Lubricants Lubricating Oils. Fogarasi Zsolt Miklós, Görög András Budapesti Műszaki- és Gazdaságtudományi Egyetem

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1 Lubricants Lubricating Oils Fogarasi Zsolt Miklós, Görög András Budapesti Műszaki- és Gazdaságtudományi Egyetem

2 Agenda MOL LUB Ltd. Lubricants Lubricating oils

3 MOL-LUB Ltd.

During the Industrial Revolution lubricants served as coolants The improvement of

4 HISTORY OF LUBRICANTS Lubricants have been present since the first mechanical parts First shafts were made of wood, and their rotation was aided by animal fats. During the Industrial Revolution lubricants served as coolants The improvement of mechanical parts and the increasingly severe conditions require continuously improving lubricants.

TASKS OF LUBRICANTS Lubricants produce a liquid

Protect and passivise surfaces, Inhibit corrosion

5 TASKS OF LUBRICANTS Lubricants produce a liquid film between moving mechanical parts. They decrease the coefficient of friction Reduce wear Protect mechanical parts from berágódás Protect and passivise surfaces, Inhibit corrosion Etc. Increase the life of equipment! Lubricants have become structural elements!

6 TYPES OF LUBRICANTS PHYSICAL STATE Gases Liquids Consistent materials Solid lubricants Application conditions determine the selection of lubricant, therefore the highest demand is for liquid lubricants

7 USE OF LUBRICATING OILS Automotive lubricants Engine oils Gear oils Industrial oils Hydraulic oils Turbine oils Compressor oils Oils for machine tools Heat transfer oils Other areas Food industry Pharmaceutical (white) oils

8 PRODUCTION OF LUBRICATING OILS Oil blending Batch operation T ( C) M (t) T (h)

9 COMPOSITION OF ENGINE OILS ~ 80% base oil Mineral Gr. I. Gr. II. Gr. III. Synthetic Gr. IV (PAO) Gr. V (other, eg. esters) ~ 20% additive Viscosity Modifier Pour Point Depressant Detergent Dispersant Anti-Wear additive Oxidation inhibitor Friction Modifier Foam Inhibitor

10 FUNCTION OF BASE OILS Role of Base Oils in Lubricants Provides some level of lubrication Solvent for additives Medium for heat transfer Cleaning agent Provides flow properties

TYPES OF BASE OILS API Base Oil categories BO Group S content (m/m) % Saturated hydrocarbons (m/m) % Viscosity Index Group I > 0,03 And/or < 90 80-119 Group II < 0,03 And > 90

11 TYPES OF BASE OILS API Base Oil categories BO Group S content (m/m) % Saturated hydrocarbons (m/m) % Viscosity Index Group I > 0,03 And/or < Group II < 0,03 And > Group III < 0,03 And > 90 > 120 Group IV Polyalphaolefins (PAO) Group V Other base oils Mineral Hydrotrated mineral Hydrocracked PAO Other (Esters, PAG) Mineral Synthetic

12 MOST IMPORTANT PARAMATER Kinematic Viscosity A fluid s resistance to gradual deformation by stress How thick the fluid is μ = π x r 4 x g x l x t = 8L x V k x (t 1 - t 2 ) μ: Kinematic Viscosity r: Radius of capillary l: Average hydrostatic head g: g force V: Volumetric speed t: Time k: Capillary constant

13 ADDITIVES Active Inactive Pour Point Depressant Tackifier Component Anti-Wear Oxidation Inhibitor Viscosity Modifier Extreme Pressure Additive Solubiliser Corrosion Inhibitor (De)Emulsifiers Friction Modifier Biocide Dispersant Foam Inhibitor Detergent

14 MOST IMPORTANT ADDITIVES Viscosity Modifier Pour Point Depressant

15 MOST IMPORTANT ADDITIVES - II Dispersant Foam Inhibitor

16 WHAT S ON THE BOTTLE?

17 Additive production Fazekas Attila Budapesti Műszaki- és Gazdaságtudományi Egyetem

18 AGENDA 1 Additive plant 2 Succinimide-type of additives 3 Lubricating grease thickener 4 Specialty additives 18

19 STRUCTURE OF THE ADDITIVE PLANT Lubricating grease and additive plant Additive plant Succinimide plant Polysuccinimide plant Surfactant plant RALOX plant Mono- and bissuccinimides Polysuccinimide Surfactants ALIP system RALOX system Grease thickener 19

20 SUCCINIMIDE-TYPE OF ADDITIVES SUCCINIMIDE AND POLYSUCCINIMIDE PLANT MANUFACTURING PROCESSES OF DETERGENT-DISPERSANT ADDITIVES: THERMAL TECHNOLOGY: Mono-succinimides Bis-succinimides Mono-bis-succinimides SOLVENT TECHNOLOGY Poly-succinimides 20

21 SUCCINIMIDE-TYPE OF ADDITIVES SUCCINIMIDE AND POLYSUCCINIMIDE PLANT THERMAL TECHNOLOGY: Maleic-acid-anhydride + Poly-iso-butylene anhidride CH C CH C O O O Maleinsavanhid MMSA=98 CH3 + R CH2 C = CH2 R CH = C CH2 CH C Poli(izo-butilén) MPIB=950 CH2 C O Poliizobutenil-borostyánkősavanhidrid MPIBBA=1048 Polyisobutenyl-succinic Acylation: PIBSA + polyvalent amines, depending on the type of additive mono- or bissuccinimide + water CH3 PIBBA + H2N (C2H4 NH)4 H O O CH3 R CH = C CH2 CH C CH2 C O N (C2H4 NH)3 C2H4-NH2 + H2O PIBBA MPIBBA=1048 Tetraetilén-pentamin MTEPA=189 O mono-szukcinimid Mmono=1219 Víz Mvíz=18 21

22 SUCCINIMIDE-TYPE OF ADDITIVES SUCCINIMIDE AND POLYSUCCINIMIDE PLANT THERMAL TECHNOLOGY: Diluting oil Filtration agents Vacuum Amines Reaction Dilution, Filtration Acylation 22

release Dilution, filtration Acylation Diluting oil Catalyst Solvent Vacuum

23 SUCCINIMIDE-TYPE OF ADDITIVES SUCCINIMIDE AND POLYSUCCINIMIDE PLANT SOLVENT TECHNOLOGY Catalytic addition ( PIB + MSA + DTBP + Xylene) Vacuum solvent release Dilution, filtration Acylation Diluting oil Catalyst Solvent Vacuum Polysuccinimide Filtration agents Reaction Solvent release Filtration Acylation 23

24 SUCCINIMIDE-TYPE OF ADDITIVES SUCCINIMIDE AND POLYSUCCINIMIDE PLANT WHY IS IT GOOD FOR US??? CLEANS AND KEEP CLEAN THE METAL COMPONENTS OF THE ENGINE INCREASES ENGINE LIFE PROTECTS SENSITIVE COMPONENTS FROM PLUGGING AND SEDIMENTS 24

25 PRODUCTION OF LUBRICATING GREASE THICKENER RALOX PLANT ALUMINIUM-COMPLEX GREASE THICKENER ALIP PRODUCTION AL + 3 R-OH AL (-O-R)3 + 3/2 H2 RALOX PRODUCTION- OLIGOMERIZATION N AL (-O-R)3 + N H2O /-(AL-O-R)-O-/N + 2 N R-OH SAPONIFICATION /-(AL-O-R)-O-/N + HOOC-R' /-(AL-COO-R')-O-/N + N R-OH ( R = C3H7; N = 3; R' = C17H35 ) 25

26 PRODUCTION OF LUBRICATING GREASE THICKENER RALOX PLANT ALIP PRODUCTION SYSTEM 26

27 PRODUCTION OF LUBRICATING GREASE THICKENER RALOX PLANT RALOX PRODUCTION SYSTEM 27

PRODUCTION, LOWER ENERGY CONSUMPTION, CONSTANT PRODUCT QUALITY COMPETITOR OF LYTHIUM GREASES

28 PRODUCTION OF LUBRICATING GREASE THICKENER : KOMAD 84xx series: BASE OIL DEPENDENT GREASE THICKENER FOR ALUMINIUM COMPLEX GREASES HIGH THERMAL STABILITY, FAST AND EASY GREASE PRODUCTION, LOWER ENERGY CONSUMPTION, CONSTANT PRODUCT QUALITY COMPETITOR OF LYTHIUM GREASES IMPORTANT TOPIC CONSIDERING THE FUTURE WHY? E-CAR BOOM PRICE OF THE LIOH RAW MATERIAL HAS DRASTICALLY EXPANDED 28

29 SPECIALTY ADDITIVES Surfactant I.: Macroemulsion Field of application: Enhanced Oil Recovery Why? Primary and Secondary Extraction Techniques: 30-60% of oil found in sites may be extracted Aim: increase efficiency of production Surfactant II.: Microemulsion Field of application: chemical treatment of gas production wells Purification of the well-run zone Extra benefits: some times oil production appeared Aim: reducing water quantity during the production 29

30 Lubricating Greases Zoltán Kató , Budapest

31 Agenda Definition of greases Composition and classification of greases Production Applications 31

Definition of grease ASTM D288: a solid to semifluid product of dispersion of a thickening agent in a liquid lubricant Dispersed phase: thickener Continous medium: lucricant (base oil) Sinitsyn:

the load reach the critical point and regains solid body properties after the removal of the stress Solid Temperature/pressure/shear Semifluid Ishchuk: dispersion of theickener and oil, where

32 Definition of grease ASTM D288: a solid to semifluid product of dispersion of a thickening agent in a liquid lubricant Dispersed phase: thickener Continous medium: lucricant (base oil) Sinitsyn: a lubricant which under certain loads and within the range of temperature application, exhibits the properties of a solid body, undergoes plastic strain and starts to flow like a fluid should the load reach the critical point and regains solid body properties after the removal of the stress Solid Temperature/pressure/shear Semifluid Ishchuk: dispersion of theickener and oil, where the dipersed phase: Forms a 3D skeleton penetrating the dispersion medium Skeleton elements have colloidal sizes in two measuring directions Is held in solution by Van der Waals and capillary forces 32

base oils (poly-alpha-olefins) Additives Like conventional lubricant additives

33 Composition ~20% additives ~0-10% additives ~4-18% thickener ~ 80% base oil ~ 70-96% base oil Base oils (MOL-LUB) Group I base oils ( cst V40) Group IV base oils (poly-alpha-olefins) Additives Like conventional lubricant additives (EP/AW, polymers, corrosion inhibitors, etc.) Other solid additives (graphite, molybdenum-sulfide.)

34 Classification of greases By composition By base oil Mineral Synthetic Semi-synthetic Bio By thickener Soap thickeners Conventional Complex Non-soap thickeners By NLGI consistency grade By application

35 Thickeners Conventional metallic soaps By reaction of a carboxylic acid and metal hydroxide O O 2C 17 H 35 C OH + Ca(OH) 2 C 17 H 35 C C 17 H 35 C O O Ca + 2H 2 O O

36 Thickeners Complex thickeners Metallic soaps containing more than one anion

37 Thickeners Non-soap thickeners Clays (bentonite) Polymers Polyurea PE, PP, PTFE

38 Ratio of manufactured greases by thickener type

000 445-475 Fluid 00 400-430 Fluid 0 355-385 Very soft 1 310-340 Soft 2 265-295

39 NLGI Consistency Grade NLGI: National Lubricating Grease Institute Penetration: after 60 strokes,at 25 C NLGI grade Penetration [0,1 mm] Appearance of grease Fluid Fluid Very soft Soft Normal grease Firm Very firm Hard Very Hard

40 Production of greases Batch process Main stages Preparation of the thickener Dispersion of the thickener in oil Cooling, additive inload Homogenisation Packaging Technology parameters depending on the thickener type T max = C P max = 0-6 barg

41 Grease cooking vessels Contactor (autclave) Duplicator

42 Production process of an Aluminium complex grease

Production process of a Li-12HSA grease Preparation of the thickener Base oil inload (30 percent of base oils) 12-HSA) inload Mixing, heating LiOH inload Mixing, heating, pressurizing Temperature on

43 Production process of a Li-12HSA grease Preparation of the thickener Base oil inload (30 percent of base oils) 12-HSA) inload Mixing, heating LiOH inload Mixing, heating, pressurizing Temperature on hold Cooling and mixing at different rates Depressurizing Dispersion of the thickener Base oil inload (the remaining 70 percent, cooling oil) Mixing, heating Polymer inload Heating, temperature on hold, intensive mixing Cooling, additive inload Cooling and mixing Additive inload Cooling Homogenizing Packaging

Additive inload Negatively affects grease structure and some grease properties Grease structure may collapse after a certain percentage More

44 Additive inload Negatively affects grease structure and some grease properties Grease structure may collapse after a certain percentage More than one additiv could perform synergic or antagonistic effect with each other Additive efficiency depends oh the type of the thickener and base oil

45 Homogenisation Increases uniformity of the thickener distribution Improves appearance of greases Improves mechanical and colloidical stability Homogenizers Pressing the grease through a narrow gap Gaulin homogenizer

46 Grease packaging

47 Advantages of grease lubrication Resists leakage through dripping, splattering Acts as a seal against water and other contaminants Lubricating sealed for life bearings Might be biodegradable Reduces noise and wibrations

48 Grease lubrication is not appropriate when Bearing rotational speed is too high Cooling is needed simultanously with lubrication It is essential to reduce frictional loss in the bearing If the same machine uses lubricant oils

49 Application of greases Antique and medieval applications (animal fats) Industrial revolution: petroleum based products (fatty acids, distillates)

Application of greases Nowadays Thickener type NLGI grade Special demands Food

thickener T max [ o C] Mechanical stability Water resistance Colloidal stability Na

150 Good Good Good Li complex 150-200 Excellent Good Good Al 70 Weak Good Good Al

50 Application of greases Nowadays Thickener type NLGI grade Special demands Food industry Main applications Bearings Propulsions Chain drives Cables Type of thickener T max [ o C] Mechanical stability Water resistance Colloidal stability Na 120 Fair Weak Fair Ca 60 Fair Excellent Good Ca complex Fair Good Good Li 150 Good Good Good Li complex Excellent Good Good Al 70 Weak Good Good Al complex Good Excellent Good Polyurea 180 Good Excellent Good Bentonite Fair Good Good

51 Inter-grease compatibility Ca Alkomplex Cacomplex Bentonite Li (12-HSA) Licomplex Polyurea Al-complex - I B I I C B Ca I - I C B C B Ca-complex B I - I I C C Bentonite I C I - I I I Li (12-HSA) I B I I - C B Li-complex C C C I C - B Polyurea B B C I B B - C: compatible I: incompatible B: limited compatibility

SELECTING PERFORMANCE GREASE: Ten Crucial Questions

SELECTING PERFORMANCE GREASE: Ten Crucial Questions Presented 4-13-2006 By Don Oldiges Principles of Selection Manufacturer recommendations Manufacturers usually provide a list of lubricants that meet