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Zero-ODP, Low GWP,
Non-Flammable Working Fluid for
Organic Rankine Cycles:
HFO-1336mzz-Z
Kostas Kontomaris, Ph.D.
DuPont Fluorochemicals
Kobe, Japan
November 21st, 2014
Reduce:
Primary Energy Use
Environmental Impact
The International Symposium on
New Refrigerants and
Environmental Technology
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Kontomaris-2014 Kobe, Japan
APPLICATION EXAMPLES
CAPw [kw]
Thigh [oC]
1-10 10-100 100-1,000
200-250 Mobile ICE (HDV; Truck; Ship; Rail)
CHP (ICE; Biomass) Industrial
Industrial
150-200 Stationary ICE CHP
CHP (ICE; Biomass) Geothermal
Geothermal Gas Turbines
100-150 Stationary ICE CHP (ICE; Biomass) Geothermal
Geothermal
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Kontomaris-2014 Kobe, Japan
APPLICATION EXAMPLES
CAPw [kw]
Thigh [oC]
1-10 10-100 100-1,000
200-250 Mobile ICE (HDV; Truck; Ship; Rail)
CHP (ICE; Biomass) Industrial
Industrial
150-200 Stationary ICE CHP
CHP (ICE; Biomass) Geothermal
Geothermal Gas Turbines
100-150 Stationary ICE CHP (ICE; Biomass) Geothermal
Geothermal
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Kontomaris-2014 Kobe, Japan
APPLICATION EXAMPLES
CAPw [kw]
Thigh [oC]
1-10 10-100 100-1,000
200-250 Mobile ICE (HDV; Truck; Ship; Rail)
CHP (ICE; Biomass) Industrial
Industrial
150-200 Stationary ICE CHP
CHP (ICE; Biomass) Geothermal
Geothermal Gas Turbines
100-150 Stationary ICE CHP (ICE; Biomass) Geothermal
Geothermal
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Kontomaris-2014 Kobe, Japan
APPLICATION EXAMPLES
CAPw [kw]
Thigh [oC]
1-10 10-100 100-1,000
200-250 Mobile ICE (HDV; Truck; Ship; Rail)
CHP (ICE; Biomass) Industrial
Industrial
150-200 Stationary ICE CHP
CHP (ICE; Biomass) Geothermal
Geothermal Gas Turbines
100-150 Stationary ICE CHP (ICE; Biomass) Geothermal
Geothermal
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Kontomaris-2014 Kobe, Japan
APPLICATION EXAMPLES
CAPw [kw]
Thigh [oC]
1-10 10-100 100-1,000
200-250 Mobile ICE (HDV; Truck; Ship; Rail)
CHP (ICE; Biomass) Industrial
Industrial
150-200 Stationary ICE CHP
CHP (ICE; Biomass) Geothermal
Geothermal Gas Turbines
100-150 Stationary ICE CHP (ICE; Biomass) Geothermal
Geothermal
Diverse Markets: Segments, Capacities, Temps and Expander Technologies
Comprehensive Portfolio of Fluids Needed
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Kontomaris-2014 Kobe, Japan
APPLICATION EXAMPLES
CAPw [kw]
Thigh [oC]
1-10 10-100 100-1,000
200-250 Mobile ICE (HDV; Truck; Ship; Rail)
CHP (ICE; Biomass) Industrial
Industrial
150-200 Stationary ICE CHP
CHP (ICE; Biomass) Geothermal
Geothermal Gas Turbines
100-150 Stationary ICE CHP (ICE; Biomass) Geothermal
Geothermal
Focus Today:
DR-2 for High Temp Apps?
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Kontomaris-2014 Kobe, Japan
Developmental Fluid: DR-2
DR-2 Chemical Formula HFO-
1336mzz(Z)
H H
F
F FF
F
F
CF3CH=CHCF3(Z)
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Kontomaris-2014 Kobe, Japan
Developmental Fluid: DR-2
DR-2 Chemical Formula HFO-
1336mzz(Z)
AEL [ppm] 500
Flammabilty Non-Flam
ODP None
GWP100 2
Tcr [oC] 171.3
Pcr [MPa] 2.90
Tb [oC] 33.4
H H
F
F FF
F
F
CF3CH=CHCF3(Z)
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Kontomaris-2014 Kobe, Japan
Developmental Fluid: DR-2
DR-2 Chemical Formula HFO-
1336mzz(Z)
AEL [ppm] 500
Flammabilty Non-Flam
ODP None
GWP100 2
Tcr [oC] 171.3
Pcr [MPa] 2.90
Tb [oC] 33.4
H H
F
F FF
F
F
CF3CH=CHCF3(Z)
Very Low GWP
And
Non-Flammable
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Kontomaris-2014 Kobe, Japan
Developmental Fluid: DR-2
DR-2 Chemical Formula HFO-
1336mzz(Z)
H H
F
F FF
F
F
CF3CH=CHCF3(Z)
No Chlorine: -Zero ODP
-Dramatically Increased Chemical Stability(*) at High Temps
(*) See Paper 2550 in Proceedings of 2014 Purdue Conference
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Kontomaris-2014 Kobe, Japan
DR-2: Pressure-Enthalpy Diagram
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
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Kontomaris-2014 Kobe, Japan
DR-2: Pressure-Enthalpy Diagram
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
Slope of
Isentropic
Lines
Subcritical Cycles:
No superheat required
to ensure dry expansion
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Kontomaris-2014 Kobe, Japan
Heat Source Temp>Tcr
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
Expander
Inlet:
Thigh=225 C
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Kontomaris-2014 Kobe, Japan
Representative Cycle Conditions
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
Expander
Inlet:
Thigh=225 C
Condenser:
Tcond=75 C
Subcooling:
DTsubc=5 K
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Kontomaris-2014 Kobe, Japan
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
Expander
Inlet:
Thigh=225 C
hexp=0.75
hpump=0.50
Condenser:
Tcond=75 C
Subcooling:
DTsubc=5 K
Representative Cycle Conditions
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Kontomaris-2014 Kobe, Japan
Optimization of High-Side Pressure
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
Expander
Inlet:
Thigh=225 C
hexp=0.75
hpump=0.50
Condenser:
Tcond=75 C
Subcooling:
DTsubc=5 K
Phigh< Pcr
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Kontomaris-2014 Kobe, Japan
200 250 300 350 400 450 500 550 600 650
0.1
1
10200 250 300 350 400 450 500 550 600 650
0.1
1
10275
o C
DR-2
250
225
50
25
Pre
ss
ure
(M
Pa
)
Enthalpy (kJ/kg)
0
100
75
125
200
150
175
Expander
Inlet:
Thigh=225 C
hexp=0.75
hpump=0.50
Condenser:
Tcond=75 C
Subcooling:
DTsubc=5 K
High-Side Pressure: Upper Limit
For Phigh>~10 MPa:
Wet Expansion
Phigh> Pcr
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15
20
25
30
35
0 1 2 3 4 5 6 7 8 9 10
Po
we
r [k
J/kg
]
Phigh [MPa]
Expander Power
Net Power
Net Cycle Power
Net Power Exhibits Maximum
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Maximization of Thermal Efficiency
5
6
7
8
9
10
11
0 1 2 3 4 5 6 7 8 9 10
Ne
t C
ycle
Th
erm
al E
ffic
ien
cy
Phigh [MPa]
Net Cycle Efficiency Exhibits Maximum
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Kontomaris-2014 Kobe, Japan
5
6
7
8
9
10
11
0 1 2 3 4 5 6 7 8 9 10
Ne
t C
ycle
Th
erm
al E
ffic
ien
cy
Phigh [MPa]
Maximization of Thermal Efficiency
Pcr
Maximum Efficiency at Phigh>Pcr 10-15% Higher Than Subcritical Cycle Efficiency
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Kontomaris-2014 Kobe, Japan
5
6
7
8
9
10
11
0 1 2 3 4 5 6 7 8 9 10
Ne
t C
ycle
Th
erm
al E
ffic
ien
cy
Phigh [MPa]
Maximization of Thermal Efficiency
Pcr
Phigh [MPa] 4 5
PR 10.7 13.3
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Kontomaris-2014 Kobe, Japan
5
6
7
8
9
10
11
0 1 2 3 4 5 6 7 8 9 10
Ne
t C
ycle
Th
erm
al E
ffic
ien
cy
Phigh [MPa]
Maximization of Thermal Efficiency
Pcr
Additional Considerations: (+) Heat Extraction from Source of Declining Temp
(-) Equipment Component Costs?
Transcritical
DR-2 ORC
with Phigh=4-5 MPa
Optimum?
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Recuperator Increases DR-2 Energy Efficiency
EXEMPLARY SUBCRITICAL CYCLE
Subcooling K 0.00
EFFCexpn 0.85
EFFICpump 0.65
Superheat K 50.00
Tcond C 25.00
Tevap C 160.00
Texpn_inlet C 210.00
Recuperator No Yes %
Cycle Thermal Effic % 17.32 25.10 44.9
Heat to Evaporator kJ/kg 327.5 225.97 -31.0
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HFC-245fa DR-2 Chemical Formula CF3CH2CHF2 HFO-1336mzz(Z)
OEL/AEL [ppm] 300 500
Flammabilty Non-Flam Non-Flam
ASHRAE Std 34
Safety Class
B1 A1
(expected)
ODP None None
GWP100 858 2
ALT [yrs] 7.7 0.060274 (22 days)
Tcr [oC] 154 171.3
Pcr [MPa] 3.65 2.90
Tb [oC] 15.1 33.4
DR-2 vs. HFC-245fa
Reference Fluid: HFC-245fa
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HFC-245fa DR-2 Chemical Formula CF3CH2CHF2 HFO-1336mzz(Z)
OEL/AEL [ppm] 300 500
Flammabilty Non-Flam Non-Flam
ASHRAE Std 34
Safety Class
B1 A1
(expected)
ODP None None
GWP100 858 2
ALT [yrs] 7.7 0.060274 (22 days)
Tcr [oC] 154 171.3
Pcr [MPa] 3.65 2.90
Tb [oC] 15.1 33.4
Tfreez [oC] -107 -90.5
DR-2 vs. HFC-245fa
Reference Fluid: HFC-245fa
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5
6
7
8
9
10
11
0 1 2 3 4 5 6 7 8 9 10
Ne
t C
ycle
Th
erm
al E
ffic
ien
cy
Phigh [MPa]
DR-2
HFC-245fa
DR-2 vs. HFC-245fa: Cycle Efficiency
Basic ORC (No Recuperator)
Thigh C 225
Tcond C 75
DTsubc K 5
hexp 0.75
hpump 0.50
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5
6
7
8
9
10
11
0 1 2 3 4 5 6 7 8 9 10
Ne
t C
ycle
Th
erm
al E
ffic
ien
cy
Phigh [MPa]
DR-2
HFC-245fa
+16.5%
DR-2 vs. HFC-245fa: Cycle Efficiency
DR-2: 99.8% Lower GWP and 16.5% Higher Efficiency!
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Summary Efforts to increase energy efficiency and growing awareness of the
environmental impacts from the use of fossil fuels will encourage
wider adoption of ORCs for power generation from low temp heat
DR-2 exhibits remarkable chemical stability at high temperatures
despite its unsaturated chemical nature; high stability to stereo-
isomerization despite thermodynamic driving force for
isomerization to trans
DR-2 offers a unique combination of properties attractive for ORC
applications:
• Attractive Safety, Health and Environmental Properties
• High Thermal and Stereo-Isomerization Stability
• Favorable Thermodynamics
A transcritical DR-2 ORC may be suitable for high temperature heat
sources; a recuperator increases efficiency of DR-2 ORCs
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Thank you!
Email:
[email protected]
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