Trends in the global grease and base oil production: Heavy

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Trends in the global grease and base oil production: Heavy Powered By Docstoc
					Use of Super Heavy Naphthenics
in Lubricant Formulations




                                 Luis Bastardo-Zambrano, PhD
                                 Nynas Naphthenics AB
                                 Nynashamn, Sweden

1      2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Outline


              Introduction: Base Oil Market Overview

              Bright Stocks

              Super heavy naphthenic oil (Naphthenic 4000) and Polyisobutenes:
                      •    Film Strength
                      •    Thickening Effect
                      •    Tackiness
                      •    Shear Stability




2      2007-11-29
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Luis Bastardo-Zambrano
               Base Oil Market Overview


 Base stock supply is estimated at 931000 barrels/day more
  than half Group I                                                                              Naphthenics
                                                                                                    9%
 Global demand may increase by 6% by 2010 (34% of it in the                         Group III
  Asia/Pacific region)^                                                                5%
                                                                                                                                                         *

 Shift to higher quality oil worldwide (Group II and Group
  III)
                                                                           Group II
 Detriment of Group I production, especially bright stocks                 20%
                                                                                                                                               Group I
 Bright stocks output fell by 8% between 1995-2005. Group I                                                                                    66%

  shut downs, will bring down bright stocks production by 10%
  in the next 10 years.*




                                                                *Tocci, L. High stakes for base oils. Lubes´n´Greases. Vol.13 (1). 2007.
                                                                ^ DeMarco, N. Total’s Take on Base Oil Balances. Lube Report. February 2007.

3      2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Bright Stocks


                High viscosity base oils refined from paraffinic crude

                Mainly use is:
                              Marine oils
                              Monograde motor oils
                              Gear oils
                              Greases
                              Other products

                Possible substitutions:
                            PIB (Polyisobutene)
                            PAO (Polyalphaolefins)
                            Heavy Naphthenics




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Luis Bastardo-Zambrano
              Super Heavy Naphthenic Oil
           The Super Heavy Naphthenic Oil used in this work (Naphthenic 4000) is a product with a very high viscosity (4800 cSt at 40°C) and excellent
            solvent power (aniline point 80°C)

           Naphthenic 4000 can be used as additive in gear oils, metalworking fluids, greases and oil treatment as well as in blends with lower viscosity
            naphthenic oils to obtain naphthenic bright stocks

           It displays interesting properties such as
                 Very good shear stability
                 High film strength
                 High tackiness
                 Very low carbon residue (<0.10%)


           Characteristics Density @           Viscosity @      Viscosity @ Flash point Pour     Aniline                  VGC        CA %
                           15oC, kg/m3         40oC, mm2/s         o      2      o
                                                                100 C, mm /s PM, C            o
                                                                                        point, C point, oC
           Test method     D4052               D445             D445         D93        D97      D611                     D2501      D2140
           ASTM
           T 4000          0.968               4800             41                238            12          80           0.882      15
          Naphthenic 4000




5      2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Tests on Naphthenic 4000

              The super-heavy naphthenic oil Naphthenic 4000 was compared with several commercial PIBs
               presenting different molecular weight



              The following properties were tested
                              Film strength
                              Thickening effect
                              Tackiness
                              Shear stability




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Luis Bastardo-Zambrano
                Main Properties of the PIBs Tested


                 Characteristics                   Method       PIB A   PIB B   PIB C   PIB D

                 Number average molecular weight   GPC          1000    1050    1600    2300

                 Viscosity @ 40°C (cSt)            ASTM D 445   4650    7750    21000   48000

                 Viscosity @ 100°C (cSt)           ASTM D 445   190     230     725     1500

                 Density @ 20°C (g/cm3)            DIN 51757    0.890   0.890   0.900   0.900

                 Pour point (°C)                   ASTM D 97    -9      -3      -4      0

                 Flash point (°C)                  ASTM D 92    180     210     215     220




7      2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Film Strength - Method


         Film strength: Ability of a lubricant to withstand the effects of                                800




                                                                                Initial Seizure Load (N)
          load                                                                                             700
                                                                                                           600
         Method used: ASTM D2783 (Four-Ball Test). Upper ball
                                                                                                           500
          under load and rotating (speed 1760 ± 40 rpm)
                                                                                                           400
         Film strength given by initial seizure                                                           300
                                                                                                           200
         Materials tested: Naphthenic 4000, PIB A and PIB D                                               100
                                                                                                             0
                                                                                                                 Naphthenic   PIB A   PIB B
                                                                                                                    4000




                                                               Naphthenic 4000 Film Strength = 2 x PIB A Film Strength
                                                               Naphthenic 4000 Film Strength 50% higher than PIB B’s


8       2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Thickening Effect - Method


                Increasing amounts of Naphthenic 4000 and the PIB having the
                 same viscosity (PIB A) were added to the naphthenic oil Base oil
                 400

                Treating rates of 10, 20, 30, 40, 50, 60, 70, 80 and 90% were
                 used

                After each addition, the viscosity of the blend was measured by
                 ASTM D 445

                A viscosity curve was obtained for each thickener




9      2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Thickening Effect – Results and Discussion (1)

                                                     5000

                                                     4500                                             4000
                                                                                                    TNaphthenic 4000
                                                                                                    PIB A
                           Viscosity at 40°C (cSt)
                                                     4000

                                                     3500

                                                     3000

                                                     2500

                                                     2000

                                                     1500

                                                     1000

                                                     500

                                                       0
                                                            0   10   20      30    40    50    60      70      80      90   100
                                                                          Treatment rate of thickener (wt-%)
10     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Thickening Effect – Results and Discussion (2)



                The PIB A has a more marked thickening effect compared to the Naphthenic
                 4000

                The difference in viscosity becomes evident at additions above 30% treating
                 rates

                The difference is most pronounced at high treating rates (> 60%)




11     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Tackiness - Method


               Tackiness is defined as the resistance to flow in
                extension and is a combination of cohesivity and
                adhesivity

               The tackiness was measured in a filament break-up
                rheometer

               The test fluid is placed between two cylindrical test
                fixtures (rheometer plates) and is submitted to an
                axial step-strain applied generating the formation of
                an elongated liquid thread




12     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               The Capillary Break-Up Extensional Rheometer: Filament Formation



                           Axial              D
                           strain

                D
                d0                            df

                 D

                           Axial              D
                           strain


13     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Tackiness Tests – Experimental Conditions

               Naphthenic 4000 and four PIBs were added to the naphthenic oils Base oil 400 and Base oil 110

               Treating rates of 0.5 % and 1.5 % were used

               The time evolution of the filament diameter for the pure and additivated oils was followed

               The final gap between the rheometer plates was set to 8 mm for the tests performed on Base oil 400
                and to 6 mm for the tests carried out on Base oil 110

               The final gap between the plates must be kept constant through a series of experiments as it is
                directly correlated to the deformation to which the material is submitted during the test




14     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Tackiness Tests on Base Oil 110 with 1.5% Treating Rate


                                               1
                    Normalized Diameter []




                                                                                                            Base Oil 110
                                                                                                            Base Oil 110+1.5% Naphthenic 4000
                                                                                                            Base Oil 110+1.5%Polymer A
                                              0.1
                                                                                                            Base Oil 110+1.5%Polymer B
                                                                                                            Base Oil 110+1.5%Polymer C
                                                                                                            Base Oil 110+1.5%Polymer D




                                             0.01
                                                    0   0.02   0.04   0.06       0.08   0.1   0.12   0.14
                                                                             Time [s]
15     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Tackiness Tests – Results and Discussion

               Naphthenic 4000 gave a tackiness increase equal to that given by the PIB B (having a viscosity at
                40°C of 7750 cSt)

               Increasing the treating rate has a positive effect both for Naphthenic 4000 and the PIB B. The effect
                is more marked with Base oil 110.

               As expected, the tackifying effect of the PIBs increases with increasing molecular weight.

               Nevertheless, the higher the molecular weight of the PIBs, the higher the sensitivity to shearing
                forces.




16     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Shear Stability Tests - Method

 Method used: CEC L 45-A-99 (Viscosity shear stability of
  transmission lubricants – Tapered roller bearing rig)                                    30

 The bearing is loaded axially with 5000 N, rotated at 1475                               25




                                                                      Viscosity lost (%)
  rev/min and maintained at a temperature of 60°C.                                         20

 The viscosity of the fluid before and after the test was measured                        15
  using the method DIN 51562. The result: % of viscosity lost by                           10
  the fluid                                                                                5

                                                                                           0
                                                                                                Naphthenic   PIB B   PIB C   PIB D
                                                                                                   4000




                                                                                            The polymer molecules break when
                                                                                            submitted to high shear stresses


17     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano
               Conclusions


                Worldwide production of base oils is shifting to higher quality products, Group II and III base oils

                These changes may cause shortage of Bright Stocks in the market

                Heavy naphthenic oils and PIBs are alternatives available right now

                The super heavy naphthenic oil Naphthenic 4000 outperforms PIBs in properties such as film strength
                 and shear stability

                Conversely, the thickening effect of PIBs is higher than that of the Naphthenic 4000

                The impact on tackiness of Naphthenic 4000 is comparable to that of the medium molecular weight
                 PIBs, while high molecular weight PIBs show a more marked tackifying effect




18     2007-11-29
Lubricants Russia – 2007

Luis Bastardo-Zambrano

				
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