Formulation of lubricants Determination of mineral oil content Rita Kapiller-Dezsőfi, Ph.D. Forensic Institute

Content Definition of base oil Grouping of base oils NTCA Content Definition of base oil Grouping of base oils Presentation of base oil groups Analyses of base oils Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Definition the base oils NTCA Definition the base oils API Base Oil Definitions Base Oil is the name given to lubrication grade oils initially produced from refining crude oil (mineral base oil) or through chemical synthesis (synthetic base oil). Base oil is typically defined as oil with a boiling point range between 550 and 1050 F (288- 566°C), consisting of hydrocarbons with 18 to 40 carbon atoms. This oil can be either paraffinic or napthenic in nature depending on the chemical structure of the molecules. Base oil + Additives Lubricants and other oils for different purposes generally lubricants are based on one type of base oil, mixtures of the base oils also are used to meet performance requirements. Can also be classified into three categories depending on the prevailing compositions: Paraffinic Naphthenic Aromatic Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: wikipédia, global industrial solutions

Hydrocarbon types of base oils NTCA Hydrocarbon types of base oils N-paraffin straight chain Good lubricity, high distillation point Iso-paraffin branched chain Good cold behavieur, enough good lubricity, difficult production Naphtene cyclo paraffin Bad lubricity reactive No good lubricity, transformer oils Aromatics Good heat release Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Grouping by lubricity NTCA Paraffinic hydrocarbones -- CnH2n+2 Iso-paraffin hydrocarbones - CnH2n+2 Naphtenes - CnH2n Aromatics - - CnHn Excellent Good Weak Bad Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Content Definition of base oil Grouping of base oils NTCA Content Definition of base oil Grouping of base oils Presentation of base oil groups Analyses of base oils Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Groups of the base oils NTCA The American Petroleum Institute (API) has categorized base oils into five categories (API 1509, Appendix E). The first three groups are refined from petroleum crude oil. Group IV base oils are full synthetic (polyalphaolefin) oils. Group V is for all other base oils not included in Groups I through IV. Group I Group I base stocks contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have viscosity index greater than or equal to 80 and less than 120. The temperature range for these oils is from 32 to 150 degrees F. Group I base oils are solvent-refined, which is a simpler refining process. This is why they are the cheapest base oils on the market. Group II Group II base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have viscosity index greater than or equal to 80 and less than 120. They are often manufactured by hydrocracking, which is a more complex process than what is used for Group I base oils. Since all the hydrocarbon molecules of these oils are saturated, Group II base oils have better antioxidation properties. They also have a clearer color and cost more in comparison to Group I base oils. Still, Group II base oils are becoming very common on the market today and are priced very close to Group I oils. Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Groups of the base oils NTCA Group III Group III base stocks contain greater than or equal to 90 percent saturates and less than or equal to 0 .03 percent sulfur and have viscosity index greater than or equal to 120. These oils are refined even more than Group II base oils and generally are severely hydrocracked (higher pressure and heat). This longer process is designed to achieve a purer base oil. Although made from crude oil, Group III base oils are sometimes described as synthesized hydrocarbons. Like Group II base oils, these oils are also becoming more prevalent. Group IV Group IV base stocks are polyalphaolefins (PAO). These synthetic base oils are made through a process called synthesizing. They have a much broader temperature range and are great for use in extreme cold conditions and high heat applications. Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Groups of the base oils NTCA Group V Group V base stocks include all other base stocks not included in Group I, II, III, IV, including silicone, phosphate ester, polyalkylene glycol (PAG), polyolester, biolubes, etc. These base oils are at times mixed with other base stocks to enhance the oil’s properties. An example would be a PAO-based compressor oil that is mixed with a polyolester. Esters are common Group V base oils used in different lubricant formulations to improve the properties of the existing base oil. Ester oils can take more abuse at higher temperatures and will provide superior detergency compared to a PAO synthetic base oil, which in turn increases the hours of use. Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Definition the base oils NTCA Definition the base oils Viscosity index: (VI) is an arbitrary measure for the change of viscosity with variations in temperature. The VI scale was set up by the Society of Automotive Engineers (SAE). The temperatures chosen arbitrarily for reference are 100 and 210 °F (38 and 99 °C). The original scale only stretched between VI=0 (lowest VI oil, naphthenic) and VI=100 (best oil, paraffinnic) but since the conception of the scale better oils have also been produced, leading to VIs greater than 100 (see below). Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: wikipedia+internet

Development of technology NTCA Development of technology 1970 1980 1990 2000 2010 Solvent technology GTL Hydroprocessing catalytic dewaxing Group I Hydrocracking catalytic dewaxing with isomerisation Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Solvent technology NTCA Group 1 Solvent Extraction Process The solvents and hardware used to manufacture solvent-refined base oils have evolved over time, but the basic strategy has not changed since 1930. The two main processing steps are: Remove aromatics by solvent extraction. Remove wax by chilling and precipitation in the presence of a different solvent Group 1 Solvent Extraction Process Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Chevron Global Lubricants 

Development of technology NTCA Development of technology 1970 1980 1990 2000 2010 Solvent technology GTL Hydroprocessing catalytic dewaxing Group I Hydrocracking catalytic dewaxing with isomerisation Group II Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Hydroprocessing Group II NTCA Production of base oils Hydrotrating Hydrocracking Catalytic Dewaxing Hydrofinishing Hydroprocessing Group II Sulphur Group II Stocks Have Lower Impurities Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Chevron Global Lubricants 

Development of technology NTCA Development of technology 1970 1980 1990 2000 2010 Solvent technology GTL Hydroprocessing catalytic dewaxing Group I Hydrocracking catalytic dewaxing with isomerisation Group II Group III Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Production of base oils NTCA Production of base oils Catalytic Dewaxing and Wax hydroisomerization Modern hydroprocessing: combins hydrocracking, isodewaxing and hydrofinishing, greater crude oil flexibility Productuinos group III - Unconventional Base Oils API defines the difference between Group II and III base oils only in terms of the VI. Base oils with a conventional VI (80 to 119) are Group II and base oils with an unconventional VI (120+) are Group III. Group III oils are also sometimes called unconventional base oils (UCBOs) or very high viscosity index (VHVI) base oils. Solvent dewaxed group III old technology Isodewaxining Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Chevron Global Lubricants 

NTCA GTL Gas to Liuquid new type of ultraperformance base oil derived from wax which is derived from natural gas via the Fischer-Tropsch process Gas to liquids (GTL) is a refinery process to convert natural gas or other gaseous hydrocarbons into longer-chain hydrocarbons such as gasoline or diesel fuel. Methane-rich gases are converted into liquid synthetic fuels either via direct conversion or via syngas as an intermediate, for example using the Fischer Tropsch or Mobil processes. The Fischer–Tropsch process involves a series of chemical reactions that produce a variety of hydrocarbon molecules according to the formula (CnH(2n+2)). The more useful reactions produce alkanes as follows: (2n + 1) H2 + n CO → CnH(2n+2) + n H2O where n is a positive integer. The formation of methane (n = 1) is generally unwanted as methane is gaseous at standard temperature and pressure. Most of the alkanes produced tend to be straight-chain, suitable as diesel fuel. In addition to alkane formation, competing reactions give small amounts of alkenes, as well as alcohols and other oxygenated hydrocarbons Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

GTL Gas to Liuquid NTCA Mobil process: Methanol is made from methane (natural gas) in a series of three reactions: Steam reforming: CH4 + H2O → CO + 3 H2   ΔrH = +206 kJ mol-1 Water shift reaction: CO + H2O → CO2 + H2   ΔrH = -41 kJ mol-1 Synthesis: 2 H2 + CO → CH3OH   ΔrH = -92 kJ mol-1 The methanol thus formed may be converted to gasoline by the Mobil process. First methanol is dehydrated to give dimethyl ether: 2 CH3OH → CH3OCH3 + H2O This is then further dehydrated over a zeolite catalyst, ZSM-5, to give a gasoline with 80% (by weight based on the organics in the product stream) C5+ hydrocarbon products. ZSM-5 is deactivated by a carbon build-up ("coking") over time in converting methanol to gasoline. The catalyst can be re-activated by burning off the coke in a stream of hot (500 °C (930 °F)) air; however, the number of re-activation cycles is limited. Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Production technology of base oils NTCA Production technology of base oils Group 1.: based on mineral oil Distillation Refining by solvent extraction – phenol, furfural, N-methyl-pyrrolidone,.. Dewaxing by solvent extraction – MEK, ABT, MIBK Hydrotrating (30 bar, 350 ̊C, Co-Mo/Fe catalyst) Group 2.: based on used oil or on mineral oil Hydrotrating (100 bar, 500 ̊C) Refining and dewaxing by solvent extraction Group 3.: based on mineral oil or gas Hydrocracking and hydrfoisomerisatio GTL Group 4.: based on gas or fuel Steam Cracking – synthetic gas Poly-alpha olefin polymerisation Group 5.: chemical process Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Content Definition of base oil Grouping of base oils NTCA Content Definition of base oil Grouping of base oils Presentation of base oil groups Analyses of base oils Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Hydrocarbon composition of base oils NTCA Hydrocarbon composition of base oils Paraffins PAO GTL Group III Group I Group II Gas oil Naphtenics Aromatics Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo Source: Mol-Lub

Different base oils NTCA Different color: dark red light yellow colorless 2008 Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2008 (MOL-LUB) NTCA Sulphur content (ppm) Max: 13030 ppm Min: 196 ppm > 10 ppm Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2008 (MOL-LUB) NTCA Density at 15 °C (Kg/m3) Max: 908 kg/m3 Min: 836,6 kg/m3 < 845 kg/m3 Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2008 (MOL-LUB) NTCA Viscosity at 40 °C (mm2/s) Max: 623,1 mm2/s Min: 10,05 mm2/s < 4,5 mm2/s Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

GC chromatograms NTCA Name Sulphur (ppm) Density at 15 °C (Kg/m3) Viscosity at 40 °C (mm2/s) SN 150/A 1311 871,2 31,99 SN-150 5618 876,3 30,93 Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

GC chromatograms Group III NTCA Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

GC chromatograms Poly-alpha olefins NTCA Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2010 (samples) NTCA Sulphur content (ppm) Max: 13300 ppm Min: 2800 ppm > 10 ppm Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2010 (samples) NTCA Density at 15 °C (Kg/m3) Max: 912,1 kg/m3 Min: 872,3 kgm3 > 845 kg/m3 Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2010 (samples) NTCA Viscosity at 40 °C (mm2/s) Max: 643,1 mm2/s Min: 29,77 mm2/s > 4,5 mm2/s Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2011 NTCA Sulphur content (ppm) Max: 10 ppm Min: 1,8 ppm Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2011 NTCA Density at 15 °C (Kg/m3) Max: 859,4 kg/m3 Min: 844 kgm3 < 845 kg/m3 Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Base oils 2011 NTCA Viscosity at 40 °C (mm2/s) Max: 23, mm2/s Min: 3,624 mm2/s < 4,5 mm2/s Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

NTCA GC chromatograms Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Content Definition of base oil Grouping of base oils NTCA Content Definition of base oil Grouping of base oils Presentation of base oil groups Analyses of base oils Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Chemical composition of base oils NTCA Chemical composition of base oils Group I paraffinic Mineral oil Group II naphtenic hydrocarbons Group III aromatic Polyalphaolefins Group IV high-purity ethylene 1-decene and 1-dodecene mixture of dimers, trimers, tetramers and higher oligomers Organic esters Group V Organic esters, diesters and polyolesters (POE) Polyphenyl ethers Silicon Silicate esters Phosphate esters Fluoronated lubricants Chlorofluorocarbons Perfluoroalkylpolyethers Fluorosilicones Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Chemical composition of base oil group V NTCA Chemical composition of base oil group V Advantages Better low- and high-temperature viscosity performance at service temperature extremes Better (higher) Viscosity Index (VI) Better chemical and shear stability Decreased evaporative loss Resistance to oxidation, thermal breakdown, and oil sludge problems Extended drain intervals, with the environmental benefit of less used oil waste generated Improved fuel economy in certain engine configurations Better lubrication during extreme cold weather starts Possibly a longer engine life Superior protection against "ash" and other deposit formation in engine hot spots (in particular in turbochargers and superchargers) for less oil burnoff and reduced chances of damaging oil passageway clogging. Increased horsepower and torque due to less initial drag on engine Improved fuel efficiency - from 1.8% to up to 5% has been documented in fleet tests Disadvantages Substantially more expensive (per volume) than mineral oils. Potential decomposition problems in certain chemical environments (predominantly in industrial use.) Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Identification FT-IR spectroscopy NTCA Analyses of Group V Identification FT-IR spectroscopy Organic esters (organic esters, diesters and polyolesters (POE) Polyphenyl ethers Silicon (Silicate esters) Phosphate esters Fluoronated lubricants (Chlorofluorocarbons, perfluoroalkylpolyethers, fluorosilicones) Other possybilities: HPLC chromatography (Knauer) Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Separation of mineral oil NTCA Separation of mineral oil Mineral oil Additives Pore size 60 Å Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Organic esters Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Polyphenyl ethers Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Polyphenyl ethers Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Silicon Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Silicon Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Phosphate esters Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses of Group V NTCA FT-IR analyses of Group V Fluorosilicones Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses in mixtures of Group V NTCA FT-IR analyses in mixtures of Group V Mixtures: mineral oil and Group V base oil Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

FT-IR analyses in mixtures of Group V NTCA FT-IR analyses in mixtures of Group V Mixtures: mineral oil and Group V base oil Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Most difficult– chemical similarities NTCA Analyses of Group IV Most difficult– chemical similarities Indicative analyses: FTIR Reaction with bromine ASTM D 1492 Indication for the unsaturation (olefins, aromatics Pure PAO: FTIR GC Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

GC chromatograms Poly-alpha olefins NTCA Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Analyses of Group IV NTCA Poly(1-decene) Poly(1-hexadecene) Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Analyses of Group IV mixtures NTCA Analyses of Group IV mixtures NMR Spectroscopy One of several types of two-dimensional nuclear magnetic resonance (NMR) spectroscopy or 2D-NMR exist. This type of NMR experiment is best known by its acronyms. Correlation spectroscopy - J-coupling - Nuclear Overhauser effect spectroscopy (NOE effects) - Heteronuclear correlation experiments HSQC (H-C J1) HMBC (H-C J2,3) Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

Challenging questions in a Customs Laboratory: NTCA Challenging questions in a Customs Laboratory: Determination the synthetic oil part in mineral oil Synthetic oils from the aspect of the tariff classification: Ester oil - FTIR spectroscopy PAO (Poly-alpha-olefin) - difficult identification Common characteristic double bond between 1st and 2nd carbone Polyisobutylene (PIB) Mixture PIB and mineral oil Pure PIB Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

NTCA q-NMR - quantitative determination using NMR spectroscopy 1H (proton) NMR spectrum - quantitative relationship between intra-molecular and inter-molecular resonances. Analyses the pure components and in complex matrix Reported quantitative inaccuracy is less then 2% (1) (important acquisition and processing parameters - optimization Internal standard Optimized T1, excitation, integration 1. Quantitative 1H NMR spectroscopy Santosh Kumar Bharti, Raja Roy: Trends in Analytical Chemistry, Vol. 35, 2012 Analyses of Lubricting oil – TAIEX Worksop, 11-12 April 2016, Cairo

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