The Application and Use of Soltex Products in Hydrocarbon Lubricants and Lubrication Systems Lubricant Market Segments

Transcription

1 The Application and Use of Soltex Products in Hydrocarbon Lubricants and Lubrication Systems Lubricant Market Segments 1

2 Base-Stocks Base-stock constitutes about 90-95% of the lube formulation Non-Synthetic Long chain hydrocarbon products derived from naturally occurring hydrocarbon mixtures, particularly from various crude oil fractions, by refining techniques such as distillation and solvent extraction Synthetic Long chain hydrocarbon products made by polymerization or oligomerization of small molecules (monomers). Do not occur naturally, man made. 2

3 Non-Synthetic American Petroleum Institute (API) classification based on method of refining and purity; Group I Group II Group III Relatively broad distribution of hydrocarbon compounds with physical properties that reflect the average of the distribution Not a single compound, hundreds of compounds of every carbon number 3

4 Non-Synthetic - API Group I Refined by distillation, freezing, filtration and solvent extraction To adjust viscosity (distillation) Remove waxes (freezing, extraction, filtration) Specifications; Greater than 0.03% sulfur Viscosity Index (VI) Saturates < 90% Being phased out 4

5 Non-Synthetic - API Group II Refined by distillation and hydrotreating Hydrotreating is reaction with hydrogen Removes waxes, non-saturates, sulfur, improves VI Specifications; < 0.03% sulfur > 90% saturates VI Most common 5

6 Non-Synthetic - API Group III Refined by severe hydrotreating, hydrocracking and hydroisomerization Removes waxes and improves VI Changes molecule?? Specifications; < 0.03% sulfur > 90% saturates VI > 120 6

7 Hydrocarbon Relationships Group I, II, III Base Oils 7

8 What is Viscosity Index (VI) Viscosity is a fluid s resistance to flow Thick oils have a high viscosity, thinner oils have a lower viscosity Viscosity is a function of temperature; at higher temperatures viscosity is lower; at lower temperatures viscosity is higher VI is the rate of change of viscosity with temperature Low VI means a relatively large change of viscosity with temperature and conversely high VI means relatively little change with temperature High natural VI is desirable 8

9 Synthetic- API Group IV Polyalphaolefins (PAO) by definition PAO are made by the oligomerization of an alpha-olefin such as decene-1(c10) Increasing PAO grades, i.e.; 4, 6, 8 10 are increasing units of decene-1 Each unit of decene-1 increases the chain length by 10 carbons 9

10 PAO Production Process The catalytic oligomerization of decene-1 to produce PAO gives a certain distribution of oligomeric units of decene but the distribution is much narrower than the carbon number distribution in Group I, II and even Group III base-stocks Further the oligomeric units can be separated by distillation to give very narrow carbon number fractions The final products are hydrogenated to very low residual unsaturation (bromine no.) 10

11 PAO Properties Since PAO are synthesized they are in effect almost single chemical compounds This unique structure allows PAO to have very low pour (no wax) points, very high flash points (no lights) and high VI compared to comparable viscosity grades of Group I and Group II base-stocks However, because of the narrow carbon distribution, PAO have poor solubility for standard lube oil additives and can adversely affect engine and equipment seals PAO are often blended with other base-stocks, particularly esters (i.e. Mobil 1, to improve additive response and seal swell properties Expensive, 3-5 times the cost of Group I, II base-stocks 11

12 PAO Chemical Structure 12

13 PAO Oligomer Distribution Wt % Dimer Trimer Tetramer Pentamer+ C Number PAO Grade

14 Synthetic - API Group III Said earlier that Group III are non-synthetic because that occur naturally in nature. However, it has been claimed that because the Group III oils have been so severely hydrotreated and hydrocracked, they no longer resemble their natural state, they thus can be classified as synthetic. This claim was upheld in court (Mobil v Castrol) Because of lower cost of Group III this decision resulted in loss of synthetic market share for PAO 14

15 Group III vs. PAO Performance The biggest drawback to Group III vs. PAO is pour point. However, maybe by addition of the right kind of viscosity modifier (VM) and/or VI improvers this problem can possibly be mitigated Work in progress with Ciba R&D using new Soltex line Of S-Flow VII and VM as additives for Group III to replace PAO Particularly applicable to 75W90 and 75W140 gear oils 15

16 Synthetic API Group V All other potential base-stocks not in Group I,II, III or IV Doesn t denote performance, can be good or bad Synthetic or non-synthetic Includes esters, polyglycols (PAG), alkylate, PIB, aromatic oils, napthenic oils 16

17 Polybutene (PB) - Conventional Made from raffinate streams that contain mixed butylenes but isobutylene is more reactive and therefore incorporated at about 85-90% in the polymer chain One olefin group per chain but not on the end Low reactivity Used mainly in industrial applications Molecular weights from 300 daltons (Soltex PB4) - 4,000 daltons (Soltex PB28) 17

18 Polyisobutylene High Reactive HR PIB is made from high purity isobutylene streams Polymer chain contains only isobutylene groups One olefin group per molecule, located either alpha or beta to the end of the polymer chain High reactivity Manufacture of fuel and lubricant additives or other derivatives where chemical reactivity is important. 18

19 Terminal Olefin Isomer Groups in Polybutene and Polyisobutylene Industry confusion over terminology and structure E-PIB, HR-PIB, Conventional PIB 19

20 PB Physical Properties For applications not involving reactivity PIB and PB can be used interchangeably PIB has a highly branched molecular structure High viscosity for a given molecular weight, good thickening power Economical viscosity modifier Very clean burning, no smoke, no residue, no metal staining Shear stable comparable to conventional base oils and PAO but superior to other polymers High VI, especially for the higher grades 20

21 PB Applications in Lubes Two cycle engine oils Clean burning Low smoke, meet JASO FD specifications No engine deposits Gear Oils and hydraulic Oils Shear stability Thickening efficiency 21

22 PB Applications in Lubes Metalworking fluids De-polymerize at high temperatures Clean surface Compressor oils Oxidation resistance Low deposit formation Engine oils HR-PIB maleic derivatives 22

23 PIB Disadvantages High inherent pour point. Doesn t respond to VI or PPD additives Low VI at low molecular weight in the range of lube base-stock Low flash point at low molecular weight in the range of lube base-stock Moderate cost 23

24 Components Problem Chemical Class/Compound Function Soltex Products 24

25 Antifoams Foam reduces efficiency of the lube oil and can result in lube oil loses Silicone polymers and organic siloxane copolymers. Also PAG, mineral oils Reduces bubble surface tension to prevent (antifoam), reduce or eliminate foam (defoamer). Used at low ppm levels. Low molecular weight PB, i.e. PB 4, 8 25

26 Antioxidants Oxidation of lube oil increases acidity causing chemical breakdown of the oil and reduces life of the oil. Depletes add pack. Aromatic amines, hindered phenolic compounds. In conjunction are synergistic Oxidation is a free radical mechanism. Antioxidant scavenges free radicals. Geometric progression Soltex FS 310 (aromatic amine), Ciba hindered phenolics. 26

27 Anti-Wear and EP Additives High loads can cause breakdown of the oil layer between moving metal surfaces causing an increase in wear. These loads are found to some extent in crankcase but largely in gears Compounds that contain the elements of P, S, Zn, sometimes Mo. React with the metal surface to form new harder metallic compound on the metal surface. High load bearing capability. Some initial wear to activate. Zinc dialkyldithiophosphate. Zn, P, S in one molecule. Sulfurized olefins. Contained in Soltex PCMO, DEO and THF additive packages (PCA products) 27

28 Zinc Dialkyldithiophosphate 28

29 Detergents Oxidation can cause breakdown of lube oil and build up of sludge and varnish on engine or machine parts Ca and Mg sulfonates, phenates, salicylates The organic metallic salts have non-polar hydrocarbon tail and polar head group. The polar head group has affinity for dirt particles and the non polar tail helps disperse the attracted dirt particle in the lube oil matrix so it can be removed by filtration Soltex NeutralCal 10, PCA 400. (Note: Neutral sulfonates are better detergents compared to over-based, more active ingredient per molecule.) 29

30 Dispersants Oxidation of oil can cause sludge and varnish formation PIB succinimides, succinic anhydrides, succinic esters. Detergents and dispersants are sometimes the same compound and/or can do both functions Dispersants help disperse dirt, sludge and varnish particles in the lube oil matrix so they can be removed by filtration. Work in conjunction with detergent. Soltex PCA 9050 (PIBSA), PCA 9070 (PIBSI-950), PCA 9070 (PIBSI-2300) These are ashless dispersants and can be used alone as ashless detergent/dispersant 30

31 Emulsifiers Many metalworking fluids, particularly cutting fluids are oil-in-water emulsions. The oil, containing wear and anticorrosion additives, provide lube function, water removes heat PIB succinic anhydrides Emulsify oil in water. Soltex PCA 9050 (PIBSA-950) 31

32 Friction Modifiers (Boundary Lubricants) Break down of oil film at moderate loads can result in metal to metal contact between moving parts and increase wear Organic fatty acids, esters and amides Polar head group attaches to metal surface, long hydrocarbon tail provides lubricity Tall oil fatty acid, Soltex PCA 9050 (non-acidic) Ashless 32

33 Performance Boosters Oxidation of oil can cause build up of acidic products. Also use of high sulfur fuels can increase acidity of lube oil. Results in increased corrosion and wear. Over-based Ca, Mg salts of sulfonic acids High alkalinity (TBN) neutralizes acid Soltex PCA

34 Pour Point Depressants (PPD) Group I, II, III base-stocks contain wax impurities. At low temperatures wax crystals form and separate from the oil causing the oil to thicken and eventually not be able to flow. This is called the pour point, but is approached gradually. Polymethylmethacrylates (PMMA) most effective PMMA interferes with the wax crystal growth and prevents crystallization and wax separation. (Note: base-stocks that do not contain wax and have inherent pour points, i.e. PIB,PAO, do no respond to PPD. Soltex S-Flow PMMA products; S-Flow P750, P711, P811, P821 S-Flow P821 is most general purpose. Also refer to TDS and Ciba presentation Mixtures of S-Flow and Group III to compete with PAO 34

35 Viscosity Modifiers (VM) Base oils alone have relatively low viscosity and require thickeners to achieve specifications esp. for gear oils PMMA, PIB, olefin copolymers (OCP) Increase viscosity of the base oil and improve VI, also know as VI improvers. PMMA are most effective, PIB is most shear stable, OCP are most economical. Soltex S-Flow V1201(PMMA); BSR 900, PB 124, 128 (PIB) Soltex OCP 25, 35, 50 liquids. Concentration is about 9-10% in Group II base oil. Number refers to Shear Stability Index (SSI). The lower SSI products are more shear stable, but are lower molecular weight and require higher use levels. API approved Soltex OCP 2400, 2500 solids. SSI 45. OCP 2500 is API approved. 35

36 Tackifiers Gear oils and greases require components that allow the lubricant to better adhere to the metal surface. High molecular weight PIB, 50,000 to 4,000,000 daltons. Dissolved in Group II oil. FDA approved products are dissolved in white mineral oil or PAO. Concentration in range of 5 10%. Provides tackiness Soltac 922 (general purpose), Soltac 222 (for grease, NSF approved), Soltac 428 (for gear, NSF approved) Undiluted PB 124, 128 also used. 36

37 Other Components Demulsifiers aids in removing water from hydrocarbon fuels and lubricants Metal deactivators Inhibits corrosion effects of oxygen and decrease metal interaction with oxygen compounds Surfactants Provides enhanced friction reduction and allows oil to spread over metal surfaces Seal swell agents Increases volume of elastomeric seals to counteract seal shrinkage characteristics of some synthetic oils and base-stocks Soot control Keeps soot in suspension in diesel oils. Soot comes from contamination from the combustion chamber and incomplete diesel fuel combustion 37

38 Surface Active Agents (Surfactants) Boundary lubricants, EP additives, detergents, dispersants work by similar mechanism; polar head group reacts with the metal surface (or dirt particle), non-polar tail extends into the lubricant matrix 38

39 Additive Packages Components are combined into complete packages that provide the formulator with all requirements for finished lube Two-cycle engine oil (2-T) Passenger car motor oil (PCMO) Diesel engine oil (DEO) Tractor hydraulic fluid (THF) 39

40 Two-Cycle Engine Oil JASO requirements Low Ash Power sports including motorcycles, snowmobiles, air cooled engines Higher value market ISO requirements Corresponds to JASO NMMA requirements Marine, water cooled engines Ashless Lower value market 40

41 JASO Performance Classification The performance level of two cycle oils is classified into three categories, FB,FC, FD from lowest to highest performance Tests measure lubricity, initial torque, detergency, exhaust smoke, exhaust system blocking FC is low smoke two cycle oils superior to FB in terms of exhaust smoke and exhaust blocking FD is improved version of FC in terms of detergency performance at high temperatures Must also meet physio-chemical property requirements for viscosity, flash point, sulfated ash 41

42 Performance Equivalents JASO FB, FC, FD corresponds to ISO-L-EGB, ISO-L-EGC, ISO-LEGD JASO is Japanese Standards Organization. Developed JASO standards originally for improved motorcycle oils ISO is International Organization for Standards. Classification system developed to correspond to JASO testing. Testing can be done at SwRI, Lube Tech (?) 42

43 NMMA Requirements Current performance classification is TCW3 Testing includes bench tests for fluidity, lubricity, viscosity Engine testing for ring sticking and carbon build up on pistons Engine tests include one BRP 40 hp, one Johnson 70 hp, and two consecutive Mercury 15 hp tests and two lubricity tests. Performance based qualifications program. Conducted by sanctioned lab, expensive. 43

44 PCA 9055 Ashless additive package for formulated for low smoke two cycle motor oils Meets or exceeds NMMA TCW3 performance requirements Meets or exceeds JASO FD and ISO-L-EGD performance requirements Treat rate of % in Group II base oil. Use with PB 24 in place of brightstock to assure low smoke performance 44

45 Typical Low Smoke Two-Cycle Formulation Component Wt% Group II PB Kerosene 13.3 PCA S-Flow P Property Value 40 deg C cst Viscosity Index > 140 Pour Point < -40 deg C 45

46 Passenger Car Motor Oil Performance criteria by established by American Petroleum Institute (API) S designation is for spark ignited engines, such as gasoline or propane fueled engines Alphabetical designation supersedes previous letter, i.e. SJ, Sl, SM Testing is done according to series of API Sequence Tests SwRI, Lubrizol, Afton certified test facilities Very expensive 46

47 PCMO API Service Categories Obsolete SA, older engines SB, older engines SC, model year 1967 and older SD, model year 1971and older SE, model year 1979 and older SF, model year 1988 and older SG, model year 1993 and older SH, model year 1996 and older 47

48 PCMO API Service Categories Current SJ, for 2001 and older engines SL, for 2004 and older engines SM, for all cars currently in use. Introduced in November Improved oxidation resistance, improved deposit protection, better wear protection and better low temperature performance over the life of the oil Reference; api.org/eolcs 48

49 Diesel Engine Oil Performance criteria by established by American Petroleum Institute (API) C designation is for compression ignited engines such as diesel engines The latest category usually, but not always, include properties of earlier category Testing is done according to series of API Sequence Tests specific to service class SwRI, Lubrizol, Afton certified test facilities Very expensive 49

50 DEO API Service Classifications CA, CB, CC, CD, CD-II, CE, are obsolete CF, introduced in 1994 for off road indirect injected diesel engines using fuel with greater than 0.5% S. Can be used in place of CD oils CF-2, introduced in 1994 for severe duty two stroke diesel engines. Can be used in place of CD-II oils CF-4, introduced in For high speed four stroke natural aspirated and turbocharged diesel engines. Can replace CD and CE oils 50

51 DEO API Service Classifications Continued CG-4, introduced in 1995, for high speed four stroke diesel engines using fuel with less than 0.05 % S. Can replace CD, CE, CF-4 and CG-4 oils CH-4, introduced in 1998, for high speed four stroke diesel engines designed to meet 1998 emissions standards. Can use in place of CD, CE, CF-4 and CG-4 CI-4, introduced in September 2002, for high speed four stroke diesel engines designed to meet 2004 exhaust standards using fuels with sulfur up to 0.5 % Formulated for durability where engine gas recirculation (EGR) is used. Can be used in place of CD, CE, CF,-4, CG-4 and CH-4 oils 51

52 Soltex PCA 2877 Multifunctional lube oil additive package used to formulate high quality mono-grade and multi-grade gasoline and diesel engine oils with properties similar to a wide range of API classifications. Contains detergents, dispersants, antioxidants, friction modifiers, rust and oxidation inhibitors Non-detergent VI improvers required to meet multi-grade viscosity classifications Performance boosters required to meet high TBN (>10) specifications 52

53 Soltex PCA 2877 Treat Rates in Group I, II Base Oils Wt % Perf. Equiv. PCA 2877 PCA 400 PCA 9070 SM SL 4.81 CH-4/SJ/SH SJ/SH 4.80 SG/SD/CF SG/SF/SE/CD 4.00 SE/CC 3.21 SD/CC 3.10 SC/CC 2.29 SB/SC/CB

54 Soltex PCA 2886 Multifunctional lube oil additive package used to formulate high quality mono-grade and multi-grade gasoline and diesel engine oils with properties similar to a wide range of API classifications. Less active than PCA 2877, contains Mo Contains detergents, dispersants, antioxidants, friction modifiers, rust and oxidation inhibitors Non-detergent VI improvers required to meet multigrade viscosity classifications 54

55 Soltex PCA 2886 Treat Rates in Group I, II Base Oils Perf. Equiv. Wt % SM 10.0 SL 9.5 SJ 9.3 SH 9.1 SG

56 Soltex PCA 2861 High performance diesel engine oil additive package for high speed turbocharged engines operating on fuel containing up to 0.5% S Contains ashless dispersant, ZDDP, metallic detergents. Meets are exceeds the requirements of API, ACEA, and major engine manufacturers including, Cummins, Global DHD-1, Mack and Volvo Non-detergent VM with SSI of recommended for multigrade oils 56

57 Soltex PCA 2861 Treat Rates Perf. Equiv. SAE Base Oil Wt% CI-4,CH-4,CG-4 15W40 Group I, II 12.0 CF-4,CF/SL, SJ CI-4,CH-4,CG-4 10W30 Group II 12.0 CF-4,CF/SL, SJ CG-4, CF-4, CF-2 30/40/50 Group I, II 8.4 CF, Sl, SJ CF,-4, CF, Sl, SJ 10W/20W Group I, II 8.4 CF Only

58 Soltex PCA 5715 Economy grade tractor hydraulic fluid Safely used in most sump-type agricultural equipment including John Deere, Case and New Holland, Massey Ferguson and Ford Provides gear wear protection, maintains hydraulic system performance and prevents oxidation to prolong fluid life. Treat rate is 4.0 wt% in Group I,II base oil. 58