U.S. patent application number 17/745256 was filed with the patent office on 2022-09-01 for base oils and methods of making the same.
The applicant listed for this patent is Novvi LLC. Invention is credited to Eduardo BARALT, Liwenny HO, Wui Sum Willbe HO, Jason Charles ROSALLI, Benton THOMAS, Jason WELLS.
Application Number | 20220275306 17/745256 |
Document ID | / |
Family ID | 1000006335133 |
Filed Date | 2022-09-01 |
United States Patent
Application |
20220275306 |
Kind Code |
A1 |
BARALT; Eduardo ; et
al. |
September 1, 2022 |
BASE OILS AND METHODS OF MAKING THE SAME
Abstract
A process for the preparation of saturated hydrocarbon base oils
is provided, comprising oligomerization of a feed mixture that has
an average carbon number in the range of 14 to 18 to produce an
oligomer product comprising dimers, trimers, and higher oligomers,
where the dimer has a branching proximity (BP) of 20 or greater,
isomerization of at least the dimer portion, and hydrogenation of
the isomerized product. The dimer portion is separated from the
oligomer product, and a saturated hydrocarbon base oil is obtained
comprising greater than 90% dimers having an average carbon number
in the range of from 29 to 36, and the dimer portion having a
weight average molecular weight in the range of 422 to 510, where
the dimers have an average Branching Index (BI) in a range of 22 to
26 and an average paraffin branching proximity (BP) in a range of
from 18 to 26.
Inventors: |
BARALT; Eduardo; (Houston,
TX) ; WELLS; Jason; (Fremont, CA) ; ROSALLI;
Jason Charles; (Oakland, CA) ; HO; Wui Sum
Willbe; (Oakland, CA) ; HO; Liwenny; (Oakland,
CA) ; THOMAS; Benton; (Elizabethtown, NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Novvi LLC |
Emeryville |
CA |
US |
|
|
Family ID: |
1000006335133 |
Appl. No.: |
17/745256 |
Filed: |
May 16, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16630324 |
Jan 10, 2020 |
11332690 |
|
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PCT/US18/41993 |
Jul 13, 2018 |
|
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17745256 |
|
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62532773 |
Jul 14, 2017 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 177/00 20130101;
C10M 2203/024 20130101; C10G 2300/4081 20130101; C10G 2400/10
20130101; C10N 2030/02 20130101; C10M 105/04 20130101; C10G 11/05
20130101; C10N 2030/74 20200501 |
International
Class: |
C10M 177/00 20060101
C10M177/00; C10G 11/05 20060101 C10G011/05; C10M 105/04 20060101
C10M105/04 |
Claims
1. A process for the preparation of a saturated hydrocarbon base
oil, comprising: forming an oligomerization reaction mixture
comprising an oligomerization catalyst system and an olefin monomer
feed mixture, wherein the olefin monomer feed mixture has an
average carbon number in the range of 14 to 18; oligomerizing the
olefin monomer feed mixture in the reaction mixture to produce an
oligomer product comprising dimers, trimers, and higher oligomers,
isomerizing at least the dimer portion of the oligomer product in
the presence of an acid catalyst to form a mixture of branched
hydrocarbons; hydrogenating the isomerized branched hydrocarbons,
to a Bromine Index below 1000 mg Br.sub.2/100 g as determined in
accordance with ASTM D2710-09; and separating the dimer portion of
the hydrogenated oligomer product, whereby a saturated hydrocarbon
base oil is obtained comprising greater than 90 wt % dimers having
an average carbon number in the range of from 29 to 36, the dimer
portion having a weight average molecular weight in the range of
from 422 to 510, wherein the dimers of the oligomer product, in a
case where the dimers are hydrogenated to a Bromine Index below
1000 mg Br.sub.2/100 g as determined in accordance with ASTM
D2710-09, without subsequent isomerizing, have an average paraffin
branching proximity (BP) as determined by 13C NMR of 20 or greater,
and wherein the isomerized and hydrogenated dimers of the saturated
hydrocarbon base oil have an average branching index (BI) as
determined by 1H NMR that is in the range of from 22 to 26, and an
average paraffin branching proximity (BP) as determined by 13C NMR
in a range of from 18 to 26, wherein the branching index (BI) is
determined as follows: branching index (BI)=(total content of
methyl group hydrogens/total content of hydrogens)*100, and wherein
the paraffin branching proximity (BP) is determined as follows:
paraffin branching proximity (BP)=(number of .epsilon. carbon
groups/total number of carbon groups)*100, where an .epsilon.
carbon group is defined as a carbon group that is separated from
any terminal carbon atom groups or branching carbon groups by at
least 4 carbon groups
2. The process according to claim 1, wherein the oligomerization
conditions during oligomerization result in dimers of the oligomer
product that, in a case where the dimers are hydrogenated to a
Bromine Index below 1000 mg Br.sub.2/100 g as determined in
accordance with ASTM D2710-09, without subsequent isomerizing, have
an average a paraffin branching proximity (BP) of 22 or
greater.
3. The process according to any preceding claim, comprising
performing the isomerization after oligomerization of the olefin
feed mixture had been performed.
4. The process according to any preceding claim, wherein at least a
portion of the isomerization is performed simultaneously with
oligomerization.
5. The process according to any preceding claim, wherein the olefin
monomer feed mixture comprises a first feedstock comprising C14 to
C18 alpha olefin monomers selected from the group consisting of
tetradecene, pentadecene, hexadecene, heptadecene and
octadecene.
6. The process according to any preceding claim, further comprising
preparing an olefin monomer feed mixture comprising C14 to C18
alpha olefin monomers by dehydration of C14 to C18 primary alcohols
selected from the group consisting of 1-tetradecanol,
1-pentadecanol, 1-hexadecanol, 1-heptadecanol and
1-octadecanol.
7. The process according to any preceding claim, wherein the olefin
monomer feed mixture comprises olefin monomers selected from the
group consisting of unsaturated, linear alpha-olefins; unsaturated,
normal internal-olefins; branched alpha-olefins; branched
internal-olefins; and combinations thereof.
8. The process according to any preceding claim, where the olefin
monomer feed mixture comprises a mixture of linear alpha-olefins
and/or linear internal-olefins.
9. The process according to any preceding claim, wherein the olefin
monomer feed mixture comprises olefin monomers selected from the
group consisting of unsaturated olefin comprises, linear
alpha-olefins; linear internal-olefins; branched alpha-olefins;
branched internal-olefins; and combinations thereof.
10. The process according to any preceding claim, wherein the
olefin monomer feed mixture comprises a first feedstock comprising
less than 36% by weight of branched olefin monomers.
11. The process of any preceding claim, wherein the olefin monomer
feed mixture comprises a first feedstock comprising less than 20%
by weight of branched olefin monomers.
12. The process of any preceding claim, wherein the olefin monomer
feedstock comprises a first feedstock comprising less than 10% by
weight of branched olefin monomers.
13. The process of any preceding claim, wherein the olefin monomer
feedstock comprises a first feedstock comprising less than 5% by
weight of branched olefin monomers.
14. The process of any preceding claim, wherein an amount of decene
in any of first and/or second feedstocks of the olefin monomer
feedstock is less than 20% by weight.
15. The process of any preceding claim, wherein an amount of decene
in any of first and/or second feedstocks of the olefin monomer
feedstock is less than 10% by weight.
16. The process of any preceding claim, wherein an amount of decene
in any of first and/or second feedstocks of the olefin monomer
feedstock is less than 5% by weight.
17. The process of any preceding claim, further comprising
oligomerizing the olefin monomer feed under conditions to at least
partially isomerize the dimers, trimers, and higher oligomers.
18. The process of any preceding claim, wherein the unreacted
monomer is distilled from the unsaturated oligomers and recycled in
a subsequent oligomerization reaction.
19. The process of any preceding claim, wherein isomerizing of the
oligomer product is performed in the absence of hydrogen.
20. The process according to any preceding claim, wherein an amount
of cracked byproducts generated during isomerizing of the oligomer
product is less than 10%.
21. The process according to any preceding claim, wherein an amount
of cracked byproducts generated during isomerizing of the oligomer
product is less than 5%.
22. The process according to any preceding claim, wherein an amount
of cracked byproducts generated during isomerizing of the oligomer
product is less than 1%.
23. The process according to any preceding claim, wherein
isomerizing of the oligomer product is performed at a temperature
in the range of from 125.degree. C. to 300.degree. C., and a
pressure in the range of from 1 PSI to 100 PSI of inert gas, in the
presence of an acid catalyst selected from the group consisting of
solid metals or metal oxides or their mixture of Group IVB, VB, VIB
and Group metal oxides or mixed oxides of Group IIA to VA; mixed
metal oxides comprising WO.sub.x/ZrO.sub.2 type catalyst; solid
natural or synthetic zeolites; and layered material, crystalline or
amorphous material of silica, alumina, silicoaluminate,
aluminophosphate, aluminum silicophosphate.
24. The process according to any preceding claim, wherein the dimer
portion of the isomerized oligomer product is separated by
distillation from the isomerized oligomer product.
25. The process of any preceding claim where the oligomerization
reaction is carried out at a temperature range from 10-110.degree.
C.
26. The process of any preceding claim, wherein the oligomerization
catalyst is selected from the group consisting of zeolites,
Friedel-Crafts catalysts, Bronsted acids, Lewis acids, acidic
resins, acidic solid oxides, acidic silico aluminophosphates, Group
IVB metal oxides, Group VB metal oxides, Group VIB metal oxides,
hydroxide or free metal forms of Group VIII metals, and any
combination thereof.
27. The process of any preceding claim, wherein the oligomerization
reaction catalyst is BF.sub.3, and the promoter is an alcohol
and/or an ester.
28. The process of any preceding claim, wherein the oligomerization
is carried out in at least one continuously stirred reactor under
oligomerization conditions with an average residence time of 60 to
400 minutes.
29. The process of any preceding claim, wherein the oligomerization
is carried out in at least one continuously stirred reactor under
oligomerization conditions with an average residence time of 90 to
300 minutes.
30. The process of any preceding claim, wherein the oligomerization
is carried out in at least one continuously stirred reactor under
oligomerization conditions with an average residence time of 120 to
240 minutes.
31. The process of any preceding claim, wherein the acid catalyst
used for isomerizing the unsaturated polyolefin is a zeolite having
a Constraint Index of about 2 to about 12.
32. The process of any preceding claim, wherein the acid catalyst
used for isomerizing the unsaturated polyolefin is a zeolite
containing one or more Group VI B to VIII B metal elements.
33. The process of any preceding claim, wherein the pour point of
the isomerization product is at least -9.degree. C. less than that
of the oligomer product prior to isomerization.
34. The process according to any preceding claim, wherein the pour
point of the isomerization product is at least -15.degree. C. less
than that of the oligomer product prior to isomerization.
35. The process according to any preceding claim, wherein the pour
point of the isomerization product is at least -21.degree. C. less
than that of the oligomerization product prior to
isomerization.
36. The process according to any preceding claim, wherein the dimer
product of the saturated hydrocarbon base oil has <5 wt %
naphthalenes after isomerization and hydrogenation.
37. The process according to any preceding claim, wherein the dimer
product of the saturated hydrocarbon base oil has <2.5 wt %
naphthalenes after isomerization and hydrogenation.
38. The process of any preceding claim, wherein the dimer product
of the saturated hydrocarbon base oil has <1 wt % naphthalenes
after isomerization and hydrogenation.
39. The process of any preceding claim, wherein a percent yield of
isomerized dimers produced in the isomerization is >90 wt.
%.
40. The process according to any preceding claim, wherein a percent
yield of isomerized dimers produced in the isomerization >95 wt.
%.
41. The process according to any preceding claim, wherein a percent
yield of isomerized dimers produced in the isomerization >97.5
wt. %.
42. The process according to any preceding claim, wherein a percent
yield of isomerized dimers produced in the isomerization is >99
wt. %.
43. The process according to any preceding claim, wherein the base
oil has a kinematic viscosity of measured at 100.degree. C. by ASTM
D445 of 3.7 cSt to 4.8 cSt.
44. The process according to any preceding claim 1, wherein the
base oil has a kinematic viscosity of measured at 100.degree. C. by
ASTM D445 of 3.8 cSt to 4.5 cSt.
45. The process according to any preceding claim, wherein the
saturated base oil has a Viscosity Index 125 or greater.
46. The process according to any preceding claim, wherein the
saturated base oil has a Viscosity Index 130 or greater.
47. The process according to any preceding, wherein the base oil
has a Viscosity Index 135 or greater.
48. The process according to any preceding claim, wherein the base
oil has a Viscosity Index 140 or greater.
49. The process according to any preceding claim, wherein the base
oil has a Viscosity Index of 150 or greater.
50. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1800 cP.
51. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1700 cP.
52. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1600 cP.
53. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1500 cP.
54. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1400 cP.
55. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1300 cP.
56. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1200 cP.
57. The process according to any preceding claim, wherein the base
oil has a CCS at -35.degree. C. less than 1100 cP.
58. The process according to any preceding claim, wherein the base
oil has a Noack volatility less than 14%.
59. The process according to any preceding claim, wherein the base
oil can be characterized by a Noack volatility of less than
13%.
60. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 12%.
61. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 11%.
62. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 10%.
63. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 9%.
64. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 8%.
65. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 7%.
66. The process according to any preceding claim, wherein the base
oil can be characterized by Noack volatility of less than 6%.
67. The process according to any preceding claim, wherein the base
oil can be characterized by pour point of less than -27.degree.
C.
68. The process according to any preceding claim, wherein the base
oil can be characterized by pour point of less than -30.degree.
C.
69. The process according to any preceding claim, wherein the base
oil can be characterized by pour point of less than -33.degree.
C.
70. The process according to any preceding claim, wherein the base
oil can be characterized by pour point of less than -36.degree.
C.
71. The process according to any preceding claim, wherein the base
oil can be characterized by pour point of less than -39.degree.
C.
72. The process according to any preceding claim, wherein the base
oil can be characterized by pour point of less than -42.degree.
C.
73. The process according to any preceding claim, where a catalyst
provided during isomerization is other than a catalyst provided
during oligomerization.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of U.S. patent
application Ser. No. 16/630,324 filed on Jan. 10, 2020, now U.S.
Pat. No. 11,332,690, which is a national stage application of
PCT/US2018/041993, filed Jul. 13, 2018, claims priority to U.S.
provisional application No. 62/532,773, filed on Jul. 14, 2017, the
entire contents of the each of which is hereby incorporated by
reference herein as if recited in full herein.
FIELD OF THE INVENTION
[0002] Aspects of present disclosure generally relate to synthetic
hydrocarbon base oils. Described herein are isoparaffin oligomers
derived from alpha-olefins and/or linear internal olefins with
improved low temperature properties by catalytic isomerization of
the oligomers. The resulting product may be capable of providing an
excellent lubricant base oil.
BACKGROUND
[0003] The automotive industry is placing greater demands on engine
oils, operating at higher temperatures for longer times and
requiring lower viscosity engine oil formulations such as OW-30 and
OW-20 engine oils. These lower weight engine oils improve vehicle
fuel economy by lowering friction losses. This desire for lower
weight engine oils is driving a demand for low viscosity PAOs, such
as those around 4 cSt kinematic viscosity. Allowing for engine oils
with decreased viscosity while maintaining low Noack volatility and
good low-temperature performance properties.
[0004] Poly Alpha Olefins (PAOs) and Poly Internal Olefins (PIOs)
make up important classes of hydrocarbon lubricating oils. They are
typically produced by the polymerization of alpha-olefins or
internal-olefins in the presence of a Friedel Crafts catalyst such
as AlCl.sub.3, BF.sub.3, or BF.sub.3 complexes. For example,
1-octene, 1-decene, 1-dodecene, and 1-tetradecene have been used to
manufacture PAOs. C8-C18 internal olefins have been used to
manufacture PIOs. Fractionation and hydrogenation typically follow
oligomerization of the olefins to remove any remaining unsaturated
monomer moieties.
[0005] The poly alpha olefin products are typically obtained with a
wide range of viscosities varying from low molecular weight and low
viscosity of about 2 cSt at 100.degree. C., to higher molecular
weight, viscous materials which have viscosities exceeding 100 cSt
at 100.degree. C. The poly alpha olefins may be produced by the
polymerization of olefin feed in the presence of a catalyst, such
as, AlCl.sub.3, and BF.sub.3 complexes. Processes to produce poly
alpha olefin lubricants are disclosed, for example, in U.S. Pat.
Nos. 3,382,291; 4,172,855; 3,742,082; 3,780,128; 3,149,178;
4,956,122; and 5,082,986. Poly alpha olefins and poly internal
olefins lubricants are discussed in Synthetic Lubricants and
High-Performance Functional Fluids, Revised and Expanded. Edited by
Leslie R. Rudnick and Ronald L. Shubkin CRC Press 1999. The
polymerization reaction is typically conducted in the absence of
hydrogen; the lubricant range products are thereafter polished or
hydrogenated to reduce the residual unsaturation.
[0006] Prior efforts to prepare various PAOs that can meet the
increasingly stringent performance requirements of modern
lubricants and automotive engine oil particularly have favored low
viscosity polyalphaolefin base oils derived from 1-decene
alpha-olefins, alone or in some blend with other mineral, or
Fischer-Tropsch derived base oils. However, the polyalphaolefins
derived from 1-decene can be prohibitively expensive and its supply
is limited. Thus, a need exists for low viscosity base oils which
are made from olefins other than 1-decene and that exhibit
properties such as relatively low Noack volatility, calculated
according to ASTM D 5800 Standard Test Method for Evaporation Loss
of Lubricating Oils by the Noack Method, low cold-crank viscosity
(i.e. dynamic viscosity according to ASTM D 5293, CCS), and/or
additional SAE OW low temperature viscometric requirements.
[0007] The properties of a particular grade of PAO are typically
dependent on the alpha olefin feedstock used to make that product.
Commercially, some C28 to C36 oligomers of alpha olefins are made
from a mixed feed of C8, C10 and C12 alpha olefins, with 1-decene
being incorporated for the purpose of imparting the most desirable
properties.
[0008] In contrast, 4 cSt PAOs and PIOs made without decene have
yielded base oils lacking in one or more important physical
properties (e.g., viscosity index, Noack volatility, and low
temperature CCS). Thus, PAOs made from C8 through C12 mixed
alpha-olefin feeds, such as the C28 to C36 oligomers may have the
advantage that they lower the amount of decene that is needed to
impart predetermined properties. However, they still do not
completely remove the requirement for providing decene as a part of
the oligomer, in order to impart the appropriate physical
properties. Therefore, there is a need for products that
incorporate alpha olefins other than C8, C10 and C12, to make
polyolefin base oils.
[0009] Poly internal-olefins (PIOs) are typically produced by the
polymerization of internal-olefins in the presence of a Friedel
Crafts catalyst such as AlCl.sub.3, BF.sub.3, or BF.sub.3
complexes. C8-C18 internal olefins have been used to manufacture
PIOs. Oligomerization of these olefins is typically followed by
fractionation and hydrogenation to remove any remaining unreacted
hydrocarbons and unsaturated moieties. Such PIOs have been prepared
with properties including 4.33 cSt viscosity at 100.degree. C.,
20.35 Vis at 40.degree. C., 122 Viscosity Index, pour point of
-51.degree. C. and Noack volatility of 15.3 (Data taken from
Synthetic Lubricants and High-Performance Functional Fluids,
Revised and Expanded. Edited by Leslie R. Rudnick and Ronald L.
Shubkin CRC Press 1999.) This product has excellent low pour point,
but the VI is too low, and the Noack Volatility too high, for
modern OW engine oils. Therefore, a need for a non-1-decene based
polyolefin exists in the market.
[0010] Other examples of processes for making PIOs can be found,
for example, in EP 1,104,747, EP 0,776,960, and U.S. Pat. No.
4,910,355.
[0011] Furthermore, conventional processes to make these PAOs and
PIOs may also result in the production of significant quantities of
cross-oligomers that do not have the desired properties for a 4 cSt
base oil. Accordingly, narrow distillation cuts must typically be
taken to select only the oligomers having the desired properties,
resulting in undesirably low yields of functional product.
[0012] Therefore, there remains a need for a base oil composition
having properties within commercially acceptable ranges for
physical properties including one or more of the viscosity, Noack
volatility, and low temperature cold-cranking viscosity, for use
for example in automotive and other applications. Furthermore,
there remains a need for base oil compositions having improved
properties and methods of manufacture thereof, where the base oil
compositions have reduced amounts of 1-decene incorporated therein,
and may even preferably eliminate the use of 1-decene in the
manufacture thereof.
[0013] Large quantities of poly alpha olefins are used in a variety
of lubricating applications. However, PAOs existing in the market
today are derived from fossil fuels. Another potential source for
making polyolefin base oils is from renewable sources. Therefore,
it is desirable to produce base oils and PAOs from renewable
sources. Alpha olefins can be made via dehydration of a fatty
alcohol.
[0014] Naturally occurring sources of said renewable alcohols do
not have high concentration of C8-C12 length alcohols, and instead
have a high concentration of alcohols in the range of C14-C18.
Previous attempts to use linear alpha olefins in the C14-C18 range,
without 1-decene, made poly alpha olefins with unacceptably high
pour points lubricants, i.e. higher than -24.degree. C., that are
unsuitable for use in a variety of different lube oils, including
OW engine oils. High pour points increase the cold-cranking
viscosity at -35.degree. C. (ASTM D5293-02). Accordingly, there is
a need for polyolefins with low enough pour points that the
cold-cranking viscosities are suitable for OW engine oils, while
exhibiting volatilities that are acceptable.
[0015] Up to now, however, commercially successful poly alpha
olefin base oils have been limited to those comprising C8, C10 and
C12 linear alpha-olefins. No commercial process has been
demonstrated to convert other olefins to polyolefins with
advantageously low pour points, CCS at -35.degree. C. and low Noack
volatility properties for PAO based lubricant oils. Aspects of the
present disclosure are directed to overcoming this and other
deficiencies in the art.
SUMMARY OF THE INVENTION
[0016] Aspects of the present disclosure relate to a process for
the manufacture of branched saturated hydrocarbons, which may be
suitable for use as synthetic base oils or base oil components. In
accordance with aspects of the present disclosure, a new
alternative process has been discovered for producing polyolefin
base oils from olefins, such as from alpha-olefins, or mixtures of
alpha and internal-olefins, as well as optionally internal-olefins.
C14 to C18 alpha or internal-olefins are used in this process as
the primary feedstocks for oligomer manufacturing, thereby easing
the demand for high price 1-decene and other crude oil or synthetic
gas based olefins as feedstocks, and making available alternate
sources of olefin feedstocks such as those derived from C14-18
alcohols. Provided herein are also base oils and lubricant
compositions derived from one or more olefin co-monomers, where
said olefin co-monomers are oligomerized to dimers, trimers, and
higher oligomers. In a preferred embodiment, the process according
to aspects of the disclosure isomerizes at lease the dimer portion
of the oligomers. The resulting dimers have excellent pour point,
volatility and viscosity characteristics and additive solubility
properties.
[0017] Briefly, in a first aspect of the present disclosure, a
process for preparing a C14 to C18 olefin oligomer with excellent
low temperature properties is provided, comprising: forming a
reaction mixture of an oligomerization catalyst system and a C14 to
C18 olefin monomer feed mixture, polymerizing the olefin monomer
feed in the reaction mixture to produce an oligomer product. In one
embodiment, the dimer portion produced by the oligomerization has a
branching proximity of 20 or greater. At least the dimer portion of
the oligomerization product is isomerized in the presence of an
acid catalyst. The isomerized oligomer product is hydrogenated, and
the dimer fraction can be separated, such as by distillation, such
that a polyolefin lubricant composition comprising an average
carbon number in the range of C29-C36 is obtained. In one
embodiment, the resulting polyolefin base oil may have a weight
average molecular weight between 422 and 510, and pour point of
-27.degree. C. or below, having a kinematic viscosity at
100.degree. C. in the range of from about 3.7 to about 4.8 cSt,
with a branching index (BI) greater than 22, but less than 26, a
Noack weight loss in the range of from about 6 to about 14%, and a
viscosity index greater than 124.
[0018] Other aspects, features and embodiments of the present
disclosure are provided in the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a block diagram illustrating a process embodiment
including: a 1-stage and optionally a 2-stage oligomerization
reaction, recycling of the unreacted monomer back into the 1st
stage of the oligomerization process, hydrogenation of the
oligomers, and fractional distillation to separate the oligomers
into 1 or even 2 base oil distillate cuts (a and b bottoms
product).
[0020] FIG. 2 shows a block diagram showing a process embodiment
including the preparation of an internal olefin feedstock by the
catalytic isomerization of a linear alpha olefin, and the optional
distillation of an unsaturated monomer co-product.
[0021] FIG. 3. Carbon labeling representation for a representative
example of isomers of a GTL C30H62 paraffin used for lubricant
applications.
[0022] FIG. 4. Representative example of 1-Decene trimer 4 cSt
PAO.
[0023] FIG. 5. Representative example of a 4 cSt base oil typical
of a isodewaxed oils or Gas to liquids (GTL) base oils.
[0024] FIG. 6. The reaction process for a representative example of
an isomerized 4 cSt 1-tetradecene and 1-hexadecene 4 cSt Dimer.
[0025] FIG. 7. Branching index (BI) for an embodiment of a
hydrogenated 1-tetradecene and 1-hexadecene dimer 4 cSt polyolefin
lube oil made without isomerization.
[0026] FIG. 8. Embodiments of isomerization and hydrogenation of
C14 and C16 olefins dimers.
[0027] FIG. 9. Illustrates an embodiment of oligomerization of
alpha olefins, followed by either (A) both isomerization followed
by hydrogenation of the oligomer product, or (B) hydrogenation
alone.
DETAILED DESCRIPTION
[0028] According to aspects of the disclosure, olefin oligomers are
obtained by providing at least one C14-C18 olefin monomer, or a
mixture of two or more of said olefin monomers (e.g., as shown in
box 1 of FIGS. 1 and 2). The olefin monomer can also be prepared by
providing linear or branched alpha olefins (such as C14-C18
branched alpha olefin monomers), or optionally a linear or branched
internal olefin. The olefin monomer is oligomerized, for example
either with itself, or with a second olefin (e.g., as shown in
boxes 2a-2c of FIGS. 1 and 2), which may be an internal olefin
monomer having a different chain length and/or different average
double bond position, and/or may be a C14 to C18 alpha olefin
monomer, such as a linear alpha-olefin monomer. In one embodiment,
where one of the olefin monomers used to form the oligomer is a C14
alpha olefin monomer, the other olefin monomer may have a chain
length greater than C14. For example, if a C14 linear alpha olefin
monomer is used as the first olefin, the second olefin monomer may
comprise a C15 to C18 linear alpha olefin monomer. In the process
embodiment shown in FIG. 1, one or more olefin feeds (e.g., Olefins
1, 2 and 3 in boxes 2a-2c), are combined together to form the
olefin mixture in box 1, where the one or more olefin feeds can
comprise alpha olefins, and/or may in certain embodiments comprise
internal olefins. In the process embodiment shown in FIG. 2, at
least one of the olefin feeds is subjected to an isomerization
process to result in an isomerized olefin (e.g., Olefin
Isomerization in box 2b) having an isomerized double bond position,
and this isomerized olefin feed can be optionally combined with
another olefin feed (e.g., Olefin 1 in box 2), to provide the
olefin mixture in box 1. The olefin mixture of box 1 may be exposed
to Boron Trifluoride and an alcohol or ester promoter in an
oligomerization stage, as shown in boxes 3 and 5 of FIGS. 1 and 2,
to form an oligomer from the olefin monomer mixture in reaction
vessel shown in box 1 of FIGS. 1 and 2. Optionally a second stage
reactor can be used to further react the olefin mixture under
different reaction conditions as shown in box 5 of FIGS. 1 and 2,
and may provide a dimer portion of the oligomer product that has a
branching proximity of 20 or greater. The BF.sub.3 promotor adduct
may be separated and recycled back to the oligomerization reactor
as shown in box 6 of FIGS. 1 and 2. The unreacted monomer can be
removed, and optionally recycled back into the starting olefin
mixture, as shown in box 7 of FIGS. 1 and 2, or collected as an
unsaturated co-product. In one embodiment, the resulting mixture of
oligomers is isomerized to increase the degree of branching as
shown in box 8 of FIGS. 1 and 2, and hydrogenated, as shown in box
9 of FIGS. 1 and 2. The dimer fraction may be separated therefrom,
as shown in box 10 to produce a hydrocarbon base oil with desirable
physical properties for use as an engine oil base oil, such as
properties suitable for OW formulations and above, as shown in box
11. A bottoms product may be recovered as shown in box 11 suitable
as a higher viscosity blend stock for engine oil applications or a
base oil for higher viscosity industrial or other vehicle
lubricants. Optionally a saturated or unsaturated lights co-product
may be recovered as shown in box 13. In one embodiment, the
resulting dimer may have a KV100 between 3.7 and 4.8 cSt, with a
viscosity index of 125 or greater, with a pour point between
-27.degree. C. and -45.degree. C., with a CCS at -35 C of less than
1800 cP, and a Noack volatility of less than 14%.
[0029] Aspects of the present disclosure relate to a method for
making saturated C28-C36 hydrocarbons useful for engine oil
applications. In one embodiment, olefins ranging from 14 to 18
carbons in size are exposed to a strong Lewis acid catalyst such as
BF.sub.3 coupled with a promoter molecule. According to one
embodiment, the unreacted monomer is distilled off, and the
resulting oligomers are further isomerized in the absence of
hydrogen. The dimers may be separated by distillation, and have
ideal properties for use in an engine oil formulation, with a
relatively high VI, low CCS, low Noack, and low Pour Point.
Feedstock Selection
[0030] In one embodiment, a feed alpha olefin, such as C14 to C18,
can be either an alpha olefin, or may be an olefin feed that has
been produced by isomerizing an alpha olefin to form an internal
olefin prior to oligomerization, via selective internal
isomerization of the .alpha.-olefin using a catalyst (which may be
an inexpensive catalyst), and under isomerization conditions that
may inhibit olefin deterioration and side reactions, such as
skeletal isomerization, oligomerization, and cracking.
[0031] Aspects of the disclosure relate to the surprising discovery
that an oligomer derived from C14-C18 alpha olefins and/or internal
olefins can have the desired viscosity, Noack volatility, and/or
low temperature COS viscosity, such as values of these properties
that are within commercially preferred ranges. According to aspects
of the disclosure, by controlling the oligomerization reaction
conditions and the degree of branching through isomerization of the
oligomers, a mixture of C14-C18 olefins, such as olefins selected
from the group consisting of 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene, 1-octadecene, (and/or optionally
branched structural isomers of these olefins) and/or internal
olefins derived from linear internal or branched internal
pentadecenes, hexadecenes, heptadecenes and octadecenes, can
produce dimers offering excellent low temperature performance, high
viscosity index, and low volatility. In one embodiment, the olefin
monomers of the feed mixture may be selected from the group
consisting of unsaturated, linear alpha-olefins, unsaturated,
linear internal olefins, branched alpha olefins, branched internal
olefins, and combinations thereof. In yet another embodiment, the
olefin monomers of the feed mixture may comprise a mixture of
linear alpha olefins and/or linear internal olefins. According to
certain embodiments, the longer linear paraffin branches produced
from C14-C18 olefins increases the VI and reduce the CCS of the
oligomers, while the pour point of the oligomers can be reduced by
the introduction of branching through isomerization of the
dimer.
[0032] In one embodiment of the disclosure, the feedstocks used to
form the oligomers are C14 to C18 olefins comprising less than 36%
by weight of branched olefins. In yet another embodiment, the
feedstock used to form the oligomers are C14 to C18 olefins
comprise less than 20% by weight of branched olefins monomers. In
yet another embodiment, the feedstocks used to form the oligomers
are C14 to C18 olefins comprise less than 10% by weight of branched
olefins. In yet another embodiment, the feedstock used to form the
oligomers are C14 to C18 olefins comprise less than 5% by weight of
branched olefins.
[0033] Furthermore, in one embodiment, an amount of decene in the
feedstock mixture is less than 20% by weight. In yet another
embodiment, an amount of decene in the feedstock mixture is less
than 10% by weight. In yet another embodiment, an amount of decene
in the feedstock mixture is less than 5% by weight. In yet another
embodiment an amount of decene in the feedstock mixture is less
than 1% by weight.
[0034] In some variations, about 100% of the carbon atoms in the
olefin feedstocks described herein originate from renewable carbon
sources. In some variations, about 100% of the carbon atoms in the
olefin co-monomer originate from renewable carbon sources. For
example, an alpha-olefin co-monomer may be produced by
oligomerization of ethylene derived from dehydration of ethanol
produced from a renewable carbon source. In other variations, at
least 90%, and even at least 95% of the carbon atoms in the
renewable feedstocks originate from renewable carbon sources.
[0035] In some variations, alpha olefin monomers may be produced by
dehydration of a primary alcohol other than ethanol that is
produced from a renewable carbon source. In one embodiment, the C14
to C18 alpha olefin monomers used as feedstocks for the
oligomerization are derived from the dehydration of C14 to C18
primary alcohols selected from the group consisting of
1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, and
1-octadecanol. In yet another embodiment, C14 to C18 primary
alcohols are converted to the C14 to C18 alpha olefin monomers, and
isomerized to form the isomerized C14 to C18 olefin monomer of the
feed-stock product by exposure to a di-functional catalyst (e.g., a
catalyst capable of both dehydrating the primary alcohols to form
alpha olefin monomers, and isomerizing the alpha-olefin monomers to
internal olefins).
[0036] In some embodiments, hydrocarbon terpene feedstocks derived
from renewable resources are coupled with one or more olefins that
are derived from renewable resources.
[0037] Oligomerization Process
[0038] According to one embodiment of the process of forming the
oligomer composition, an alpha olefin [e.g., 1-tetradecene] is
either mixed with an alpha or internal olefin [e.g. 3-hexadecene
internal olefin], or polymerized solely (i.e. with itself) by
either by semi-batch or continuous mode in a single stirred tank
reactor, and/or by continuous mode in a series of stirred tank
reactors using catalysts such as BF.sub.3 and/or BF.sub.3 promoted
with a mixture of linear alcohol and an alkyl acetate ester.
[0039] In one embodiment, the oligomerization reaction conditions
are controlled to impart a defined amount of isomerization, and to
produce an at least partially branched unsaturated oligomer. That
is, the oligomerization process conditions may be selected to not
only oligomerize, but also at least partially isomerize, with the
isomerization being controlled to a predetermined extent to avoid
excessive branching of the dimer product at the oligomerization
stage. In one embodiment, any isomerization occurring during
oligomerization is controlled such that the dimer product resulting
from the oligomerization has an average branching proximity (BP),
of 20 or greater, and even 22 or greater. The branching proximity
is a measure of the % equivalent recurring methylene carbons in the
dimers, which are four or more removed from a carbon end group or
branching carbon group (e.g., the epsilon carbons as shown in FIG.
3), and may be determined according to the following formula:
paraffin branching proximity (BP)=(number of .epsilon. carbon
groups/total number of carbon groups)*100,
[0040] where an .epsilon. carbon group is defined as a carbon group
that is separated from any terminal carbon atom groups or branching
carbon groups by at least 4 carbon groups. That is, higher
branching proximities may indicate a more linear molecule and/or
longer hydrocarbon chains between branches (e.g., more recurring
methylene carbons), whereas lower branching proximities may
indicate more branching in the molecule and/or shorter hydrocarbon
chains between branches (e.g., fewer recurring methylene carbons).
Note that the branching proximity (BP) is typically measured for a
saturated compound, and thus any calculation of branching proximity
of the dimer product produced in the oligomerization step would
involve hydrogenation of the dimer product prior to branching
proximity (BP) measurement. That is, in order to determine the
branching proximity (BP) of the dimers produced in the
oligomerization process itself (i.e., without any subsequent
isomerization), the dimers may be hydrogenated to a Bromine Index
below 1000 mg Br.sub.2/100 g as determined in accordance with ASTM
D2710-09. However, as described in further detail below, in
preparing a base oil comprising dimers according to aspects of the
present disclosure, the oligomerized dimer product may be subject
to further isomerization post-oligomerization, and prior to
hydrogenation, to achieve the product. That is, while hydrogenation
of the oligomerized dimers can be performed for the purposes of
determining the branching proximity (BP) achieved after an
oligomerization process, embodiments of the disclosure provide that
a final saturated hydrocarbon base oil is prepared by performing
hydrogenation only after a subsequent isomerization process
post-oligomerization has been performed.
[0041] In one embodiment, the mixture of C14 to C18 olefin monomers
are oligomerized in the presence of BF.sub.3 and/or BF.sub.3
promoted with a mixture of an alcohol and/or an ester, such as a
linear alcohol and an alkyl acetate ester, using a continuously
stirred tank reactor with an average residence time of 60 to 400
minutes. In another embodiment, the C14 to C18 olefin monomers are
oligomerized in the presence of BF.sub.3 and/or promoted BF.sub.3
using a continuously stirred tank reactor with an average residence
time of 90 to 300 minutes. In yet another embodiment, the C14 to
C18 olefin monomers are oligomerized in the presence of BF.sub.3
and/or promoted BF.sub.3 using a continuously stirred tank reactor
with an average residence time of 120 to 240 minutes. A temperature
of the oligomerization reaction may be in a range of from
10.degree. C. to 110.degree. C.
[0042] Suitable Lewis acids catalysts for the oligomerization
process include metalloid halides and metal halides typically used
as Friedel-Crafts catalysts, e.g. AlCl.sub.3, BF.sub.3, BF.sub.3
complexes, BCl.sub.3, AlBr.sub.3, TiCl.sub.3, TiCl.sub.4,
SnCl.sub.4, and SbCl.sub.5. Any of the metalloid halide or metal
halide catalysts can be used with or without a co-catalyst protic
promoter (e.g. water, alcohol, acid, or ester). In one embodiment,
the oligomerization catalyst is selected from the group consisting
of zeolites, Friedel-Crafts catalysts, Bronsted acids, Lewis acids,
acidic resins, acidic solid oxides, acidic silica
aluminophosphates, Group IVB metal oxides, Group VB metal oxides,
Group VIB metal oxides, hydroxide or free metal forms of Group VIII
metals, and any combination thereof.
[0043] In one embodiment, the reaction mixture is distilled to
remove the unreacted monomer. For example, the unreacted monomer
may be separated from the oligomer product, such as via
distillation, and can be recycled back into the mixture of the
first and/or second feedstocks for oligomerization thereof.
According to one aspect of the present disclosure, the unsaturated
monomer free oligomer may be further isomerized without cracking in
the absence of hydrogen, such as via isomerization in the presence
of a catalyst.
[0044] Proper control of the oligomerization reaction conditions
may be provided to ensure at least the dimer portion of the
oligomers does not become too branched. In one embodiment, dimers
resulting from oligomerization of C14-C18 olefins will have an
average branching proximity (BP) of 20 or greater per 100 carbons.
For example, if the dimers resulting from the oligomerization were
to be hydrogenated to a Bromine Index below 1000 mg Br.sub.2/100 g
as determined in accordance with ASTM D2710-09, without a
subsequent isomerizing step, the resulting hydrogenated dimers
would exhibit an average paraffin branching proximity (BP) as
determined by 13C NMR of 20 or greater per 100 carbons. In yet
another embodiment, the dimers have an average branching proximity
of 22 or greater. Dimers with lower branching proximity (below 20)
as a result from isomerization during oligomerization may not
maintain the necessary amount of linearity after the subsequent
isomerization, and thus may exhibit excessive branching of the
final dimer product, and a base oil with an excessively low VI
(<124) and a dynamic viscosity that is undesirably high
(>1800 cP).
[0045] In another embodiment, the unsaturated oligomer product is
fractionated by distillation to remove the unreacted monomer
portion, and the dimers and heavier oligomers are isomerized
simultaneously.
[0046] Isomerization Process
[0047] In one embodiment, the oligomer product is next subjected to
isomerization. Isomerization can be achieved either under hydrogen
atmosphere (hydroisomerization), or in the absence of hydrogen.
Isomerization (either in the presence or absence of hydrogen) can
introduce additional branching through the rearrangement of the
oligomer molecular structure, which may be critical to reducing
pour point and improving low temperature fluidity. A
hydroisomerization process requires hydrogen, and typically
requires a high pressure and prior catalyst activation.
Accordingly, in certain embodiments a non hydroisomerization
process may be preferred because of the resulting improved product
distribution, product quality, lower capital cost of process
equipment, simplicity of operation, and high efficiency.
[0048] In one embodiment, any isomerization catalyst that is
conventionally used for isomerization processes may be used. In one
aspect, an acid catalyst for isomerization can be homogeneous acid
catalysts, such as AlCl.sub.3, BF.sub.3, halides of Group IIIA, or
modified form of these catalysts, or other typical Friedel-Crafts
catalysts, such as the halides of Ti, Fe, Zn, and the like. The
acid catalyst can also be selected from the group consisting of
solid metals or metal oxides or their mixture of Group IVB, VB, VIB
and Group metal oxides or mixed oxides of Group IIA to VA; other
mixed metal oxides (such as WO.sub.x/ZrO.sub.2 type catalyst),
solid natural or synthetic zeolites, and layered material,
crystalline or amorphous material of silica, alumina,
silicoaluminate, aluminophosphate, aluminum silicophosphate. These
solid acidic catalysts may also contain other Group VIII metals
such as Pt, Pd, Ni, W, etc., as promoters. Generally, it is
preferred to use a solid, regenerable catalyst for process economic
reason and for better product quality. The preferred catalysts
include: ZSM-5, ZSM-11, ZSM-20, ZSM-22, ZSM-23, ZSM-35, ZSM-48,
zeolite beta, MCM22, MCM49, MCM56, SAPO-11, SAPO-31, zeolite X,
zeolite Y, USY, REY, M41S and MCM-41, WO.sub.x/ZrO.sub.2, etc. The
solid catalyst can be used by itself or co-extruded with other
binder material. Typical binder material includes silica, alumina,
silicoalumina, titania, zirconia, magnesia, rare earth oxides, etc.
The solid acidic catalyst can be further modified by Group III
metals, such as Pt, Pd, Ni, W, etc. The modification can be carried
out before or after co-extrusion with binder material. Sometimes
the metal modification provides improvement in activity, sometimes
it is not necessary. An example of discussion of catalysts and
their preparation can be found in U.S. Pat. No. 5,885,438 which is
incorporated herein by reference. Furthermore, in one embodiment
the catalyst provided during isomerization is a different catalyst
than that provided during oligomerization, for example to provide
for differing extents and types of isomerization that what may
occur during the oligomerization process.
[0049] In one embodiment, the acid catalyst provided for
isomerizing the unsaturated polyolefin produced in the
oligomerization process is a zeolite having a Constraint Index of
about 2 to about 12. In another embodiment, the acid catalyst
provided for isomerizing the unsaturated polyolefin produced in the
oligomerization process is a zeolite containing one or more Group
VI B to VIII B metal elements.
[0050] In one embodiment, the isomerization can be carried out in
any of a fixed-bed, continuous operation, in batch type operation
or in continuous stir tank operation. Generally, the residence time
of the oligomer product under the isomerization conditions (e.g.,
residence time in fixed-bed reactor) may range from a few seconds
to up to one or two days depending on reaction temperature,
catalyst activity and catalyst particle size. For economic reasons,
it may be preferred to use shorter residence times, if sufficient
isomerization can be achieved to give improved properties. In one
embodiment, residence time of 10 minutes to 20 hours residence time
may be suitable.
[0051] In one embodiment, the isomerization is conducted at
temperatures in the range of about 200.degree. C. to about
400.degree. C., and preferably at about 225.degree. C. to about
300.degree. C., and at pressures of about 0 kPa to about 13.79 MPa
(about 0 psi to about 2,000 psi) and preferably about 35.5 kPa
(about 15 psi) (atmospheric pressure) to about 6.895 MPa (about
1,000 psi), and even in a range of from 6.89 kPa (1 psi) to 689 kPa
(100 psi). During the isomerization, the hydrocarbon cracking may
be minimal, and even less than <1%, and so overall yield loss
may be reduced while maintaining desired base oil properties (Vis,
VI, CCS at -35 100.degree. C. and PP).
[0052] In one embodiment, the pour point of the isomerized product
is at least -9.degree. C. less than that of the oligomer product
prior to isomerization. In yet another embodiment, the pour point
of the isomerized product is at least -15.degree. C. less than that
of the oligomer product prior to isomerization. In yet another
embodiment, the pour point of the isomerized product is at least
-21.degree. C. less than that of the oligomer product prior to
isomerization.
[0053] Cracked byproducts, naphthalenes and aromatics compounds can
be formed during the isomerization of the oligomerized olefin.
Naphthenic compounds are cyclic saturated hydrocarbons, also known
as cycloparaffins. Naphthenic compounds may contain one ring
structure (monocycloparaffins) or two rings (dicycloparaffins) or
several rings (multicycloparaffins).
[0054] It is preferred that cracked hydrocarbons, naphthalenes and
aromatic compounds are not formed, or are only formed in trivial
amounts, during the isomerization of polyolefins, as they can
adversely affect conversion and properties of the final product,
specially viscosity index (VI), oxidation stability and Noack
volatility. In one embodiment, the oligomers formed from C14 to C18
olefin monomers are isomerized under conditions wherein the amount
of cracked byproducts generated during isomerization are less than
10% by weight. In another embodiment, the oligomers formed from C14
to C18 olefin monomers are isomerized under conditions wherein the
amount of cracked byproducts generated during isomerization are
less than 5% by weight. In yet another embodiment, the oligomers
formed from C14 to C18 olefin monomers are isomerized under
conditions wherein the amount of cracked byproducts generated
during isomerization are less than 1% by weight. In yet another
embodiment the isomerized oligomers contain less than 5%
naphthalenes by weight. In another embodiment, the isomerized
oligomers contain less than 2.5% naphthalenes by weight. in yet
another embodiment the isomerized oligomers contain less than 1%
naphthalenes by weight. In yet another embodiment, a base oil
product comprising the dimers formed by the oligomerization and
isomerization, may comprise the cracked byproducts in a wt % that
is the same or less than the amount generated during the
isomerization. For example, in one embodiment, the base oil can
comprise cracked byproducts generated during isomerization that are
less than 10% by weight of the base oil. In another embodiment, the
base oil comprises cracked byproducts generated during
isomerization than are less than 5% by weight of the base oil. In
yet another embodiment, the base oil comprises of cracked
byproducts generated during isomerization are less than 1% by
weight of the base oil. In yet another embodiment the base oil
contains less than 5% naphthalenes by weight. In another
embodiment, the contains less than 2.5% naphthalenes by weight. In
yet another embodiment the base oil contains less than 1%
naphthalenes by weight.
[0055] In one embodiment, the isomerization reaction has a
relatively high conversion rate for conversion of dimers to
isomerized dimer products. For example, according to one
embodiment, a percent yield of isomerized dimers produced in the
isomerization is greater than 90% by weight of the dimers. In
another embodiment, a percent yield of isomerized dimers produced
in the isomerization is greater than 95% by weight. In another
embodiment, a percent yield of isomerized dinners produced in the
isomerization is greater than 97.5% by weight. In another
embodiment, a percent yield of isomerized dimers produced in the
isomerization is greater than 99% by weight.
[0056] Hydrogenation Process
[0057] In one embodiment, the product of the isomerization process
is next hydrogenated. For example, a palladium on carbon catalyst,
or supported nickel, or other well-known hydrofinishing catalysts
may be used. Hydrogenation conditions include can include, for
example, temperatures of from about 25.degree. C. to about
400.degree. C., and hydrogen pressure of about 1 to about 100
atmospheres. The hydrogenated product generally has a low bromine
index of less than about 1000 as measured by ASTM D2710-0.
[0058] As described in further detail below, in one embodiment, the
isomerization is followed by hydrogenation of the branched
hydrocarbons produced in the isomerization process. For example,
hydrogenation may be performed to achieve a hydrogenated product
having a bromine index of less than 1000 mg Br/100 g (ASTM
D2710-09). Hydrogenation processes are described in, e.g., see U.S.
Pat. Nos. 7,022,784 and 7,456,329, which are incorporated herein by
reference.
[0059] In a further embodiment, the oligomer product is
hydrogenated to form a saturated oligomer product comprising a
mixture of branched saturated hydrocarbons including hydrogenated
dimer, trimer, and higher oligomers. According to one aspect, the
mixture of branched saturated hydrocarbons is hydrogenated to the
extent that the Bromine Index is below 1000 mg Br/100 g, as
measured by ASTM D2710-0.
[0060] Base Oil
[0061] In one embodiment, the dimer portion of the hydrogenated
oligomer product is separated from the remaining oligomer product,
such as for example by taking one or more distillation cuts of the
hydrogenated oligomer product.
[0062] In one embodiment, the saturated hydrocarbon base oil
comprises greater than 90 wt % of the dimers, with the dimers
having an average carbon number in the range of from 29 to 36, and
the dimer portion having a weight average molecular weight in the
range of from 422 to 510. Furthermore, according to embodiments
herein, the dimers of the saturated base oil can comprise an
average branching index (B)) as determined by 1H NMR that is in the
range of 22 to 26, and an average paraffin branching proximity (BP)
as determined by 13C NMR in a range of from 18 to 26. The average
paraffin branching proximity (BP) is discussed above, and is a
measure of the content of recurring methylene groups in the dimer
portion. The branching index is a measure of the extent of
branching, and can be determined according to the following
formula:
Branching index (BI)=(total content of methyl group hydrogens/total
content of hydrogens)*100
[0063] It has unexpectedly been discovered that, by controlling
conditions during the base oil production process, including the
oligomerization and isomerization steps, to provide a dimer product
with branching characterized by the branching index and/or
branching proximity described herein, a base oil product can be
achieved with improved physical properties that may be suitable for
automotive engine oil and other applications. Further detail
regarding the properties of the base oil is described below.
[0064] To further clarify aspects of the present disclosure, it is
noted that PAO dimers made from C14-C18 alpha olefins (i.e.,
without exposure to an isomerization catalyst post-oligomerization)
may have relatively high pour points which can prevent them from
being used in engine oil formulations. Comparative Example A is a
dimer of C14 and C16 alpha olefins that was hydrogenated without
exposure to an isomerizing Zeolite catalyst, and which has a BI of
22.51 and a branch proximity of 22.28; the pour point is
-27.degree. C. and a CCS at -35.degree. C. of 2322 cP. Example 2
according to aspects of this disclosure is a dimer of same ratio of
C14 to C16 alpha olefins as Comparative Example A, but which has
been further isomerized by exposure to a Zeolite catalyst before
hydrogenation, and which after hydrogenation exhibits a BI of 23.96
and a BP of 20.49; consequently, the pour point is -36.degree. C.
and a CCS at -35.degree. C. of 1795 cP. This demonstrates that the
isomerization process improves the pour point and CCS of the
product.
[0065] In one embodiment, the isomerization of the oligomerized
product produces an oligomer that, after hydrogenation and
distillation, has a paraffin branching proximity (BP) of greater
than 18 and less than 26 per 100 carbons and with branching index
(BI) between 22 and 26 per 100 carbons. For a base oil and/or dimer
product having branching proximity and branching index within these
ranges, sufficient long chain branches remaining intact, while
branching is also provided to a sufficient extent, resulting in a
base oil with a viscosity index greater than about 125, with a pour
point below -27.degree. C., and CCS at -35.degree. C. of less than
1800 cP.
[0066] An example of a resulting isomer structure can be seen in
FIG. 6, with a representative process shown in FIG. 8. In this
structure, a branching index (BI) is 24.2 per 100 carbons and a
branching proximity (BP) is 20.0 per 100 carbons. By contrast, FIG.
7 demonstrates a process and product by oligomerization and
hydrogenation of C14 and C16 dimers, without a separate
isomerization process, which results in less branched structures
having a lower branching index of less than 19, and a higher
branching proximity of greater than 26. Similarly, referring to
FIG. 4, a conventional 1-decene trimer has a lower branching index
of 19.4 and a lower branching proximity of 3, whereas, referring to
FIG. 5, an oligomer produced by Fisher-Tropsch synthesis has a
lower branching index of 19.4, and a higher branching proximity of
26.7. FIG. 9 further demonstrates the results for a process that
performs isomerization prior to hydrogenation (path A), versus a
process that only performs hydrogenation (path B). Accordingly,
providing a dimer product with the branching proximity (BP) and/or
branching index (BI) as described herein, such as via isomerization
processes performed post-oligomerization and prior to
hydrogenation, can allow for production of a base oil having the
improved physical properties.
[0067] In one embodiment, the dimer produced according to aspects
of this disclosure, a C28 to 036 dimer, makes about a 4 cSt base
oil and the physical properties of the composition may have similar
and/or improved physical properties as those that have yet only
been achievable using solely 1-decene, or PAOs or those that
incorporate significant amounts of 1-decene as a feedstock, such as
PAOs derived from a mixed alpha-olefin feed of C10/C12, C8/C10/C12,
C10/C12/C14 (i.e., cross-oligomers of 010 and C12, and
cross-oligomers of C8, C10 and C12). For example, aspects of the
disclosure may provide a base oil comprising the dimer product
with, e.g., about a 4 cSt KV100 base fluid, such as in a range of
from about 3.7 to about 4.8 cSt, with excellent Noack volatility,
such as less than 14%, less than 1800 CCS at -35.degree. C. and
viscosity index (VI) greater than 125.
[0068] Furthermore, according to one aspect, the base oil
composition comprising the dimer is substantially absent of any
1-decene. For example, embodiments of the base oil may comprise
less than 5% by weight of 1-decene in either monomer, dimer, or
trimer form, as well as higher oligomer forms, such as less than 3%
by weight of 1-decene, and even less than 1% by weight of
1-decene.
[0069] Previous attempts to utilize the long chain alpha olefins
for a 4 cSt base fluid yielded hydrocarbon lubricants that were
deficient in one or more necessary physical parameters and they are
included here for comparison. Comparative Example A shows PAO made
from C14 and C16 alpha olefins, where the oligomers are not
isomerized, the product has a CCS at -35.degree. C. of 2400 cP,
that is too high to be desirable for engine oils application due to
rapid gelation characteristics. Changing the C14 and C16 content
can help reduce the pour point, as shown by Reference A in the
below table (from U.S. Pat. No. 4,218,330). However, the extra
addition of C14 into the dimer is detrimental to the volatility as
it is increased past the desirable range of <14%. Comparative
Example B is made with C14 only dimers, and exhibits too low of a
viscosity at 100.degree. C., and too high a volatility, with its
average carbon number of C28 below the desired C29-36 range without
isomerization of the oligomers. Comparative Example C contains C16
alpha olefins only and has C32 average carbon length and an
extremely low Noack volatility without isomerization of the
oligomers. Instead, it has been discovered that oligomers of
alpha-olefins with an average carbon number greater than about C12
require isomerization after oligomerization, as disclosed herein,
to bring the cold temperature properties to a desirable range for
engine oils. Surprisingly, by controlling the oligomer chain
length, branching index, and branching proximity through
isomerization of the oligomers, as in Example 1 and 2, oligomers
from long chain LAOs can be prepared that exhibit desirable engine
oil properties.
TABLE-US-00001 TABLE 1 Olefin feed ratio effect on the properties
on the C14-C16 dimers. 100.degree. C. Pour Noack viscosity, point,
Volatility, Example Feed Olefins cSt VI .degree. C. % loss
Comparative C14/C16 30/70 4.13 128 -27 12.6 Example A Example 1
C4/C16 30/70 4.23 125 -39 12.9 Example 2 C14/C16 30/70 4.24 128 -36
13.2 Reference A C14/C16 68/32 4.15 137 -26 >15 Comparative C14
100 3.01 134 -30 16.1 Example B Comparative C16 100 4.30 151 -15
6.4 Example C Example 3 C16 100 4.02 131 -33 13.9 Example 4 C16 100
4.01 132 -30 13.3
[0070] For synthetic base oils such as PAO based on C8, C10, C12,
or any combination of C8 through C12 alpha olefins, the Branching
Index (BI) has been found to correlate with improved lubricant
properties for hydrocarbon base oils. Specifically, commercial PAO
base oils based on C8 through C12 alpha olefins, as shown in
Reference B (Commercial sample of a 4 cSt PAO) in Table 2, require
a Branching Index below about 22 to obtain desired properties.
Oligomers from C8-C12 olefins with branching index greater than
about 22 have excessive branching which constrains the lubricant
properties, particularly with respect to viscosity index.
Similarly, the Fischer-Tropsch process which produces gas to liquid
(GTL) hydrocarbon lubricants with approximately 4 cSt at
100.degree. C. among other viscosity products, seen in Reference C
and D, it is preferred to have a branching index below 22 to
achieve useful cold flow properties for an engine oil, as seen in
U.S. Pat. No. 7,018,525. In contrast, as has been discovered
herein, when using C14 or greater olefins, a branching index above
22 and a branching proximity of above 18 have been found to give
superior lubricant properties, particularly with respect to VI, CCS
at -35.degree. c., and Noack volatility.
TABLE-US-00002 TABLE 2 Branching Index and average carbon number
for samples of 4 cSt GTL, PAO and this invention. Branching avg
carbon Sample # Material id index number Example 2 C14/C16 isom
23.96 30.8 Reference B GTL 19.7 27.8 Reference C GTL 19 27.4
Reference D C8/C10/C12 PAO 21.8 32.4
TABLE-US-00003 TABLE 3 General comparison of 4 cSt C14-C16 dimer
with PAO and GTL 4cSt products. BI BP VI PP NV CCS @ -35 C. Example
2 24 20 128 <-33 <13 <1800 PAO .ltoreq.22 .ltoreq.16
124-126 <-54 <14 <1500 GLT 4 <20 >26 >140 -27 14
>1800
[0071] According to one embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits improved properties, such
as volatility and cold temperatures properties suitable for use in
automotive engine oil formulations. In one embodiment, the
saturated hydrocarbon base oil comprising the dimer product
exhibits a Noack Volatility as measured by ASTM D5800 that is less
than 14%. In yet another embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits a Noack Volatility as
measured by ASTM D5800 that is less than 13%. In yet another
embodiment, the saturated hydrocarbon base oil comprising the dimer
product exhibits a Noack Volatility as measured by ASTM D5800 that
is less than 12%. In yet another embodiment, the saturated
hydrocarbon base oil comprising the dimer product exhibits a Noack
Volatility as measured by ASTM D5800 that is less than 11%. In yet
another embodiment, the saturated hydrocarbon base oil comprising
the dimer product exhibits a Noack Volatility as measured by ASTM
D5800 that is less than 10%. In yet another embodiment, the
saturated hydrocarbon base oil comprising the dimer product
exhibits a Noack Volatility as measured by ASTM D5800 that is less
than 9%. In yet another embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits a Noack Volatility as
measured by ASTM D5800 that is less than 8%. In yet another
embodiment, the saturated hydrocarbon base oil comprising the dimer
product exhibits a Noack Volatility as measured by ASTM D5800 that
is less than 7%. Generally, the Noack Volatility will be at least
6%.
[0072] According to yet another embodiment, the saturated
hydrocarbon base oil comprising the dimer product exhibits a Pour
Point as measured by ASTM D97-17 of less than -27.degree. C.
According to yet another embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits a Pour Point as measured
by ASTM D97-17 of less than -30.degree. C. According to yet another
embodiment, the saturated hydrocarbon base oil comprising the dimer
product exhibits a Pour Point as measured by ASTM D97-17 of less
than -33.degree. C. According to yet another embodiment, the
saturated hydrocarbon base oil comprising the dimer product
exhibits a Pour Point as measured by ASTM D97-17a of less than
-36.degree. C. According to yet another embodiment, the saturated
hydrocarbon base oil comprising the dimer product exhibits a Pour
Point as measured by ASTM D97-17a of less than -39.degree. C.
According to yet another embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits a Pour Point as measured
by ASTM D97-17a of less than -42.degree. C.
[0073] According to one embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits a Cold Crank Simulated
(CCS) dynamic viscosity as measured by ASTM D5293 at -35.degree. C.
of 1800 cP or less. According to yet another embodiment, the
saturated hydrocarbon base oil comprising the dimer product
exhibits a Cold Crank Simulated (CCS) dynamic viscosity as measured
by ASTM D5293-15 at -35.degree. C. of 1700 cP or less. According to
yet another embodiment, the saturated hydrocarbon base oil
comprising the dimer product exhibits a Cold Crank Simulated (CCS)
dynamic viscosity as measured by ASTM D5293-15 at -35.degree. C. of
1600 cP or less. According to yet another embodiment, the saturated
hydrocarbon base oil comprising the dimer product exhibits a Cold
Crank Simulated (CCS) dynamic viscosity as measured by ASTM
D5293-15 at -35.degree. C. of 1500 cP or less. According to yet
another embodiment, the saturated hydrocarbon base oil comprising
the dimer product exhibits a Cold Crank Simulated (CCS) dynamic
viscosity as measured by ASTM D5293-15 at -35.degree. C. of 1400 cP
or less. According to yet another embodiment, the saturated
hydrocarbon base oil comprising the dimer product exhibits a Cold
Crank Simulated (CCS) dynamic viscosity as measured by ASTM
D5293-15 at -35.degree. C. of 1300 cP or less. According to yet
another embodiment, the saturated hydrocarbon base oil comprising
the dimer product exhibits a Cold Crank Simulated (CCS) dynamic
viscosity as measured by ASTM D5293-15 at -35.degree. C. of 1200 cP
or less According to yet another embodiment, the saturated
hydrocarbon base oil comprising the dimer product exhibits a Cold
Crank Simulated (CCS) dynamic viscosity as measured by ASTM
D5293-15 at -35.degree. C. of less than 1100 cP.
[0074] Furthermore, in one embodiment, the saturated hydrocarbon
base oil comprising the dimer product exhibits a KV(100) as
measured by ASTM D445-17a that is in the range of from 3.7 cSt to
4.8 cSt. In another embodiment, the saturated hydrocarbon base oil
comprising of the dimer product exhibits a KV100 as measured by
ASTM D445-17a is in the range of from 3.8 cSt to 4.5 cSt.
[0075] In another embodiment, the saturated hydrocarbon base oil
comprising the dimer product exhibits a viscosity index as measured
by ASTM D2270 of 125 or greater. In yet another embodiment, the
saturated hydrocarbon base oil comprising the dimer product
exhibits a viscosity index as measured by ASTM D2270 of 130 or
greater. In yet another embodiment, the saturated hydrocarbon base
oil comprising the dimer product exhibits a viscosity index as
measured by ASTM D2270 of 135 or greater. In yet another
embodiment, the saturated hydrocarbon base oil comprising the dimer
product exhibits a viscosity index as measured by ASTM D2270 of 140
or greater. In yet another embodiment, the saturated hydrocarbon
base oil comprising the dimer product exhibits a viscosity index as
measured by ASTM D2270 of 150 or greater.
[0076] In yet another embodiment, the saturated hydrocarbon base
oil has a Noack Volatility that is related to the KV100 by the
following equation:
Noack volatility<-16.583(KV100){circumflex over (
)}2+125.36(KV100)+223.8
[0077] In yet another embodiment, the CCS at -35 is related to the
KV 100 by the following equation:
CCS viscosity at -35.degree. C.<-1333.3(KV100){circumflex over (
)}2+11933(KV100)-24900.
EXAMPLES
[0078] The following examples are meant to illustrate embodiments
of the present disclosure, and it will be recognized by one of
ordinary skill in the art in possession that numerous modifications
and variations are possible. Therefore, it is to be understood that
embodiments of the invention may be practiced otherwise than as
specifically described herein.
Example 1
[0079] An olefin mixture of 30% 1-tetradecene and 70% 1-hexadecene
with less than 8% branched and internal olefins was obtained, and
the mixture was oligomerized under BF.sub.3 pressure with a
co-catalyst comprising a short chain alcohol and ester. Semi
continuous addition of olefins and co-catalyst was used. The
monomer was then distilled off and the bottoms were isomerized
using a zeolite on alumina catalyst at 250.degree. C. for 8 hours
in a batch reactor. The isomerized oligomers were then hydrogenated
to a Bromine Index of less than 1000 mg Br/100 g. The hydrogenated
dimers were then distilled away from the trimer and heavier
oligomers and had an average branching proximity of 22.3.
Example 2
[0080] Oligomerization reaction and feeds were carried out in
accordance with Example 1. The remaining monomer was distilled off
and the resulting oligomers were exposed to a zeolite on alumina
catalyst at 270.degree. C. for 8 hours in a batch reactor.
Example 3
[0081] A 1-hexadecene olefin feed with less than 8% branched and
internal olefins was obtained. The 1-hexadecene feed was
oligomerized under BF.sub.3 pressure with a co-catalyst comprising
of a short chain alcohol and ester. Semi continuous addition of
olefins and co-catalyst was used. The unreacted monomer was then
distilled off and the bottoms were isomerized using a zeolite on
alumina catalyst at 290.degree. C. for 4 hours in a batch reactor.
The isomerized oligomers were then hydrogenated to a Bromine Index
of less than 1000 mg Br/100 g. The Hydrogenated dimers were then
distilled away from the trimer and heavier oligomers.
Example 4
[0082] Oligomerization feed and reaction was carried out in
accordance with Example 3. The remaining monomer was distilled off
and the resulting oligomers were exposed to a zeolite on alumina
catalyst at 270.degree. C. for 4 hours.
Definitions
[0083] Olefin
[0084] The term "Olefin" as used herein refers a hydrocarbon
containing at least one carbon-carbon double bond. For example,
according to aspects of the disclosure herein, an olefin may
comprise a hydrocarbon chain length of from C14 to C18, and may
have a double bond at an end (primary position) of the hydrocarbon
chain (alpha-olefin) or at an internal position (internal-olefin).
In one embodiment, the olefin is a mono-olefin, meaning that the
olefin contains only a single double-bond group.
[0085] Alpha Olefins
[0086] The term "Alpha Olefin" as used herein refers an olefin that
has a carbon-carbon double bond at an end of the olefin hydrocarbon
chain (terminal position). For example, according to aspects of the
disclosure herein, alpha olefins may comprise a hydrocarbon chain
size of from C14 to C18, such as compounds having a chemical
formula where the olefin has no more carbons than the specified
carbon number of C14 to C18, e.g., C14H28, C16H32 and C18H36. In
one embodiment, the alpha olefin is a mono-alpha-olefin, meaning
that the alpha olefin contains only a single double-bond group.
[0087] Linear Alpha Olefin (LAO)
[0088] The term "Linear Alpha Olefin" as used herein refers an
olefin that is linear (i.e., unbranched), and has a double bond at
an end of the olefin hydrocarbon chain (terminal position). For
example, according to aspects of the disclosure herein, alpha
olefins may comprise a hydrocarbon chain length of from C14 to C18,
such as compounds having a chemical formula where the olefin has no
more carbons than the specified carbon number of C14 to C18, e.g.,
C14H28, C16H32 and C18H36. In one embodiment, the linear alpha
olefin is a mono-alpha-olefin, meaning that the alpha olefin
contains only a single double-bond group.
[0089] Internal Olefins
[0090] The term "Internal Olefin" as used herein refers an olefin
that has an internal carbon-carbon double bond that is interior to
the terminal end of the olefin hydrocarbon chain (e.g., at a
position other than the alpha-position), and does not contain a
carbon-carbon double bond at the terminal position. For example,
according to aspects of the disclosure herein, internal olefins may
comprise a hydrocarbon chain size of from C14 to C18, such as
compounds having a chemical formula where the olefin has no more
carbons than the specified carbon number of C14 to C18, e.g.
C14H28, C16H32 and C18H36. In one embodiment, the internal olefin
is a mono-internal-olefin, meaning that the internal olefin
contains only a single double-bond group.
[0091] Linear Internal Olefins
[0092] The term "Linear Internal Olefin" as used herein refers an
olefin that is linear (i.e., unbranched), and that has a
carbon-carbon double bond that is interior to the terminal end of
the olefin hydrocarbon chain (e.g., at a position other than the
alpha-position), and does not contain a carbon-carbon double bond
at the terminal position. For example, according to aspects of the
disclosure herein, linear internal olefins may comprise a
hydrocarbon chain length of from C14 to C18, such as compounds
having a chemical formula where the olefin has no more carbons than
the specified carbon number of C14 to C18, e.g. C14H28, C16H32 and
C18H36. In one embodiment, the linear internal olefin is a
mono-internal-olefin, meaning that the linear internal olefin
contains only a single double-bond group.
[0093] Linear Mono-Olefins
[0094] Mixture of olefins or alkenes distinguished from other
olefins with a similar molecular formula by linearity of the
hydrocarbon chain length and a distribution of double bond
positions in the molecule, from alpha to internal position. For
example, according to aspects of the disclosure herein, linear
mono-olefins may comprise a hydrocarbon chain length of from C14 to
C18 with a chemical formula C14H28, C16H32, C18H36.
[0095] Isomerized Olefin
[0096] The term "Isomerized Olefin" is used herein to refer to an
olefin feed and/or mixture that has been subjected to an
isomerization process, such that an average double-bond position in
the olefin and/or olefins feed has been shifted from a position
close to or at the terminal double position (alpha position), to a
distribution of cis/trans double bond positions more interior along
the chain length. For example, in one embodiment, isomerized
olefins can be formed by isomerization of linear alpha olefins
(LAO), which have their double bond at the terminal end of the
hydrocarbon chain, to linear internal olefins having an average
double bond position more interior along the chain.
[0097] Branched Alpha-Olefins
[0098] The term "Branched Alpha-Olefin" is used herein to refer to
an olefin that has alkyl (such as methyl or ethyl) branch groups
along the hydrocarbon chain length of the olefin, and has a double
bond at an end of the olefin hydrocarbon chain (primary position).
For example, according to aspects of the disclosure herein,
branched alpha olefins may comprise C14 to C18 olefins. In one
embodiment, the branched alpha olefin is a mono-alpha-olefin,
meaning that the branched alpha olefin contains only a single
double-bond group.
[0099] Branched Internal Olefins
[0100] The term "Branched Internal-Olefin" is used herein to refer
to an olefin that has alkyl (such as methyl or ethyl, or even
longer) branch groups along the hydrocarbon chain length of the
olefin, and has a double bond that is interior to the terminal end
of the olefin hydrocarbon chain (e.g., at a position other than the
alpha-position), and does not contain a carbon-carbon double bond
at the terminal position. For example, according to aspects of the
disclosure herein, branched internal olefins may comprise C14 to
C18 olefins. In one embodiment, the branched internal olefin is a
mono-alpha-olefin, meaning that the branched alpha olefin contains
only a single double-bond group.
[0101] Dimer
[0102] The term "Dimer" as used herein refers to molecules formed
by the combination of two monomers via a chemical process, where in
monomers may be the same or different type of monomer unit. The
dimer may be formed by chemical reaction and/or other type of
bonding between the monomers. In one embodiment, a dimer is the
product of oligomerization between two olefin monomers.
[0103] Oligomer
[0104] The term "oligomer" as used herein refers to a molecule
having 2-100 monomeric units, and encompasses dimers, trimers,
tetramers, pentamers, and hexamers. An oligomer may comprise one
type of monomer unit or more than one type of monomer unit, for
example, two types of monomer units, or three types of monomer
units. "Oligomerization" as used herein refers to the formation of
a molecule having 2-100 monomeric units from one or more monomers,
and encompasses dimerization, trimerization, etc. of one type or
different types of monomer, and also encompasses the formation of
adducts and/or complexes between the same or more than one type of
monomer.
[0105] Dimer Total Carbon Number
[0106] The term "Dimer Total Carbon Number" is used herein to refer
to a total number of carbons in the dimer. Accordingly, a "C29-C36"
dimer as referred to herein is a dimer have a total number of
carbon atoms in a range of from 29 to 36.
[0107] Terpenes
[0108] The term "Terpenes" as used herein refers to compounds
having multiples of units of isoprene, which has the molecular
formula C.sub.5H.sub.8. The basic molecular formula of terpenes are
multiples of that, (C.sub.5H.sub.8).sub.n where n is the number of
linked isoprene units, and terpenes can be derived biosynthetically
from such units of isoprene. Monoterpenes consist of two isoprene
units and have the molecular formula C.sub.10H.sub.16.
Sesquiterpenes consist of three isoprene units.
[0109] Renewable
[0110] The term "Renewable" as used herein means any biologically
derived composition, including fatty alcohols, olefins, or
oligomers. Such compositions may be made, for nonlimiting example,
from biological organisms designed to manufacture specific oils, as
discussed in WO 2012/141784, but do not include petroleum distilled
or processed oils such as, for non-limiting example, mineral oils.
A suitable method to assess materials derived from renewable
resources is through "Standard Test Methods for Determining the
Biobased Content of Solid, Liquid, and Gaseous Samples Using
Radiocarbon Analysis" (ASTM D6866-12 or ASTM D6866-11). Counts from
.sup.14C in a sample can be compared directly or through secondary
standards to SRM 4990C. A measurement of 0% .sup.14C relative to
the appropriate standard indicates carbon originating entirely from
fossils (e.g., petroleum based). A measurement of 100% .sup.14C
indicates carbon originating entirely from modern sources (See,
e.g., WO 2012/141784, incorporated herein by reference).
[0111] Base Oil
[0112] The term "Base Oil" as used herein refers an oil used to
manufacture products including dielectric fluids, hydraulic fluids,
compressor fluids, engine oils, lubricating greases, and metal
processing fluids.
[0113] Viscosity Index
[0114] The term "Viscosity index" as used herein refers to
viscosity index as measured according to "Standard Practice for
Calculating Viscosity Index From Kinematic Viscosity at 40 and
100.degree. C." (ASTM D2270) published by ASTM International, which
is incorporated herein by reference in its entirety.
[0115] Kinematic Viscosity
[0116] The term "Kinematic Viscosity" as used herein refers to
viscosities at 40.degree. C. and at 100.degree. C. measured
according to "Standard Test Method for Kinematic Viscosity of
Transparent and Opaque Liquids (and Calculation of Dynamic
Viscosity)" (ASTM D445-17a) published by ASTM International, which
is incorporated herein by reference in its entirety.
[0117] Cold-Cranking Simulator Viscosity
[0118] The term "Cold-Cranking Simulator Viscosity" (abbreviated
CCS) refers to cold cranking simulator viscosity as measured
according to "Standard Test Method for Apparent Viscosity of Engine
Oils Between -5 and -35.degree. C. Using the Cold-Cranking
Simulator" (ASTM D5293) published by ASTM International, which is
incorporated herein by reference in its entirety.
[0119] Pour Point
[0120] The term "Pour Point" refers to temperature at which a
lubricant becomes semi solid and at least partially loses its flow
characteristics, and is measured according to "Standard Test Method
for Pour Point of Petroleum Products" (ASTM D97) published by ASTM
International, which is incorporated herein by reference in its
entirety.
[0121] Noack Volatility
[0122] The term "Noack Volatility" is used herein to a measure of
evaporative weight loss as carried out according to "Standard Test
Method for Evaporation Loss of Lubricating Oils by the Noack
Method" (ASTM D5800), or "Standard Test Method for Evaporation Loss
of Lubricating Oils by Thermogravimetric Analyzer (TGA) Noack
Method" (ASTM D6375, TGA-Noack method), each published by ASTM
International, and each of which is incorporated herein by
reference in its entirety.
[0123] Bromine Index
[0124] The term "Bromine Index" is used herein to refer to a test
for determining the degree of unsaturation of a product, such as a
hydrogenated oligomer and/or dimer product, and can be determined
in accordance with ASTM D2710-09, which is incorporated by
reference herein in its entirety.
[0125] Branching Index (BI)
[0126] The term "Branching Index" is referred to herein as a
measure of the percentage of methyl protons divided by the total
number of protons (non-benzylic) in a sample, such as a sample
comprising a dimer or oligomer. According to one embodiment, the
Branching Index can be calculated using 1H NMR, by determining the
percent of the non-benzylic methyl hydrogen content in the range of
0.5 to 1.05 ppm, per the total non-benzylic aliphatic hydrogen
content in the range of 0.5 to 2.1 ppm. The formula for calculating
the Branching Index is as follows:
Branching Index (BI)=(total content of methyl group hydrogens/total
content of hydrogens)*100.
[0127] Measurement of the Branching Index is further described in
U.S. Pat. Nos. 6,090,989 and 7,018,525, both of which are hereby
incorporated by reference herein in their entireties.
[0128] Branch Proximity (BP)
[0129] The term "Branching Proximity" is used herein is used to
refer to the % equivalent recurring methylene carbons, which are
four or more removed from a carbon end group or branching carbon
group (e.g., the epsilon carbons as shown in FIG. 3). In one
embodiment, the Branching Proximity can be evaluated using 13C NMR,
by measuring a peak corresponding to the recurring methylene
carbons (e.g., at about 29.8 ppm), and determining the content as a
percent of all carbon atoms measured in the 13C NMR spectrum.
According to one aspect, the Branching Proximity may be determined
according to the following formula:
Branching Proximity (BP)=(number of .epsilon. carbon groups/total
number of carbon groups)*100,
[0130] where an .epsilon. carbon group is defined as a carbon group
that is separated from any terminal carbon atom groups or branching
carbon groups by at least 4 carbon groups. Further description of
the measurement of the Branching Proximity is described in U.S.
Pat. No. 6,090,989, and further description of epsilon carbons is
providing in U.S. 2008/0171675, both of which are hereby
incorporated by reference herein in their entireties.
[0131] PIOs
[0132] PIOs refer to dimer, trimer or larger oligomer that is the
product of an oligomerization which uses internal olefins as the
feedstock.
[0133] PAOs
[0134] PAOs refer to dimer, trimer or larger oligomer that is the
product of an oligomerization which uses alpha olefins as the
feedstock.
[0135] Aspects of the invention may further be described with
respect to the following embodiments:
[0136] Embodiment 1: A process for the preparation of a saturated
hydrocarbon base oil, comprising: [0137] forming an oligomerization
reaction mixture comprising an oligomerization catalyst system and
an olefin monomer feed mixture, wherein the olefin monomer feed
mixture has an average carbon number in the range of 14 to 18;
[0138] oligomerizing the olefin monomer feed mixture in the
reaction mixture to produce an oligomer product comprising dimers,
trimers, and higher oligomers, [0139] isomerizing at least the
dimer portion of the oligomer product in the presence of an acid
catalyst to form a mixture of branched hydrocarbons; [0140]
hydrogenating the isomerized branched hydrocarbons, to a Bromine
Index below 1000 mg Br.sub.2/100 g as determined in accordance with
ASTM D2710-09; and [0141] separating the dimer portion of the
hydrogenated oligomer product, whereby a saturated hydrocarbon base
oil is obtained comprising greater than 90 wt % dimers having an
average carbon number in the range of from 29 to 36, the dimer
portion having a weight average molecular weight in the range of
from 422 to 510, [0142] wherein the dimers of the oligomer product,
in a case where the dimers are hydrogenated to a Bromine Index
below 1000 mg Br.sub.2/100 g as determined in accordance with ASTM
D2710-09, without subsequent isomerizing, have an average paraffin
branching proximity (BP) as determined by 13C NMR of 20 or greater,
and [0143] wherein the isomerized and hydrogenated dimers of the
saturated hydrocarbon base oil have an average branching index (BI)
as determined by 1H NMR that is in the range of from 22 to 26, and
an average paraffin branching proximity (BP) as determined by 13C
NMR in a range of from 18 to 26, [0144] wherein the branching index
(BI) is determined as follows:
[0144] branching index (BI)=(total content of methyl group
hydrogens/total content of hydrogens)*100, and [0145] wherein the
paraffin branching proximity (BP) is determined as follows:
[0145] paraffin branching proximity (BP)=(number of .epsilon.
carbon groups/total number of carbon groups)*100, [0146] where an
.epsilon. carbon group is defined as a carbon group that is
separated from any terminal carbon atom groups or branching carbon
groups by at least 4 carbon groups.
[0147] Embodiment 2: The process according to embodiment 1, wherein
the oligomerization conditions during oligomerization result in
dimers of the oligomer product that, in a case where the dimers are
hydrogenated to a Bromine Index below 1000 mg Br.sub.2/100 g as
determined in accordance with ASTM D2710-09, without subsequent
isomerizing, have an average a paraffin branching proximity (BP) of
22 or greater.
[0148] Embodiment 3: The process according to any preceding
embodiment, comprising performing the isomerization after
oligomerization of the olefin feed mixture had been performed.
[0149] Embodiment 4: The process according to any preceding
embodiment, wherein at least a portion of the isomerization is
performed simultaneously with oligomerization.
[0150] Embodiment 5: The process according to any preceding
embodiment, wherein the olefin monomer feed mixture comprises a
first feedstock comprising C14 to C18 alpha olefin monomers
selected from the group consisting of tetradecene, pentadecene,
hexadecene, heptadecene and octadecene.
[0151] Embodiment 6: The process according to any preceding
embodiment, further comprising preparing an olefin monomer feed
mixture comprising C14 to C18 alpha olefin monomers by dehydration
of C14 to C18 primary alcohols selected from the group consisting
of 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol
and 1-octadecanol.
[0152] Embodiment 7: The process according to any preceding
embodiment, wherein the olefin monomer feed mixture comprises
olefin monomers selected from the group consisting of unsaturated,
linear alpha-olefins; unsaturated, normal internal-olefins;
branched alpha-olefins; branched internal-olefins; and combinations
thereof.
[0153] Embodiment 8: The process according to any preceding
embodiment, where the olefin monomer feed mixture comprises a
mixture of linear alpha-olefins and/or linear internal-olefins.
[0154] Embodiment 9: The process according to any preceding
embodiment, wherein the olefin monomer feed mixture comprises
olefin monomers selected from the group consisting of unsaturated
olefin comprises, linear alpha-olefins; linear internal-olefins;
branched alpha-olefins; branched internal-olefins; and combinations
thereof.
[0155] Embodiment 10: The process according to any preceding
embodiment, wherein the olefin monomer feed mixture comprises a
first feedstock comprises less than 36% by weight of branched
olefin monomers.
[0156] Embodiment 11: The process of any preceding embodiment,
wherein the olefin monomer feed mixture comprises a first feedstock
comprising less than 20% by weight of branched olefin monomers.
[0157] Embodiment 12: The process of any preceding embodiment,
wherein the olefin monomer feedstock comprises a first feedstock
comprising less than 10% by weight of branched olefin monomers.
[0158] Embodiment 13: The process of any preceding embodiment,
wherein the olefin monomer feedstock comprises a first feedstock
comprising less than 5% by weight of branched olefin monomers.
[0159] Embodiment 14: The process of any preceding embodiment,
wherein an amount of decene in any of first and/or second
feedstocks of the olefin monomer feedstock is less than 20% by
weight.
[0160] Embodiment 15: The process of any preceding embodiment,
wherein an amount of decene in any of first and/or second
feedstocks of the olefin monomer feedstock is less than 10% by
weight.
[0161] Embodiment 16: The process of any preceding embodiment,
wherein an amount of decene in any of first and/or second
feedstocks of the olefin monomer feedstock is less than 5% by
weight.
[0162] Embodiment 17: The process of any preceding embodiment,
further comprising oligomerizing the olefin monomer feed under
conditions to at least partially isomerize the dimers, trimers, and
higher oligomers.
[0163] Embodiment 18: The process of any preceding embodiment,
wherein the unreacted monomer is distilled from the unsaturated
oligomers and recycled in a subsequent oligomerization
reaction.
[0164] Embodiment 19: The process of any preceding embodiment,
wherein isomerizing of the oligomer product is performed in the
absence of hydrogen.
[0165] Embodiment 20: The process according to any preceding
embodiment, wherein an amount of cracked byproducts generated
during isomerizing of the oligomer product is less than 10%.
[0166] Embodiment 21: The process according to any preceding
embodiment, wherein an amount of cracked byproducts generated
during isomerizing of the oligomer product is less than 5%.
[0167] Embodiment 22: The process according to any preceding
embodiment, wherein an amount of cracked byproducts generated
during isomerizing of the oligomer product is less than 1%.
[0168] Embodiment 23: The process according to any preceding
embodiment, wherein isomerizing of the oligomer product is
performed at a temperature in the range of from 125.degree. C. to
300.degree. C., and a pressure in the range of from 1 PSI to 100
PSI of inert gas, in the presence of an acid catalyst selected from
the group consisting of solid metals or metal oxides or their
mixture of Group IVB, VB, VIB and Group metal oxides or mixed
oxides of Group IIA to VA; mixed metal oxides comprising
WO.sub.x/ZrO.sub.2 type catalyst; solid natural or synthetic
zeolites; and layered material, crystalline or amorphous material
of silica, alumina, silicoaluminate, aluminophosphate, aluminum
silicophosphate.
[0169] Embodiment 24: The process according to any preceding
embodiment, wherein the dimer portion of the isomerized oligomer
product is separated by distillation from the isomerized oligomer
product.
[0170] Embodiment 25: The process of any preceding embodiment where
the oligomerization reaction is carried out at a temperature range
from 10-110.degree. C.
[0171] Embodiment 26: The process of any preceding embodiment,
wherein the oligomerization catalyst is selected from the group
consisting of zeolites, Friedel-Crafts catalysts, Bronsted acids,
Lewis acids, acidic resins, acidic solid oxides, acidic silico
aluminophosphates, Group IVB metal oxides, Group VB metal oxides,
Group VIB metal oxides, hydroxide or free metal forms of Group VIII
metals, and any combination thereof.
[0172] Embodiment 27: The process of any preceding embodiment,
wherein the oligomerization reaction catalyst is BF.sub.3, and the
promoter is an alcohol and/or an ester.
[0173] Embodiment 28: The process of any preceding embodiment,
wherein the oligomerization is carried out in at least one
continuously stirred reactor under oligomerization conditions with
an average residence time of 60 to 400 minutes.
[0174] Embodiment 29: The process of any preceding embodiment,
wherein the oligomerization is carried out in at least one
continuously stirred reactor under oligomerization conditions with
an average residence time of 90 to 300 minutes.
[0175] Embodiment 30: The process of any preceding embodiment,
wherein the oligomerization is carried out in at least one
continuously stirred reactor under oligomerization conditions with
an average residence time of 120 to 240 minutes.
[0176] Embodiment 31: The process of any preceding embodiment,
wherein the acid catalyst used for isomerizing the unsaturated
polyolefin is a zeolite having a Constraint Index of about 2 to
about 12.
[0177] Embodiment 32: The process of any preceding embodiment,
wherein the acid catalyst used for isomerizing the unsaturated
polyolefin is a zeolite containing one or more Group VI B to VIII B
metal elements.
[0178] Embodiment 33: The process of any preceding embodiment,
wherein the pour point of the isomerization product is at least -9
less than that of the oligomer product prior to isomerization.
[0179] Embodiment 34: The process according to any preceding
embodiment, wherein the pour point of the isomerization product is
at least -15.degree. C. less than that of the oligomer product
prior to isomerization.
[0180] Embodiment 35: The process according to any preceding
embodiment, wherein the pour point of the isomerization product is
at least -21.degree. C. less than that of the oligomerization
product prior to isomerization.
[0181] Embodiment 36: The process according to any preceding
embodiment, wherein the dirtier product of the saturated
hydrocarbon base oil has <5 wt % naphthalenes after
isomerization and hydrogenation.
[0182] Embodiment 37: The process according to any preceding
embodiment, wherein the dimer product of the saturated hydrocarbon
base oil has <2.5 wt % naphthalenes after isomerization and
hydrogenation.
[0183] Embodiment 38: The process of any preceding embodiment,
wherein the dimer product of the saturated hydrocarbon base oil has
<1 wt % naphthalenes after isomerization and hydrogenation.
[0184] Embodiment 39: The process of any preceding embodiment,
wherein a percent yield of isomerized dinners produced in the
isomerization is >90 wt. %.
[0185] Embodiment 40: The process according to any preceding
embodiment, wherein a percent yield of isomerized dimers produced
in the isomerization >95 wt, %.
[0186] Embodiment 41: The process according to any preceding
embodiment, wherein a percent yield of isomerized dimers produced
in the isomerization >97.5 wt. %.
[0187] Embodiment 42: The process according to any preceding
embodiment, wherein a percent yield of isomerized dimers produced
in the isomerization is >99 wt, %.
[0188] Embodiment 43: The process according to any preceding
embodiment, wherein the base oil has a kinematic viscosity of
measured at 100.degree. C. by ASTM D445 of 3.7 cSt to 4.8 cSt.
[0189] Embodiment 44: The process according to any preceding
embodiment, wherein the base oil has a kinematic viscosity of
measured at 100.degree. C. by ASTM D445 of 3.8 cSt to 4.5 cSt.
[0190] Embodiment 45: The process according to any preceding
embodiment, wherein the saturated base oil has a Viscosity Index
125 or greater.
[0191] Embodiment 46: The process according to any preceding
embodiment, wherein the saturated base oil has a Viscosity Index
130 or greater.
[0192] Embodiment 47: The process according to any preceding
embodiment, wherein the base oil has a Viscosity Index 135 or
greater.
[0193] Embodiment 48: The process according to any preceding
embodiment, wherein the base oil has a Viscosity Index 140 or
greater.
[0194] Embodiment 49: The process according to any preceding
embodiment, wherein the base oil has a Viscosity Index of 150 or
greater.
[0195] Embodiment 50: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1800 cP.
[0196] Embodiment 51: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1700 cP.
[0197] Embodiment 52: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1600 cP.
[0198] Embodiment 53: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1500 cP.
[0199] Embodiment 54: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1400 cP.
[0200] Embodiment 55: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1300 cP.
[0201] Embodiment 56: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1200 cP.
[0202] Embodiment 57: The process according to any preceding
embodiment, wherein the base oil has a CCS at -35.degree. C. less
than 1100 cP.
[0203] Embodiment 58: The process according to any preceding
embodiment, wherein the base oil has a Noack volatility less than
14%.
[0204] Embodiment 59: The process according to any preceding
embodiment, wherein the base oil can be characterized by a Noack
volatility of less than 13%.
[0205] Embodiment 60: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 12%.
[0206] Embodiment 61: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 11%.
[0207] Embodiment 62: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 10%.
[0208] Embodiment 63: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 9%.
[0209] Embodiment 64: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 8%.
[0210] Embodiment 65: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 7%.
[0211] Embodiment 66: The process according to any preceding
embodiment, wherein the base oil can be characterized by Noack
volatility of less than 6%.
[0212] Embodiment 67: The process according to any preceding
embodiment, wherein the base oil can be characterized by pour point
of less than -27.degree. C.
[0213] Embodiment 68: The process according to any preceding
embodiment, wherein the base oil can be characterized by pour point
of less than -30.degree. C.
[0214] Embodiment 69: The process according to any preceding
embodiment, wherein the base oil can be characterized by pour point
of less than -33.degree. C.
[0215] Embodiment 70: The process according to any preceding
embodiment, wherein the base oil can be characterized by pour point
of less than -36.degree. C.
[0216] Embodiment 71: The process according to any preceding
embodiment, wherein the base oil can be characterized by pour point
of less than -39.degree. C.
[0217] Embodiment 72: The process according to any preceding
embodiment, wherein the base oil can be characterized by pour point
of less than -42.degree. C.
[0218] Embodiment 73: The process according to any preceding claim,
where a catalyst provided during isomerization is other than a
catalyst provided during oligomerization.
* * * * *