Title of Invention

ALKYLATION OF OLIGOMERS TO MAKE SUPERIOR LUBRICANT OR FUEL BLENDSTOCK

Abstract A process and method for making a superior lubricant or distillate fuel component by the oligomerization of a mixture comprising olefins to form an oligomer and the alkylation of the oligomer with isoparaffins to produce an alkylated ("capped") olefin oligomer preferably using an acidic chloroaluminate ionic liquid catalyst system. Preferably the ionic liquid catalyst system comprises a Bronsted acid.
Full Text FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(Sec section 10, rule 13)
ALKYLATION OF OLIGOMERS TO MAKE SUPERIOR LUBRICANT OR FUEL BLENDSTOCK"


CHEVRON U.S.A. INC., 6001 Bollinger Canyon Road, Building T, 3 Floor, San Ramon, CA 94583, United States of America

rd

The following specification particularly describes the invention and the manner in which it is to be performed.


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BACKGROUND OF THE INVENTION
5
Olefin oligomers and relatively long chain olefins can be used in the production of fuel and lubricant components or blendstocks. One problem with the use of olefin oligomers in either of the above uses is that the olefinic double bond can be undesirable. Oiefinic double bonds cause problems in both fuels 10 and in lubricants. Olefin oligomers can further oligomerize forming 'gum deposits in the fuel. Olefins in fuel are also.associated with air quality problems. Olefins can also oxidize which can be a particular problem in lubricants.- One way of minimizing the problem is to hydrogenate some or all of the double bonds to form saturated hydrocarbons. A method of doing this is 15 described in US published Application US 2001/0001804 which is incorporated herein in its entirety. Hydrogenation can be an effective way to minimize the concentration of olefins in the lubricant or fuel however it requires the presence of hydrogen and a hydrogenation catalyst both of which can be expensive. Also excessive hydrogenation can lead to hydrocracking. Hydrocracking can 20 increase as one attempts to hydrogenate the olefins to Increasingly lower
concentrations. Hydrocracking is generally undesirable as it produces a lower . molecular weight material where the goal in oligomerization is to produce a ■ higher molecular weight material. Directionally it would generally be preferred to increase, not decrease the average molecular weight of the' material. Thus 25 using the hydrogenation method it is desired to hydrogenate the olefins as deeply as possible while minimizing any hydrocracking or hydrodealkylation. This is inherently difficult and tends to be a compromise;
Hydrocracking of a slightly branched, hydrocarbon material can also lead to less branching. Cracking tend" to be favored at the tertiary and secondary 30 centers. For example a branched hydrocarbon can crack at a secondary center forming two more linear molecules which is also directionally undesirable.
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potentially, Ionic Liquid catalyst systems can be used for the oligomerization of olefins such as normal alpha olefins to make olefin oligomers- A Patent that describes the use of an ionic liquid catalyst to make
5 Its entirety- A published application that discloses a process for oiigomerization of alpha olefins in ionic liquids is EP 791,643.
tonic Liquid catalyst systems have also been used for isoparaffins — olefins alkylation reactions. Patents that disclose a process for the alkylation of isoparaffins by olefins are US 5,750,455 and US 6,028,024.
10 It would be desirable to have a process for making a lubricant or
distillate fuel starting materials with low degree of unsaturation (low concentration of doubte bonds) and thus reducing the need for exhaustive hydrogenation while preferably maintaining or more preferably increasing the average molecular weight and branching of the material. The present invention
15 provides a new process with just such desired features.
SUMMARY OF THE INVENTION
the present invention provides a process for making a fuel or lubricant
component by the oiigomerization of olefins to make olefin oligomers of. desired
20 chain length range followed by alkylation of the olefin oligomer with an.,
isoparaffin t° "cap" at least a portion of the double bonds of the olefin.
oligomers ..
A particular embodiment of the present invention provides a process for making
a fuel, or lubricant component, comprising:
25 passing a feed stream comprising one or more olefins to an ionic liquid
oiigomerization zone, at oiigomerization conditions; recovering an oiigomerized olefinic intermediate from said tonic liquid oiigomerization zone;
passing the oligpmerized olefinic intermediate and an isoparaffin to a
30 ionic liquid alkylation zone comprising an acidic chloroaluminate ionic
liquid, at alkylation conditions; and
recovering an effluent from the ionic liquid alkylation zone 'comprising an alkylated oligomeric product.
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Oligornerization of two or more olefin molecules results in the formation
of an olefin oligomer that generally comprises a long branched chain molecule
with one remaining double bond. The present invention provides a novel way
to reduce the concentration of double bonds and at the same time enhance the
5 quality of the desired fuel or lubricant. This invention also reduces the amount
of hydrafinishing that Is needed to achieve a desired product with low olefin
concentration. The olefin concentration can be determined by Bromine Index
or Bromine Number. Bromine Number can be determined by test ASTM D
1159. Bromine Index can be determined by ASTM D 2710. Test methods D
10 1159 and ASTM D 2710 are incorporated herein by reference in their entirety.
Bromine index is effectively the number of milligrams of Bromine (Br2) that
react with 100 grams of sample under the conditions of the test. Bromine
Number is effectively the number of grams of bromine that will react with 100
grams of specimen under the conditions of the test.
IS In a preferred embodiment of the present invention HCl or a component
that directly or indirectly works as a proton source is added to the reaction
mixture. Although not wishing to be limited by theory, it is believed that the
presence of a Bronsted acid such as HCl greatly enhances the activity and
acidity of the Ionic liquid catalyst system.
20 Among other factors, the present invention involves a surprising new
way of making a lubricant base oil or fuel blendstock that has reduced levels of olefins without hydrogenation or with minimal hydrafinishing. The present invention also increases the value of the resultant olefin oligomers by increasing the molecular weight of the oligomer and increasing the branching 25 by incorporation of tsoparaffin groups into the oligomers skeletons. These properties can both add significant value to the product particularly when starting with a highly linear hydrocarbon such as the preferred feeds to the present invention (i.e. Fischer-Tropsch derived hydrocarbons). The present invention is based on the use of an acidic chloroaluminate ionic liquid catalyst 30 to alkylate an oligomerized olefin with an isoparaffin under relatively mild
conditions. Surprisingly, the alkytation optionally can occur under effectively the same conditions as oligomerization. This surprising finding that alkyfatton and oligomerization reactions can occur using effectively the same ionic liquid
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catalyst system and optionally under similar or even the same conditions can ■ be used to make a highly Integrated, synergistic process resulting in an alkylated oligomer product having desirable properties.
A preferred catalyst system of the present invention is an acidic 5 chlonoaluminate ionic liquid system. More preferably the acidic chloroaluminate Ionic liquid system is used In the presence of a Bronsted acid. Preferably the Bronsted acid is a halohalide and most preferably is HC1.
DETAILED DESCRIPTION OF THE INVENTION 10
The present invention provides a novel process for the production of fuel or lubricant components by the acid catalyzed oligomerization of olefins and alkylation of the resulting oligomers with isoparaffins in an ionic liquid medium to form a product having greatly reduced olefin content and improved quality. 15 Amazingly, we found that ofigomerization of an olefin and alkylation of an olefin and/or Its oligomers with an isoparaffin can be performed together in a single reaction zone or alternatively in two separate zones. The alkylated or partially alkylated oligomer stream that results has very desirable properties for use as a fuel or lubricant blendstock. In particular the present invention provides a ' 20 process for making a distillate fuel, lubricant, distillate fuel component, lubricant component, or solvent having improved properties such as increased branched, higher molecular weight, and lower Bromine Number.
An advantage of the 2 step process (otigomerization followed by alkylation in a separate zone) over a one step alkylation/oligomerization process is that the 25 two separate reaction zones can be tailored and optimized independently to achieve the desired end products. Thus the conditions for oligomerization zones can be different than the alkylation zone conditions. Also the ionic liquid catalyst can be different in the different zones. For instance it may be preferable to make the alkylation zone more acidic than the oligomerization 30 zone this may involve the use of an entirely different ionic liquid catalyst in the two zones or can be achieved by addition of a Brdnsted acid to the alkylation zone.
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In a preferred embodiment of the present invention the ionic liquid used in" alkylation zone and in the oligomierization zone is the same. This helps save on catalyst costs, potential contamination issues, and provides synergy opportunities in the process.
In the present Application distillation data was generated for several of the products by Simulated Distillation lonic Liquids
lonic liquids are a category of compounds which are made up entirely of Eons and are generally liquids-at or below process temperatures. Often salts which are composed entirely of ions are solids with high melting points, for example, above 450 degrees C. These solids are commonly known as "molten salts" when heated to above their melting points. Sodium chloride, for example, is a common "molten salt*, with a melting point of 800 degree C. Ionic liquids differ from "molten salts', in that they have low melting points, for example, from -100 degrees C to 200 degree C. lonic liquids tend to be liquids over a very.wide temperature range, with some having a liquid range of up to 300 degrees C or higher, lonic liquids are generally non-volatile, with effectively no vapor pressure. Many are alr and water stable, and can be good solvents for a wide variety of inorganic, organic, and polymeric materials.
The properties of ionic liquids can be tailored by varying the cation and anion pairing lonic liquids and some of their commercial applications are described, for example, in J. Chem. Tech. Biotechnol, 68:351-356 (1997); J. Phys. Condensed Matter, 5:(supp 34B):B99-B106 (1993); Chemical and Engineering News, Mar. 30,1998, 32-37; J. Mater. Chem., *:2627-2636 (1998); and Chem. Rev., '99:2071-2084 (1999), the contents of which are hereby incorporated fay reference.
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Many ionic liquids are amine-based. Among the most common ionic liquids are those formed by reacting a nitrogen-containing heterocyclic ring (cyclic amines), preferably nitrogen-containing aromatic rings (aromatic amines), with an alkylating agent {for example, an alkyl halide) to form a quaternary 5 ammonium salt, followed by ion exchange or other suitable reactions to introduce the appropriate counter anionic species to form ionic liquids. Examples of suitable heteroaromatic rings include pyridine and its derivatives, imidazole and its derivatives, and pyrrole and Its derivatives. These rings can be alkylated with varying alkylating agents to incorporate a broad range of alkyl 10 . groups on the nitrogen including straight, branched or cyclic C1-2o alkyl group, but preferably C1-12 alkyl groups since alkyl groups larger than C1-C12 may product undesirable solid products rather than the intended ionic liquids. Pyridinium and imidazolium-based ionic liquids are perhaps the most commonly used ionic liquids. Other amine-based ionic liquids including cyclic 15 and non-cyclic quaternary ammonium salts are frequently used. Phosphonium and sulphonium-based ionic liquids have also been used.
Counter anions which have been used include chloroaluminate, bromoaluminate, gallium chloride, tetrafluoroborate, tetrachloroborate,
20 hexafluorophosphate, nitrate, trifluoromethane sulfonate, methyl sulfonate, p-toluenesulfonate, hexafiuoroantimonate, hexafluoroarsenate, tetrachloroaluminate, tetrabromoaluminate, perchlorate, hydroxide anion, copper dichlqride anion, Iron trichloride anion, antimony hexafluoride, copper dichloride anion, zinc trichloride anion, as well as various lanthanum,
25 potassium, lithium, nickel, cobalt, manganese, and other metal ions. The ionic liquids used in the present.invention are preferably acidic haloaluminates and preferably chloroaluminates.'
The form of the cation in the ionic liquid in the present invention can be selected . 30 from the group consisting of pyridiniums, and imidazoliums. Cations that have been found to be particularly useful in the process of the present invention include pyridinium-based cations. •
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Preferred ionic liquids that can be used in the process of the present invention include acidic chloroaluminate ionic liquids. Preferred ionic liquids used in the present invention are acidic pyridinium chloroaluminates. More preferred lonic liquids useful in the process of the present invention are alkyV-pyridinium 5 chloroalumi nates. Still more preferred ionic liquids useful in the process of the present invention are alkyl-pyridinium chloroaluminates having a single linear alkyl group of 2 to 6 carbon atoms tn length. One particular ionic liquid that has proven effective is 1-butyl-pyridinlum chloroaluminate. In a more preferred embodiment of the present invention 1-butyl-pyridnium 10 chloroaluminate is used in the presence of a BrOnsted acid. Not to be limited by theory, the BrOnsted acid acts as a promoter or co-catalyst. Examples of BrOnsted acids are Sulfuric; HCI, HBr, HF, Phosphoric, HI, etc. Other protic acids or species that directly or indirectly aid in supplying protons to the catalyst system may also be used as Bronsted acids or in place of Bronsted acids. 15
The Feeds
In the process of the present invention one of the Important feedstocks comprises a reactive olefinic hydrocarbon. The reactive olefinic group provides the reactive site for the oligomerization reaction as well as the alkylation reaction. 20 The olefinic hydrocarbon can be a fairly pure olefinic hydrocarbon cut or can be a mixture of hydrocarbons having different chain lengths thus a wide boiling range. . The olefinic hydrocarbon can be terminal olefin (an alpha olefin) or can be internal olefin (internal double bond). The olefinic hydrocarbon chain can be ■ either straight chain or branched or a mixture of both. The feedstocks useable in 25 the present invention can include unreactive diluents such, as norma! paraffins. In one embodiment of the present invention the olefinic feed comprises a mixture of mostly linear olefins from C2 to about C30- The olefins are mostly but not entirety alpha olefins.
in another embodiment of the present invention the olefinic feed can comprise 30 - at least 50 % of a single alpha olefin species.
(n another embodiment of the present invention the olefinic feed can be comprised of an NAO cut from a high purity Normal Alpha Olefin (NAO) process made by ethylene oligomerization.
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In an embodiment of the present invention some or all of the olefinic feed to the process of the present invention comprises thermally cracked hydrocarbons, preferably cracked wax, more preferably cracked wax from a Fischer-Tropsch (FT) process. A process for making olefins by cracking FT products is disclosed 5 in US Patent 6,497,812 which is incorporated herein by reference in its entirety. In the process of the present invention- another important feedstock is an isoparaffin. The simplest isoparaffin is isobutane. Isopentanes, isohexanes, ■ Isoheptanes, and other higher isoparaffins are also useable in the process of the present invention. Economics and availability are the main drivers of the 10 isoparaffins selection. Lighter isoparaffins tend to be less expensive and more available due to their low gasoline blend value (due to their relatively high vapor pressure). Mixtures of light isoparaffins can also be used in the present . invention. Mixtures such as C4-C5 isoparaffins can be used and may be advantaged because of reduced separation costs. The isoparaffins feed stream 15 may also contain diluents such as normal paraffins. This can be a cost savings by reducing the cost of separating isoparaffins from close boiling paraffins. -Normal paraffins will tend to be unreactive diluents in the process of the present invention..
In an optional embodiment of the present Invention the resultant alkylated
20 oligomer made in the present invention can be hydrogenated to further decrease
the concentration of olefins and thus the Bromine Number. After hydrogenation"
the lubricant component or base oil has a Bromine Number of less than 0.8,
preferably less than 0.5, more preferably less than 0.3, still more preferably less
than 0.2. "'.*""
25 In order to achieve a high degree of capping (alkylation) of the product an
excess of isoparaffin Is used. The mole ratio of paraffin to olefin is generally at least 1.1:1, preferably at least 5:1, more preferably at least 8:1, still more preferably at least 10:1. Other techniques can be used to achieve the desired high apparent paraffin to olefin mole ratio; such as use of a multistage process' 30 with interstage addition of reactants. Such techniques known in the art can be used to achieve very high apparent mole ratios of isoparaffin to olefin. This can help to avoid oligomerization of the olefin and achieve a high degree of capping
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■ (alkylation) when desired. Interstage injection of reactants is taught in US Patent 5,149,894 which is herein incorporated by reference in its entirety.
Oiigomerization conditions for-the process of the present invention include a temperature of from about 0 to about 150 degrees C, preferably from about 10 5 to about 100 degrees C, more preferably from about 0 to about 50.
Alkylation conditions for the process of the present invention include a
■ temperature of from about 15 to about 200 degrees C, preferably from about 20
to about 150 degrees C, more preferably from about 25 to about 100, and most
preferably from 50 to 100 degrees C.
10 In summary, the potential benefits of the process of the present invention
include:
• Reduced capital cost for hydrotreatlng/hydrofinishing
• Lower operating cost due to reduced hydrogen and extensive 15 hydrogenation requirements

• Potential use of the same ionic liquid catalyst for oiigomerization and alkylation steps
• Improved branching characteristics of the product
• Increased overall molecular weight of the product
20 . Incorporation of low cost feed (isoparaffins) to increase liquid yield
of high value distillate fuel or lubricant components
• Production of a distillate fuel component, base oil or lubricant
component having unique, high value properties
25
EXAMPLES Example 1: Preparation of Fresh 1-Butvl-pvridinium Chloroaluminate Ionic Liquid"
1-butyl-pyridinium chloroaluminate is a room temperature ionic liquid prepared 30 . by mbdng neat 1-butyl-pyridinium chloride (a solid) with neat solid aluminum trichloride in an inert atmosphere. The syntheses of 1-butyl-pyridinium chloride and the corresponding 1-butyl-pyridinium chloroaluminate are described below. In a 2-L Teflon-lined autoclave, 400 gm (5.05 mol.) anhydrous pyridine (99.9%
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pure purchased from Aldrich) were mixed with 650 gm (7 mol.) 1-chlorobutane (99.5% pure purchased from Aldrich). The neat mixture was sealed and let to stir at 125°C under autogenic pressure over night. After cooling off the autoclave and venting It, the reaction mix was diluted and dissolved in 5 chloroform and transferred to a three liter round bottom flaskl Concentration of the reaction mixture at reduced pressure on a rotary evaporator (in a hot water bath) to remove excess chloride, un-reacted pyridine and the chloroform solvent gave a tan solid product. Purification of the product was done by dissolving the obtained solids in hot acetone and precipitating the pure product 10 through cooling and addition of diethyl ether. Filtering and drying under vacuum and heat on a rotary evaporator gave 750 gm (88% yields) of the desired product as an off-white shinny soild. 1H-NMR and 13C-NMR were ideal for the desired 1-buty!-pyridinium chloride and no presence of impurities was observed by NMR analysis. 15
1-Butyl-pyridtnium chloroaluminate was prepared by slowly mixing dried 1-butyi-pyridinium chloride and anhydrous aluminum chloride (AlCIa) according to the following procedure. The 1-butyI-pyridinium chloride (prepared as described above) was dried under vacuum at 80°C for 48 hours to get rid of 20 residua] water (1-butyi-pyridiniuni chloride is hydroscopic and readily absorbs water from exposure to air). Five hundred grams (2.91 mol.) of the dried 1-butyE-pyridinlum chloride were transferred to a 2-Liter beaker In a nitrogen. atmosphere in a glove box. Then, 777.4 gm (5.83 mol.) of anhydrous powdered A1Cl3 (99.99% from Aldrich) were added in small portions (while 25 stirring) to. control the temperature of the highly exothermic reaction. Once all the AICI3 was added, the resulting amber-looking liquid was left to gently stir overnight in the glove box. The liquid was then filtered to remove any un-dissolved AlCl3. The resulting acidic 1-butyl-pyridinium chloroaluminate was used as the catalyst for the Examples in the Present Application. 30
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Example 2
Alky;ation of 1-Decene Oligomers
5 ■ .
Oligomerization of 1-decene and alkylation of the oligomer were done according to the procedures described be!ow. In a 300 cc autoclave equipped with an overhead stirrer, 100 gm of 1-decene was mixed in with 20 gm of 1-methyl-tributyl ammonium chloroaluminate. A small amount of HCl {0.35 gm) 10 was introduced to the mix as a promoter and the reaction mix was heated to 50°C with vigorous stirring for 1 hr. Then, the stirring was stopped and the reaction was cooled down to room temperature and let to settle. The organic layer (insoluble in the ionic liquid) was decanted off and washed with 0.1N KOH. The organic layer was separated and dried' over anhydrous MgSO4. The
15 colorless oily substance was analyzed by SIMDIST. The oligomeric product has a Bromine Number of 7.9. Table 1 below shows the SJMDIST analysis of the oligomerization products.
Alkylations of the oligomers of 1-decene with isobutane In1-butyipyridinium 20 chloroaluminate and in methyl-tributy! ammonium chloroaluminate (TBMA) ionic liquids were done according to the procedures described below. In a '300 cc autoclave fitted with an overhead stirrer, 26 gm of the oligomer and 102 gm of Isobutane were added to 21 gm of methyl-tributyi-amrnonlum chloroaluminate ionic liquid. To this mixture, 0.3 gm of HCl gas was added and the reaction 25 was heated to 50°C for 1 hr while stirring at >1000 rpm. Then the reaction was stopped and the products were collected to a simller procedure as described above for the oligomerization reaction. The collected products, colorless oil, have a Bromine Number of 3.2. Table 1 shows the Simulated Distillation (SIMDIST) analysis of the oligomer alkylation products.
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Alkylation of 1-decene oligomers was repeated using the same procedure described above, but 1-butyipyridinium chioroaluminate was used in place of methyl-tributyl-ammonium chioroaluminate as the ionic liquid catalyst system. 5 Alkylation of the oligomer in butylpyridinium gave a product with a bromine index of 2.7. The Simulated Distillation data is shown in Table 1.
Table 1

SIIWDIST TBP (WT%) 1-Decene Oligomers
°F 1-Decene oligomers Alkylation in 1-butylpyridinlum chioroaluminate 1-Decene
oligomers
alkylation
in TBMA
TBP@0.5 330 298 296
TBP@5 608 341 350
TBP@10 764 574 541
TBP@15 789 644 630
TBP@20 856 780 756
TBP@30 944 876 854
TBP@40 1018 970 960
TBP@50 1053 1051 1050
TBP@60 1140. 1114 . 1118
TBP@70 1192 1167 1173
TBP@80 • 1250 1213 1220
TBP@90 1311 1263 1268
TBP@95 1340 1287 1291
TBP@99.5 1371 1312 1315
10 Alkyiation of 1 -decene oligomers with isobutane results with products that have much reduced olefinlcity. The alkylated oligomers appear also to have increased amounts of low boiling cuts by few percentage points. The increase in the low boiling cuts is possibly due to branching introduced by alkylation, and perhaps to some cracking activities, ft seems, nevertheless, that alkyiation of
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'olefinic oligomers whether it is simultaneous oligomerization/alkytation or oligomerization followed by alkylation, dearly leads to high quality lubricants or fuel blendstocks.
5 Oiigomerization of olefins followed by alkylation of the oligomeric intermediates with an isoparaffin is an alternative to making high quality lubricants or fuels. Olefin oligomers exhibit good .physical lubricating properties. Also introducing branching in the oligomers by alkylation. with the appropriate isoparaffins enhances the chemical properties, of the final products by reducing the 10 olefinidty of the oligomers and, hence, producing chemically and thermally more stable products.
Example 3
Oiigomerization of 1-Decene in Ionic Liquids in the Present of iso-Butane
15
Oiigomerization of 1-decene was carried out iri addic 1-butyl-pyridinium
. chloroaluminate in the presence of 10 mole% of isobutane'. The reaction was
done in the presence of HCI as a promoter. The procedure below describes, in
general, the process. To 42 gm of 1-buty!-pyridinium chloroaluminate in a 300
20 cc autodave fitted to an overhead stirrer, 101 gm of 1-decene and 4.6 gm of isobutane were added and the autoclave was sealed. Then 0.4 gm of HCI was introduced and the stirring started. The reaction was heated.to 50 °C. The reaction was exothermic and the temperature quickly jumped to 88 °C. The temperature En few minutes went back down to 44 °C and was brought up to 50
25 °C and the reaction was vigorously stirred at about 1200 rpm for an hour at the autogenic pressure (-atmospheric pressure in this case). Then, the stirring was stopped and the reaction was cooled to'room temperature. The contents were allowed to settle and the organic layer (immiscible in the Ionic liquid) was decanted off and washed with 0.1 N KOH aqueous solution. The colorless oil 30 was analyzed with simulated distillation and bromine analysis. The Bromine Number- was 2.6. The Bromine Number is much less than that usually observed for the 1-decene.oligomerization in the absence of Isobutane. The Bromine Number for 1-decene oiigomerization in the absence of iC4 is in the


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range of 7.5-7.9 based on the catalyst, contact time and catalyst amounts used In the oligomerization reaction.
Table 2 compares the Bromine Numbers of the starting 1-decene, 1-decene 5 oligomerization products in the presence of C4, 1-decene oligomerization products without 1C4, and the alkylatioo products of 1-decene oligomers with-excess 1C4.
Table 2

Material 1- Oligomertzation- Oligomerization Alkylated 1-
Decene alkylation of 1-
Decene wlth 10
mol% lC4 Products of1-Decene/NolC4 decene oligomers
Bromine
Number 114 2.6 7.9 2.8

The data above suggests that the chemistry can be done by either alkylating the oligomers in situ (where isoparaffins are introduced into the oligomerization reactor) or in a two step process comprised of oligomerization of an olefin 15 followed by alkyiation of the oligomeric intermediates. White both processes yield products that are similar or close in properties, the two step'process may allow more room' for product tailoring by simply tailoring and tuning each reaction independently from the other.
20 Example 4:
Oligomerization of a Mixture of Alpha Olefins in the Presence of iso-Butane
A 1:1:1 mixture of 1-hexene:1-octene: 1-decene was oligomerised in the
25 presence of isobutane at the reaction conditions described earlier for
' oligomerization of Indecene in the presence of isobutane (100 gm olefins, 20
gm IL- catalyst, 0.25 gm HCI as co-catalyst, 50°C, autogenic pressure, 1hr).
The products were separated from the lL catalyst, and the IL layer was rinsed
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with hexane, which was decanted off and added to the products. The products and the hexane wash were treated with 0.1N NaOH to remove any residua) AlCl3. The organic layers were collected and dried over anhydrous MgSCU-Concentration (on a rotary evaporator at reduced pressure, in a water bath at 5 -70 degrees C) gave the oiigomeric product as viscous yellow oils. Table 3 below shows the Simulated Distillation, viscosity, and pour point and cloud point data of the alkylated oiigomeric products of the olefinic mixture in the presence of isobutane. "
Table 3




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Example S:
Oligomerization of 1-Decene in Ionic Liquids in the Presence of Varying
iso-Butane Concentrations
5 Oligomerization of 1-decene was carried out in acidic 1-butyI-pyridinium chloroaluminate in trie presence of varying mo!e% of isobutane. The reaction was done in the presence of HCI as a promoter (co-catalyst). The procedure below describes, in general, the process. To 42 gm of 1-buty]-pyrid(nium chloroaluminate in a 300 cc autoclave fitted to an overhead stirrer, 101 gm of 1-10 decene and 4.6 gm of isobutane were added and the autoclave was sealed. Then 0,2-0.5 gm of HCI was introduced into the reactor, and then, started the . stirring, the reaction is exothermic and the temperature quickly jumped to 88°C. The temperature dropped down quickly to the mid 40s and was brought up to 50 °C and kept at around 50°C for the remainder of the reaction time. 15 ■ The reaction was vigorously stirred for about an hour at the autogenic pressure. The stirring was stopped, and the reaction was cooled to room temperature. The contents were allowed to settle and the organic layer (immiscible in the ionic liquid) was decanted off and washed with 0.1 N KOH aqueous solution. The recovered oils were characterized with simulated distillation, bromine 20 analysis, viscosity, viscosity indices, and pour and cloud points.
Table 4 below show the properties of the resulting oils of different 1-decene/isobutane ratios. All the reactions were run for approximately 1 hr at 50 degrees C in the presence of 20 gm of ionic liquid catalyst.
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Table 4

........

°F
TBP ©0.5 301 311 322 329 331
TBP@5 340 •382 539 605 611
TBP@10 440 453- 663 746 775
TBP @20 612 683 •792 636 896
TBP @30 798 842 894 928 986
TBP@40 931 970 963 999 1054
TBP @50 1031 1041 1007 1059 " 1105
TBP @60 1098 1099 1067 1107 1148
TBP@70 1155 1154 1120 1154 1187
TBP @B0 1206 1205 1176 1200 1223
TBP @90 1258 - 1260 1242 1252 1278
TBP @95 - 1284 1290 1281 1282 1305
TBP ©99.5 1311 1326 1324 1313 1335
' " ■
. The data shown in Table 4 dearly indicate that the amount of isobutane added to the reaction does influence the boiling range of the produced oils. As shown
5 in the in Table 4, there are more in - the lower boiling cuts at higher concentration of isobutane in the reaction. This indicates that more alkyiation is taking part in the reaction when more isobutane Is present. When more isobutane is present, 1-decene alkyiation with. lC4 to make C14 and decene dimer alkyiation to make C24 will be more prevalent than at lower
10 concentrations of isobutane. Therefore, the degree of branching and oligomerization can be tailored by the choice of olefins, iso'paraffins, olefinisoparaffin ratios, contact time and the reaction conditions.-The alkylated oligomers will no longer take part in further oligomerization due to "capping" off their olefinlc sites, and the final oligomeric chain will be shorter.
15 perhaps than the normal oligomeric products but with more branching.
While the oligomerization pathway is the dominant mechanism, it is very clear . that alkyiation of 1-decene and tts oligomers with isobutane does take part in • the chemistry.
18

WO 2007/078607

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Table 5 below compares some physical properties of the products obtained from the reactions of Table '4
Table 5 5

VI 145 171 148 190 150
Vls@100 9.84 7.507 9.73 7.27 11:14
VIS@40 61.27 37.7 59.63 33.5 70.21
Pour' Point -42 -42' - .44 -52
Cloud Point -63 -64 -69 -28

Bromine Number ' 3.1 0.79 2.2 3.8 6.1
The oligomenzation/alkylation run @ 1-decene/iC4 ratio of 5.5 was repeated several times at the same feed ratios and conditions. The viscosity@l 00 in the repeated samples ranged from 6.9-11.2. The VI ranged from 156-172. Ail the 10 repeated samples contained low boiling cuts (below 775 degrees F) ranging from 10%-15%. The low boiling cut appears to influence the VI.
The Bromine Numbers shown" in Table 5 are much less than usually observed for the 1-decene oligomerization in the absence of isobutane'. The Bromine
15 Number for 1-decene oligomerization in the absence of lC4 is in the range of 7.5-7.9 based on the catalyst, contact time and catalyst amounts used in the oligomerization reaction. Table 6 below compares the Bromine Number analysis of 1-decene, simultaneous oligomerization and atkyiation of 1-decene, 1-decene oligomerization only products, and the alkylated oligomers
20 (oligomerization followed by atkyiation). By looking at these values, one can see the role of the incorporation of isobutane on the olefinicity of the final products.


WO 2007/078607

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Table 6

Material 1- Oligomerization 1-Decene Alkylated 1-
Decene with10mol%
iC4, (20 mol%
iC4) Oligomerization decene
oligomers with
iC4
Br2 Number
114 6.1,(2-2} 7.9 2.8
Bromine Number data of the alkylated oligomeric products and the products of the simultaneous oligomerization/alkylatlon are very comparable when higher 5 concentrations of iC4 are included in the reaction.
20

WO 2007/078607

PCT/US2006/046944

WE CLAIM;
1. A process for making a fuel or lubricant component, comprising:
passing a feed stream comprising one or more olefins to an ionic liquid
5 . oligomerization zone, at oligomerization conditions;
recovering an oligomerized olefinic intermediate from said ionic liquid
oligomerization zone;
passing the oligomerized olefinic intermediate and an isoparaffin to a
ionic liquid alkylation zone comprising an acidic chloroaluminate ionic
10 liquid, atatkytation conditions; and
recovering an effluent from the ionic liquid alkylation zone comprising an
alkylated oligomeric product.
2. The process of claim 1 wherein the tonic liquid alkylation zone further
15 comprises a Bronsted acid.
3. The process of claim 1 wherein said alkylated oligomeric product is used
as a fuel or a fuel blendstock.
20 4. The process of claim 1 wherein said alkylated oligomeric product is used as a lubricant base oil or a lubricant blendstock:
5.' The process of claim 1 wherein the mole ratio of oligomerized olefinic intermediate to isoparaffin is at least 0.5. 25 ■
6. The process of claim 1 wherein said alkylated oligomeric product has a
Bromine Number of less than 2.7.
7. A process of claim 1 wherein the alkylated oligomeric product has a
30 TBP@50 of at feast 1000 degrees F by Simulated Distillation and a
Bromine Number of less than 4.


WO 2007/078607

PCT/US2006/046944

8. The process of claim 1 wherein said alkylated oligomeric product has a
Bromine Number of less than 3. •
9. The process of claim 1 wherein the isoparaffin is selected from the group
5 consisting of isobutane, isopentane, and a mixture comprising isobutane
and isopentane. ■
10. The process of daim 1 wherein the alkylated oligomeric product is
subjected to hydrogenation to produce a low olefin lubricant base oil.
10 -
11. The process of daim 10 wherein said low olefin lubricant base oil has a
Bromine Number of less than 0.2 by ASTM D 1159.
12. The process of claim 1 wherein the feed stream comprising one or more
15 olefins comprises at least one alpha olefin.
13. The process of daim 1 wherein the feed stream comprisingone or more
olefins comprises at least 50 mole % of a single alpha olefin species.
20 14. The process of daim 1 wherein the feed stream comprising one or more olefins comprises a mixture of alpha olefins.
1-5. The process of claim 1 wherein the alkylated oligomeric produd Is
subjected to hydrogenation to form a low olefin content alkylated
25 ■ oligomer.
'16/ The process of claim 15 wherein the low olefin content alkylated
oligomer has a Bromine Number of less than 0.2 as measured by ASTM D1159. 30
17. The process of daim 1 wherein the ionic liquid oligomerization zone comprises an add chloroaluminate ionic liquid catalyst.
22

18. The process of claim 1 wherein the ionic liquid oligomerization zone and thc ionic liquid alkylation zone comprise a different ionic liquid catalyst.
\9. The process of claim I wherein the ionic liquid oligomerizalion zone and the ionic liquid alkylation zone comprise the same ionic liquid catalyst.
20. The process of claim 19, wherein the ionic liquid alkylation zone further comprises a Bronsted acid.
Dated this 08th day of July. 2008
23

Documents:

1448-MUMNP-2008-ABSTRACT(10-7-2008).pdf

1448-MUMNP-2008-ABSTRACT(21-7-2011).pdf

1448-MUMNP-2008-ABSTRACT(GRANTED)-(21-3-2012).pdf

1448-MUMNP-2008-ABSTRACT.doc

1448-MUMNP-2008-ABSTRACT.pdf

1448-MUMNP-2008-CANCELLED PAGES(2-3-2012).pdf

1448-MUMNP-2008-CLAIMS(10-7-2008).pdf

1448-MUMNP-2008-CLAIMS(AMENDED)-(16-1-2012).pdf

1448-MUMNP-2008-CLAIMS(AMENDED)-(19-10-2011).pdf

1448-MUMNP-2008-CLAIMS(AMENDED)-(2-3-2012).pdf

1448-MUMNP-2008-CLAIMS(AMENDED)-(21-7-2011).pdf

1448-MUMNP-2008-CLAIMS(AMENDED)-(22-11-2011).pdf

1448-MUMNP-2008-CLAIMS(GRANTED)-(21-3-2012).pdf

1448-MUMNP-2008-CLAIMS(MARKED COPY)-(16-1-2012).pdf

1448-MUMNP-2008-CLAIMS(MARKED COPY)-(2-3-2012).pdf

1448-MUMNP-2008-CLAIMS.doc

1448-MUMNP-2008-CLAIMS.pdf

1448-MUMNP-2008-CORRESPONDENCE(01-09-2008).pdf

1448-MUMNP-2008-CORRESPONDENCE(15-10-2008).pdf

1448-MUMNP-2008-CORRESPONDENCE(16-1-2012).pdf

1448-MUMNP-2008-CORRESPONDENCE(19-10-2011).pdf

1448-MUMNP-2008-CORRESPONDENCE(2-3-2012).pdf

1448-MUMNP-2008-CORRESPONDENCE(22-12-2008).pdf

1448-MUMNP-2008-CORRESPONDENCE(27-4-2009).pdf

1448-MUMNP-2008-CORRESPONDENCE(30-10-2008).pdf

1448-MUMNP-2008-CORRESPONDENCE(IPO)-(22-3-2012).pdf

1448-MUMNP-2008-CORRESPONDENCE.pdf

1448-MUMNP-2008-DESCRIPTION (COMPLETE).pdf

1448-MUMNP-2008-DESCRIPTION(COMPLETE)-(10-7-2008).pdf

1448-MUMNP-2008-DESCRIPTION(COMPLETE).doc

1448-MUMNP-2008-DESCRIPTION(GRANTED)-(21-3-2012).pdf

1448-MUMNP-2008-FORM 1(10-7-2008).pdf

1448-MUMNP-2008-FORM 1(21-7-2011).pdf

1448-MUMNP-2008-FORM 1.pdf

1448-MUMNP-2008-FORM 18(15-10-2008).pdf

1448-MUMNP-2008-FORM 2 (TITLE PAGE).pdf

1448-MUMNP-2008-FORM 2(COMPLETE)-(10-7-2008).pdf

1448-MUMNP-2008-FORM 2(GRANTED)-(21-3-2012).pdf

1448-MUMNP-2008-FORM 2(TITLE PAGE)-(10-7-2008).pdf

1448-MUMNP-2008-FORM 2(TITLE PAGE)-(21-7-2011).pdf

1448-MUMNP-2008-FORM 2(TITLE PAGE)-(GRANTED)-(21-3-2012).pdf

1448-MUMNP-2008-FORM 2.doc

1448-MUMNP-2008-FORM 2.pdf

1448-MUMNP-2008-FORM 26(22-12-2008).pdf

1448-mumnp-2008-form 3(10-7-2008).pdf

1448-MUMNP-2008-FORM 3(21-7-2011).pdf

1448-MUMNP-2008-FORM 3(27-4-2009).pdf

1448-MUMNP-2008-FORM 3(30-10-2008).pdf

1448-MUMNP-2008-FORM 3.pdf

1448-MUMNP-2008-FORM 5.pdf

1448-MUMNP-2008-FORM PCT-IB-373(21-7-2011).pdf

1448-MUMNP-2008-FORM PCT-ISA-273(21-7-2011).pdf

1448-MUMNP-2008-MARKED COPY(21-7-2011).pdf

1448-MUMNP-2008-PCT OTHER (01-09-2008).pdf

1448-MUMNP-2008-PCT-IB-301(01-09-2008).pdf

1448-MUMNP-2008-PCT-IB-304(01-09-2008).pdf

1448-MUMNP-2008-PCT-IB-304.pdf

1448-MUMNP-2008-PCT-IB-308(01-09-2008).pdf

1448-MUMNP-2008-PCT-IB-311(01-09-2008).pdf

1448-MUMNP-2008-PCT-IB-373(30-10-2008).pdf

1448-MUMNP-2008-PCT-ISA-202(01-09-2008).pdf

1448-MUMNP-2008-PCT-ISA-210(01-09-2008).pdf

1448-MUMNP-2008-PCT-ISA-210.pdf

1448-MUMNP-2008-PCT-ISA-220(01-09-2008).pdf

1448-MUMNP-2008-PCT-ISA-237(01-09-2008).pdf

1448-MUMNP-2008-PCT-ISA-237(30-10-2008).pdf

1448-MUMNP-2008-PCT-RO-101(01-09-2008).pdf

1448-MUMNP-2008-PCT-RO-102(01-09-2008).pdf

1448-MUMNP-2008-PCT-RO-105(01-09-2008).pdf

1448-MUMNP-2008-PCT-RO-146(01-09-2008).pdf

1448-MUMNP-2008-REPLY TO EXAMINATION REPORT(21-7-2011).pdf

1448-MUMNP-2008-REPLY TO HEARING(22-11-2011).pdf

1448-MUMNP-2008-SPECIFICATION(AMENDED)-(21-7-2011).pdf

1448-MUMNP-2008-US DOCUMENT(21-7-2011).pdf

1448-MUMNP-2008-WO INTERNATIONAL PUBLICATION REPORT A2.pdf

1448-MUMNP-2008-WO INTERNATIONAL PUBLICATION REPORT A3(21-7-2011).pdf

1448-MUMNP-2008-WO INTERNATIONAL PUBLICATION REPORT A3.pdf

1448-mumnp-2008-wo international publication report(10-7-2008).pdf

1448-MUMNP-2008-WO PUBLICATION REPORT(01-09-2008).pdf


Patent Number 251544
Indian Patent Application Number 1448/MUMNP/2008
PG Journal Number 12/2012
Publication Date 23-Mar-2012
Grant Date 21-Mar-2012
Date of Filing 10-Jul-2008
Name of Patentee CHEVRON U.S.A. INC.
Applicant Address 6001 BOLLINGER CANYON ROAD, BUILDING T, 3RD FLOOR, SAN RAMON, CA 94583,
Inventors:
# Inventor's Name Inventor's Address
1 ELOMARI, SALEH 4460 ROLLING MEADOWS COURT, FAIRFIELD, CA 94534,
2 KRUG, RUSSELL 44 OLYMPIA WAY, NOVATO, CA 94949,
3 HARRIS, THOMAS, V. 183 W. SEAVIEW DRIVE, BENICIA, CA 94510,
4 DRIVER, MICHAEL, S. 135 GARDENSIDE DRIVE #214, SAN FRANCISCO, CA 94131,
PCT International Classification Number C07C1/00
PCT International Application Number PCT/US2006/046944
PCT International Filing date 2006-12-07
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/316,154 2005-12-20 U.S.A.