APPLICATIONS FOR REFRIGERATION

OILS

Copyright of Shell Lubricants 2010 1

MARKETS FOR REFRIGERATOR OILS

Industrial and commercial applications

25 % 75 %

Customers doing their own

Hermetically
sealed units OEM owned service outfitsMarket
(domestic
applications) trends

Third-party or independent

service companies

20 % 80 %
Initial fill Service / maintenance
Copyright of Shell Lubricants 2
 MARKET SEGMENT CHARACTERISTICS

•Medium to big size customers (including

•Direct sales to OEMs, often OEMs) but relatively small volumes
according to their specifications •Typical figures:
•Volume/customer ~ 20-40 t/year
•Few, big players buy big •Unit Proceeds ~ 1750 $/t
volumes at low prices. •Gross Margin ~ 750 $/t
• Brand elements: performance, service,
•Typical figures: quality, “no-worries”, OEM approvals

Volume/customer ~ 500-1000 t/yr •Non-direct, channelled sales (via revellers)

Unit Proceeds ~ 1000- 1500 $/t •Lots of small/medium customers.
Gross Margin ~ 3000 -500 $/t
•Typical figures:
•Volume/customer ~ 1-5 t/year
•Price and technical performance •Unit Proceeds ~ 2000 $/t
key parts of the marketing mix •Gross Margin ~ 1000 $/t
•Brand elements: margin opportunities,
brand reputation, OEM approvals

Copyright of Shell Lubricants 3

RETAIL FOOD STORE: 40 % OF POWER FOR COOLING

Food stuff refrigeration

Others
26% 20%

Bakery
Airconditioning
5%
20%

Lighting
29%

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REFRIGERATOR OILS USED IN MOST SECTORS

Auto
Gen.Eng. Marine Transport Food Mining Chemicals
Manuf.

Hydraulics

Gears

Refrigerators

Turbines

Greases

Services

Copyright of Shell Lubricants 5

 TREND TO ENVIRONMENTALLY FRIENDLY REFRIGERANTS

Montreal Kyoto NH3

Safet HFC
NH3 R 12
y (CFC) (R 134a) HC
R 22
1920 (HCFC)

CO2

Copyright of Shell Lubricants 6

 ENVIRONMENTAL IMPACT OF REFRIGERANTS

Ozone Depletion Potential (ODP) Reference: R 11

ODP=1, GWP=1

Natural
Refrigerants
e.g. Ammonia,
Propane

Global Warming Potential (GWP)

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OEM´S PERSPECTIVE

▪ Shell not visible as marketer for synthetic refrigerator oils

Market Trends OEMs + Refrigeration Service Companies

Strong liason with one oil supplier,
◼ Example: York (including Sabroe and Gram) & Mobil
GPOs important part of OEM service business
◼ Example: Axima (former Sulzer-Escher-Wyss): Shell minded

Copyright of Shell Lubricants 8

MARKET TRENDS

▪ Sector approach
▪ OEM and Service Companies
▪ Competitors
▪ Car Airconditioning

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LATEST TRENDS AT GLOBAL FOOD CUSTOMERS

Examples: Coca Cola, Nestlé

▪ React on EPA recommendation to withdraw from

refrigerants with global warming potential and to use natural
refrigerants only
▪Replace R 134 a by other refrigerants e.g. ammonia and / or
CO2

Copyright of Shell Lubricants 10

APPLICATION SPECIFIC INFORMATION ABOUT LUBES

Copyright of Shell Lubricants 11

 REFRIGERATION COMPRESSOR LUBRICATION

Wax Fluidity
Precipitation Valve cooking
Condens
Expansion valve er

Evaporat to 250°C
or
Misci- down to
bility -100°C Misci-
80-120°C bility
Receive
r
Dilution, Miscibilty, Copper plating

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TASKS OF A REFRIGERATOR OIL

▪ Lubrication of bearings, cylinders, pistons

▪ Sealing of pressurised areas
▪ Cooling of hot compressor spots
▪ Prevent corrosion
▪ Electrical insulation
▪ Reduce noise level

Copyright of Shell Lubricants 13

CLASSIFICATION ACCORDING ISO AND DIN
STANDARDS

Refrigerant DIN 51503-1

Ammonia KA
Ammonia immiscible KAA
Ammonia miscible KAB
HFC immiscible
HFC miscible KD
CFC, HCFC miscible KC
Carbon dioxide miscible
Hydrocarbons miscible KE

Copyright of Shell Lubricants 14

WHY IS GOOD MISCIBILITY IMPORTANT ?

▪ Avoid deposits in evaporator

▪ Safe oil return to the compressor
▪ Efficient heat transfer
Oil Deposits
Refrigerant

Low Temperatures

Oil Deposits
Evaporator

Copyright of Shell Lubricants 15

MATERIAL COMPATIBILITY TEST

▪ Stability test for construction

materials, refrigerant and oil
▪ Test conditions:
▪ 14 days, 200°C, 0.7 g
refrigerant, 0.7 g refrigerator
copper wire
oil

steel sheet
▪ Result: Visual rating of
▪ oil colour, sludge
▪ copper surface
▪ steel surface (oil and gas
phase)
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CHEMICAL STABILITY TEST WITH REFRIGERANT

▪ Stability test for refrigerator

oils under refrigerant
atmosphere
▪ Result: Time to colour
change of the oil phase at
250°C
Oil
Refrigerant

Copyright of Shell Lubricants 17

 ADVANTAGES OF REFRIGERATOR OILS ALLOWING
LOWER EVAPORATION AND HIGHER END
TEMPERATURES

▪Expanded range of compressor operation for most efficient

conditions and/or to cope with overload operation
▪ Full system reliability even under severest conditions
▪ Longer oil service interval even under critical operation

Copyright of Shell Lubricants 18

PHYSICAL PROPERTIES OF REFRIGERANT-OIL-MIXTURES

▪ Refrigerant compressor lubrication

▪ Hygroscopic properties
▪ Floc point
▪ Chemical stability
▪ Miscibility
▪ Viscosity-Pressure-Temperature Charts

Copyright of Shell Lubricants 19

 SPECIAL HANDLING FOR HYGROSCOPIC GRADES

Conditions: 25°C, 75% relative humidity

Water mg/kg
2000
PAG 1 PAG 2

1600
PAG 3

1200 Ester ISO 15

800
Refrigeration Oil S4 FR-F 32

400
Refrigeration Oil S4 FR-F 100
Naphthenic based fridge oil
0
0 4 8 12 16 20 24
hours

Copyright of Shell Lubricants 20

DISSOLVED REFRIGERANT REDUCES VISCOSITY

Kinematic Viskosity [mm²/s]

10000

1000 Oil + R 22 Refrigerator Oil

P = 2 bar
100

10
Oil + R 12
P = 2 bar
1
-30 -20 -10 0 10 20 30 40 50 60 70 T [°C]

Copyright of Shell Lubricants 21

PHASE SEPARATION ON LOW TEMPERATURE SIDE

Temperature [°C]
50
Homogeneous
40
refrigerant-oil-
30 mixture (70% refrigerant/
20 30% oil) separates into
10 single phase 2 phases when cooled
0 down:
-10 2 phases 1. 4% refrigerant 96% oil
-20 2. 65% refrigerant, 35% oil
-30
-40
-50
-60
-70
0 10 20 30 40 50 60 70 80 90 100 m% Oil

Copyright of Shell Lubricants 22

IMPACT OF REFRIGERANT TYPE ON MISCIBILITY

Temperature [°C]
50
40
30 Mineral oil with
20
10 R 502
0
-10
R 22
Two phase
-20
area R 114
-30
-40
-50
-60
-70
0 10 20 30 40 50 60 70 80 90 100 m% Oil

Copyright of Shell Lubricants 23

 R 22: BETTER MISCIBILITY WITH ALKYLBENZENES

Temperature [°C]
10
0
-10 Refrigerant: R 22
-20
-30
Naphthenic fridge oil
-40 Napht.Alkylbenzene
Hybrid
-50
-60
Rerigeration Oil S4 F-V
-70
-80 m% Oil
0 10 20 30 40 50 60 70 80 90 100

Copyright of Shell Lubricants 24

 REQUIREMENTS FOR REFRIGERATOR OILS

Safe lubrication Viscosity

No wax precipitation Low temp.
fluidity
Safe oil return Miscibility

No cooking, decomp. Thermal stability

Inert with refrigerant Chemical stabili

Sealing Material Compatibility

Copyright of Shell Lubricants 25

 VISCOSITY-PRESSURE-TEMPERATURE CHARTS -
EXAMPLE
Shell Global Solutions Shell Global Solutions Shell Global Solutions
Density: Shell Clavus R68 - R410A Vapour-Pressure: Shell Clavus R68 - R410A Viscosity - Vapour Pressure: Shell Clavus R68 - R410A

1090 50 5000
48 2000
1080 1000
46 700
500
1070 44 300 M%Oil
M%Öl
o
°C 200
42 150

kinematic viscosity / mm²/s

o
°C 100
1060 90 100
-20 40 80
60 95
1050 38
-10 40 90
36 30
25
1040 0 34 80 20 85
15
32 80
1030 10
30 10
9
vapour pressure / bar 70 8 75
1020 20 28 7
density / kg/m³

6 70
30 26
1010 5
24 60
4
40
1000 22
30
20 50 25
50
20 M%Oil
M%Öl
990
18 15 70
60 12
16 40 75
980 10 80

vapour pressure / bar

8 85
70 14
30 6 90
970 12 5
80 4
10 20 3 95
960
90 8
10 2
950 6 1.5 97,5
0
4 -10 1
940 -20 0.8
2
930 0 0.5
70 75 80 85 90 95 100 70 75 80 85 90 95 100 0.4
-20 -10 0 10 20 30 40 50 60 70 80 90

concentration / M% Oil concentration / M% Oil temperature / °C

11/00
Shell Research and Technology Centre Hamburg, PAE Labor 11/00 Shell Research and Technology Centre Hamburg, PAE Labor 11/00 Shell Research and Technology Centre Hamburg, PAE Labor

Copyright of Shell Lubricants 26

LAB AND BENCH TESTS WITH SHELL REFRIGERATOR OILS

▪Compressor test (Bitzer) of Refrigeration Oil S4 FR-F with R 404

A

Copyright of Shell Lubricants 27

PROBLEM AREAS IN REFRIGERATION SYSTEMS

Issue Explanation How to fix it

Severe wear Viscosity too low at start- crankcase heating
(crankcase bearing up: select proper lubricant
mainly) - refrigerant dilution at
standstill
- immiscibility at standstill
Oil shortage: clean system
- foaming of the lubricant lubricant with better
foaming properties
System stops at Blocking of expansion installation of dryer /
certain valve / clean system / select
Temperature (re- capillary tube blocking: lubricant with lower
start possible after ice formation / wax floc-point
warm up) separation
Reduction of Lubricant covers surface clean system /
system efficiency of lubricant with better
heat exchanger: foaming properties
- foaming of the lubricant
Poor fluidity of the Select lubricant with
lubricant lower viscosity /
Copyright of Shell Lubricants lubricant with better 28

miscibility
PROBLEM AREAS IN REFRIGERATION SYSTEMS

Issue Explanation How to fix it

Valve coking Valve overheated Adjust system
sludge / deposit Thermal stability of conditions
formation lubricant insufficient Select high quality
lubricant
Copper plating Compressor overheated Adjust system
Thermal / chemical conditions
stability of lubricant Select high quality
unsufficient lubricant
Oil filter blocking in Lubricant oxidation by air Seal system
ammonia systems intake (evaporation Select lubricant with
temperature below – better oxidation
28°C) stability

Copyright of Shell Lubricants 29

PRODUCT STORY

Copyright of Shell Lubricants 30

REFRIGERATION OIL S4 FR-V

▪ Fully synthetic based on alkylbenzene

▪ Excellent high temperature and oxidation stability
▪Excellent sludge and deposit control particularly when used
with ammonia
▪Recommended for severe requirements with ammonia
especially high temperatures or below –33°C evaporation
▪Allows lower evaporation temperatures than naphthenic
based oils
▪ Fully miscible with mineral oils

Copyright of Shell Lubricants 31

REFRIGERATION OIL S4 FR-F

▪ Fully synthetic based on ester

▪ Excellent thermal and chemical stability
▪ Very good solubility with R 134a and R 23
▪ Favourable low temperature fluidity
▪ Long service life
▪Compatible with elastomers commonly used in refrigeration
systems

Copyright of Shell Lubricants 32

APPROVALS FOR REFRIGERATION OIL S4 FR-F

Shell Clavus R 22 32 46 68 100

Bitzer X X X
Bock X X X X X
Grasso piston X X
Grasso screw X X X

Copyright of Shell Lubricants 33

LOWER EVAPORATION AND HIGHER COMPRESSION
END TEMPERATURES WITH SYNTHETIC OILS

Evaporation Compression

Refrigeration Oil S4 FR-V

Naphthenic fridge oil

Temperature

Copyright of Shell Lubricants 34

 TYPICAL LIMITS FOR EVAPORATION TEMPERATURES

Lowest Evaporation Temperatures with Ammonia

0

-10
Temperature [°C]

-20

-30

-40

-50

-60

-70

-80 ISO 15 ISO 32 ISO 46 ISO 68

Naphthenic fride oils

Copyright of Shell Lubricants Refrigeration Oil S4 FR-V 35
 SYNTHETIC OILS:
FULLY RELIABLE EVEN UNDER SEVERE OPERATION

Max. Discharge Temeperature [°C]

150

140

130

120
Refrigeration Oil S4 FR-V Source: Gram (York)

Naphthenic fridge oils

Copyright of Shell Lubricants 36
CUSTOMER BENEFITS OF REFRIGERATION OIL S4 FR-V

EXAMPLE: SHELL MARINE PRODUCTS

▪ Help to protect valuable cargo and goods

▪ Reduce down time cost
▪ Peace of mind

Copyright of Shell Lubricants 37

COMPETITORS

▪ ExxonMobil:Mobil has comprehensive product range, now

focussing on synthetics only. Exxon impact = ??
▪ ICI: Market leader for ester based lubricants, sell also R 134 a

▪ CPI: comprehensive products portfolio, very aggressive

▪ Fuchs (former Fuchs-DEA): comprehensive product portfolio,

focus on Europe, very aggressive

Copyright of Shell Lubricants 38

PHASE SEPARATION ON LOW TEMPERATURE SIDE

Temperature [°C]
50
Homogeneous refrigerant-oil
40
mixture (70% refrigerant/
30 30% oil) separates into
20 2 phases when cooled down
10 single phase 1. 4% refrigerant 96% oil
0 2. 65% refrigerant, 35% oil
-10 2 phases
-20
-30
-40
-50
-60
-70
0 10 20 30 40 50 60 70 80 90 100 m% Oil

Copyright of Shell Lubricants 39

SAFE OIL RETURN DUE TO BEST MISCIBILITY

Miscibilty gaps of R 134 a and ester oils ISO 32

Temperature [°C]
60

40

20
Refrigeration Oil
0 S4 FR- F32
DEA SEZ 32
-20

-40 Fuchs E 32 Quelle:

Forschungsrat Kältetechnik e.V.

-60
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Oil quote

Copyright of Shell Lubricants 40

SAFE OIL RETURN DUE TO BEST MISCIBILITY

Miscibility gaps of R 407 c and ester oils ISO 32

Temperature [°C] Refrigeration Oil S4
80
FR- F32
60
ICI RL 32 S
40
Mobil EAL 32
20
ICI RL 32 S
0
Fuchs E 32
-20

-40 Quelle:

DEA SEZ 32
Forschungsrat Kältetechnik e.V.

Mobil
-60
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Oil quote

Copyright of Shell Lubricants 41

SAFE OIL RETURN DUE TO BEST MISCIBILITY

Miscibility gaps of R 404 A and ester oils ISO 32

Temperature [°C]
80
Refrigeration Oil
60 S4 FR- F32 Mobil EAL 32
40

20 ICI RL 32 S

-20
Fuchs E 32
DEA SEZ 32
Quelle:
-40 Forschungsrat Kältetechnik e.V.

-60
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Copyright of Shell Lubricants Oil quote 42
 AREAS OF FULL MISCIBILITY WITH R 407 C

DEA SEZ 32 -20°C ...+40°C

ICI RL 32 H +12°C ..
+55°C

Mobil EAL 32 -32°C ...................+72°C

-54°C .............................+75°C
Refrigeration Oil S4 FR- F32 Quelle:
Forschungsrat Kältetechnik e.V.

Copyright of Shell Lubricants 43

 AREAS OF FULL MISCIBILITY WITH R 407 C

Fuchs E 68 -40°C+15°C

ICI RL 68 S +20°C+35°C

Mobil EAL 68 -32°C ..........................+65°C

Refrigeration Oil S4 FR- F 68 -32°C ...........................+68°C

Quelle:
Forschungsrat Kältetechnik e.V.

Copyright of Shell Lubricants 44

 AREAS OF FULL MISCIBILITY WITH R 404 A

DEA SEZ 32 -45°C-10°C

Fuchs E 32 -60°C ...-10°C

ICI RL 32 S not fully miscible

-60°C ...............................
+40°C
Refrigeration Oil S4 FR- F32
Quelle:
Forschungsrat Kältetechnik e.V.

Copyright of Shell Lubricants 45

BITZER APPROVAL OF REFRIGERATION OIL S4 FR- F32

▪ Compressor test back-to-back with Bitzer factory fill oil (=

former DEA, now Fuchs)
▪ Hydrolytic stability

All tests were successfully run at PAE laboratory

Copyright of Shell Lubricants 46

 BEST CLEANLINESS WITH REFRIGERATION OIL S4 FR- F32

Valve plates suction side after PAE compressor test

Type: Bitzer II/X, R 404 A, 250 h, 90°C, Start-Stop-Operation

Oil A Refrigeration Oil S4 FR- F32

Copyright of Shell Lubricants 47

REFRIGERATION OIL S2 FR-A FOR AMMONIA
REFRIGERATION

Copyright of Shell Lubricants 48

 REFRIGERATION OIL S2 FR-A - BACKGROUND
INFORMATION

▪ Historically the US market used yellow refrigerant oils (YRO) in

both ammonia and halocarbon service
▪ In early 1980s, problems occurred with YRO in rotary screw
compressors in ammonia service

◼ Excessive foaming
◼ Excessive oil consumption and oil carry over
◼ Rapid increase in oil viscosity
◼ Excessive system deposits

▪ Some oil manufacturers controlled some of these problems

by selective selective base stock blending

Copyright of Shell Lubricants 49

 REFRIGERATION OIL S2 FR-A - BACKGROUND
INFORMATION

▪ By the mid-1980s, many OEMs were introducing paraffinic

mineral oil and/or PAO based lubricants for ammonia RSC

◼ In 1995, with naphthenic oil sales falling, work was

started on the present day Refrigeration Oil S2 FR-A
◼ In 1999-2000, modifications were made to this
formulation and the present day Refrigeration Oil S2 FR-
A was developed

Copyright of Shell Lubricants 50

FIELD TESTING OF REFRIGERATION OIL S2 FR-A

Growers Ice in Salinas California

◼ Long time customer, used naphthenic mineral oil in
ammonia rotary screw compressors
◼ Customer experienced operational problems

◼ Problematic oil foaming,

◼ Excessive oil consumption,
◼ Oil carry over,
◼ Rapid suction screen plugging, and
◼ O-ring deterioration

Copyright of Shell Lubricants 51

FIELD TESTING OF REFRIGERATION OIL S2 FR-A

From May 1998 through June 2001at Growers Ice, Salinas

California

◼ Evaluated Refrigeration Oil S2 FR-A in three 600 HP FES

Model 625 ammonia screw compressors
◼ Field test: Oil was drained from the units, charged with
Refrigeration Oil S2 FR-A and operated for 10 days
◼ After 10 days (~120 hours) the oil was drained and replaced
with new Refrigeration Oil S2 FR-A
◼ The suction strainers were cleaned, the oil separators and oil
filter were replaced

Copyright of Shell Lubricants 52

 REFRIGERATION OIL S2 FR-A - RESULTS FROM TEST AT
GROWERS ICE

Customer noticed immediate improvements:

◼ Eliminated oil foaming problem

◼ Reduced oil consumption and oil carry over

◼ No suction screen plugging

◼ Had minor problem with O-ring deterioration

◼ Refrigeration Oil S2 FR-A did not change color

Copyright of Shell Lubricants 53

53
 REFRIGERATION OIL S2 FR-A FIELD TEST AT GROWERS
ICE COMPANY

UNIT 3 - 600 HP FES AMMONIA SCREW

COMPRESSOR
Unit Hours Appearance Viscosity Water TAN RBOT Trace Metals Analysis
Running at 40°C cSt KF, ppm D 664 D 2272 Iron Zinc
Other Metal
0, Initial Clear, pale 61.1 < 50 0.08 707 Nil Nil <3

1007* Clear, pale 60.0 < 50 0.08 512 Nil Nil <3

1518* Clear, pale 60.3 < 50 0.08 430 Nil Nil < 3

2259 Clear, dark

pale 59.3 Not run 0.08 Not run Nil 17 <3

2771* Clear, dark

pale 58.4 < 50 0.08 321 4 41 <3

3500 Hazy, red 60.8** 143 0.08** 218** 2** 68** <
3**

6200 Clear, red 59.9 69 0.10 81 Nil 73 <3

* Samples run under Shell Care ** Sample dried before running test.

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REFRIGERATION OIL S2 FR-A FIELD TEST AT GROWERS
ICE COMPANY

UNIT 3 - 600 HP FES AMMONIA SCREW COMPRESSOR

Kinematic Viscosity @ 40°C [mm2/s]
80

70

60

50

40

30

20

10

0
0 1000 2000 3000 4000 5000 6000 7000
Copyright of Shell Lubricants
t [h] 55
 ACCUMULATED EXPERIENCE WITH SHELL
REFRIGERATION OIL S2 FR-A

▪ Refrigeration Oil S2 FR-A has been successfully marketed for

some years in Thailand and the US
▪ > 50 compressors have been successfully lubricated, both
screw and recip types
▪ Mainly food customers

◼ Cold storage

◼ Ice making

◼ Meat factories

Copyright of Shell Lubricants 56

CURRENT USE OF SHELL REFRIGERATION OIL S2
FR-A - RECIPS

OEM Type No.

Gram HC 8185 1
Grasso RC-612 6
RC-911 9
RC-912 10
Hasegawa VZL 62 A 2
VML 1
Mycom 42B681 1
42B1345 1
St. Regis KF6 2
KF10 2
Vilter Serial Number 60387 1
Copyright of Shell Lubricants 57
CURRENT USE OF SHELL REFRIGERATION OIL S2
FR-A - SCREWS
OEM Type No.
FES 250 HP 4
350 HP 2
700 HP 2
Model 180 1
Model 255 1
Model 352 1
Frick 100HP 1
MR1906AHVMD 1
Mycom Model 250 SUD-MX 1
VLD 1
VLD-SU 1
Reco 125 HP 1
N6B 1
Copyright of Shell Lubricants 58