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    C:NuRPortbLDCCWANW9400ILDOC-4/02/2013 Alkylation of Oligomers to Make Superior Lubricant or Fuel Blendstock 5 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.
    公开号:AU2013200816A1
    申请号:U2013200816
    申请日:2013-02-14
    公开日:2013-03-07
    发明作者:Michael S. Driver；Saleh Elomari；Thomas V. Harris；Russell Krug
    申请人:Chevron USA Inc；
    IPC主号:C07C2-00
    专利说明:
    CNRllPortDCLQWAM494001_DOC-40212113 Alkylation of Oligomers to Make Superior Lubricant or Fuel Blendstock This is a divisional of Australian Patent Application No. 2011265319, the entire contents of which are incorporated herein by reference. 5 BACKGROUND OF THE INVENTION 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 10 oligomers in either of the above uses is that the olefinic double bond can be undesirable. Olefinic double bonds cause problems in both fuels 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 15 bonds to form saturated hydrocarbons. A method of doing this is 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. 20 Hydrocracking can 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 using the hydrogenation 25 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 centers. For example a 30 branched hydrocarbon can crack at a secondary center forming two more linear molecules which is also directionally undesirable.
    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 polyalphaolefins is US 6,395,948 which is incorporated herein by reference in 5 its entirety. A published application that discloses a process for oligomerization of alpha olefins in Ionic liquids is EP 791,643. Ionic Liquid catalyst systems have also been used for isoparaffins olefins alkylation reactions. Patents that disclose a process for the alkylation of isopareffins 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 double bonds) and thus reducing the need for exhaustive hydrogenation while preferably maintaining or more preferably in creasing 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 oligomerization of olefins to make olefin oligomers of. desired 20 chain length range followed by alkylation of the olefin oligomer with an.. isoparaffin to "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 oligomerization zone, at oligomerization conditions; recovering an oligomerized olefinic intermediate from said Ionic liquid cIlgomerization 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. -2- Oligomerization 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 borids and at the'same time enhance the 5 quality of the desired fuel or lubricant. This invention also reduces the amount of hydrofinishing 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 byASTM 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 (Br 2 ) 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. 15- In a preferred embodiment of ihe present invention HCI 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 Brbnsted acd such as HCI 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 hydrofinishing. 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 isoparaffin 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 alkylation optionally can occur under effectively the same conditions as oligomerization. This surprising finding that alkylation and oligomerization reactions can occur using effectively the same ionic liquid 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 chloroalurninate ionic liquid system. More preferably the acidic chloroaluminate ionic liquid system Is used In the presence of a Br6nsted acid. Preferably the Brbnsted acid is a halohalide and most preferably is HCi. 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 alkylati6n 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 oligomerization of an oldfin 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 oligorner 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 (oligomerization 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 Bro5nsted acid to the alkylation zone. -4- In a preferred embodiment of the present invention the ionic liquid used in alkylation zone and in the oligonmierization zone is the same. This helps save . on catalyst costs, potential contamination issues, and provided synergy opportunities in the process. 5 In the present Application distillation data was generated for several of the products by Simulated Distillation (SIMDIST). Simulated, Distillation (SIMDIST) . Involves the use of ASTM~D 6352 or ASTM D 2887 as appropriate. ASTM D 6352 and ASTM D 2887 are incorporated herein by reference in their entirety. Distillation curves can also be generated using ASTM D86 which is 10 Incorporated herein by reference in its entirety. . Ionic Liquids . . Ionic liquids are a category of coinpounds which are made up entirely of ions and are generally liquids-at or below process temperatures. Often salts which 15 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, frorri -100 20 degrees C-to 200 degree C. Ionic liquids tend to be liquIds over a very,wide . temperature range, with sbme having a liquid range of up to 300 degrees C or higher. Ionic liquids are generally non-volatile, with effectively no vapor pressure. lany are air and water stable, and can be good solvents for a wide variety of inorganic, organic, and polymeric materials. 25 The properties of Ionic liquids can be tailored by varying the cation and anion pairing , Ionic liquids and some of their commercial applications are described, for example, in J. Chem. Tech. Blotechnol, 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. 30 R6v., 99:2071-2084 (1999), the contents of which are hereby incorporated by reference.
    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 C120 alkyl group, but preferably C 1 1 2 alkyl groups since alkyl groups larger than C-C 12 may produce 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 nori-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, methylsulfonate, p tolu enesulfonate, hexafluoroantimonate, hexafluoroarsenate, tetrachloroaluminate, tetrabromoal umin ate, perchlorate, hydroxide anion, copper dichloride anion, iron trichloride anion, antimony hexafluoride, copper dichioride 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 presentinvention 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 imidazollums. Cations that have been found to be particularly useful in the process of the present invention include pyridinium-based cations. -6- Preferred ionic liquids that can bi 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 ionic liquidss useful in the process of the present invention are alkyl-pyridinium 5 chloroaluminates. 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 in length. One particular ionic liquid that has proven effective is 1-butyl-pyridinium chloroaluminatb. In a more preferred embodiment of the present invention 1 -butyl-pyridnium 10 chloroaluminate is used in the presence of a Br6nsted 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 acid' or in place pf 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 olefinid 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 normal 'paraffins, In one embodiment of the present invention the olefinic feed comprises a mixture of mostly linear olefins from C 2 to abodt C 3 o. The olefins are mostly but not entirely alpha olefins. - In another embodiment of the present invention the olefinic feed can comprise 30 at least 50 % of a single alpha olefin species. In 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. -7- 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 makin' 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 (dye to their relatively high vapor pressure). Mixtures of light isoparaffins can also be used In the present invention. Mixtures such as04-Cs Isoparaffins can be used and may be advantaged because of reduced separation costs. The soparaffins 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 70 oligomer made in the present invention can be hydrogenated to further decrease the concentration of drefins 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
    --
    (alkylation) when desired. Interstate 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 frorn 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 hydrotreating/hydroflnishing a Lower operating cost due to reduced hydrogen and extensive 15 hydrogenation requirements * Potential use of the same ionic liquid catalyst for oligornerization 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-Butyl-pyridinium Chloroaluminate Ionic Liquid 1buty-pyridinium chiloroaluminate is a room temperature ionic liquid prepared 30 by mixing 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% - pure purchased from Aldrich) were mixed with 650 gm (7 mol.) 1--chiorobutane (99.5% pure purchased from Aldrich). The neat mixture was sealed and let to stir at '125 0 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 flask. 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 (8&% yields) of the desired product as an off-white shinny solid. 'H-NMR and 1 3 C-NMR Were ideal for the desired 1-butyl-pyridinium chloride and no presence of impurities was - . observed by NMR analysis. 15 1-Butyl-pyridinium chloroaluminate was prepared by slowly mixing dried 1-butyl-pyridinium chloride and anhydrous aluminum chloride (AiCl 3 ) according to the following procedure. The 1-butyl-pyridinium chloride (prepared as described above) was dried under vacuum at 800C for 48 hours to get rid of 20 residual water (1-butyl-pyridiniuna chloride is hydroscopic and readily absorbs water from exposure to air). Five hundred grams (2.91 mol.) of the dried 1-butyl-pyridinium 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 AIC1 3 (99.99% from Aldrich) were added in small portions (while 25 stirring) to. control the temperature of the highly exothermic reaction. -Once all the A1C1 3 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 AiC 3 . The resulting acidic 1-butyl-pyridinium chloroaluminate was used as the catalyst for the Examples in the Present Application. 30 -10-
    OH
    3 CH 3 Nk) HaC c 2 Equiv, AIC1 3 AZg7 neat mixte, 125" C, autogenicc pressure Example 2 AlkyLation of 1-Decene Oiomers 5 Ollgomerization of 1-decene and alkylation of the oligomer were done according to the procedures described below. 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 ammonlpm chloroaluminate. A small amount of HC (0.35 gm) 10 was introduced to the mix as a promoter and the reaction mix was heated to 50 0 C with vigorous stirring for 1 hr. Then, the stirring wvas 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 Q.1N KOH. The organic layer was separated and dried over anhydrous MgSO 4 . The 15 colorless olly substance was analyzed by SIMDIST. The oligomeric product has a Bromine Number of 7.9. Table I below shows the SIMDIST analysis of the oligomerization products. Alkylations of the oligomers of 1-decene with lsobutane in,1-butylpyridinium 20 chloroaluminate and in methyl-tributy ammonium chloroaluminate (TBMA) iornic 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-tributyl-ammonium chloroalurminate ionic liquid. To this mixture, 0.3 gm of HCI gas was added and the reaction 25 was heated to 50"C for I hr while stirring at >1000 rpm. Then the reaction was stopped and the products were collected in a similar procedure as described above for the oligomerization reaction. The collected products, colorless oil, have a Bromine Number of 3.2. Table I shows the Simulated Distillation (SIMDIST) analysis of the oligomer alkylation products. -11- Alkylation of 1-decene oligomers was repeated using the same procedure described above, but 1-butyipyridinium chloroaluminate was used in place of rnethyl-tributyl-ammonium chloroaluminate as the ionic liquid catalyst system. 5 Alkylation of the oligomer in butylpyridinium gave a product with a bromine index of 2.7. The Simulatec Distillation data is shown in Table 1. - Table I 1-Decene I-Decene oligomers 1-Decene Oligorniers Alkylation in 1- oligomers SIMDIST butylpyridinlur alkylation TBP (WT%) "F chloroaluminate 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 Alkylation of I -decerje oligomers with isobutane results with products that have much reduced olefinicity. The alkylated oligonpers 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. It seems, nevertheless, that alkylation of -12- .
    olefinic oligomers whether it is simultaneous oligomerization/alkylation or oligomerization followed by alkylation, clearly leads to high quality lubricants or fuel blendstocks. 5 Oligomerization 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 ollgomer by alkylation with the appropriate isoparaffins enhances the chemical properties of the final products by reducing the 10 olefinicity of the oligomers and, hence, producing chemically and thermally more stable products. Example 3 OlIgomerizatlon of 1-Decene in Ionic Liquids in the Present of Iso-Butane 15 Oligomerization of 1-decene was carried out Iri acidic 1-butyl-pyridinium chloroaldminate 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-butyl-pyridinium chloroaluminate in a 300 20 cc autoclave 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 In few minutes went back down to 44 0C and was brought up to 50 25 0C and th6 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.iN 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.oligornerization In the absence of Isobutane. The . Bromine Number for 1-decene oligomerization in the absence of iC4 is.in the -13range 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 IC4, 1-decene oligomerization products without i0 4 , and the alkylation products of 1-decene oligomers with excess iC4. Table 2 Material 1- Ollgomerization- Oligomerization Alkylated 1 Decene alkylatlon of 1- Products of 1- decene oligomers Decene with 10 Decene/No IC4 mol% IC4 Bromine Number . 114 2.6 7.9 2.8 10 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 alkylation of the oilgbmerlc Intermediates.. While 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 Oleflns 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 oligomerizatlon of 1-decene In the presence of isobutane (100 gm olefins, 20 gm IL catalyst, 0,25 gm HCI as co-catalyst, 50 0 C, a6togenic pressure, ihr). The products were separated from the IL catalyst, and the IL layer was rinsed with hexane, which was decanted off and added to the products. The products and the hexahe wash were treated with 0.1N NaOH to remove any residual AICi 3 . The organic layers were collected and dried over anhydrous MgSO 4 . Concentration (on a rotary evaporator at reduced pressure, in a water bath at 5 -70 degrees C) gave the oligomeric product as viscous yellow oils. Table 3 below shows the Simulated Distillation, viscosity, and pour point and cloud point data of the alkylated oligomeric products of the olefinic mixture in the presence of isobutane. Table 3 Oligomers of SIMDIST Cc,C;,C 10 " WI 1C4 TBP (WT%), *F TBP @0.5 313 TBP@5 - 450 TBP @10 599 TBP @15 734 TBP @20 831 TBP @30 . 953 TBP @40 1033 TBP @50- . . 1096 TBP @60 1157 TBP @70 1220 TOP.B@80 1284 TBP @90 1332 TBP@95. - 1357 TBP g99.5 1384 Physical Properties: VI - 140 VIS@10O 7.34 CST V1S@40 42 CST Pour Point e54 0C Cloud Point . <-52 0C Bromine # 3.1 10 -- 15-- . Example 5: 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-butyl-pyridinium chloroaluminate in the presence of varying mole% 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-butyl-pyridinium 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 0 C. The temperature dropped down quickly to the mid 40s and was brought .up to 50 "C and kept at around 500C 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.IN 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. -16- Table 4 SIMDIST C 1 &/1C4=0.8 C 10 liC 4 =1 C1O m JiC4=4 CI0/iC 4 =5.5 C10'C 4 =9 TBP (WT%), *F TSP @0.5 301 311 322 329 331 TBP @5 340. 382 539 605 611 TBP @10 440 453- 663 746 -775 TBP @20 612 583 -792 836 896 TBP @30 798 842 894 98 986 TBP @40 931 970 963 999 1054 TBP @50 1031 1041 1007 1059 1105 TBP @60 1098 1099 1067 1107 1148 TBP @70 1155 1.154 1120 1154 1187 TBP @80 1206 1205 1176 1200 1228 TBP @90 1258 1280 1242 1252 1278 TBP @95 1284 1290 1281 1282 1305 TBP @99.5 1311 1326 1324 1313 1335 The data shown in Table 4 clearly 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 Ia -the lower boiling cuts at higher concentration of isobutane in the reaction. This indicates that more alkylation is taking part in the reaction when more isobutane is present. When more isobutane is present, 1-decene alkylation with. iC 4 to make C 14 and decene *limer alkylation to make C 24 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, isdparaffins, olefin/isoparaffin ratios, contact time and the reaction conditions.
    The alkylated oligomers will no longer take part In further oligomerization due to "cappIng" off their olefinic sites, and the final oligomeriQ 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 alkylation of 1-decene and its oligomers with isobutane does take part in the chemistry. -17- Table 5 below compares some physical properties of the products obtained from the reactions of Table 4 Table 5 5.
    C10 /IC 4 =0.8 CI0iC 4 =1 C10=/iC4=4 C10/1IC 4 =5.5 ClO-iC 4 =9 VI 145 171 148 190 150 Vis@100 9.84 7.507 9.73 7.27 11:14 VIS@40 61.27 37.7 59.63 33.5 70.21 Pour -44 -52 Point -42 -42 Cloud -69 -28 Point -63 -64 Bromine Number 3.1 0.79 2.2 3.8 6.1 The oligomerization/alkylation run @ 1-decene/iC 4 ratio of 5.5 was repeated several times at the same feed ratios and conditions. The viscosity@ 100 in the repeated samples ranged from 6.9-11.2. The VI ranged from 156-172. All the 10 repeated samples contained low boiling cuts (below 775 degrees F) ranging frorn 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-decenQ oligomerlzation in the absence of IC 4 .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 alkylation of 1-decene, 1.-decene oligomerization only products, and the alkylated oligomers 20 (oligomerization followed by alkylation). By looking at these values, one can see the role of the Incorporation of Isobutane on the olefinicity of the final products. -18-- Table 6 Material 1- Oligomerization 1-Decene Alkylated 1 Decene with 10 mol% Oligomerization decene iC4, (20 mol% oligomers with iC4) iC4 Br 2 Number 114 O.1, (2.2) 7.9 2.8 Bromine Number data of the alkylated oligomeric products and the products of the simultaneous oligomerization/alkylation are very comparable when higher 5 concentrations of [CA are included In the reaction. -19-
    权利要求:
    Claims (20)
    [1] 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 zon6 passing the oligomerized olefinic intermediate and an isoparaffin to a ionic liquid alkylatiori zone comprising an acidic chloroaluminate ionic 10 liquid, at alkylation conditions; and recovering an effluent from the ionic liquid alkylation zone comprising an alkylated oligomeric product.
    [2] 2. The process of claim I wherein the Ionic liquid alkylation zohe further 15 comprises a Brtrlsted acid.
    [3] 3. The process of claim I wherein said alkylated oligomeric product is used as a fuel or a fuel blendstock. 20
    [4] 4. The process of claim 1 wherein said alkylated oligomeric product is used as a lubricant base dil or a lubricant bl6ndstock.
    [5] 5. The process of claim I wherein the mole ratio of oligomerized dlefinic intermediate to isoparaffin is at least 0.5. 25
    [6] 6. 'The process of claim 1 wherein said alkylated oligomeric product has a . - Bromine Number of less than 2.7.
    [7] 7. A process of claim 1 wherein the aikylated oligomeric product has a 30 TBP@50 of at least 1000 degrees F by Simulated Distillation and a Bromine Number of less than 4. -20-
    [8] 8. The process of claim 1 wherein said alkylated oligomeric product has a Bromine Number of less than 3..
    [9] 9. The process of claim I wherein the isoparaffin is selected from the group 5 consisting of isobutane, isopentane, and a mixture comprising isobutane and isopentane.
    [10] 10. The process of claim 1 wherein the alkylated oligomeric product is subjected to hydrogenation to produce a low olefin lubricant base oil. 10
    [11] - 11. The process of claim 10 wherein said low olefin lubricant base oil has a Bromine Number of less Ihan 0.2 by ASTM D 1159.
    [12] 12. The process of claim 1 wherein the feed stream comprising one or more 15 blefins comprises at least one alpha olefin.
    [13] - 13. The process of claim 1 wherein the feed stream comprising-one or more oleffins comprises at least 50 mole % of a single alpha olefin species. - 20
    [14] 14. The process of claim 1 wherein the feed stream comprising one or more olefins comprises a mixture of alpha olefins.
    [15] 15. The process of claim I wherein the alkylated ollgomeric product is subjected to hydrogenation to form a low olefin content alkylated - 25. oligomer.
    [16] 16; The process of claim 15 wherein the low olefin content alkylated ollgomer has a Bromine Number of less than 0.2 as measured by ASTM D 1159. 30
    [17] 17. The process of claim I wherein the ionic liquid oligomerization zone comprises an acid chloroaluminate ionic liquid catalyst.
    [18] 18. The-process of claim 1 wherein the ionic liquid oligomerization zone and the ionic liquid alkylation zone comprise a different ionic liquid catalyst.
    [19] 19. The process of claim I wherein the ionic liquid oligomerization zone and 5 the Ionic liquid alkylation zone comprise the same ionic liquid catalyst.
    [20] 20. The process of claim 19 wherein the Ionic liquid alkylation zone further comprises a Bronsted acid. -22-
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    同族专利:
    公开号 | 公开日
    AU2013200816B2|2013-06-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2013-10-10| FGA| Letters patent sealed or granted (standard patent)|
    2016-06-30| MK14| Patent ceased section 143(a) (annual fees not paid) or expired|
    优先权:
    申请号 | 申请日 | 专利标题
    US11/316,154||2005-12-20||
    AU2011265319A|AU2011265319B2|2005-12-20|2011-12-19|Alkylation of oligomers to make superior lubricant or fuel blendstock|
    AU2013200816A|AU2013200816B2|2005-12-20|2013-02-14|Alkylation of Oligomers to Make Superior Lubricant|AU2013200816A| AU2013200816B2|2005-12-20|2013-02-14|Alkylation of Oligomers to Make Superior Lubricant|
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