Additives

Improving performance

Balázs BALASKÓ

Dec 4th, 2019

Anti-Wear

Oxidation

Inhibitor

ADDITIVES as seen previously

InactiveActive

Pour Point

Depressant

Viscosity

Modifier

(De)E-

mulsifiers

Foam

Inhibitor

Biocide

Solubiliser

Detergent

Extreme

Pressure

Additive

Corrosion

Inhibitor

Dispersant

Tackifier

Component

Friction

Modifier

Anti-

Wear

Oxidati

on

Inhibitor

ADDITIVES grouping by Rudnick

Deposit Control Additives

Pour

Point

Depres-

sant

Viscosity

Modifier

Foam

InhibitorBiocide

Solubili

ser

Deter-

gentEP

Additive

Corrosi

on

Inhibitor

Disper-

sant

Tacki-

fier

Friction

Modifier

Film Forming Additives AW/EP Additives

Viscosity control Additives Misc. Additives

(De)

Emulsi-

fiers

EP

Additive

Anti-

WearFriction

Modifier

Oxidati

on

Inhibitor

ADDITIVES grouping

Deposit Control Additives

Pour

Point

Depres-

sant

Viscosity

Modifier

Foam

InhibitorBiocide

Solubili

ser

Deter-

gent

Corrosi

on

Inhibitor

Disper-

sant

Tacki-

fier

Film Forming Additives

Viscosity control Additives Misc. Additives

(De)

Emulsi-

fiers

Oxidati

on

Inhibitor

ADDITIVES OF LUBRICANTS (examples)

Active substances

Deter-

gent

Disper-

sant

Friction

Modifier

Area of application

Anti-

Wear

EP

Additive

Alkyl-phenols, BHTAminesZDDP

Automotive and ind. oilsMetalworking fluids

Overbased sulphonatesEngine oilsCompressor oilsMetalworking fluids

Polyalkyl succinimides Engine oils and transmission fluids

Graphite, MoS2

Esters, amides

GreasesGear oilsMetalworking fluids

ZDDPAutomotive and ind. oilsGreasesMetalworking fluids

PolysulphidesDithiocarbamates

GreasesGear oilsMetalworking fluids

Solubili

ser Iso-alcohols Metalworking fluids

ADDITIVES OF LUBRICANTS (examples)

Active substances

Pour

Point

Depres-

sant

Viscosity

Modifier

Foam

Inhibitor

Biocide

Corrosi

on

Inhibitor

Tacki-

fier

Area of LUB application

Emul-

sifiers

PMA, polymethacrylatesPAMA

Automotive and industrial oils

OCP, olefin copolymersStyrene-based

Engine oilsMultigrade hydraulic oils

Organomodified siloxanesEngine oilsHydraulic oils, circulation oilsMetalworking fluids

Hydroxyethyl-triazineformaldehyde-condensates

Metalworking fluids

Alkylamines, borates (Fe)Benzotriazole (Cu)Nitrates, nitrites (Al)

Metalworking fluidsInsulation oils typicallyEngine coolants

PIB GreasesSlideway oils

Etoxylated alcoholsAlkyl succinic acid derivatives Metalworking fluids

Demul-

sifiers Alkyl-benzene Hydraulic oil, circulation oils

Oxidati

on

Inhibitor

NATURE OF ADDITIVES: anti-oxidantsingle effect utilized in multiple industries

EFFECT / FUNCTION

INDUSTRY

CHEMICAL STRUCTURE

2,6-di-tert-butyl-4-methylphenol a.k.a. BHT (butylated hydroxytoluene)

Lubricants

Plastics

Food

Cosmetics

Radical scavenger

Corrosi

on

Inhibitor

EP

Additive

Anti-

Wear

Oxidati

on

Inhibitor

NATURE OF ADDITIVES: AW additivemultiple effects targeting a single industry

EFFECT / FUNCTION

INDUSTRY

CHEMICAL STRUCTURE

ZDDP

Dimer, trimer, tetramer, etc.

Lubricants

Radical scavenger

Surface absorption of thermal degradation products

More on FM/EP/AW additivesLubricating regimes

Boundary

Surfaces in contact

Chemistry-dependent

Mixed

Hydrodynamic / elastohydrodyn.

Partial fluid film

Chemistry and viscosity-dependent

Full fluid film

Viscosity-dependent

No wear

Source:Lubrizol

Viscosity * Speed / Load

Stribeck curve

10

ADDITIVE ASSETS OF MOL-LUB

Lubricating greaseand additive plant

Grease plant Additive plant

Pilot plant

Dithio-carbamate

plant

Succinimideplant

Mono- and bissuccinimides

Poly-succinimide

plant

Polysuccinimide

Surfactantplant

Surfactants

RALOX plant

ALIP system

RALOX system

11

Viscosity

Modifier

GROUP OF MOLECULES: BACK TO CHEMISTRYDithiocarbamate (Szhb plant)

Polyalkyl-Succinimides

Vegetable oil amide surfactant

Aluminum-oxo-stearate

Corrosi

on

Inhibitor

EP

Additive

Anti-

Wear

Oxidati

on

Inhibitor

Disper-

sant

Emulsi-

fiers

Grease

thicke-

ner

12

AT PILOT PLANT SZAZHALOMBATTA

CS2-BASED SYNTHESIS (TOXIC INGREDIENTS)

Dibutylamine + Carbondisulphide + Dichloromethane Methylene-bis(dibutyl-dithiocarbamate)

+ water + NaCl

Intermedier: N-subst. dithiocarbamic acid sodium salt

ASHLESS MULTIFUNCTIONAL ADDITIVE

EP/AW

Antioxidant

Corrosion inhibitor

EP/AW: DITHIOCARBAMATE PRODUCTION

NaOH

+ ++ NaOH

13

FOR SITE VISIT: SUCCINIMIDE AND POLYSUCCINIMIDE PLANT

THERMAL TECHNOLOGY (DISPERSANT ONLY):

Maleic-acid-anhydride + Poly-iso-butylene Polyisobutenyl-succinicanhidride

Acylation: PIBSA + polyamines mono- or bissuccinimide + water

CH–C

CH–C O

O

O

+ R – CH2 – C = CH2 → R – CH = C – CH2 – CH – C

CH3

CH2– C O

O

O

CH3

Maleinsavanhid MMSA=98

Poli(izo-butilén) MPIB=950

Poliizobutenil-borostyánkősavanhidrid MPIBBA=1048

PIBBA + H2N – (C2H4 – NH)4 H →

R – CH = C – CH2 – CH – C

O

CH3

PIBBA MPIBBA=1048

Tetraetilén-pentamin MTEPA=189

CH2– C

O

N–(C2H4–NH)3–C2H4-NH2 + H2O

mono-szukcinimid Mmono=1219

Víz Mvíz=18

DISPERSANTS: SUCCINIMIDE PRODUCTION

14

SOLVENT TECHNOLOGY

Catalytic addition ( PIB + MSA + DTBP (cat.) + Xylene)

Vacuum solvent release

Dilution, filtration

Acylation

Polysuccinimide

FOR SITE VISIT: SUCCINIMIDE AND POLYSUCCINIMIDE PLANT

DISPERSANTS: SUCCINIMIDE PRODUCTION

15

SURFACTANT PRODUCTION

Surfactant mixture additive

Field of application:

Enhanced Oil Recovery together with a polymer

(macroemulsion)

Non-ionic component: vegetable oil amide

Anionic component (proprietary patented by Pannon Univ.)

FOR SITE VISIT: SUCCINIMIDE AND POLYSUCCINIMIDE PLANT

16

SPECIAL ADDITIVES: GREASE THICKENER

Greases can be classified based on their thickeners as well(Li, LiX, CaS, CasX, AlX, polymer, etc.)

Aluminum-complex grease thickener manufacturing

Grease precursor (intermedier)

Two stage process:

Al-isopropoxide (ALIP)

Al-oxo-stearate

Complex formation is finalized during greasemanufacturing with benzoic acid

Marketable product as an intermedier forgrease manufacturers (35% market share in EU)

FOR SITE VISIT: RALOX PLANT

17

THE FUTURE OF ADDITIVES

Additives are vital components formodern lubricants

Additive development is appliedscience and chemistry:

Application focused

Experiment-based

…with dead-ends

MOL- LUB places strong focus onits additive product portfoliodevelopment according to itsStrategy 2030

BACKUP

Technology

19

SUCCINIMIDE-TYPE OF ADDITIVES

SUCCINIMIDE AND POLYSUCCINIMIDE PLANT

THERMAL TECHNOLOGY:

Reaction Dilution, Filtration Acylation

Vacuum

Amines

Filtration agentsDiluting oil

20

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

Reaction

Solvent release Filtration Acylation

Vacuum

Polysuccinimide

Filtration agents

21

PRODUCTION OF LUBRICATING GREASE THICKENER

ALIP PRODUCTION SYSTEM

RALOX PLANT

22

RALOX PRODUCTION SYSTEM

PRODUCTION OF LUBRICATING GREASE THICKENER

RALOX PLANT