1. Manufacture grease makes simple

2. Content Simple Lithium, Lithium Complex Grease production
New way to improve production efficiency
Background of calcium sulfonate grease
New calcium sulfonate grease making process
Finished based grease performance
Performance enhancement

3. Performance Additives
Typical Grease Composition
Base Stock %
Performance Additives
0 - 4%
Soap
10%

4. Function and Chemical Composition Simple Soap
Organic Fatty Acid + Metallic Hydroxide = Soap
Lithium 12 Hydroxystearate Soap H O C 2 3 + L i - 1 y d r o x s t e a c h u m

5. Function and Chemical Composition Complex Soap
Thickener structure formed by two or more compounds:
Long chain fatty acid
Short chain carboxylic acid
Optionally intermediate chains
Lithium Complex Soap H O C 2 3 + 4 L i - 8 1 y d r o x s t e a c h u m A z l p S

6. Fiber formation, cooling
Grease Manufacturing
Saponification stage
Fiber formation, cooling
Is There a Better Method ?
Foam
Data extracted from “A Comparison of Grease Manufacturing Methods”, K. R. Masters, Stratco.
Presented at the European Lubricating Grease Institute AGM, 1992, Chester, UK

7. New Product An oil-based dispersed micron sized anhydrous lithium hydroxide
Fluid, pumpable, mineral oil-based; PAO based product is available
Anhydrous – a virtually waterless process, reduced foaming and less energy consumption
Micron sized particles (~100 times smaller than lithium hydroxide monohydrate)
Greater surface area
Enhanced reactivity
Good storage stability
Stable – no evidence of reacting to CO2 and moisture in the air
Anhydrous
Smaller particle size
Oil based fluid

8. Lithium Hydroxide Monohydrate Crystals
LIOH.H20
New Product . .

9. Comparison between Lithium Hydroxide Monohydrate and new product
Physical form
White crystals
Opaque dispersion in oil
% lithium hydroxide
57%, balance is water
36%, anhydrous
Packaging
Bags
Drums or bulk
Particle size
micron
<10 micron
Method of addition
Added as powder or as slurry in water
Meter in via pump

10. Grease Manufacturing A Simple Lithium Grease Recipe
Material
LiOH•H2O
New Product
12-HSA
9.8kg
Base oil
90kg
88.7kg*
Lithium base
1.37kg
2.10kg
Target soap content (% wt)
10.0
* Less oil is needed due to oil introduced by Lubrizol® 5280GR

11. Process Profiles: Simple Lithium Grease50
100
150
200
250 0%
20%
40%
60%
80%
100%
Time %
Temperature deg C
Ref Li OS

12. Process Profiles: Lithium-Complex Greases
LiOH dispersion
Lithium Complex 50
100
150
200
250 0%
20%
40%
60%
80%
100%
Time %
Temperature deg C
Ref LiX OS

13. Lithium Grease 12-HSA 9.8% New Product 2.1% Oil from new product 1.3%
Base oil, 600N
88.7%
Water
(byproduct)
- 0.6%
Test
Result
Dropping point
ASTM D2265
202° C
ASTM D218 P0
P60
P1000
224
222
232
Soap content
10%

14. Lithium-Complex Grease
12-HSA
9.6%
Azelaic acid
3.0%
New Product
4.1%
Oil from new product
2.6%
Base oil
84.4%
Water (byproduct)
-1.2%
Test
Result
Dropping point
ASTM D2265
>285° C
ASTM D P0
P60
P1000
297
288
Soap content
13%

15. Lithium-Complex Grease Property Comparison
Grease C
Grease D
Base
LiOH-H2O
New Product
Soap content (% Wt)
10.7%
10.4%
ASTM D128: neutralization #
1.3b
1.0b
ASTM D217: penetration P0
278
270
P60
279
275
P10K
---
296
ASTM D2265: dropping point
284° C
309° C

16. Benefits of New Product
Faster soap manufacture
Reactivity greatly enhanced by small particle sizes/larger surface areas
Faster saponification - acid and base both present in oil phase
Less foaming during heating to slow process down
No added water to remove
Increased manufacture throughput with existing equipment
Shorter manufacture cycle, more batches can be made
Slightly larger batches allowed due to reduced foaming

17. Benefits of New Product
Manufacture cost savings
Shorter production time, increased capacity with existing equipments, lower unit manufacture cost
Lower peak reaction temperature, energy savings
Minimum water to be removed, energy savings
High quality, more consistent products, less costly batch re-work
Operational
Pumpable liquid, the quantity added can be very easily and precisely controlled.
Comes in drums or bulk, no dusty waste sacks to dispose
Safer handling compared to dusty solid powder of lithium hydroxide monohydrate
No need for a special pre-mixing side vessel for making water and lithium hydroxide monohydrate slurry
Minimum foaming hazard
Less waste oil disposal; less steam during soap manufacture

18. Benefits of New Product
Lithium complex greases
New Product enables a reliable, single step process for making lithium-complex grease, with less work-off
The product has a high dropping point (> 300° C)
The period of time at max temperature of approx 200° C is much reduced
Simple procedure using New Product enables high-quality lithium complex greases to be made in plants with basic grease kettles
Ester or vegetable-based grease
New Product is proven to be effective in making lithium and lithium- complex soaps in esters and vegetable oils
This is not possible for conventional LiOH.H2O process where hydrolysis of ester or vegetable oils during saponification is a concern

19. Calcium Sulfonate Grease make simple

20. Calcium Sulfonate Grease
Calcite-thickened greases have been known since the 1960’s
Typically made from overbased calcium sulfonates
High dropping point, and good mechanical stability
Strong, inherited EP/antiwear performance:
Timken
Four ball wear
Four ball weld
Further additized for enhanced performance

21. High Temperature Grease Growth Trend
Calculated annual
growth rate 8%
5.3%
2.3%
Fastest growing type of greases
High temperature, wet and heavy load operation conditions:
Mining, Steel Mills, Railroad, Paper Mills, Truck, Marine, etc
Inherent AW/EP:
Food grade (H1 and H2)
13.6%
Source: NLGI Survey

22. High Temperature Grease Comparison
Li Complex
Al Complex
Polyurea
Ca sulfonate
Advantage
Multi-purpose
Good pumpability
Readily available
Water resistance
Ashless
Excellent oxidation resistance
Low noise
Seal for life
Inherent EP/AW
Good mechanical stability
Good corrosion resistance
Disadvantage
Additives needed for performance
Rising raw material cost
Poor oxidation resistance
Manufacturing requirements high
Poor mechanical stability
Needs additive for Rust, EP and corrosion
Poor low temperature Pumpability
Availability

23. Calcium Sulfonate Grease
Colloidally Stable Wafer-Like Calcite Crystals in Oil
Calcium Sulfonate Hydrocarbon and Oil Tails
Colloidal Dispersion of Amorphous CaCO3
in Oil Stabilized by Surfactants
Converting Process
Promoter Solvent
Calcium sulfonate greases begin as an colloidal dispersion of amorphous calcium carbonate particles in oil. Conversion to the crystalline carbonate form is accomplished by promoters to form a platelet-like structure. The size of these calcite particle have been measured to be in the nanoparticle range, which is very important for their performance characteristics.

24. Extreme Pressure Contact Zone
Metal surface
Voids
Contacting
Surfaces
Mating
Surface
Asperities
If one were to look at the extreme contact zone of a metal under a microscope, one would see irregularities on the surface. There are voids and contacting surfaces also called asperities that would contact one another upon movement and if no additive were present they would wear or weld. Standard grease contain EP agents such as sulfur additives or anti-wear agents like ZDP’s to protect the surface.
These additives would adhere to the surface and upon extreme pressure and heat they would decompose on the surface and actually adsorb into the metal. These surfaces are weaker than the metal themselves are easily removed upon metal contact, thereby reducing the temperature and preventing welding from occurring

25. Extreme Pressure Contact Zone with Sulfonate Grease
Metal surface
Calcium sulfonate grease
Contacting
Surfaces
Now looking at the same extreme pressure contact zone with a calcium sulfonate greases one can expect to see that these small particles filled in the voids between the metal surface by adhering to the surface with their polar head groups. These crystalline structures are capable of protecting the surface by having their platelet structure momentarily sheared under load conditions which prevents the metal surfaces from experiencing contact.

26. New Calcium Sulfonate grease precursor
A new, enhanced 400TBN calcium sulfonate grease substrate
Simple predictable grease procedure
“Add water, oil, cook, you get grease!”
Excellent AW/EP performance
Superior water spray off properties

27. New Calcium Sulfonate grease precursor Vs. Conventional Process
Conventional Sulfonate Grease Process
New Sulfonate Grease Process
Temp (°C)
Add 12-Hydroxystearic acid
160
Add oil
Remove H2O
Add lime and
boric acid
solutions
140
Add acetic acid
120
Add water and
Sulphonic acid,
Add oil
100
Add oil
Remove H2O 80
cool
Stir, increase temp 60
Charge starting Materials:
Lubrizol ® 86GR, base oil, water 40 20 60
120
180
240
300
360
420
Process Time (Minutes)
Lubrizol®86GR all ingredients are added up front
Conventional sulfonates require multiple steps

28. Performance of Calcium Sulfonate grease from new process1 2 3 4
Base oil added
325N Group I
600N Group I
Bright Stock
PAO-100
Oil 40°C
32.9
49.8
121.3
305
Total oil (%wt)
56.5
59.7
62.6
66.9
D217 Penetration
297
290
266
303
D2265 (Dropping Point °C)
>316
D2509 (Timken load, lbs) 60 70
D2596 (Four-Ball EP, kg)
400
D2266 (Four-Ball Wear, mm)
0.28
0.31
0.30
0.40
D1743 (Rust, distilled water)
pass
fail, tr
D1264 (Wash out, %)
3.3
1.6
1.4
1.3
D4049 (Spray off, %)
24.4
8.1
14.2
6.8

29. Comparison of Ca Sulfonate Greases
Competitive Process
New Precursor
D2266 ( mm) - 4ball wear
0.33
0.31
D2265 (ºC) - DP
>316
D2596 (kg) – 4Ball EP
400
D1264 (%) – Water Washout
2.4
1.6
D4049 – Water Spray-off 67
8.1
D2509 (#) Timken 60 70

30. Advantages of New Calcium Sulfonate grease precursor
Synthetic calcium sulfonate – security of supply
Simple, fast, Lubrizol unique procedure requires only water as promoter
Compatible with Group I, Group II, and synthetic oils
Ca sulfonate greases base on new precursor provides
High dropping points
Excellent AW/EP
Good rust protection
Excellent water spray off protection

31. Thank you!