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CO2 Refrigeration Presentation
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CO2Refrigerant for Industrial Refrigeration
Part I - Sub-critical refrigeration cycles
Prepared byNiels P Vestergaard
Content - Part IØ HistoryØ FactsØ Refrigeration cycles with CO2
§ Transcritical§ Subcritical
§ Cascade systems§ DX – systems§ Pump circulating systems
Ø CO2 compared with R717 & R134aØ Safety valvesØ OilØ Design pressureØ Why CO2
Ø RegulationØ Components for CO2
CO2 cooling
Climate change
Kyoto Protocol
Environment
Saving energy
Cooling
CO2 for Industrial refrigeration
History
1850 199319601920 ----------1930
The peak of utilizingCO2 as refrigerant
Reinvention of CO2-refrigeration technology(G. Lorentzen)
CO2 CompressorApprox. 1900
HistoryCO2 utilized as refrigerant in sub- and supercritical refrigeration systems
Proposal to use CO2as a refrigerant(Alexander Twining,British patent)
HistoryMarine refrigerant systems registered at Lloyds in London
Source: S.A. Andersen ”Køleanlæg i skibe og på land” 1971In 1970 S. Forbes Pearson, UK made an general view over the most commonused refrigerant used in marine refrigeration systems registered at Lloyds inLondon
CO2
Facts
CO2(Carbon Dioxide / R744)
• Natural substance
• Refrigerant classified as non-toxic and non- flammable fluid
• Concentration in the atmospheric air approx. 0,04% (volume)
Refrigerationcycles with
CO2
CO2 look like all the otherrefrigerants, but …….
Log p,h-Diagram of CO2
1
10
100
1000
-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100
Temperature (Deg.C)
Pres
sure
(bar
)
Liquid
Solid
Vapour
Supercritical
CO2 Phases
Triple point5.2 bar
- 56.6 Deg.C
Critical point
73.6 bar
31. Deg.C
1
10
100
-200 -100 0 100 200 300 400 500
Enthalpy (J)
Pres
sure
(bar
)
Supercritical
Solid - Vapour vapour
Liquid - vapour
Liquid
Solid
Solid -Liquid
- 78,4 Deg.C
Log p,h-Diagram of CO2
73,6
+31 Deg.C
Criticalpoint
- 56,6 Deg.C5,2
Triple(freezing)
point
NOYESNONOToxic
1-32601300Global Warming Potential (GWP) *
73.631.1
113132.4
37.372
40.7101.2
Critical pressure in bar°C
5.18-56.6
0.06-77.7
0.028-100
0.004-103
Triple point in bar°C
NO(YES)NONOFlammable or explosive
0000Ozone Depletion Potential (ODP) *YESYESNONONatural substanceCO2NH3R404aR134aRefrigerant
CO2 properties compared with various refrigerants
* prEN 378-1 (2003)
10 bar (-40 Deg.C)
35 bar (0 Deg.C)
Subcritical refrigeration procesExample –10/35 bar
10 bar (-40 Deg.C)
65 bar (25 Deg.C)
Subcritical refrigeration procesExample –10/65 bar
Transcritical(supercritical)refrigeration
process
90 bar
Supercritical refrigeration process
26,5 bar (-10 Deg.C)
90 bar
Supercritical refrigeration processGas cooling
26,5 bar (-10 Deg.C)
95 Deg.C35 Deg.C Gas cooling
Residential CO2 heatpumpapplication for hot waterproduction
CO2 Automotiveaircondition application
1
1,5
2
2,5
3
70 75 80 85 90 95 100 105 110
Compressor outlet pressure [bar]
CO
P
Max
100 bar
100 bar,COP = 2,46
90 bar,COP = 2,51
90 bar
COP = (∆hEVAP*m )/ (∆hComp-is*m)
∆hComp-is
80 bar
80 bar,COP = 1,72
∆hEVAP
35 oC
Supercritical refrigeration procesInfluence of compressor outlet pressure
Supercritical CO2 heat pumps
Patents:A number of patents has to be taken intoconsideration
Sub critical refrigerationprocess, e.g.
• Cascade system• DX systems• Pump circulating systems
R717
CO2
+30 Deg.C (12 bar)
-20 Deg.C (1,9 bar)
+30 Deg.C
-20 Deg.C-15 Deg.C
-40 Deg.C
Pres
sure
Enthalpy
-15 Deg.C (23 bar)
-40 Deg.C (10 bar)
Pres
sure
Enthalpy
CO2
R717
Principal diagram717 - CO2 cascade system
-40 Deg.C
CO2-evaporator
CO2 compressor
CO2-receiver
CO2-R717 Heat exchanger
R717
CO2
-45 Deg.C (0,5 bar)
-40 Deg.C (10 bar)
+30 Deg.C
-45 Deg.C
-40 Deg.C
-40 Deg.C
Enthalpy
Enthalpy
Pres
sure
Pres
sure
+30 Deg.C (12 bar)
CO2
R717
Principal diagram717 - CO2 brine system
-40 Deg.C
CO2-R717 Heat exchanger
CO2-receiver
CO2-evaporator
R717
CO2
+30 Deg.C (12 bar)
-20 Deg.C (1,9 bar)
-15 Deg.C (23 bar)
-40 Deg.C (10 bar)
+30 Deg.C
-20 Deg.C
-40 Deg.C
-40 Deg.C
Pres
sure
Pres
sure
Enthalpy
Enthalpy
CO2
R717
+8 Deg.C
+8 Deg.C (43 bar)
Principal diagram717 - CO2 cascade system with CO2hot gas defrosting
-15 Deg.C
CO2-R717 Heat exchanger
CO2 compressor
CO2 defrostcompressor
CO2-receiver
CO2-evaporator
Principal diagram CO2 cascade system with 2temperature levels (e.g supermarket refrigeration)
R717,R404, R134a,….
CO2
Pump circulating system
DX system
+30 Deg.C
-12 Deg.C-7 Deg.C
-7 Deg.C
-20 Deg.C
CO2 applicationCO2 compared with R134a and R717
111[K]∆T
250250250[kW]CapacityWet return lineCO2R717R134aRefrigerant
9,423,012,6[m/s]Velocity0,36600,03750,0263[bar]∆p
26099982968[mm2]Area
583661[mm]Diameter
0,80,80,8[m/s]VelocityLiquid line
33101221331941[mm2]Area
65125202[mm]Diameter
CO2Smallpipediameter!
Leqv = 50 [m]Pump circ.: ncirc = 3Evaporating temp.: TE = -40 [Deg.C]
Wet return / Liquid linesWet reurn
Liquid
CO2Area -Liquid
line44%
Area -Wet
returnline56%
R717
Area -Wet
returnline92%
Area -Liquid
line8%
R134aArea -Liquid
line9%
Area -Wet
returnline91%
111[K]∆T
250250250[kW]CapacityWet return lineCO2R717R134aRefrigerant
9,423,012,6[m/s]Velocity0,36600,03750,0263[bar]∆p
26099982968[mm2]Area0,80,80,8[m/s]VelocityLiquid line
33101221331941[mm2]Area
CO2Liquidfraction ishigh
Leqv = 50 [m]Pump circ.: ncirc = 3Evaporating temp.: TE = -40 [Deg.C]
Wet return / Liquid linesWet reurn
Liquid
111[K]∆T
250250250[kW]CapacityDry suction lineCO2R717R134aRefrigerant
17,642,923,3[m/s]Velocity0,36630,03750,0261[bar]∆p
9753531089[mm2]Area352137[mm]Diameter
0,80,80,8[m/s]VelocityLiquid line
1956707519413[mm2]Area5095157[mm]Diameter
Dry suction / Liquid lines
CO2Smallpipediameter!
Leqv = 50 [m]Evaporating temp.: TE = -40 [Deg.C]Condensing temp.: TC = -15 [Deg.C]
Dry suction
Liquid
111[K]∆T
250250250[kW]CapacityDry suction line
CO2R717R134aRefrigerant
17,642,923,3[m/s]Velocity
0,36630,03750,0261[bar]∆p
9753531089[mm2]Area
0,80,80,8[m/s]VelocityLiquid line
1956707519413[mm2]Area
CO2
Area -Dry
suctionline67%
Area -Liquid
line33%
R134
Area -Dry
suctionline95%
Area -Liquid
line5%
R717
Area -Dry
suctionline95%
Area -Liquid
line5%
CO2Liquidfraction ishigh
Leqv = 50 [m]Evaporating temp.: TE = -40 [Deg.C]Condensing temp.: TC = -15 [Deg.C]
Dry suction / Liquid linesDry suction
Liquid
250250250[kW]Capacity
CO2R717R134aRefrigerant
1,08,813,1[-]Compressor capacity relative12410921628[m3/h]Compressor capacity
Evaporating temp.: TE = -40 [Deg.C]Condensing temp.: TC = -15 [Deg.C]
CO2Compressorshave highcapacity
Compressor capacityCompressor
333[m]High "h"CO2R717R134aRefrigerant
0,885,2114,91[oC]Pump inlet pressure - ∆t0,3290,2030,418[bar]Pump inlet pressure - ∆p
CO2Sub cooling (∆t)is small
Liquid pumpPumpe
h
Pump
0,1
1
10
100
1000
10000
-50 -40 -30 -20 -10 0 10 20 30 40
Temperature [oC]
[kg/
m3]
CO2 Vapour [m3/kg]
CO2 Liquid [m3/kg]
R134a Vapour [m3/kg]
R134a Liquid [m3/kg]
R717 Vapour [m3/kg]
R717 Liquid [m3/kg]
log Density - R134a - R717 - CO2
CO2Density differencebetween liquid andvapour is small
Density - CO2
0
200
400
600
800
1000
1200
1400
-50 -40 -30 -20 -10 0 10 20 30 40
Temperature [Deg.C]
[kg/
m3 ]
CO2 Liquid
CO2 Vapour
100
300
500
700
900
1100
1300
1500
-50 -40 -30 -20 -10 0 10 20 30 40temperature [oC]
[kg/
m3]
CO2Liquid-vapour[m3/kg]
R134aLiquid-vapour[m3/kg]
R717Liquid-vapour[m3/kg]
Difference between liquid and vapour density
F
F = ( density liquid – density vapour)
liquid
Vapour
SUMMARYCO2 application:
• Pipe dimensions in CO2 systems are small
• Due to very small vapour volume, CO2 systems are verydynamic
• Liquid pumps in CO2 systems are sensitive to capacitychanges (low sub cooling & gas bobbles are difficult toget rid of at high temperatures.)
• Compressors with big capacity steps can createproblems (small vapour volume).
• Frequency converters are an obvious possibility !
Safety valves
CO2
1
10
100
-200 -100 0 100 200 300 400 500
Enthalpy (J)
Pres
sure
(bar
)
Supercritical
Solid - Vapour
vapour
Liquid - vapour
Liquid
Solid
Solid -Liquid
73,6
- 56,6 Deg.C5,2
- 78,4 Deg.C
+31 Deg.CSafety valves
Safety valve 20 barliquid
Safety valve 20 barliquid
78% solid CO2 atthe triple point
Safety valve 35 barvapour
Safety valve 35 bar
0% solid CO2 at thetriple point
Safety valve 50 barvapour
Safety valve 50 bar
5% solid CO2 at thetriple point
Designpressure
Design pressure is depending of:
• Pressure during operation• Pressure during ”stand still”:• Temperature requrements for
defrosting• Pressure tolerances for safety
valves (10 – 15 %)
R717
CO2
Controlling thepressure during”stand still”
Saturated pressure CO2
CO2
20
25
30
35
40
45
50
55
60
-30 -20 -10 0 10 20Design temperature (Deg.C)
Pres
sure
(bar
) Design pressure (bar-g): Ps + 15 %
"Saturated"pressure (bar-a)
Ps + 10% (bar-g)
PS 50
PS 40
PS 25
Practical limit: PS ≥ Psaturated +15%
Design pressurePressure peaks 5%
Saturated pressure10%Safety valve
Design pressure
CO2 and oil
§High affinity to water§Long term stability of oil§”Clean” refrigerant system required
§Oil separation and returnsystem§Long term oil accumulation in
e.g. evaporators
Challenge
§Simple(system requirements like HCFC / HFC )
§Special demand:§Oil drain from low temperature
receiver ( oil density lower thanCO2 -opposite NH3)
Oil return system
§No special requirements(system requirements like HCFC / HFC )
§Special demand:§High filtration demanded§Multistage coalescing filters§Active carbon filter
Oil separation system
High affinity to waterLowHydrolysis
High (miscible)Low (immiscible)Solubility
POEPolyol Ester Oil
PAOPolyalfaolefin(Synthetic Mineral Oil)
Oil type
Common used oil type in CO2 systemsCO2 and oil
Why CO2 ?
HouseholdCompressors
ApplianceControls
IndustrialRefrigeration
Petro-Chemical
Refrigeration and Air Conditioning
R717R600a R134a R1270R410
• All valves are suitable for Ammonia• All valves are in steel• ”Big” valves in small quantity• Requirements for type approvals,
traceability etc.
Danfoss IndustrialRefrigeration A/S
Commercial/Supermarket
SVA-HS
• Small valves made ofe.g. brass, copper
• Valves are NOTapplicable for Ammonia
• Large quantity
CO2
IndustrialRefrigeration
Commercial/SupermarketCO2 – Drivers
Why CO2 ?
EnvironmentPhase out CFC, HCFC: Change to CO2(ODP (Ozone Depletion Potential), GWP (Global Warming Potential) )
SafetyIncreased restrictions on toxic/flammable refrigerants (e.g.requirements for systems with big R717 charge)
Cost• Reduced running cost due to increased
efficiency (compressor efficiency, heat transfer)• Reduced cost on refrigerants.• Reduced size on components.
E
E
E E
CO2componentsfor industrialrefrigeration
High pressure components - CO2
CO2Refrigerant for Industrial Refrigeration
Part II - Properties, compatibility & chemical reactions
Prepared byFinn Broesby Olsen &Niels P Vestergaard
Content - Part IIØ Safety aspects with CO2
Ø Chemical reaction with water and other impurities in CO2 systemsØ Removing water from CO2 systems
§ Filter driersØ Water (moisture) in CO2 systems
§ Solubility§ Moisture indicators
§ Cascade systemsØ How can water penetrate into CO2 systemsØ Compatibility with metal, elastomere
Safety aspectswith CO2
CO2(Carbon Dioxide / R744)
• Natural substance
• Refrigerant classified as non-toxic and non- flammable fluid
• Concentration in the atmospheric air approx. 0,04% (volume)
Safety Aspects of CO2
Carbon dioxide replaces air, and causes lack of oxygen. At presence of sufficient oxygen, CO2 has a narcotic effect at strongerconcentration. With smaller amounts, CO2 has a stimulating effect on the respiratory center. Due to the acidic characteristics of CO2, acertain local irritating can appear, particularly on the mucous membrane of nose, throat and eyes as well as induce coughing. The symptomsassociated with the inhalation of air containing carbon dioxide are, with increasing carbon dioxide concentrations.
The data, valued for adults with good health, are as follows:
§ 0,04% Concentration in the atmospheric air
§ 2% 50% increase in breathing rate
§ 3% 10 Minutes short term exposure limit; 100% increase in breathing rate
§ 5% 300% increase in breathing rate, headache and sweating may begin after about an hour
(Com.: this will tolerated by most persons, but it is physical burdening)
§ 8% Short time exposure limit
§ 8-10% Headache after 10 or 15 minutes. Dizziness, buzzing in the ears,blood pressure increase,
high pulse rate, excitation, and nausea.
§ 10-18% After a few minutes, cramps similar to epileptic fits, loss of con-sciousness, and shock
(i.e.; a sharp drop in blood pressure) The victims recover very quickly in fresh air.
§ 18-20% Symptoms similar those of a stroke.
(source: AGA Gas Handbook)
Chemical reaction withwater and other impurities
in CO2 systems
If water ispresent in CO2systems, waterreacts with CO2and createsCarbonic acid.
Theconcentration isdepending onthe water content
Strong acid
Water in CO2 systems
Water in CO2 systemsHeavy corrosion in a steelpipe from a CO2 systemcaused by Carbonic acid.
Corrosion will not take placein a well maintained CO2refrigeration system.
X-ray defraction:
Crystal structure analysis ofthe steel pipe.
Water in CO2 systems
With very highconcentration of water inCO2 systems, the CO2gas hydrate can beperformed. CO2 gashydrate looks like ice,but exists also at highertemperatures
The CO2 gas hydrate cancreate problems in e.g.filters
CO2 gas hydrate - CO2(H2O)8
Ammonia in CO2 systems
• The solid substance Ammonium Carbamate is formed immediately ifCO2 gets in contact with ammonia.
• Ammonium Carbamate is a corrosive substance (white powder)
• Ammonium Carbamate will dissolve, if it is heating up to a temperaturehigher than approx. 60 Deg. C
• If oxygen is present in CO2 system, it will react with the PAO oil•Oxygen can be present e.g. from corrosion in tubes
• Organic Acid and Water are generated
• The Organic Acids from oxidation are relatively strong acids
PAO Polyalfaolefin Oil in CO2 systems(Synthetic Mineral Oil)
PEO Polyol Ester Oil in CO2 systems
• If water is present in CO2 system, it will react with Ester oil•Organic Acid and Alcohol are generated
• The Organic Acid is relative weak acid
Removing water from CO2systems
Filter drier in CO2 systems
Desiccant core absorbingwater from refrigerant(Molecular Sieves)
Filter mat collecting solidcontaminants
Molecular Sieves in CO2 systems
CO2 penetrates through the micropores unlike other refrigerants likeR134a. If water is present, it will also penetrate through the microporesand throw CO2 out, due to difference in polarity of water and CO2.
CO2 driers with Molecular Sieves are very efficient.
Refrigerantmolecules andmicropore sizein Zeolite LTA
Molecular Sieves water uptake in CO2 systems
Molecular Sieves water uptakeCO2 /R134a systems
CO2 R134a
The efficiency of the molecular sieves with CO2 and R134a are almost identical
Water (moisture) in CO2
Water Solubility in Refrigerants.Liquid Phase
(Y-Axis Linear)
0
500
1000
1500
2000
2500
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
Temperature [oC]
mg
of w
ater
/kg
refr
iger
ant [
ppm
]
Water Solubility in Refrigerants. Gas Phase(Y-Axis Linear)
0
200
400
600
800
1000
1200
1400
1600
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
Temperature [oC]
mg
of w
ater
/kg
of re
frig
eran
t [pp
m]
CO2
CO2
R134aR134a
0
200
400
600
800
1000
1200
1400
1600
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
Temperature [oC]
mg
of w
ater
/kg
of re
frige
rant
[ppm
]
CO2
NH3 R134a
R22
R404A
Water Solubility in Refrigerants. Gas Phase(Y-Axis Linear)
CO2
0102030405060708090
100
-50 -40 -30 -20 -10 0 10 20
Temperature [oC]
mg
of w
ater
/kg
of re
frig
eran
t[p
pm]
CO2 + H20 gas Phase
CO2 +ICE
CO2 +Water
Danfoss Sight Glass SGN in CO2
01020
30405060
708090
100
-50 -40 -30 -20 -10 0 10 20
Temperature [oC]
mg
of w
ater
/kg
refr
iger
ant [
ppm
]
”Wet”
”Dry”
Water in CO2 systems
CondenserEvaporator
CO2 system with filter drier and indicator
Filter drier Moisture indicator
How can water penetrate into a CO2 system?ØThe pressure of CO2 systems is always above the atmospheric
pressure; therefore there are not the same risks, as e.g. in NH3systems, that air / water penetration into a leaking CO2 system,however permeation of water into the system is still possible.
Water in CO2 systems
Ø When charging CO2, there are different specifications of CO2. Someof them allow relative high amounts of water.
ØCO2 is treated as a very safe refrigerant, and is therefore handledwithout following the normal safety requirements. If a system isopened up, air can penetrate into it, and the moisture can condenseinside the tubes. If the system is not evacuated properly, some watermay well be retained.
ØBy charging lubricant (oil) to the compressor.
ØBy decomposition of oil
Ø CO2 is compatible with almost all common metallic materials, unlikeNH3. There are no restrictions from a compatibility point of view, whenusing copper or brass.
CO2 compatibility with metal and polymers
Ø The compatibility of CO2 and polymers is much more complex. BecauseCO2 is a very inert and stable substance, the chemical reaction withpolymers is not critical.
Ø The main concern with CO2 is the physiochemicaleffects, such as permeation, swelling and the generation of cavities andinternal fractures. These effects are connected with the solubility anddiffusivity of CO2 in the actual material.
Ø The compatibility of CO2 and polymers can be sensitive.
CO2 compatibility with metal and polymers
Ø CO2 penetrates into polymers, but has difficulties to get out fast.
Ø CO2 pressure, temperature and pressure change are important factors
But !
Ø In sub-critical CO2 refrigeration the pressure is relative low (< 50 bar)and further more pressure changes take place relative slow.Experience has shown that standard CR O-rings can be used with CO2,under these conditions.
Ø CO2 is a natural non-toxic/non-flammable substance
Ø CO2 is a relative unreactive refrigerant
Ø All reaction involving CO2 need water to take place.
Ø The acceptable water content in CO2 systems is much lowerthan in other refrigeration systems
Ø Water, oxygen, oxides, oil, contaminants and system metalsare the most important chemical reactants. Also in systemswith CO2.
SUMMARY
Thank youfor attention!
Questions ?