC used mainly in semiconductor manufacturing but with unknown GWP and
safety behavior. It may be considered for further evaluation but it can't be selected until further
research. R14 is a PFC with a high GWP value of 7390. Instead, R32 presents a good performance
with medium to low GWP at 675. R23 is an HFC with a very high GWP at 14800. R21 is an HCFC
with medium ODP and is under phase out. R152a is a promising and environmentally friendly choice
with good performance. Finally the list above includes ethane and propane, two well known HCs, and
ammonia, the only non organic candidate. These fluids have a low environmental impact but are
highly flammable and need special attention and safety measures. Ammonia is also dangerously toxic.
12
Based on this discussion the list of selected fluids narrows only to ethane, R41 (under lack of data),
propane, R32, ammonia and R152a.
5,5
R22
5 Ethane Ammonia
R41
R143a
R32
R14 Propane
4,5 R23 R21
R152a
R141b
Butane R142b
R422a, R417a
R422a R134a
4
R116 R125, R124, R123
R423a
Pentane Cyclohexane
Toluene
Δη (%)
R245fa
R245ca
R236fa R236ea
3,5
2,5
2
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5 5,5
Evaporation pressure (MPa)
Figure 5. Effect of the ORC evaporation pressure on the overall efficiency improvement of the V18
MAN 51/60 DF natural gas power plant for selected working fluids. Condenser pressure is 0.1MPa in
all cases and Rankine cycles are simple without superheating.
The effect of the ORC evaporation pressure on the efficiency improvement of the power plant may
be shown for selected fuels in Figure 5. Results are given for subcritical pressures and simple non-
superheated cycles in all cases. Given the Montreal Protocol prohibition CFCs are not considered any
further and Figure 5 contains only R22 for comparison. As shown, an increase of the evaporation
13
pressure is always beneficial leading to better plant efficiencies for all fluids. It can be seen that the
effect of the evaporation pressure is more dramatic at low pressures. As the evaporation pressure
increases the slope of the curve of the efficiency improvement Δ𝜂 reduces and even negative
improvement values can be taken when attaining the critical pressure of a fluid. In this respect one can
set a limiting upper evaporation pressure at about 85-95% of the critical pressure value of each fluid.
The optimum evaporation pressure for a fluid is therefore dictated by its critical pressure and fluids
with higher critical pressures have greater potential for efficiency enhancement. Accordingly, ethane,
R41, R32 and ammonia may further improve their performance at elevated pressures. Maximum
pressure is set for ethane at 4.5MPa, for R41 at 5MPa and for R32 at 5MPa. Ammonia has an
extremely high critical pressure of 11.333 MPa but results show that above 5MPa further improvement
of about 1% is only possible. To avoid risk of leakages and increased costs for special safety measures
the maximum pressure for ammonia was set also at 5MPa. Finally, propane is found to maximize
performance at 3.5MPa and R152a at 4MPa.
6
5,5
Δη (%)
5 Ethane at 4.5MPa
R32 at 5MPa
R41 at 5MPa
4,5 R152 at 4Mpa
Ammonia at 5MPa
Propane at 3.5 Mpa
4
300 350 400 450 500
Superheating temperature (K)
Figure 6. Effect of the ORC superheating temperature on the overall efficiency improvement of
the V18 MAN 51/60 DF natural gas power plant for selected working fluids.
Except propane which is an isentropic fluid, all other fluids selected so far are wet. For a wet fluid
and a simple non-superheating Rankine cycle an increase of the evaporation pressure results in a
reduction of the quality of the saturated gas-liquid mixture taken after expansion. This means an
increase of the percentage of liquid state at the final stages of turbine expansion and a danger for
turbine blade erosion and wear. In all these cases simple Rankine cycle is inappropriate and
superheating of the fluid vapor above the saturation temperature must be followed. The effect of the
superheating temperature on the efficiency improvement of the power plant is illustrated for the cases
of ethane, R41, propane, R32, ammonia and R152a at Figure 6. Each fluid is assumed at its optimum
pressure mentioned before and superheating temperature is increased so that after expansion the fluid
to be slightly superheated. As can be seen, an increase of the superheating temperature always leads to
an overall efficiency improvement. Maximum efficiencies are attained at about 360K for ethane, 400K
for R41, 375K for propane, 435K for R32, 480K for ammonia and 410K for R152a. The
14
characteristics of these optimum ORC cycles are summarized at Table 7. Among the selected fluids
the ORC cycle of R32 is selected as the most appropriate due to high thermodymamic performance,
low environmental impact and low flammability-toxicity. Such a cycle may provide an overall
efficiency improvement of the order of 5.52%, as shown in Table 7. This improvement is also
translated into a reduction of the fuel consumption by 12.69%.
Table 7. Comparative characteristics of superheated exhaust heat recovery Rankine cycles and
overall plant efficiency improvements for the selected working fluids.
Fluid Maximum Power
Pump Turbine Evaporation ORC ORC
ASHRAE mass cycle plant Δ𝜂
power power pressure Power efficiency
Code flow temperature efficiency (%)
(kW) (kJ/kg) (MPa) (kW) (%)
(kg/s) (K) (%)
Ethane 14.72 148.72 2844.99 360 4.5 2696.27 25.98 43.68 5.71
R41 15.63 108.58 2838.96 400 5.0 2730.38 26.31 43.75 5.79
Propane 17.85 130.51 2386.34 375 3.5 2255.83 21.74 42.74 4.78
R32 19.68 99.32 2703.64 435 5.0 2604.32 25.10 43.48 5.52
Ammonia 5.69 51.04 2623.21 480 5.0 2572.14 24.79 43.41 5.45
R152a 23.40 112.73 2343.77 410 4.0 2231.04 21.50 42.69 4.73
Conclusions
In the present work the ORC exhaust heat recovery of a V18 MAN 51/60DF internal combustion
engine power plant was examined. The plant was assumed to operate with natural gas at 500rpm and
design focused on the selection of an appropriate ORC working fluid on the basis of thermodynamic,
environmental and safety criteria. The study was undertaken for 37 working fluids under subcritical
Rankine cycle conditions and examined the effect of key operation conditions such as evaporation
pressure and superheating temperature. After an appropriate selection of these operation conditions for
each candidate substance, R32 was selected as the most appropriate working fluid given its high
thermodynamic performance, its low environmental impact and its low flammability-toxicity
characteristics. Analysis has shown that R32 may provide an overall efficiency improvement of the
power plant by 5.52% and a reduction of fuel consumption by 12.69%. Given the high power rating of
the V18 MAN 51/60DF engine at about 18000kW, these improvements are translated into enormous
cost savings during operation. The methodology employed in the present study may also serve as a
guideline for future optimization of other energy systems.
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16

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internal combustion engine power plant

2016 IOP Conf. Ser.: Mater. Sci. Eng. 161 012087

Please note that terms and conditions apply.

You may also be interested in:

Fire guts leading photonics centre

Proceedings of the 20th Nordic Semiconductor Meeting

Working fluid selection for the Organic Rankine Cycle (ORC)

S Douvartzides and I Karmalis

E-mail: [email protected]; [email protected]

2. Engine and fuel characteristics

Figure 1. The V18 MAN 51/60DF (dual fuel) engine.

Table 1. 18 cylinder MAN 51/60DF engine characteristics [28, 29]

3. Rankine cycle analysis

Figure 2. Schematic diagram of the ORC exhaust heat recovery system.

𝑄𝑟 = 𝑚𝐺 𝑕I − 𝑕II ≈ 𝑚𝐺 𝑐𝑣,𝑇I 𝑇I − 𝑚𝐺 𝑐𝑣,𝑇II 𝑇II

where 𝑚𝐹 is the mass flow rate of the organic fluid.

The net power produced by the Rankine cycle is calculated as

𝑃ORC = 𝑚𝐹 𝑤𝑡𝑎 − 𝑤𝑝𝑎 = 𝑄𝑟 − 𝑄𝑜𝑢𝑡

and the thermal efficiency of the Rankine cycle is given as

The overall efficiency of the ICE-ORC power plant is then calculated as

4.1. Thermodynamic selection criteria

Table 4. Thermodynamic properties of various fluids [33-37].

4.2. Environmental and safety selection criteria

Table 5. Environmental parameters and safety classification of various fluids.

R22 Chlorodifluoromethane 0.05 1810 A1

5. Results and discussion

Table 6. Comparative characteristics of the simple (non-superheated) exhaust heat recovery

Evaporation pressure (MPa)

Superheating temperature (K)

[12] Srinivasan K K, Mago P J, Krishnan S R 2010 Energy 35(6) 2387

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