Synthetic oligomer compositions and methods of manufacture
A polyalphaolefin composition is provided comprising trimers of C12 alpha-olefins and dimers of C14 alpha-olefins, where the ratio by weight of C12 trimer to C14 dimer is within a range of 4:1 by weight to 1:4 by weight, where the C12 trimer enriched polyalphaolefin has an average branching ratio <0.2 and the C14 dimer has an average branching ratio of >0.20, and where the average branching ratio for all C12 trimers and C14 dimers is between 0.19 and 0.26. The composition has a boiling point distribution where less than 30% by weight of the composition has a boiling point between 420° C. and 455° C., and the resulting base oil has a kinematic viscosity of about 3.3 to 4.7 cSt at 100° C.
1. A polyalphaolefin (PAO) composition comprising a mixture of (i) a C12 trimer-enriched oligomer fraction of trimers of C12 alpha-olefins and (ii) a C14 dimer-enriched oligomer fraction of dimers of C14 alpha-olefins, where the ratio by weight of the C12 trimer-enriched oliqomer fraction to the C14 dimer-enriched oliqomer fraction in the PAO composition is within a range of 4:1 by weight to 1:4 by weight,
where the C12 trimer-enriched oligomer fraction has an average branching ratio of <0.20 and the C14 dimer-enriched oliqomer fraction has an average branching ratio of >0.20, and where an average branching ratio for the mixture of the C12 trimer-enriched oligomer fraction and the C14 dimer-enriched oligomer fraction is between 0.19 and 0.26,
where the PAO composition has a boiling point distribution where less than 30% by weight of the PAO composition has a boiling point between 420° C. and 455° C., and
where the PAO composition has a kinematic viscosity of about 3.8 to 4.3 cSt at 100° C., and a Noack volatility between 10-13%.
2. The composition of claim 1 , wherein
(i) less than 25% by weight of the composition, or
(ii) less than 20% by weight of the composition, or
(iii) less than 15% by weight of the composition,
has the boiling point in the range of 420 to 455° C.
3. The composition of claim 1 having a Cold cracking viscosity (CCS) between 1000-1500 Centipoise.
4. The composition of claim 1 , comprising
i) less than 30 wt % trimers containing a 1-decene monomer unit,
ii) less than 20 wt % trimers containing a 1-decene monomer unit,
iii) less than 15 wt % trimers containing a 1-decene monomer unit,
iv) less than 10 wt % trimers containing a 1-decene monomer unit,
v) less than 5 wt % trimers containing a 1-decene monomer unit, or
vi) less than 1 wt % trimers containing a 1-decene monomer unit.
5. The composition of claim 1 , wherein the ratio of the C12 trimer-enriched oligomer fraction to the C14 dimer-enriched oligomer fraction dimer is
i) within a range of 3:1 to 1:3 by weight,
ii) within a range of 2:1 to 1:2 by weight, or
iii) within a range of 1.5:1 to 1:1.5 by weight.
6. A process for preparing a lubricant base oil comprising the steps of (a) acid catalyzed oligomerization of one or more alpha-olefins comprising a 1st olefin feedstock that has an average carbon length of 12 to form a 1st polyalphaolefin oligomer (1-Dodecene oligomerization); (b) distilling the 1st polyalphaolefin oligomer to recover a trimer-enriched oligomer fraction (1-C12 trimer); (c) acid catalyzed oligomerization of one or more alpha-olefins comprising a 2nd olefin feedstock that has an average carbon length of 14 to form a 2nd polyalphaolefin oligomer (1-Tetradecene oligomerization); (d) distilling the 2nd polyalphaolefin oligomer to recover a dimer-enriched oligomer fraction (1-C14 dimer); (e) blending the dimer- and trimer-enriched fractions from the 1st and 2nd polyalphaolefin oligomers to form a lubricant base oil product; and (f) hydrogenating the product before or after blending.
7. The process of claim 6 where the 1-Tetradecene oligomerization is carried out at a reaction temperature of
i) 19-100° C.,
ii) 30-95° C.,
iii) 40-90° C.,
iv) 40-85° C.,
v) 50-80° C.,
vi) 70-78° C., or
vii) 72-76° C.
8. The process of claim 6 where the 1-Dodecene oligomerization is carried out at a reaction temperature of
i) 10-100° C.,
ii) 11-90° C.,
iii) 12-80° C.,
iv) 13-70° C.,
v) 14-60° C.,
vi) 15-50° C.,
vii) 16-40° C.,
viii 17-30° C., or
ix) 18-25° C.
9. The process of claim 6 , further comprising performing the oligomerization of step (a) and/or (c) at a temperature that causes isomerization of the respective 1st olefin feedstock and/or 2 nd olefin feedstock.
10. The process of claim 6 , further comprising isomerizing the respective 1st olefin feedstock and/or 2 nd olefin feedstock prior to the oligomerization of step (a) and/or (c).
11. The process of claim 6 , wherein the 1st olefin feedstock is oligomerized under conditions that provide a C12 trimer-enriched oligomer fraction having a branching ratio of <0.20 and the 2 nd olefin feedstock is oligomerized under conditions that provide a C14 dimer-enriched oligomer fraction having a branching ratio of >0.20.
12. The process of claim 6 where the oligomerization of step (a) and/or (c) is catalyzed by BF 3 with an alcohol and/or ester promoter.
13. The process of claim 6 where the yield of 1-C12 trimer is >55%.
14. The process of claim 6 where the yield of 1-C14 dimer is >55%.
15. The process of claim 6 where the oligomers of 1-C12 and 1-C14 are hydrogenated and distilled and the distillates are blended to produce a product with a viscosity at 100° C. of 3.5-4.7 cSt, and the bottoms are blended to produce a heavier product with viscosity at 100° C. of 6 to 12 cSt.
16. The process of claim 6 in which the C12 trimer-enriched oligomer fraction has a branching ratio of <0.20 and the C14 dimer-enriched oligomer fraction has a branching ratio of >0.20.
17. The process of claim 15 in which the bottoms are blended to produce a heavier product with viscosity at 100° C. of 7 to 10 cSt.
18. The process of claim 6 where a 1-C14 LAO (linear alpha-olefin) is isomerized to form an internal olefin prior to the oligomerization of step (c).
19. The process of claim 6 wherein the resulting base oil boiling point distribution has less than 30% of total oligomers boil between 420° C. and 455° C.; and most preferred <15% of total oligomers boil between 420° C. and 455° C. where the resulting base oil has a kinematic viscosity of about 3.3 to 4.7 cSt at 100° C.
20. The process according to claim 19 wherein the resulting base oil has a kinematic viscosity at 100° C. of 3.3-4.7 Centistokes, a Noack volatility between 5-19%, and a −35° C. Cold-cranking viscosity (CCS) of 650-2100 Centipoise.
21. The process according to claim 19 wherein the resulting base oil has a kinematic viscosity at 100° C. of 3.8-4.3 Centistokes, a Noack volatility between 10-13%, and a −35° C. Cold-cranking viscosity (CCS) of 1100-1500 Centipoise.
22. A lubricant mixture comprising the PAO composition of claim 1 .
23. The lubricant mixture according to claim 22 wherein the PAO composition comprises from 1 to 90 wt % of an engine oil formulation.
24. A lubricant mixture comprising from 1-99% by weight of the product prepared according to the process of claim 6 , the resulting oil mixture having a viscosity index of greater than 125, a Noack volatility of <14% and CCS <1500 Centipoise at −35° C.