بسم هللا الرحمن الرحیم

صدق هللا العظیم

A study on rheological and Tribochemical behavior of Biogreases

based on Waste cooking oil and it’s sulfurization

El-Adly,R.A, M. Adel Yossef, Enas A. Ismail, Modather, F. Hussein and Dalia M. Abbas

Industrial Lubricants •More than 90% of all lubricants are based on petroleum •The demand for biodegradable lubricants is expected to grow at about 10% annual rate

Lubrication

Lubrication is the act of applying lubricants and lubrication substances which are capable of reducing friction between moving mechanical parts

Metal Substrate

Metal Substrate

Asperities

All surfaces, no matter how smooth they may appear to the unaided eye, when sufficiently magnified are rough and uneven. This unevenness is know as asperities.

Asperities

Asperities when rubbed together generate particulate

Adhesion and Cohesion

Adhesion is the property of a lubricant that causes it too stick or adhere to the parts lubricated.

Cohesion is the property which holds a lubricant together and resist a breakdown of the lubricant under pressure.

Adhesion

Cohesion

Moving Surface

Oil molecules

Oil molecules slide over each other

Grease Composition

Fluid Thickener Additives

Petroleum

•paraffinic •Naphthinic •Aromatics

Synthetic

•PAO •Polybutenes •Esters

Bio oil

Vegetable oils and its modified

Soap

Lithium, Sodium, Barium, Calcium, Aluminum

Non-Soap (inorganic) Clay, Graphite, Silica and Carbon Black Non-Soap (organic)

Polyurea, PTFE, Wax

•Antioxidant •Antiwear •Antirust •Anticorrosion •Extreme pressure •VI Improver •Tackifier •Pour Point depressant •Solid Boundary Lubricants •Dye

Vegetable Oils as Lubricants

Advantages:

•Good boundary lubrication properties Polar ester groups are able to adhere to metal surfaces •Excellent viscosity – temperature characteristics Narrow range of viscosity changes with temperature •Biodegradability •Compatibility with mineral oil and additive molecules

Vegetable Oils as Lubricants

Disadvantages: •Poor oxidative stability Due to the presence of bis-allylic protons •Poor low temperature fluidity Due to high molecular weight

Using elemental sulfur (10 wt % ) in presence of

nitrogen bubbling at 185 oC

Modification of waste cooking oil Through Sulfurization reaction

Characteristics WCO SWCO Test

Density, g/ml @ 25/25, oC 0.863 0.965 D.1298

Refractive index, nD20 1.4652 1.4665 D.1218

Kinematics viscosity, c St. at 40oC at 100oC

31

8.16

430 72

D.445 D.445

Viscosity index 257 216.1 D. 189

Dynamic Viscosity, @ 50 oC (rpm 30), cP

80

560 D.97

TAN, mg KOH/gm @72h 1.85 0.89 D-664

Average Molecular weight 640 925 GPC

Iodine value 43 7.6 D-5554

Oxidation stability index 19 51 Cd 12b-92

Peroxide value 5.5 0.9 ISO 3960

Pour point, oC 9 1 D91

physico-chemical properties of WCO and SWCO

Fatty acid profile for Waste cooking oil

0.66 0.43 0.28

19.3

4.96

22.94

8.29 8.63

4.95

0.66 0.43

0

5

10

15

20

25

%

Variation of Shear Stress with shear rate forPWCO at different tempertaure

Variation of Viscosity with shear rate for PWCO at different temperature

Variation of Shear Stress with shear rate forSWCO at different tempertaure

Variation of Viscosity with shear rate for SWCO at different temperature

Oxidation stability index for purified waste cooking oil and sulpherized waste cooking oil

Physico-chemical properties of bio greases based WCO&SWCO Test WCO grease SWCO grease Test method

Penetration at 25oC

Un worked

worked

276

289

262

276

ASTM D-217

Dropping point, oC 115 140 ASTM D-566

TAN, mg KOH/gm, @72h 2.1 1.5 ASTM D-664 Oil separation, Wt% 5 3.5 ASTM D-1724 Copper Corrosion 3h/100oC Ia Ia ASTM D-4048 Code grease according to

NLGI

Egyptian standard

1 1 LB LB

Apparent Viscosity, cP, @ 90 oC 89892 91023 ASTM D-189

Consistency Index 520 915 Yield stress D/cm2 29 5 33 4

Variation of shear stress with Shear rate of grease based on WCO

Variation of viscosity with Shear rate of grease based on

WCO

Variation of shear stress with Shear rate of grease

based on SWCO

Variation of viscosity with Shear rate of grease based on SWCO

Schematic view of the pin on disc apparatus

Tribological behavior of greases prepared

Oil lubricant

79.5Cm 20 Cm

33 Cm 18 Cm

Grease feeder

pin

load

Disk

Element , % Pin Disc

C Ni Mo Cr Fe Mn P S

Cu Si

0.23 0.10

0.0117 0.10 98.1 0.71

0.029 0.021 0.30 0.19

0.47 2.5 0.7 1.2

95.6 - - - - -

Chemical composition of the Pin and Disc

Biogrease Friction co-efficient

Weld load, Kg

WCO grease 0.17 175

SWCO grease 0.12 250

Tribological properties of prepared greases based on WCO &SWCO

Blank WCO

WCO Greases

SWCO Greases

SWCO Greases WCO Greases

WCO Blank

Et-OH

Conclusions: 1- Optimization and utilization of waste material that cause environmental damage and turn them into valuable materials such as waste cooking oil. 2- Environmentally friendly bio greases production using waste vegetable oils substitute for Petroleum greases.

3-The prepared bio greases show better performance concerning mechanical stability and thermal stability.

4- The physicochemical and tribological properties of the prepared biogreases show that good lubrication performance

Autoclave for Grease preparation

Penetrometer

Dropping Point

Grease-Oil Separation

Kinematics Viscosity

Potentiometer

Programmable Rheometer Model HADV-IIIULTRA

Programmable Rheometer Model LVDV-IIIULTRA

Oxidation Stability for Greases