US 2010.0160506A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0160506 A1 Wu et al. (43) Pub. Date: Jun. 24, 2010 (54) PRODUCTION OFSYNTHETIC Publication Classification HYDROCARBON FLUIDS, PLASTICIZERS (51) Int. Cl. AND SYNTHETICLUBRICANT BASE CSK 5/55 (2006.01) STOCKS FROM RENEWABLE FEEDSTOCKS CSK 5/109 (2006.01) C07D 30/03 (2006.01) (76) Inventors: Margaret May-Som Wu, Skillman, C07D 31 7/24 (2006.01) NJ (US); Karla Schall Colle, C07C I/207 (2006.01) Houston, TX (US); Ramzi Yanni (52) U.S. Cl. ......... 524/114; 524/280; 549/523: 549/229; Saleh, Baton Rouge, LA (US); 585/327 Allen D. Godwin, Seabrook, TX (57) ABSTRACT (US); John Edmond Randolph This disclosure is directed to an integrated method for making Stanat, Houston, TX (US) synthetic hydrocarbon fluids, plasticizers and polar synthetic lubricant base stocks from a renewable feedstock. More par Correspondence Address: ticularly, the disclosure is directed to a metathesis reaction of ExxonMobil Research & Engineering Company natural oil or its derivative ester and ethylene in the presence P.O. Box 900, 1545 Route 22 East of an effective amount of a metathesis catalyst to form linear Annandale, NJ 08801-0900 (US) alpha-olefins, internal olefins and reduced chain length trig lycerides. The linear alpha-olefins and/or internal olefins are polymerized to produce synthetic hydrocarbon fluids in the (21) Appl. No.: 12/633,742 presence of a suitable catalyst. The reduced chain length triglycerides are converted into polar synthetic lubricant base (22) Filed: Dec. 17, 2009 stocks or plasticizers by hydrogenation, isomerization, fol lowed by hydrogenations, or by hydroisomerization pro cesses. Alternatively, the reduced chain length triglycerides Related U.S. Application Data can also be epoxidized to form epoxidized triglyceride plas (60) Provisional application No. 61/203.523, filed on Dec. ticizers, optionally followed by carbonation, to form carbon 23, 2008. ated triglyceride plasticizers. Structures of Fatty Acids in Oils --- r H PALMIC ACID NOLEIC ACD --~~~~O C16H5202 O Mol, Wt: 256.42 17 OH 6 SEARIC ACID \ O 7 HO C18H3602 C18H3202 Mol. Wt: 284.48 Mol, Wt: 2280,45 OLEC ACID O ERURIC ACD 9 ch O OH 3. 22 YOH 21 a C22H4202 C18H3402 Mol, Wt: 338.57 Mol. Wt: 282.46 Patent Application Publication Jun. 24, 2010 Sheet 1 of 4 US 2010/O16050.6 A1 ___________)–========----------”F Patent Application Publication Jun. 24, 2010 Sheet 2 of 4 US 2010/O16050.6 A1 000 Patent Application Publication Jun. 24, 2010 Sheet 3 of 4 US 2010/O16050.6 A1 Patent Application Publication Jun. 24, 2010 Sheet 4 of 4 US 2010/O16050.6 A1 Zoot •- 0 v'91-' ZOZH+ •-=== US 2010/01 6050.6 A1 Jun. 24, 2010 PRODUCTION OF SYNTHETIC through a cross-metathesis reaction of renewable feedstocks HYDROCARBON FLUIDS, PLASTICIZERS with an alkene, such as ethylene, in the presence of a met AND SYNTHETICLUBRICANT BASE athesis catalyst. STOCKS FROM RENEWABLE FEEDSTOCKS 0007 U.S. Pat. No. 4,545,941, discloses production of certain alpha-olefins by reacting triglycerides having fatty CROSS-REFERENCE TO RELATED acid esters containing isolated carbon-carbon double bonds APPELLATIONS with ethylene at an ethylene partial pressure of about 200-550 psig in the presence of a metathesis catalyst, specifically a 0001. This application claims priority to U.S. Provisional catalyst comprising atungsten compoundandatin compound Application Ser. No. 61/203.523 filed Dec. 23, 2008, herein (e.g. tungsten hexachloride tetramethyl tin). The reaction is incorporated by reference in its entirety. carried out at a temperature of 100°F. to 500°F. 0008 Ahmad et al., Co-Metathesis Reaction of Crude FIELD Palm Oil and Ethene, Journal of the American Oil Chemists Society Pub. No. 72(6), 757-8 (1995), discloses the co-met 0002 The present disclosure relates to an integrated athesis reaction of crude palm oil with ethene in the presence method of producing synthetic hydrocarbon fluids, plasticiz of tungsten hexachloride and tetramethyl tin WClMeSn, ers and synthetic lubricant base stocks from renewable feed followed by termination of this reaction with methanol, stocks. which gives terminal alkenes. The major metathesis products are 1-decene and Me 9-decenoate. BACKGROUND 0009. The first successful metathesis conversion in the 0003 Recently, due to the high petroleum price and the field of unsaturated fatty acid esters and oils was performed in unstable nature of the oil supply, there is a strong incentive to 1972 by Boelhouwer and coworkers, viz., the selective trans produce fuels and chemical products from renewable feed formation of methyl oleate (methyl cis-9-octadecenoate), a stocks. Development and marketing of biodiesel and bioet readily available unsaturated ester, into equimolaramounts of hanol fuels are in high gear. Bio-diesel fuel made from plant 9-octadecene and dimethyl 9-octadecene-1,18-dioate, in the oils and bio-ethanol made from corn or Sugar plants are presence of the catalyst system WC1/(CH) Sn. Catalytic already in the market and are expected to grow at fast rates. To metathesis of unsaturated fatty acid esters and oils is Support this growth, a large amount of well-priced natural oils described in J. C. Mol, Catalytic Metathesis of Unsaturated and ethanol are expected to become available. These natural Fatty Acid Esters and Oils, Topics in Catalysts Vol. 27, Nos. oils have chemical compositions unsuitable for high perfor 1-4 (February 2004), which is incorporated herein by refer mance product application. CCC. 0004 Natural oils, especially plant oils, are unsuitable for O010 U.S. Patent Publication No. 2007/0179307 dis high performance synthetic lubricant base stock application closes a process for co-producing an olefinic fraction and a or polymer plasticizers, such as plasticized or flexible poly composition of diacids or diesters of fats. The process com vinyl chloride (PVC) products. This is because natural oils prises, in Succession: a) metathesis of an unsaturated fat with contain high amounts of triglycerides of unsaturated fatty ethylene in the presence of a metathesis catalyst and at least acids. The high amount of unsaturation and the high amount one non-aqueous ionic liquid; b) separating and recycling the of long chain fatty acids contribute to the poor oxidative ionic liquid used in the first step; c) separating, by distillation, stability, poor low temperature properties and poor plastici the olefinic fraction (fraction A) from the unsaturated fat zation properties. Heretofore known, synthetic lubricant base mono-ester or mono-basic acid fraction (fraction B) formed stocks or plasticizers have excellent performance. However, in step a); d) homometathesis of the mono-unsaturated fat they are all derived from non-renewable petroleum feedstock. ester or acid cut (fraction B) which allows the co-production 0005 Triglycerides are the major component in naturally ofunsaturated fat diesters or diacids (fraction C) and ethylene occurring fats and oils. A triglyceride is the condensation which is recycled to the first methathesis step of the process; product of one molecule of glycerol with three molecules of and e) optionally, recycling the ionic liquid containing the fatty acids to yield three molecules of water and one molecule catalyst used in step d). Particularly preferred starting mate of triglyceride. A fatty acid is an aliphatic compound contain rial is an oleic Sunflower seed oil, an oleic rapeseed oil or ing 4 to 24 carbon atoms and having a terminal carboxyl mono-alcohol esters of said oils, whereupon the process can radical. Naturally occurring fatty acids, with only some produce both an olefinic fraction (mainly composed of exceptions, have an even number of carbonatoms and, if any 1-decene) and a composition of diesters ordiacids wherein, in unsaturation is present, the first double bond is generally general, over half of the chains is constituted by unsaturated located between the ninth and tenth carbonatoms. The char Cs chains (mainly composed of octadecene-91,18-diacid or acteristics of the triglycerides are strongly influenced by the diester). The ethylene employed is recycled to the first meth nature of their fatty acid radicals. For a detailed description of athesis step. triglycerides refer to U.S. Pat. No. 4,545,941, incorporated 0011 Poly alpha-olefins (PAOs) comprise a class of herein by reference. hydrocarbons manufactured by the catalytic oligomerization 0006 Alpha-olefins are primarily used as intermediates in (polymerization to low-molecular-weight products) of linear the production of polyolefins, chemicals, and consumer prod alpha-olefin (LAO) monomers. LAOS typically range from ucts. For example, 1-propene is used to make polypropylene, 1-octene to 1-dodecene, with 1-decene being a preferred acrylonitrile, propylene oxide, and isopropyl alcohol. The material, although oligomeric copolymers of lower olefins major uses of 1-butene are to produce poly(1-butene) and Such as ethylene and propylene may also be used, including various four carbon aldehydes and alcohols. The higher copolymers of ethylene with higher olefins as described in alpha-olefins and internal olefins are commonly used in the U.S. Pat. No. 4,956,122 and the patents referred to therein. manufacture of synthetic lubricating oils, detergents, plasti 0012 Some PAO products have achieved importance in cizer alcohols, flavors, perfumes, dyes, pharmaceuticals, and the lubricating oil market. Specifically, PAOs may be pro resins. The major commercial source of alpha-olefins is duced by the polymerization of olefin feed in the presence of petroleum. Alpha-olefins and internal olefins can be produced a catalyst Such as AlCls, BFs, or promoted AlCls, BFs, or US 2010/01 6050.6 A1 Jun. 24, 2010 metallocene catalyst Systems promoted by a non-coordinat patibility. Soybean oil has been epoxidized (ESO) to try to ing anion or methylaluminoxane. PAOs of different viscosity improve its compatibility and performance as a plasticizer. grades are typically produced using promoted BF or AlCl Even with the polarity of the epoxide group, ESO has long catalysts.