Manufacture grease makes simple

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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

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Typical Grease Composition

Base Stock
86 - 90%

Performance Additives
0 - 4%

Soap
10%

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 Function and Chemical Composition
Simple Soap
Organic Fatty Acid + Metallic Hydroxide = Soap

Lithium 12 Hydroxystearate Soap

O H2 H2 H2 H2 H2 H2 H2 H2 -2 H2O
C C C C C C C C C + LiOHH2O
HO C C C C C CH C C CH3
H2 H2 H2 H2 H2 OH H2 H2
Lithium Hydroxide
12-Hydroxystearic acid

O H2 H2 H2 H2 H2 H2 H2 H2
C C C C C C C C C
LiO C C C C C CH C C CH3
H2 H2 H2 H2 H2 OH H2 H2

Li 12-hydroxystearate

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Function and Chemical Composition
Complex Soap
Thickener structure formed by two 1. Long chain fatty acid
or more compounds: 2. Short chain carboxylic acid
3. Optionally intermediate chains

Lithium Complex Soap

O O H2 H2 H2 O
H2 H2 H2 H2 H2 H2 H2 H2
C C C C C C C C C C C C C C
2 HO C C C C C CH C C CH3 + HO C C C C OH
H2 H2 H2 H2 H2 H2 H2 H2 H2 H2 H2
OH
Azelaic acid
12-Hydroxystearic acid

-8 H2O
+ 4 LiOHH2O Lithium Complex Soap

Lithium Hydroxide

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Grease Manufacturing
Manufacturing Cycle for Simple Lithium Grease in an
Open Kettle
Saponification stage Fiber formation, cooling
250C
Temperature (C)

200C
150C
Foam
100C
50C
0C
0.0 2.0 4.0 6.0 8.0 10.0
Time (hr)

Data extracted from A Comparison of Grease Manufacturing Methods, K. R. Masters, Stratco.

Presented at the European Lubricating Grease Institute AGM, 1992, Chester, UK

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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
Anhydrous
Enhanced reactivity
Good storage stability Smaller particle size
Stable no evidence of reacting to CO2 and Oil based fluid
moisture in the air

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Lithium Hydroxide Monohydrate Crystals

LIOH.H20

New Product
. .

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Comparison between Lithium Hydroxide
Monohydrate and new product
Lithium hydroxide New Product
monohydrate
Physical form White crystals Opaque dispersion in oil

% lithium hydroxide 57%, balance is water 36%, anhydrous

Packaging Bags Drums or bulk

Particle size 500-1000 micron <10 micron

Method of addition Added as powder or as Meter in via pump

slurry in water

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Grease Manufacturing
A Simple Lithium Grease Recipe

Material LiOHH2 New Product

O
12-HSA 9.8kg 9.8kg

Base oil 90kg 88.7kg*

Lithium base 1.37kg 2.10kg

Target soap content (% wt) 10.0 10.0

* Less oil is needed due to oil introduced by Lubrizol 5280GR

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Process Profiles: Simple Lithium Grease
Lithium

250
Temperature deg C

200

150
Ref Li
OS 196909
100

50

0
0% 20% 40% 60% 80% 100%

Time %

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Process Profiles: Lithium-Complex Greases

Lithium Complex

250
Temperature deg C

200

150
Ref LiX
LiOH
OS 196909
100 dispersion

50

0
0% 20% 40% 60% 80% 100%

Time %

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Lithium Grease
12-HSA 9.8%
New Product 2.1%
Oil from new 1.3%
product
Base oil, 600N 88.7%
Water - 0.6%
(byproduct)

Test Result
Dropping point 202 C
ASTM D2265

ASTM D218 P0 224

P60 222
P1000 232
Soap content 10%

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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 D218 P0 297
P60 288
P1000 297

Soap content 13%

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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

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 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

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 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

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 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

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Calcium Sulfonate Grease make simple

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Calcium Sulfonate Grease
Calcite-thickened greases have been known since the
1960s
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

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 High Temperature Grease Growth Trend
Worldwide Grease Production Calculated annual
growth rate
350,000,000
8%
300,000,000
Pounds of grease

250,000,000

200,000,000

150,000,000

5.3%
100,000,000
2.3%
50,000,000
13.6%
0
2001 2002 2003 2004 2005 2006
Year

LiX AlX Polyurea Ca sulfonate

Source: NLGI Survey

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 Calcium Sulfonate Grease
Colloidally Stable Wafer-Like
Calcite Crystals in Oil

Converting Process

Promoter Solvent

Colloidal Dispersion of Amorphous CaCO3

in Oil Stabilized by Surfactants
Calcium Sulfonate
Hydrocarbon and Oil Tails

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 Extreme Pressure Contact Zone

Metal surface
Contacting
Surfaces

Mating
Surface
Asperities

Voids

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Extreme Pressure Contact Zone with Sulfonate Grease

Metal surface
Contacting
Surfaces

Calcium sulfonate grease

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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

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New Calcium Sulfonate grease precursor Vs. Conventional Process

Conventional Sulfonate Grease Process New Sulfonate Grease Process

Add 12-Hydroxystearic acid Temp (C)

Add oil 160

Remove H2O
Add lime and
boric acid 140
solutions
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
0 60 120 180 240 300 360 420
Process Time (Minutes)

Lubrizol86GR all ingredients are added up front

Conventional sulfonates require multiple steps
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Performance of Calcium Sulfonate grease from new process

Grease 1 2 3 4
Base oil added 325N Group I 600N Group I Bright Stock PAO-100
Oil viscosity @ 40C 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 >316 >316 >316
D2509 (Timken load, lbs) 60 70 70 60
D2596 (Four-Ball EP, kg) 400 400 400 400
D2266 (Four-Ball Wear, mm) 0.28 0.31 0.30 0.40
D1743 (Rust, distilled water) pass pass fail, tr fail, tr
D1264 (Wash out, %) 3.3 1.6 1.4 1.3
D4049 (Spray off, %) 24.4 8.1 14.2 6.8

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Comparison of Ca Sulfonate Greases

Competitive Process New Precursor

D2266 ( mm) - 4ball wear 0.33 0.31

D2265 (C) - DP >316 >316

D2596 (kg) 4Ball EP 400 400

D1264 (%) Water Washout 2.4 1.6

D4049 Water Spray-off 67 8.1

D2509 (#) Timken 60 70

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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

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 Thank you!

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