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.

What is claimed: 
     
         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 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 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 ε carbon groups/total number of carbon groups)*100,
 
 where an ε 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 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° C. to 300° 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 x /ZrO 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° 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 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° 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° 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° 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° 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° 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° C. less than 1800 cP. 
     
     
         51 . The process according to any preceding claim, wherein the base oil has a CCS at −35° C. less than 1700 cP. 
     
     
         52 . The process according to any preceding claim, wherein the base oil has a CCS at −35° C. less than 1600 cP. 
     
     
         53 . The process according to any preceding claim, wherein the base oil has a CCS at −35° C. less than 1500 cP. 
     
     
         54 . The process according to any preceding claim, wherein the base oil has a CCS at −35° C. less than 1400 cP. 
     
     
         55 . The process according to any preceding claim, wherein the base oil has a CCS at −35° C. less than 1300 cP. 
     
     
         56 . The process according to any preceding claim, wherein the base oil has a CCS at −35° C. less than 1200 cP. 
     
     
         57 . The process according to any preceding claim, wherein the base oil has a CCS at −35° 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° C. 
     
     
         68 . The process according to any preceding claim, wherein the base oil can be characterized by pour point of less than −30° C. 
     
     
         69 . The process according to any preceding claim, wherein the base oil can be characterized by pour point of less than −33° C. 
     
     
         70 . The process according to any preceding claim, wherein the base oil can be characterized by pour point of less than −36° C. 
     
     
         71 . The process according to any preceding claim, wherein the base oil can be characterized by pour point of less than −39° C. 
     
     
         72 . The process according to any preceding claim, wherein the base oil can be characterized by pour point of less than −42° C. 
     
     
         73 . The process according to any preceding claim, where a catalyst provided during isomerization is other than a catalyst provided during oligomerization.