CA2034687A1 - C2-c5 olefin oligomerization by reduced chromium catalysis - Google Patents
C2-c5 olefin oligomerization by reduced chromium catalysisInfo
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Abstract
CATALYSIS
ABSTRACT
A process is disclosed for the oligomerization of C2-C5 alpha olefin mixtures or C3-C5 alpha-olefins alone to produce liquid olefin oligomers having high viscosity index and regio-regularity not greater than 40%, usually from 20 to 40%. Lower hydrocarbon fractions useful as gasoline and distillate fuels are also produced. The process comprises contacting the mixtures or C3-C5 alpha-olefins with a reduced valence state chromium oxide catalyst on a silica support in an oligomerization zone under oligomerization conditions comprising a temperature from 90C to 250C. The process can be carried out in dilute form using an inert solvent such as octane. The liquid oligomerization products can be produced in wide range of viscosities including the direct production of low viscosity lubricants having high viscosity index.
ABSTRACT
A process is disclosed for the oligomerization of C2-C5 alpha olefin mixtures or C3-C5 alpha-olefins alone to produce liquid olefin oligomers having high viscosity index and regio-regularity not greater than 40%, usually from 20 to 40%. Lower hydrocarbon fractions useful as gasoline and distillate fuels are also produced. The process comprises contacting the mixtures or C3-C5 alpha-olefins with a reduced valence state chromium oxide catalyst on a silica support in an oligomerization zone under oligomerization conditions comprising a temperature from 90C to 250C. The process can be carried out in dilute form using an inert solvent such as octane. The liquid oligomerization products can be produced in wide range of viscosities including the direct production of low viscosity lubricants having high viscosity index.
Description
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" C2-C5 OLEFIN OLIGOMERIZATION BY REDUCED CHROMIUM
CATALYSIS
This invention relates to a process for the oligomerization of a C2-C5 alpha-olefin feed and the olefin oligomers so produced. In particular, the invention relates to a process for the oligomerization of C3-C5 alpha-olefins or mixtures of C2-C5 alpha-olefins using reduced chromium oxide on a solid support as catalvst. The oligomer products, which may lo be either homo-oligomers of C3-C5 olefins or co-oligoemrs of C3-C5 clefins with ethylene, are useful as lubricants and lubricant additives, e.g. viscosity index improvers, of superior quality which exhibit high viscosity index and as chemical intermediates.
Efforts to improve upon the performance of natural mineral oil based lubricants by the synthesis of oligomeric hydrocarbon fluids have been the subject of important research and development in the petroleum ~` industry for at least fifty years and have led to the relatively recent market introduction of a number of superior polyalpha-olefin (PAO) synthetic lubricants, primarily based on the oligomerization of alpha-olefins or l-alkenes. In terms of lubricant property improvement, the thrust of the industrial research effort on synthetic lubricants has been toward fluids exhibiting useful viscosities over a wide range of temperature, i.e., improved viscosity index (VI), while also showing lubricity, thermal and oxidative stability and pour point equal to or better than mineral oil.
- 30 These new synthetic lubricants lower friction and hencs increase mechanical efficiency across the full spectrum of mechanical loads from worm gears to traction drives and do so over a wider range of operating conditions than mineral oil lu~ricants.
Catalysts that have been found useful in the prior art for the oligomerization of alpha-olefins to PAO
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~3~7 include Lewis acids and Ziegler catalysts. The products have been found to differ significantly in lubricant properties according to the catalyst used and the process economics arP also affected by ease of separation, corrosivity and other catalyst dependent process characteristics. Brennan, Ind. Eng. Chem. Prod.
Res. Dev. 1980, 19, 2-6, cites l-decene trimer as an example of a structure compatible with structures associated with superior low temperature fluidity wherein the concentration of atoms is very close to the center of a chain of carbon atoms. Also described therein is the apparent dependency of properties of the oligomer on the oligomerization process, i.e., cationic polymerization or Ziegler~type catalyst, known and practiced in the art.
~; A process using coordination catalysts to prepare high polymers from l-alkenes, especially chromium catalyst on a silica support, is described by Weiss et ~` al. in Jour. Catalysis 88, 424-430 (1984) and in Offen.
20 DE 3,427,319. The process and products therefrom are ; discussed in more detail hereinafter in comparison with the process and products of the instant invention.
~;~; Notwithstanding their generally superior properties, PAO lubricants are often formulated with additives to enhance those properties for specific - applications. The more commonly used additives include oxidation inhibitors, rust inhibitors, metal passivators, antiwear agents, extreme pressure additives, pour point depressants, detergent-dispersants, viscosity index (VIB) improvers, foam inhibitors and the like, as described, for . example, in Kirk-Othmer "Encyclopedia of Chemical Technology", 3rd edition, Vol. 14, pp. 477-526, to which reference is made for a description of such additives and their use. Significant improvements in lubricant technology have come from improvements in additives.
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2~687 Recently, high VI lubricant compositions (referred to herein as HVI-PAO and the HVI PAO process) comprising polyalpha-olefins and methods for their preparation employing as catalyst reduced chromium on a silica support have been disclosed in U.S. patents 4,827,064 and 4,827,073. The process comprises contacting C6-C20 1-alkene feedstock with reduced valence state chromium oxide catalyst on porous silica support under oligomerizing conditions in an oligomerization zone whereby high visco~ity, high VI
liquid hydrocarbon lubricant is produced having branch ratios less than 0.19 and pour point below -15C. The process is distinctive in that little isomerization of the olefinic bond occurs compared to known oligomerization methods to produce polyalpha-olefins using Lewis acid catalyst. Lubricants produced by the process cover the full range of lubricant viscosities and exhibit a remarkably high viscosity index (VI) and ``` low pour point even at high viscosity. The as-synthesized HVI-PAO oligomer Aas a preponderance of terminal olefinic unsaturation.
Considering the abundance of C2 to C5 alpha-olefins in the petroleum refinery, and their low cost, it has long been recognized that they could be a preferred source of low cost lubricant if they could be oligomeri~ed to provide high viscosity index lubricant : in good yield with a manageable, regenerable, non-corrosive catalyst. The olefin oligomers produced by the present process are characterised by a unique structure which confers particularly useful properties on the products. In conventional Ziegler oligomerization of alpha olefins the oligomers produced contain a high degree of structural regularity, or regio-regularity, as exhibited by a preponderance of head-to-tail bonding in the oligomerization of these alpha olefins. In the products from Ziegler catalyzed oligomerization not more than twenty percent of the `, ' ' '``:
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F-5313 - 4 - ~3~7 repeating units are linked by regular head-to-head and tail-to-tail bonding. In the olefin oligomers produced from the reduced metal oxide catalysts, however, at least twenty percent of the repeating units are bonded - 5 by irregular or head-to head or tail-to-tail connections. These C3-C5 alpha-olefin oligomers therefore have a regio-irregularity of at least twenty percent, usually from 20 to 40 percent, and in most cases, not more than 60 percent (where 100%
regio-regularity corresponds with all head-to-tail connections for the recurring oligomeric units). Thus, in most cases, from 60 to 80 percent of the the recurring connections in the oligomer are linked by regular head-to-tail bonding.
1~ According to the present invention, olefin oligomers produced from C3-C5 olefins, either alone or with co-oligomerized ethylene units, have a regio~irregularity of at least 20, and usually from 20 - to 40 percent.
o The oligomers can be produced by contacting C3-C5 alpha-olefins or a mixtura of C2 to C5 alpha-olefins with a reduced metal oxide catalyst, preferably a reduced chromium oxide on a solid, porous support. The -~ catalyst is usually produced by oxidation at a temperature of 200C to 900C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the oxide of the metal to a lower valence state.
The olefin oligomers are characteristically liquids having a viscosity measured at 100C of lO,OOOmm2/s (cS) useful as lubricant basestock or used as VI
improvers. The oligomers may be hydrogenated to produce a saturated hydrocarbon product.
The process of the present invention comprises the steps of: contacting C3-C5 alpha-olPfins or a mixture f C2 to C5 alpha-olefins with chromium catalyst on a solid support, which catalyst has been treated by .:
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oxidation at a temperature of 200 to 900C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the catalyst. The contacting takes place under conditions sufficient to produce liquid olefin oligomers having a viscosity measured at 100C of lO,OOOmm /s (cS) useful as lubricant basestock or used as VI improvers. The oligomers are hydrogenated to produce a saturated hydrocarbon.
Propylena, l-butene or l-pentene can, individually, be oligomerized in a similar manner and the olefin oligomers are separated by distillation to recover a gasoline boiling range overhead fraction, a distillate boiling range overhead fraction, and a lube boiling range bottoms fraction.
The present process provides excellent yields of a saturated hydrocarbon lubricant fraction from the oligomerization of C3-C5 alpha-olefins or a mixture of C2 to C5 alpha-olefins. The oligomerization of ethene, propylene or 1-butene or l-pentene to produce the lubricant fraction results in a product particularly distinguished by a high viscosity index representative of superior lubricant properties. The lighter oligomer or hydrocarbon fraction separated from the oligomerization mixture is useful as gasoline or distillate product.
The oligomer products containing unsaturated doub~e bonds are suitable as chemical intermediates for further functionalization, e.g., reaction with maleic anhydride to form adducts which can be used as intermediates for the production of lubricant additives.
In the following description, unless otherwise stated, all references to properties of oligomers or lubricants of the present invention refer as well to hydrogenated oligomers and lubricants wherein hydrogenation of the oligomer product is carried out as ' :-, ~
F-5313 - 6 - ~ 7 will usually be preferred in order to reduce residual unsaturation.
The C3-C5 alpha olefin oligomers and the oligomers of C3-C5 alpha olefins with ethylene are unique in their structure compared with conventional - polyalphaolefins (PA0) from l-decene, for example.
. Polymerization with the reduced metal, e.g. chromium, catalyst described hereinafter leads to an oligomer substantially free of double bond isomerization.
Conventional PAO, on the other hand, promoted by BF3 or Al c13 forms a carbonium ion which,in turn, promotes isomerization of the olefinic bond and the formation of multiple isomers. The HVI PAO produced in the referenced invention has a structure with a CH3/CHH2 15 ratio <0.19 compared to a ratio of >0.20 for PAO.
The c2-C5 feedstocks used in the present invention are particularly inexpensive and common materials found - in the petroleum refinery complex. Readily available sources include fluid catalytic cracker operation; in particul~r, the product of FCC unsaturated gas plant.
The olefins are also available from the various steam cracking processes, e.g., light naphtha or liquified petroleum gas (LPG).
The mixtures of propylene, l-butene or l-pentene and ethylene can be used in a molar ratio from 100:1 to 1:1 (C3-C5:C2), with a preferred molar ratio from about 20 to 1.
In the oligomerization of propylene, l-butene or l-pentene, the alpha-olefin can be used either in pure form or diluted with ethylene or other inert materials for production of the oligomers. The liquid products, after hydrogenation to remove unsaturation have higher viscosity indices than similar alpha-olefins oligomerized by conventional acid catalysts such as aluminum chloride or boron trifluoride. To produce the low molecular weight liquid products suitable for use as lube basestock or as blending stock with other lube "
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stock, the oligomerization is carried out at a temperature higher (90-250C) than the temperature suitable to produce higher molecular weight polyalpha-olefins but when ethylene is used as a co-monomer, lower temperatures may be used, for example, down to about 0c, so that the temperature -~ range for for the production of the ethylene-- containing oligomers is typically from 0 to about 250C.
The present alpha-olefin oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alphaolefins are not isomerized. These reactions include alpha-olefin ~ oliqomerization by supported metal oxide catalysts, ,15 such as Cr compounds on silica or other supported IUPAC
Periodic Table Group VIB compounds. The catalyst most preferred is a lower valence Group VIB metal oxide on an inert support. Preferred supports include silica, `alumina, titania, silica alumina, magnesia and the like. The support material binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 x lO 7mm are preferred.
The support material usually has high surface area and large pore volumes with average pore si~e of 25 40 to 350 x lO 7mm (40 to 350 angstroms). The high surface area is beneficial for supporting large amount of highly dispersive, active chromium metal centers and to give maximum efficiency of metal usage, resulting in very high activity catalyst. The support should have 30 large average pore openings of at least 40 x lO 7mm (40 angstroms), with an average pore opening of >60 to 300 x lO 7mm (>60 to 300 angstroms) preferred. This large pore opening will not impose any diffusional restriction of the reactant and product to and away from the active catalytic metal centers, thus further optimizing the catalyst productivity. Also, for this catalyst to be used in fixed bed or slurry reactor and .. ,, ~, , ,.,.. " .... ; , : ~3~68~
~ to be recycled and regenerated many times, a porous - support with good physical strength is preferred to prevent catalyst particle attrition or disintegration during handling or reaction.
The supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for ` example, ethanol, methanol, or acetic acid. The solid catalyst precursor is then dried and calcined at 200 to 900C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, CO, H2, NH3, H2S, CS2, CH3SCH3, CH3SSCH3,metal alkyl containing compounds such as ~3Al, R3B,R2Mg, RLi, R2Zn, where R is alkyl, alkoxy, aryl and the like. Preferred are CO or H2 or metal alkyl containing compounds.
Alternatively, the Group VIB metal may be applied to the substrate in reduced form, such as CrII
compounds. The resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature, e.g. 0C, to about 250C at a pressure of lO to 34600 kPa (O.l atmosphere to 5000 psi). Contact time of both the olefin and the catalyst can vary from one second to 24 hours. The catalyst can be used in a batch type reactor, a continuous stirred tank reactor or in a fixed bed, continuous-flow reactor.
In general the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is then mixed and dried at room temperature. The dry solid gel is purged at successively higher temperatures to about 600C for a period of about 16 to 20 hours. Thereafter the catalyst is cooled under an inert atmosphere to a temperature of about 250 to 450C and a stream of pure reducing agent, such as C0, is contacted therewith. When sufficient CO
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has passed through to reduce the catalyst there is a distinct color change from bright orange to pale blue.
Typically, the catalyst is treated with an amount of C0 equivalent to a two-~old stoichiometric excess to reduce the catalyst to a lower valence CrII state.
Finally the catalyst is cooled to room temperature and is ready for use.
As referenced hereinbefore, the use of supported Cr metal oxide in different oxidation states to polymerize alpha olefins from C3 to C20 (DE 3427319 to H. L. Krauss and Journal of Catalysis 88, 424-430, 1984) using a catalyst prepared by CrO3 on silicais known. The referenced disclosures teach that polymerization takes place at low temperature, usually less than 100C, to give adhesive polymers and that at high temperature, the catalyst promotes isomerization, cracking and hydrogen transfer reactions. The present process produces liquid, low molecular weight oligomeric products using reaction conditions and catalysts which minimize side reactions such as l-olefin isomerization, cracking, hydrogen transfer and aromatization. The reduced metal oxide catalysts do not cause a significant amount of side reactions even at the higher temperaturesat which oligomeric, low molecular weight fluids are produced. These catalysts therefore minimize side reactions but oligomerize olefins to give low molecular weight polymers with high efficiency. Although the exact nature of the supported Cr oxide is difficult to determine, it is thought that the catalyst of the present invention is rich in Cr(II) supported on silica, which is more active to catalyze alpha-olefin oligomerization at high reaction temperature without causing significant amounts of isomerization, cracking or hydrogenation reactisns.
However, the catalysts described the cited references can be richer in Cr (III) and they catalyze alpha-olefin polymerization at low reaction temperature ,, :' :
' - F-5313 - lo - ~ 7 to produce high molecular weight polymers and at higher temperatures undesirable isomerization, cracking and hydrogenation reaction takes place.
: The catalysts for this invention thus minimize all side reactions but oligomerize olefins to give low ~ molecular weight polymers with high efficiency. It is well known in the prior art ~hat chromium oxides, especially chromia with average +3 oxidation states, either pure or supported, catalyze double bond lo isomerization, dehydrogenation, cracking, etc.
However, catalysts as prepared in the cited references can be richer in Cr (III). They catalyze alpha-olefin polymerization at low reaction temperature to produce high molecular weight polymers. However, as the references teach, undesirable isomerization, cracking and hydrogenation reaction takes place at higher temperatures. In contrast, high temperatures are needed in this invention to produce lubricant products.
The prior art also teaches that supported Cr catalysts rich in Cr(III) or higher oxidation states catalyze l-butene isomerization with 103 higher activity than polymerization of l-butene. The quality of the catalyst, method of preparation, treatments and reaction conditions are critical to the catalyst performance and composition of the product produced and distinguish the present invention over the prior art.
In the instant invention very low catalyst concentrations based on feed, from 10 wt~ to 0.01 wt%, are used to produce oligomers; whereas, in the cited references catalyst ratios based on feed of 1:1 are used to prepare high polymer. Resorting to lower catalyst concentrations in the present invsntion to produce lower molecular weight material runs counter to conventional polymerization theory, compared to the results in the cited references.
The oligomers of 1-olefins of this invention usually have much lower molecular weights than the ~ .
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:. 2 ~ 3 l~ 7 polymers produced in cited reference which are semi-solids, with very high molecular weights and are - not suitable as lubricant basestocks. These high polymers usually have no detectable amount of dimer or trimmer (C10-C30) components from synthesis. These high polymers also have very low unsaturations.
However, products in this invention are free-flowing liquids at room temperature, suitable for use as lube basestock and additives, e.g. VI improvers.
Ethylene and C3-C5 alpha-olefins are abundant and cheap raw materials. According to the present invention, C3-C5 alpha-olefins or mixed C2-C5 alpha-olefins, either in dilute form or in pure form can be upgraded into a wide range of hydrocarbon products. The high boiling components can be used as high quality lubricants with high viscosity index. The low boiling components can be used as gasoline, distillate or starting material for syn~hetic detergents, additives to fuel, lubricants or plastics.
The catalyst for the conversion is a supported metal oxide such as group VIB and group VIIIB oxides on silica catalyst. The mixtures of propylene, l-butene or 1-pentene and ethylene can be used in a molar ratio from 100 to l to 1 to 1, with a preferred molar ratio _5 of 20 to 1.
The use of activated supported metal oxide catalyst to produce a wide range of hydrocarbons from C2-C5 alpha-olefin mixtures is unique. The lube fraction of the hydrocarbons have high viscosity indic~s. The catalyst employed in the present invention is a solid catalyst and is significantly easier to handle than conventional Ziegler catalyst and other solution catalyst. The by-products with low boiling points have carbon numbers from C5 to C30.
These by-products have unsaturated olefin double bonds and can be used as starting materials for synthesis of ` ~-5313 12 -2 ~ 8 7 detergents, fuel or lube additives. The catalyst used are non-corrosive and are regenerable.
- In the oligomerization of propylene, l-butene or l-pentene, the alpha-olefin can be used either in pure , form or in diluted form for upgrading into gasoline : distillate and lube products over solid coordination catalyst. The fuel range products are high quality fuel with low sulfur and aromatic contents. The lube products, after hydrogenation to remove unsaturation have higher viscosity indices than such alpha-olefins oligomerized by conventional acid catalysts such as aluminum chloride or boron tri-fluoride.
In the present invention, lube compositions from the oligomerization of C2-C5 alpha-olefin mixtu~es or C3-C5 alpha-olefins can be produced with viscosities betw~en 3mm /s and 5000mm /s measured at lO0C.
It has been found that the products of the instant invention exhibit a very unique structure that confers upon the products the properties of novel compositions.
In conventional Ziegler oligomerization of alpha olefins it is well known in the art that the oligomers produced contain a high degree of structural reqularity, or regio-regularity, as exhibited by a preponderance of head-to-tail bonding in the oligomerization of these alpha olefins. In the products from Ziegler catalyzed oligomerization not more than twenty percent of the repeating units are linked by head-to-head and tail-to-tail bonding. In . the present invention it has been found that at least forty percent of the repeating units are bonded by head-to-head or tail-to-tail connections. The C3-C5 alpha-olefin oligomers of the present invention contain not more than 60% regio-regularity, where 100%
regio-regularity corresponds with all head-to-tail connections for the recurring oligomeric unit.
In Table l the results of the spectroscopic determination of the regio-regularity of the products :,.
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, 5~ 7 of the present invention are presented (nos. 3-5) as well as the results fxom the products of 1-decene and 1-hexene oligomerization. The C-13 NMR spectra and the INEPT (Insensitive Nuclei Enhancement by Polarization Transfer) spectra of four products prepared from Cr/SiO2 catalyzed HVI-PAO oligomerization process reactions of l-decene, 1-hexene, l-butene and propene are presented. For each oligomer, the chemical shifts of the methylene and methine carbons of the backbone are calculated and assigned based on different combinations of regio-irregularity. From the 2/4J
INEPT spectrum which selectively detects only the methine carbons, the amount of regio-regularity of each oligomer is estimated. Entries 1-4 compare four different alpha-olefins as the starting material. The results indicate that the oligomers from the higher olefins are formed in a more regio-regular fashion than the lower olefins.
Table 1 StartingViscosity @
No. Olefin 100C,cS %Reqio-Reaularity 1 l-decene 145.0 >58 2 1-hexene 92.8 -51 25 3 1-butene 103.7 -48 4 propene 95.3 -41 1-butene 2.8 ~38 In the following examples the process of the present invention are illustratPd. In the invention, propylene and mixtures of ethylene and propylene are oligomerized using reduced chromium oxide on a silica support as catalyst. The catalyst is prepared following the procedure described in the preceding examples.
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~3~687 Example 1 Catalyst Preparation and Activation Procedure 1.9 grams of chromium (II) acetate (Cr2(0COCH3)42H20)(5.58 mmole) (commercially obtained) is dissolved in 50 ml of hot acetic acid. Then 50 grams of a silica gel of 8-12 mesh size, a surface area of 300 m2/g, and a pore volume of 1 ml/g, also is added. Most of the solution is absorbed by the silica gel. The final mixture is mixed for half an hour on a rotavap at room temperature and dried in an open-dish at room temperature. First, the dry solid (20 g) is purged with N2 at 250C in a tube furnace. The furnace temperature is then raised to 400C for 2 hours. The temperature is then set at 600C with dry air purging for 16 hours. At this time the catalyst is cooled under N2 to a temperature o 300C~ Then a stream of pure co (99.99% from Matheson) is introduced for one hour. Finally, the catalyst is cooled to room temperature under N2 and ready for use.
Example 2 A Cr/SiO2 catalyst was prepared as described in Example 1.
~` 3 gram of the activated Cr/SiO2 catalyst was packed in a fixed bed down flow reactor of 9.5 mm inside diameter (3/8" id). Propylene of 5 gram per hour was reacted over the catalyst bed heated to 180-19OC and at 1620 kPa (220 psig). After 16 hours, 56.2 gram of liquid product and 24.9 gram of gas were collected. The gas product analyzed by gc contained 95% propylene. The liquid product had the following compositions:
C6 Cg C12 C15 C18 C21 C24 C27 C30+
wt% 10.6 11.2 8.~ 7.4 3.3 3.9 2.9 3.9 48.3 The products from C6 to C12, after hydrogenation, can be used as gasoline components. The products from .
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C12 to C24 can be used as distillate components. The unhydrogenated lube product, most C27 and higher hydrocarbons and isolated after distillation at 180 C/13.3 kPa (O.lmm Hg), have a viscosity at 100C of 28.53 cS and VI of 78. The unhydrogenated lube product had higher VI than the same viscosity oil produced from propylene by AlC13 or BF3 catalyst, as summarized below.
Unhydrogenated 10 Catalyst lube yieldV@100C,mm2/s VI
AlC13/Hcl 87 29.96 38 BF3H20 23 7.07 46 The unhydrogenated lube product from Cr/SiO2 catalyst has simpler C13-NMR spectrum than lube by acid catalyst.
Example 3 The procedure of Example 2 was followed, except that the reaction was run at 170C and 2170-2860 kPa (300-400 psig). After 14 hours reaction, 47.5 grams ~0 liquid and 18.4 g gas (mostly propylene) were collectedO The liquid product had the following composition, analyzed by gc:
6 Cg C12 C15 to C20 C20 to C30 C30+
4.51 5.53 5.01 12.22 5.30 67.43 The unhydrogenated lube fraction after distillation to remove light end at 160C/13.3 kPa (O.lmm Hg), had viscosity at 100C of 39.85 and VI of 81.
Example 4 A Cr/SiO2 catalyst was prepared as in Example 1.
To a tubular reactor packed with three grams of 1~
Cr on silica catalyst, propylene of 5 g/hr and ethylene 1.13 g/hr (~olar ratio of C3/C2 = 3) were fed through at 190C and 1480-2172 kPa (200-300 psig). The liquid , ~ ~;3 ~
product weighed 68 grams, after 15 hours on stream.
This once-through liquid yield was 75%. The gas contained ethylene and propylene which can be recycled.
The liquid product was centrifuged to remove thP small amount of solid particles. The clear liquid was fractionated to give 50~ light fraction boiling below 145C at 1.33 kPa (0.01 m~Hg) and 50% unhydrogenated lube product. The unhydrogenated lube product had V~100 (viscosity at 100C) = 46.03 m~l/s (cS), V~40 lO (viscosity at 40C) = 703.25 mm2/s (cS) and VI = 112.
The light fractions are unsaturated olefinic hydrocarbons with six to 25 carbons. The IR showed tha presence of internal and vinylidene double bonds.
These olefins can be used as starting material for - 15 synthesis of other value-added products, such as detergents, additives for lube or fuel. These light - fractions can also be used as gasoline or distillates.
This example demonstrates that one can produce lube with high VI from ethylene and propylene mixture over an activated Cr on silica catalyst. The light product can be useful as chemicals or fuel.
ExamPle 5 The run in Example 2 was continued for another 23 hours and 78 grams liquid product was collected. The once-through liquid yield was 54%. This liquid product was centrifuged to remove the solid precipitate. The clear product was fractionated to give 35% light liquid boiling below 145C at 13.3 kPa (0.1 mmHg) and 65%
viscous unhydrogenated lube product. The unhydrogenated lube product had V@100 = 72.40 mmZ/s (cS), V@40 = 980.73 mm2/s (cS) and VI = 144.
Example 6 The reactor, propylene and ethylene feed rates ~ 35 were the same as in Example 4. In addition, n-octane was fed through the reactor at 10 ml~hr as solvent at 185C. After 17 hours on stream, 228 grams of liquid ~ ,~
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product was collected. Material balance indicated that all ethylene and propylene was converted into liquid product. The liquid, after filtering off trace solid, was fractionated to give four fractions:
Fraction 1, boiling below 130C, 118g, mostly n-octane solvent;
Fraction 2, up to 123 C/l. 33 kPa (O.ol mmHg), 32g.;
Fraction 3, up to 170C/1.33 kPa (0.01 mmHg), 27g;
and Fraction 4, residual product, 40 g.
Fraction 4 has the following viscometric properties:
V~lO0 = 30.99 mm2/s (cS), V@40 = 343.44 mm2/s (cS), VI
15 = 126.
This Example demonstrates that the presence of an inert solvent is advantageous to produce lower viscosity lube. The presence of an inert solvent also prevents the reactor from plugging by trace solid formation~
Example 7.
This Example illustrates the preparation of polypropylene liquid product using both a reduced metal catalyst (Ex. 7) and a Ziegler catalyst (Ex. 7B).
Example 7A
An activated chromium on silica catalyst (15 grams) and purified n-decane (400 ml) were charged into an one-liter autoclave with stirring under nitrogen atmosphere. When the autoclave temperature reached 30 160C, liquid propylene was fed at 50 ml/hr until 375 ml was charged into the reactor. After 16 hours at 160RC, the slurry product was discharged, filtered to remove solid catalyst and distilled up to 120C at 13.3 kPa (0.1 mmHg) vacuum to remove light ends. The " 35 product yields and properties are summarized in Table 2.
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` F-5313 - 18 -- G2 ~ ; 6 8 7 Example 7B
Preparation of polypropylene liquid product by Ziegler catalyst, ZrCp2Cl2/MAO.
A solution catalyst containing 0.17 mmole zirconocene dichloride and 88 mmole methylaluminoxane in lS0 ml toluene was add to an one-liter autoclave at 25C. Propylene was then added at 50 ml/hr until 375 ~ ml was charged into the reactor. After 16 hours, the catalyst components were deactivated by adding l ml water. The liquid product was isolated by drying and filtration to remove solid components. The lube product was isolated as in Example 7A. The product yields and properties are summarized in Table 2 below.
The polymer structures produced by the use of the chromium catalyst are uniquely irregular. The C13 NMR
spectra of these two examples indicated that the chromium product of Example 7A is much~less regular than the Ziegler product of Example 7B. The amount of this regio-irregularity can be determined by the C-13 2/4J INEPT (Insensitive Nuclei Enhancement by Polarization Transfer) NMR technique. The INEPT
spectra of the products of Examples 7A and 7B showed the different types of the methine carbons in the backbones of chromium product and the Ziegler productO
The data in Table 2 show that the chromium product had better thermal stability than the regular Ziegler ~` product, when cracked at 280C under nitrogen atmosphere for 24 hours.
Example 8 Preparation of poly l-butene liquid products, using a reduced metal catalyst (Ex. 8A) and a Ziegler catalyst (Ex. 8B).
Example 8A
Poly-l-butene was produced in a continuous, down-flow fixed bed reactor. The reactor was constructed of 9.5 min outside diameter (3/8" o.d.) /
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F-5313 - 19 - ~ 3 ~ 6 8 7 stainless steel tube. The ~ottom of the reactor contained 18 grams of clean 14/20 mesh quartz chips, supported on a coarse frit of 6 mm diameter. Three gram activated chromium catalyst was charged into the tube. The top of the reactor tube was packed with quartz chips to serve as a feed preheater. The reactor tube was wrapped with a heat-conducting jacket. The reactor temperature, 125C, was measured and controlled with a thermocouple located at the middle oE the jacket. l-Butene liquid was pumped through a 50 ml Hoke bomb packed with Deox and 13X molecular sieve of equal volume to remove oxygenates and water contaminants. l-Butene was fed into the reactor from the top. Reactor pressure, 2310 kPa (320 psig), was lS controlled by a grove-loader at the reactor outlet.
The effluent was collected at the reactor bottom and the lube product was isolated by distillation up to 140~C at 13.3 kPa (0.1 mmHg) vacuum. The product properties are summarized in Table 2.
20Example 8B.
Preparation of poly-1-butene liquid product by Ziegler catalyst, ZrCp2C12/MAO
The product was prepared as in Example 7B, except l-butene was used as feed. The product yield and properties are summarized in Table 2.
The C13 NMR spectra of the two products of Examples 8A and 8B show that the chromium product of Example 8A is much less regular than the Ziegler product of Example 8B a~ well, by comparison with spectra reported in the literature for Ziegler polymers. The data in Table 2 show that the chromium product of Example 8A had better thermal stability than the regular Ziegler product of Example 8B, when cracked at 280C under nitrogen atmosphere for 24 hours.
Example 9~
Preparation of ethylene/propylene copolymer, using a reduced metal catalyst and a Ziegler catalyst.
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F-5313 - 20 - 2~3~687 Example 9A
As Example 7A, except gaseous ethylene (25.2 g/hr) andpropylene (25 g/hr) were fed simultaneously into the autoclave at 185C. The product yield and properties : 5 are summarized in Table 2~
; Example 9B
.- Preparation of ethylene/propylene copolymer liquid product by Ziegler catalyst, ZrCp2C12/MAO
As Example 7B, except ethylene (25.2 g/hr) and propylene (25 g/hr) were fed simultaneously into the autoclave at 60~C.
The product yield and properties are summarized in Table 2. The C13 NMR spectra of the products indicated that the chromium product of Example 9A is much less regular than the Ziegler product of Example 9B.
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Example 10 A polypropylene liquid product was prepared using a reduced metal catalyst, in a similar manner to Example 7A, except th~ autoclave was heated to 800C.
The product yield and properties are summarized in Table 3 below.
Example 11.
An ethylene/propylene copolymer liquid was prepared as dezxcribed in Example 10, except ethylene (16.7 g/hr) and propylene (25g/hr~ were fed simultaneously into the autoclave at 95C. The product yield and properties are summarized in Table 3.
Table 3.
Product Yields and Properties of Example 10 and 11 Example 10 Example 11 Catalyst Cr/SiO2 Cr/SiO2 Feed C3= C2=/C3=
Yield - -Product properties MWn 3900 4880 MWD 2.74 2.85 The estimated amounts of regio-irregularity of these products together with the reported data from the products obtained by Ziegler catalysts are summarized in Table 4.
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F--5313 -- 23 - ~3~6~;37 Table 4 Product Re~io-Irregularity Sample Catalyst MWn Mole~
of irregular propylene Example 7A Cr(II)/SiO2 1532 37 Example 10 Cr(II)/SiO2 3900 21 Reference V(mmh)3/AlEt2Al 3900 14 Reference TiCl4/MgCl2/AlEt2Al - 4 Reference Ti(OBu)4/MgCl2/AlEt2Al 8 Example 7B ZrCp2Cl2/MAO 400 <5 -* Y. Doi et al., "C13-NMR Chemical Shift of Regio-Irregular Polypropylene" Macromolecules 20 616-S20 (1987).
As these results show, the polypropylenes by chromium catalyst have much higher amounts of regio-irregularity than products by other catalysts.
These unique structure features are responsible for its better thermal stability as shown above.
The C3-C5 homo-polymer or co-polvmer with ethylene can be used as blending components with mineral oil or low viscosity synthetic lubricants to improve viscosities and VIs. The blending results with mineral oil or synthetic oil are summarized in Table 5 below. As these blending example show, products from Example 10 and 11 improve the oil viscosity and ~I.
The products of Examples 10 and 11 have low molecular weights, in the range of thousands and may therefore be ` expected to have much better shear stabilities than comparable polymers of higher molecular weight.
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~3~87 Table 5 Blending Results with oils Blendina Stock V~100C,mm2/s V. 40C.mm2/s VI
~ineral Oil4.19 21.32 97 10% Ex. 10 product 9.44 60.19 138 10% Ex. 11 product19.48 128.74 173 Synthetic oil5.61 28.94 136 10% Ex. 10 product10.70 67.09 149 10% Ex. 10 product16.93 108.34 170 5% Ex. 11 product 8.09 46.36 148 5% Ex. 11 product 10.50 58.56 170 Although the present invention has been dsscribed : with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considsred to be within the purview and scope of the appended claims.
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" C2-C5 OLEFIN OLIGOMERIZATION BY REDUCED CHROMIUM
CATALYSIS
This invention relates to a process for the oligomerization of a C2-C5 alpha-olefin feed and the olefin oligomers so produced. In particular, the invention relates to a process for the oligomerization of C3-C5 alpha-olefins or mixtures of C2-C5 alpha-olefins using reduced chromium oxide on a solid support as catalvst. The oligomer products, which may lo be either homo-oligomers of C3-C5 olefins or co-oligoemrs of C3-C5 clefins with ethylene, are useful as lubricants and lubricant additives, e.g. viscosity index improvers, of superior quality which exhibit high viscosity index and as chemical intermediates.
Efforts to improve upon the performance of natural mineral oil based lubricants by the synthesis of oligomeric hydrocarbon fluids have been the subject of important research and development in the petroleum ~` industry for at least fifty years and have led to the relatively recent market introduction of a number of superior polyalpha-olefin (PAO) synthetic lubricants, primarily based on the oligomerization of alpha-olefins or l-alkenes. In terms of lubricant property improvement, the thrust of the industrial research effort on synthetic lubricants has been toward fluids exhibiting useful viscosities over a wide range of temperature, i.e., improved viscosity index (VI), while also showing lubricity, thermal and oxidative stability and pour point equal to or better than mineral oil.
- 30 These new synthetic lubricants lower friction and hencs increase mechanical efficiency across the full spectrum of mechanical loads from worm gears to traction drives and do so over a wider range of operating conditions than mineral oil lu~ricants.
Catalysts that have been found useful in the prior art for the oligomerization of alpha-olefins to PAO
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~3~7 include Lewis acids and Ziegler catalysts. The products have been found to differ significantly in lubricant properties according to the catalyst used and the process economics arP also affected by ease of separation, corrosivity and other catalyst dependent process characteristics. Brennan, Ind. Eng. Chem. Prod.
Res. Dev. 1980, 19, 2-6, cites l-decene trimer as an example of a structure compatible with structures associated with superior low temperature fluidity wherein the concentration of atoms is very close to the center of a chain of carbon atoms. Also described therein is the apparent dependency of properties of the oligomer on the oligomerization process, i.e., cationic polymerization or Ziegler~type catalyst, known and practiced in the art.
~; A process using coordination catalysts to prepare high polymers from l-alkenes, especially chromium catalyst on a silica support, is described by Weiss et ~` al. in Jour. Catalysis 88, 424-430 (1984) and in Offen.
20 DE 3,427,319. The process and products therefrom are ; discussed in more detail hereinafter in comparison with the process and products of the instant invention.
~;~; Notwithstanding their generally superior properties, PAO lubricants are often formulated with additives to enhance those properties for specific - applications. The more commonly used additives include oxidation inhibitors, rust inhibitors, metal passivators, antiwear agents, extreme pressure additives, pour point depressants, detergent-dispersants, viscosity index (VIB) improvers, foam inhibitors and the like, as described, for . example, in Kirk-Othmer "Encyclopedia of Chemical Technology", 3rd edition, Vol. 14, pp. 477-526, to which reference is made for a description of such additives and their use. Significant improvements in lubricant technology have come from improvements in additives.
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2~687 Recently, high VI lubricant compositions (referred to herein as HVI-PAO and the HVI PAO process) comprising polyalpha-olefins and methods for their preparation employing as catalyst reduced chromium on a silica support have been disclosed in U.S. patents 4,827,064 and 4,827,073. The process comprises contacting C6-C20 1-alkene feedstock with reduced valence state chromium oxide catalyst on porous silica support under oligomerizing conditions in an oligomerization zone whereby high visco~ity, high VI
liquid hydrocarbon lubricant is produced having branch ratios less than 0.19 and pour point below -15C. The process is distinctive in that little isomerization of the olefinic bond occurs compared to known oligomerization methods to produce polyalpha-olefins using Lewis acid catalyst. Lubricants produced by the process cover the full range of lubricant viscosities and exhibit a remarkably high viscosity index (VI) and ``` low pour point even at high viscosity. The as-synthesized HVI-PAO oligomer Aas a preponderance of terminal olefinic unsaturation.
Considering the abundance of C2 to C5 alpha-olefins in the petroleum refinery, and their low cost, it has long been recognized that they could be a preferred source of low cost lubricant if they could be oligomeri~ed to provide high viscosity index lubricant : in good yield with a manageable, regenerable, non-corrosive catalyst. The olefin oligomers produced by the present process are characterised by a unique structure which confers particularly useful properties on the products. In conventional Ziegler oligomerization of alpha olefins the oligomers produced contain a high degree of structural regularity, or regio-regularity, as exhibited by a preponderance of head-to-tail bonding in the oligomerization of these alpha olefins. In the products from Ziegler catalyzed oligomerization not more than twenty percent of the `, ' ' '``:
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F-5313 - 4 - ~3~7 repeating units are linked by regular head-to-head and tail-to-tail bonding. In the olefin oligomers produced from the reduced metal oxide catalysts, however, at least twenty percent of the repeating units are bonded - 5 by irregular or head-to head or tail-to-tail connections. These C3-C5 alpha-olefin oligomers therefore have a regio-irregularity of at least twenty percent, usually from 20 to 40 percent, and in most cases, not more than 60 percent (where 100%
regio-regularity corresponds with all head-to-tail connections for the recurring oligomeric units). Thus, in most cases, from 60 to 80 percent of the the recurring connections in the oligomer are linked by regular head-to-tail bonding.
1~ According to the present invention, olefin oligomers produced from C3-C5 olefins, either alone or with co-oligomerized ethylene units, have a regio~irregularity of at least 20, and usually from 20 - to 40 percent.
o The oligomers can be produced by contacting C3-C5 alpha-olefins or a mixtura of C2 to C5 alpha-olefins with a reduced metal oxide catalyst, preferably a reduced chromium oxide on a solid, porous support. The -~ catalyst is usually produced by oxidation at a temperature of 200C to 900C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the oxide of the metal to a lower valence state.
The olefin oligomers are characteristically liquids having a viscosity measured at 100C of lO,OOOmm2/s (cS) useful as lubricant basestock or used as VI
improvers. The oligomers may be hydrogenated to produce a saturated hydrocarbon product.
The process of the present invention comprises the steps of: contacting C3-C5 alpha-olPfins or a mixture f C2 to C5 alpha-olefins with chromium catalyst on a solid support, which catalyst has been treated by .:
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F-5313 - 5 - ~?~J l~L'~
oxidation at a temperature of 200 to 900C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the catalyst. The contacting takes place under conditions sufficient to produce liquid olefin oligomers having a viscosity measured at 100C of lO,OOOmm /s (cS) useful as lubricant basestock or used as VI improvers. The oligomers are hydrogenated to produce a saturated hydrocarbon.
Propylena, l-butene or l-pentene can, individually, be oligomerized in a similar manner and the olefin oligomers are separated by distillation to recover a gasoline boiling range overhead fraction, a distillate boiling range overhead fraction, and a lube boiling range bottoms fraction.
The present process provides excellent yields of a saturated hydrocarbon lubricant fraction from the oligomerization of C3-C5 alpha-olefins or a mixture of C2 to C5 alpha-olefins. The oligomerization of ethene, propylene or 1-butene or l-pentene to produce the lubricant fraction results in a product particularly distinguished by a high viscosity index representative of superior lubricant properties. The lighter oligomer or hydrocarbon fraction separated from the oligomerization mixture is useful as gasoline or distillate product.
The oligomer products containing unsaturated doub~e bonds are suitable as chemical intermediates for further functionalization, e.g., reaction with maleic anhydride to form adducts which can be used as intermediates for the production of lubricant additives.
In the following description, unless otherwise stated, all references to properties of oligomers or lubricants of the present invention refer as well to hydrogenated oligomers and lubricants wherein hydrogenation of the oligomer product is carried out as ' :-, ~
F-5313 - 6 - ~ 7 will usually be preferred in order to reduce residual unsaturation.
The C3-C5 alpha olefin oligomers and the oligomers of C3-C5 alpha olefins with ethylene are unique in their structure compared with conventional - polyalphaolefins (PA0) from l-decene, for example.
. Polymerization with the reduced metal, e.g. chromium, catalyst described hereinafter leads to an oligomer substantially free of double bond isomerization.
Conventional PAO, on the other hand, promoted by BF3 or Al c13 forms a carbonium ion which,in turn, promotes isomerization of the olefinic bond and the formation of multiple isomers. The HVI PAO produced in the referenced invention has a structure with a CH3/CHH2 15 ratio <0.19 compared to a ratio of >0.20 for PAO.
The c2-C5 feedstocks used in the present invention are particularly inexpensive and common materials found - in the petroleum refinery complex. Readily available sources include fluid catalytic cracker operation; in particul~r, the product of FCC unsaturated gas plant.
The olefins are also available from the various steam cracking processes, e.g., light naphtha or liquified petroleum gas (LPG).
The mixtures of propylene, l-butene or l-pentene and ethylene can be used in a molar ratio from 100:1 to 1:1 (C3-C5:C2), with a preferred molar ratio from about 20 to 1.
In the oligomerization of propylene, l-butene or l-pentene, the alpha-olefin can be used either in pure form or diluted with ethylene or other inert materials for production of the oligomers. The liquid products, after hydrogenation to remove unsaturation have higher viscosity indices than similar alpha-olefins oligomerized by conventional acid catalysts such as aluminum chloride or boron trifluoride. To produce the low molecular weight liquid products suitable for use as lube basestock or as blending stock with other lube "
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stock, the oligomerization is carried out at a temperature higher (90-250C) than the temperature suitable to produce higher molecular weight polyalpha-olefins but when ethylene is used as a co-monomer, lower temperatures may be used, for example, down to about 0c, so that the temperature -~ range for for the production of the ethylene-- containing oligomers is typically from 0 to about 250C.
The present alpha-olefin oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alphaolefins are not isomerized. These reactions include alpha-olefin ~ oliqomerization by supported metal oxide catalysts, ,15 such as Cr compounds on silica or other supported IUPAC
Periodic Table Group VIB compounds. The catalyst most preferred is a lower valence Group VIB metal oxide on an inert support. Preferred supports include silica, `alumina, titania, silica alumina, magnesia and the like. The support material binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 x lO 7mm are preferred.
The support material usually has high surface area and large pore volumes with average pore si~e of 25 40 to 350 x lO 7mm (40 to 350 angstroms). The high surface area is beneficial for supporting large amount of highly dispersive, active chromium metal centers and to give maximum efficiency of metal usage, resulting in very high activity catalyst. The support should have 30 large average pore openings of at least 40 x lO 7mm (40 angstroms), with an average pore opening of >60 to 300 x lO 7mm (>60 to 300 angstroms) preferred. This large pore opening will not impose any diffusional restriction of the reactant and product to and away from the active catalytic metal centers, thus further optimizing the catalyst productivity. Also, for this catalyst to be used in fixed bed or slurry reactor and .. ,, ~, , ,.,.. " .... ; , : ~3~68~
~ to be recycled and regenerated many times, a porous - support with good physical strength is preferred to prevent catalyst particle attrition or disintegration during handling or reaction.
The supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for ` example, ethanol, methanol, or acetic acid. The solid catalyst precursor is then dried and calcined at 200 to 900C by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, CO, H2, NH3, H2S, CS2, CH3SCH3, CH3SSCH3,metal alkyl containing compounds such as ~3Al, R3B,R2Mg, RLi, R2Zn, where R is alkyl, alkoxy, aryl and the like. Preferred are CO or H2 or metal alkyl containing compounds.
Alternatively, the Group VIB metal may be applied to the substrate in reduced form, such as CrII
compounds. The resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature, e.g. 0C, to about 250C at a pressure of lO to 34600 kPa (O.l atmosphere to 5000 psi). Contact time of both the olefin and the catalyst can vary from one second to 24 hours. The catalyst can be used in a batch type reactor, a continuous stirred tank reactor or in a fixed bed, continuous-flow reactor.
In general the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is then mixed and dried at room temperature. The dry solid gel is purged at successively higher temperatures to about 600C for a period of about 16 to 20 hours. Thereafter the catalyst is cooled under an inert atmosphere to a temperature of about 250 to 450C and a stream of pure reducing agent, such as C0, is contacted therewith. When sufficient CO
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has passed through to reduce the catalyst there is a distinct color change from bright orange to pale blue.
Typically, the catalyst is treated with an amount of C0 equivalent to a two-~old stoichiometric excess to reduce the catalyst to a lower valence CrII state.
Finally the catalyst is cooled to room temperature and is ready for use.
As referenced hereinbefore, the use of supported Cr metal oxide in different oxidation states to polymerize alpha olefins from C3 to C20 (DE 3427319 to H. L. Krauss and Journal of Catalysis 88, 424-430, 1984) using a catalyst prepared by CrO3 on silicais known. The referenced disclosures teach that polymerization takes place at low temperature, usually less than 100C, to give adhesive polymers and that at high temperature, the catalyst promotes isomerization, cracking and hydrogen transfer reactions. The present process produces liquid, low molecular weight oligomeric products using reaction conditions and catalysts which minimize side reactions such as l-olefin isomerization, cracking, hydrogen transfer and aromatization. The reduced metal oxide catalysts do not cause a significant amount of side reactions even at the higher temperaturesat which oligomeric, low molecular weight fluids are produced. These catalysts therefore minimize side reactions but oligomerize olefins to give low molecular weight polymers with high efficiency. Although the exact nature of the supported Cr oxide is difficult to determine, it is thought that the catalyst of the present invention is rich in Cr(II) supported on silica, which is more active to catalyze alpha-olefin oligomerization at high reaction temperature without causing significant amounts of isomerization, cracking or hydrogenation reactisns.
However, the catalysts described the cited references can be richer in Cr (III) and they catalyze alpha-olefin polymerization at low reaction temperature ,, :' :
' - F-5313 - lo - ~ 7 to produce high molecular weight polymers and at higher temperatures undesirable isomerization, cracking and hydrogenation reaction takes place.
: The catalysts for this invention thus minimize all side reactions but oligomerize olefins to give low ~ molecular weight polymers with high efficiency. It is well known in the prior art ~hat chromium oxides, especially chromia with average +3 oxidation states, either pure or supported, catalyze double bond lo isomerization, dehydrogenation, cracking, etc.
However, catalysts as prepared in the cited references can be richer in Cr (III). They catalyze alpha-olefin polymerization at low reaction temperature to produce high molecular weight polymers. However, as the references teach, undesirable isomerization, cracking and hydrogenation reaction takes place at higher temperatures. In contrast, high temperatures are needed in this invention to produce lubricant products.
The prior art also teaches that supported Cr catalysts rich in Cr(III) or higher oxidation states catalyze l-butene isomerization with 103 higher activity than polymerization of l-butene. The quality of the catalyst, method of preparation, treatments and reaction conditions are critical to the catalyst performance and composition of the product produced and distinguish the present invention over the prior art.
In the instant invention very low catalyst concentrations based on feed, from 10 wt~ to 0.01 wt%, are used to produce oligomers; whereas, in the cited references catalyst ratios based on feed of 1:1 are used to prepare high polymer. Resorting to lower catalyst concentrations in the present invsntion to produce lower molecular weight material runs counter to conventional polymerization theory, compared to the results in the cited references.
The oligomers of 1-olefins of this invention usually have much lower molecular weights than the ~ .
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:. 2 ~ 3 l~ 7 polymers produced in cited reference which are semi-solids, with very high molecular weights and are - not suitable as lubricant basestocks. These high polymers usually have no detectable amount of dimer or trimmer (C10-C30) components from synthesis. These high polymers also have very low unsaturations.
However, products in this invention are free-flowing liquids at room temperature, suitable for use as lube basestock and additives, e.g. VI improvers.
Ethylene and C3-C5 alpha-olefins are abundant and cheap raw materials. According to the present invention, C3-C5 alpha-olefins or mixed C2-C5 alpha-olefins, either in dilute form or in pure form can be upgraded into a wide range of hydrocarbon products. The high boiling components can be used as high quality lubricants with high viscosity index. The low boiling components can be used as gasoline, distillate or starting material for syn~hetic detergents, additives to fuel, lubricants or plastics.
The catalyst for the conversion is a supported metal oxide such as group VIB and group VIIIB oxides on silica catalyst. The mixtures of propylene, l-butene or 1-pentene and ethylene can be used in a molar ratio from 100 to l to 1 to 1, with a preferred molar ratio _5 of 20 to 1.
The use of activated supported metal oxide catalyst to produce a wide range of hydrocarbons from C2-C5 alpha-olefin mixtures is unique. The lube fraction of the hydrocarbons have high viscosity indic~s. The catalyst employed in the present invention is a solid catalyst and is significantly easier to handle than conventional Ziegler catalyst and other solution catalyst. The by-products with low boiling points have carbon numbers from C5 to C30.
These by-products have unsaturated olefin double bonds and can be used as starting materials for synthesis of ` ~-5313 12 -2 ~ 8 7 detergents, fuel or lube additives. The catalyst used are non-corrosive and are regenerable.
- In the oligomerization of propylene, l-butene or l-pentene, the alpha-olefin can be used either in pure , form or in diluted form for upgrading into gasoline : distillate and lube products over solid coordination catalyst. The fuel range products are high quality fuel with low sulfur and aromatic contents. The lube products, after hydrogenation to remove unsaturation have higher viscosity indices than such alpha-olefins oligomerized by conventional acid catalysts such as aluminum chloride or boron tri-fluoride.
In the present invention, lube compositions from the oligomerization of C2-C5 alpha-olefin mixtu~es or C3-C5 alpha-olefins can be produced with viscosities betw~en 3mm /s and 5000mm /s measured at lO0C.
It has been found that the products of the instant invention exhibit a very unique structure that confers upon the products the properties of novel compositions.
In conventional Ziegler oligomerization of alpha olefins it is well known in the art that the oligomers produced contain a high degree of structural reqularity, or regio-regularity, as exhibited by a preponderance of head-to-tail bonding in the oligomerization of these alpha olefins. In the products from Ziegler catalyzed oligomerization not more than twenty percent of the repeating units are linked by head-to-head and tail-to-tail bonding. In . the present invention it has been found that at least forty percent of the repeating units are bonded by head-to-head or tail-to-tail connections. The C3-C5 alpha-olefin oligomers of the present invention contain not more than 60% regio-regularity, where 100%
regio-regularity corresponds with all head-to-tail connections for the recurring oligomeric unit.
In Table l the results of the spectroscopic determination of the regio-regularity of the products :,.
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, 5~ 7 of the present invention are presented (nos. 3-5) as well as the results fxom the products of 1-decene and 1-hexene oligomerization. The C-13 NMR spectra and the INEPT (Insensitive Nuclei Enhancement by Polarization Transfer) spectra of four products prepared from Cr/SiO2 catalyzed HVI-PAO oligomerization process reactions of l-decene, 1-hexene, l-butene and propene are presented. For each oligomer, the chemical shifts of the methylene and methine carbons of the backbone are calculated and assigned based on different combinations of regio-irregularity. From the 2/4J
INEPT spectrum which selectively detects only the methine carbons, the amount of regio-regularity of each oligomer is estimated. Entries 1-4 compare four different alpha-olefins as the starting material. The results indicate that the oligomers from the higher olefins are formed in a more regio-regular fashion than the lower olefins.
Table 1 StartingViscosity @
No. Olefin 100C,cS %Reqio-Reaularity 1 l-decene 145.0 >58 2 1-hexene 92.8 -51 25 3 1-butene 103.7 -48 4 propene 95.3 -41 1-butene 2.8 ~38 In the following examples the process of the present invention are illustratPd. In the invention, propylene and mixtures of ethylene and propylene are oligomerized using reduced chromium oxide on a silica support as catalyst. The catalyst is prepared following the procedure described in the preceding examples.
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~3~687 Example 1 Catalyst Preparation and Activation Procedure 1.9 grams of chromium (II) acetate (Cr2(0COCH3)42H20)(5.58 mmole) (commercially obtained) is dissolved in 50 ml of hot acetic acid. Then 50 grams of a silica gel of 8-12 mesh size, a surface area of 300 m2/g, and a pore volume of 1 ml/g, also is added. Most of the solution is absorbed by the silica gel. The final mixture is mixed for half an hour on a rotavap at room temperature and dried in an open-dish at room temperature. First, the dry solid (20 g) is purged with N2 at 250C in a tube furnace. The furnace temperature is then raised to 400C for 2 hours. The temperature is then set at 600C with dry air purging for 16 hours. At this time the catalyst is cooled under N2 to a temperature o 300C~ Then a stream of pure co (99.99% from Matheson) is introduced for one hour. Finally, the catalyst is cooled to room temperature under N2 and ready for use.
Example 2 A Cr/SiO2 catalyst was prepared as described in Example 1.
~` 3 gram of the activated Cr/SiO2 catalyst was packed in a fixed bed down flow reactor of 9.5 mm inside diameter (3/8" id). Propylene of 5 gram per hour was reacted over the catalyst bed heated to 180-19OC and at 1620 kPa (220 psig). After 16 hours, 56.2 gram of liquid product and 24.9 gram of gas were collected. The gas product analyzed by gc contained 95% propylene. The liquid product had the following compositions:
C6 Cg C12 C15 C18 C21 C24 C27 C30+
wt% 10.6 11.2 8.~ 7.4 3.3 3.9 2.9 3.9 48.3 The products from C6 to C12, after hydrogenation, can be used as gasoline components. The products from .
., :
, , " ; ';' , 6~3 ~
C12 to C24 can be used as distillate components. The unhydrogenated lube product, most C27 and higher hydrocarbons and isolated after distillation at 180 C/13.3 kPa (O.lmm Hg), have a viscosity at 100C of 28.53 cS and VI of 78. The unhydrogenated lube product had higher VI than the same viscosity oil produced from propylene by AlC13 or BF3 catalyst, as summarized below.
Unhydrogenated 10 Catalyst lube yieldV@100C,mm2/s VI
AlC13/Hcl 87 29.96 38 BF3H20 23 7.07 46 The unhydrogenated lube product from Cr/SiO2 catalyst has simpler C13-NMR spectrum than lube by acid catalyst.
Example 3 The procedure of Example 2 was followed, except that the reaction was run at 170C and 2170-2860 kPa (300-400 psig). After 14 hours reaction, 47.5 grams ~0 liquid and 18.4 g gas (mostly propylene) were collectedO The liquid product had the following composition, analyzed by gc:
6 Cg C12 C15 to C20 C20 to C30 C30+
4.51 5.53 5.01 12.22 5.30 67.43 The unhydrogenated lube fraction after distillation to remove light end at 160C/13.3 kPa (O.lmm Hg), had viscosity at 100C of 39.85 and VI of 81.
Example 4 A Cr/SiO2 catalyst was prepared as in Example 1.
To a tubular reactor packed with three grams of 1~
Cr on silica catalyst, propylene of 5 g/hr and ethylene 1.13 g/hr (~olar ratio of C3/C2 = 3) were fed through at 190C and 1480-2172 kPa (200-300 psig). The liquid , ~ ~;3 ~
product weighed 68 grams, after 15 hours on stream.
This once-through liquid yield was 75%. The gas contained ethylene and propylene which can be recycled.
The liquid product was centrifuged to remove thP small amount of solid particles. The clear liquid was fractionated to give 50~ light fraction boiling below 145C at 1.33 kPa (0.01 m~Hg) and 50% unhydrogenated lube product. The unhydrogenated lube product had V~100 (viscosity at 100C) = 46.03 m~l/s (cS), V~40 lO (viscosity at 40C) = 703.25 mm2/s (cS) and VI = 112.
The light fractions are unsaturated olefinic hydrocarbons with six to 25 carbons. The IR showed tha presence of internal and vinylidene double bonds.
These olefins can be used as starting material for - 15 synthesis of other value-added products, such as detergents, additives for lube or fuel. These light - fractions can also be used as gasoline or distillates.
This example demonstrates that one can produce lube with high VI from ethylene and propylene mixture over an activated Cr on silica catalyst. The light product can be useful as chemicals or fuel.
ExamPle 5 The run in Example 2 was continued for another 23 hours and 78 grams liquid product was collected. The once-through liquid yield was 54%. This liquid product was centrifuged to remove the solid precipitate. The clear product was fractionated to give 35% light liquid boiling below 145C at 13.3 kPa (0.1 mmHg) and 65%
viscous unhydrogenated lube product. The unhydrogenated lube product had V@100 = 72.40 mmZ/s (cS), V@40 = 980.73 mm2/s (cS) and VI = 144.
Example 6 The reactor, propylene and ethylene feed rates ~ 35 were the same as in Example 4. In addition, n-octane was fed through the reactor at 10 ml~hr as solvent at 185C. After 17 hours on stream, 228 grams of liquid ~ ,~
'- ; ` "~ ` ~ ~ . ' F-5313 - 17 - 2~ 3 ~ ~ 8 ~
product was collected. Material balance indicated that all ethylene and propylene was converted into liquid product. The liquid, after filtering off trace solid, was fractionated to give four fractions:
Fraction 1, boiling below 130C, 118g, mostly n-octane solvent;
Fraction 2, up to 123 C/l. 33 kPa (O.ol mmHg), 32g.;
Fraction 3, up to 170C/1.33 kPa (0.01 mmHg), 27g;
and Fraction 4, residual product, 40 g.
Fraction 4 has the following viscometric properties:
V~lO0 = 30.99 mm2/s (cS), V@40 = 343.44 mm2/s (cS), VI
15 = 126.
This Example demonstrates that the presence of an inert solvent is advantageous to produce lower viscosity lube. The presence of an inert solvent also prevents the reactor from plugging by trace solid formation~
Example 7.
This Example illustrates the preparation of polypropylene liquid product using both a reduced metal catalyst (Ex. 7) and a Ziegler catalyst (Ex. 7B).
Example 7A
An activated chromium on silica catalyst (15 grams) and purified n-decane (400 ml) were charged into an one-liter autoclave with stirring under nitrogen atmosphere. When the autoclave temperature reached 30 160C, liquid propylene was fed at 50 ml/hr until 375 ml was charged into the reactor. After 16 hours at 160RC, the slurry product was discharged, filtered to remove solid catalyst and distilled up to 120C at 13.3 kPa (0.1 mmHg) vacuum to remove light ends. The " 35 product yields and properties are summarized in Table 2.
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` F-5313 - 18 -- G2 ~ ; 6 8 7 Example 7B
Preparation of polypropylene liquid product by Ziegler catalyst, ZrCp2Cl2/MAO.
A solution catalyst containing 0.17 mmole zirconocene dichloride and 88 mmole methylaluminoxane in lS0 ml toluene was add to an one-liter autoclave at 25C. Propylene was then added at 50 ml/hr until 375 ~ ml was charged into the reactor. After 16 hours, the catalyst components were deactivated by adding l ml water. The liquid product was isolated by drying and filtration to remove solid components. The lube product was isolated as in Example 7A. The product yields and properties are summarized in Table 2 below.
The polymer structures produced by the use of the chromium catalyst are uniquely irregular. The C13 NMR
spectra of these two examples indicated that the chromium product of Example 7A is much~less regular than the Ziegler product of Example 7B. The amount of this regio-irregularity can be determined by the C-13 2/4J INEPT (Insensitive Nuclei Enhancement by Polarization Transfer) NMR technique. The INEPT
spectra of the products of Examples 7A and 7B showed the different types of the methine carbons in the backbones of chromium product and the Ziegler productO
The data in Table 2 show that the chromium product had better thermal stability than the regular Ziegler ~` product, when cracked at 280C under nitrogen atmosphere for 24 hours.
Example 8 Preparation of poly l-butene liquid products, using a reduced metal catalyst (Ex. 8A) and a Ziegler catalyst (Ex. 8B).
Example 8A
Poly-l-butene was produced in a continuous, down-flow fixed bed reactor. The reactor was constructed of 9.5 min outside diameter (3/8" o.d.) /
..
. . .
F-5313 - 19 - ~ 3 ~ 6 8 7 stainless steel tube. The ~ottom of the reactor contained 18 grams of clean 14/20 mesh quartz chips, supported on a coarse frit of 6 mm diameter. Three gram activated chromium catalyst was charged into the tube. The top of the reactor tube was packed with quartz chips to serve as a feed preheater. The reactor tube was wrapped with a heat-conducting jacket. The reactor temperature, 125C, was measured and controlled with a thermocouple located at the middle oE the jacket. l-Butene liquid was pumped through a 50 ml Hoke bomb packed with Deox and 13X molecular sieve of equal volume to remove oxygenates and water contaminants. l-Butene was fed into the reactor from the top. Reactor pressure, 2310 kPa (320 psig), was lS controlled by a grove-loader at the reactor outlet.
The effluent was collected at the reactor bottom and the lube product was isolated by distillation up to 140~C at 13.3 kPa (0.1 mmHg) vacuum. The product properties are summarized in Table 2.
20Example 8B.
Preparation of poly-1-butene liquid product by Ziegler catalyst, ZrCp2C12/MAO
The product was prepared as in Example 7B, except l-butene was used as feed. The product yield and properties are summarized in Table 2.
The C13 NMR spectra of the two products of Examples 8A and 8B show that the chromium product of Example 8A is much less regular than the Ziegler product of Example 8B a~ well, by comparison with spectra reported in the literature for Ziegler polymers. The data in Table 2 show that the chromium product of Example 8A had better thermal stability than the regular Ziegler product of Example 8B, when cracked at 280C under nitrogen atmosphere for 24 hours.
Example 9~
Preparation of ethylene/propylene copolymer, using a reduced metal catalyst and a Ziegler catalyst.
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F-5313 - 20 - 2~3~687 Example 9A
As Example 7A, except gaseous ethylene (25.2 g/hr) andpropylene (25 g/hr) were fed simultaneously into the autoclave at 185C. The product yield and properties : 5 are summarized in Table 2~
; Example 9B
.- Preparation of ethylene/propylene copolymer liquid product by Ziegler catalyst, ZrCp2C12/MAO
As Example 7B, except ethylene (25.2 g/hr) and propylene (25 g/hr) were fed simultaneously into the autoclave at 60~C.
The product yield and properties are summarized in Table 2. The C13 NMR spectra of the products indicated that the chromium product of Example 9A is much less regular than the Ziegler product of Example 9B.
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Example 10 A polypropylene liquid product was prepared using a reduced metal catalyst, in a similar manner to Example 7A, except th~ autoclave was heated to 800C.
The product yield and properties are summarized in Table 3 below.
Example 11.
An ethylene/propylene copolymer liquid was prepared as dezxcribed in Example 10, except ethylene (16.7 g/hr) and propylene (25g/hr~ were fed simultaneously into the autoclave at 95C. The product yield and properties are summarized in Table 3.
Table 3.
Product Yields and Properties of Example 10 and 11 Example 10 Example 11 Catalyst Cr/SiO2 Cr/SiO2 Feed C3= C2=/C3=
Yield - -Product properties MWn 3900 4880 MWD 2.74 2.85 The estimated amounts of regio-irregularity of these products together with the reported data from the products obtained by Ziegler catalysts are summarized in Table 4.
: ` :
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F--5313 -- 23 - ~3~6~;37 Table 4 Product Re~io-Irregularity Sample Catalyst MWn Mole~
of irregular propylene Example 7A Cr(II)/SiO2 1532 37 Example 10 Cr(II)/SiO2 3900 21 Reference V(mmh)3/AlEt2Al 3900 14 Reference TiCl4/MgCl2/AlEt2Al - 4 Reference Ti(OBu)4/MgCl2/AlEt2Al 8 Example 7B ZrCp2Cl2/MAO 400 <5 -* Y. Doi et al., "C13-NMR Chemical Shift of Regio-Irregular Polypropylene" Macromolecules 20 616-S20 (1987).
As these results show, the polypropylenes by chromium catalyst have much higher amounts of regio-irregularity than products by other catalysts.
These unique structure features are responsible for its better thermal stability as shown above.
The C3-C5 homo-polymer or co-polvmer with ethylene can be used as blending components with mineral oil or low viscosity synthetic lubricants to improve viscosities and VIs. The blending results with mineral oil or synthetic oil are summarized in Table 5 below. As these blending example show, products from Example 10 and 11 improve the oil viscosity and ~I.
The products of Examples 10 and 11 have low molecular weights, in the range of thousands and may therefore be ` expected to have much better shear stabilities than comparable polymers of higher molecular weight.
~ ~.
~3~87 Table 5 Blending Results with oils Blendina Stock V~100C,mm2/s V. 40C.mm2/s VI
~ineral Oil4.19 21.32 97 10% Ex. 10 product 9.44 60.19 138 10% Ex. 11 product19.48 128.74 173 Synthetic oil5.61 28.94 136 10% Ex. 10 product10.70 67.09 149 10% Ex. 10 product16.93 108.34 170 5% Ex. 11 product 8.09 46.36 148 5% Ex. 11 product 10.50 58.56 170 Although the present invention has been dsscribed : with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considsred to be within the purview and scope of the appended claims.
~.
.
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Claims (28)
1. A process for the preparation of liquid hydrocarbons suitable as lubricant basestocks from a mixture of C2-C5 alpha-olefins, comprising:
contacting the mixture under oligomerization conditions, at reaction temperature of 0 to 250°C
and at a pressure from 10 to 34600 kPa with a chromium catalyst on a porous support, which catalyst has been treated by oxidation at a temperature of 200 to 900°C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the chromium of the catalyst to a lower valence state, whereby liquid olefin oligomers are produced.
contacting the mixture under oligomerization conditions, at reaction temperature of 0 to 250°C
and at a pressure from 10 to 34600 kPa with a chromium catalyst on a porous support, which catalyst has been treated by oxidation at a temperature of 200 to 900°C in the presence of an oxidizing gas and then by treatment with a reducing agent at a temperature and for a time sufficient to reduce the chromium of the catalyst to a lower valence state, whereby liquid olefin oligomers are produced.
2. The process of claim 1 wherein the liquid olefin oligomers ars distilled under conditions sufficient to recovre a gasoline boiling range overhead fraction, a distillate boiling range overhead fraction, and a lube boiling range bottoms fraction.
3. The process of claim 1 containing the further step of hydrogenating the liquid olefin oligomers, or a fraction thereof, under conditions sufficient to convert the olefin oligomers or the fraction into saturated hydrocarbons.
4. The process of claim 1 or 2 wherein the mixture of alpha-olefins consists essentially of propylene and ethylene present in a molar ratio of propylene to ethylene of between 10 and 1.
5. The process of any one of the preceding claims wherein the reaction temperature is between 90-250°C.
6. The process of any one of the preceding claims wherein the lubricant basestock has a viscosity between 3 and 5000mm2/s, measured at 100 ° C.
7. The process of any one of the preceding claims wherein the liquid hydrocarbons contain a light olefinic hydrocarbon fraction containing between about 6 and 25 carbon atoms useful as gasoline and distillate fuels.
8. The process according to one of the preceding claims wherein the oligomerization conditions further comprise addition of inert solvent whereby low viscosity lubricant basestock is produced having a high viscosity index.
9. The process according to one of the preceding claims wherein the inert solvent comprises C6-C12 saturated hydrocarbons.
10. The process of any one of the preceding claims wherein the reducing agent comprises carbon monoxide, oligomerization temperature is 100-200°C, pressure is between 790 abd 2170 kPa, and the yield of lube product having a viscosity at 100°C greater than 35mm2/s is greater than 35%.
11. The process of any one of the preceding claims wherein the porous support comprises silica.
12. The process of any one of the preceding claims wherein the mixture is contacted in a fixed bed reactor or a continuous stir tank reactor.
13. The process of claim 2 comprising the further step of hydrogenating the liquid olefin oligomers.
14. The process of any one of the preceding claims wherein the liquid oligomers contain at least 40 wt. percent C30+ lubricant range oligomers.
15. The process of claim 2 wherein the contacting is conducted at a temperature of 135°C
at a pressure of 520 kPa and the bottoms fraction has a viscosity at 100°C of at least 90mm2/s and viscosity index of at least 80.
at a pressure of 520 kPa and the bottoms fraction has a viscosity at 100°C of at least 90mm2/s and viscosity index of at least 80.
16. The process of claim 1 or 2 wherein the alpha-olefin comprises propene or l-butene.
17. A liquid composition comprising the product of the oligomerization of a C3 to C5 alpha-olefin, mixtures of C3 to C5 l-olefins or mixtures of C3 to C5 l-olefins with ethylene, under oligomerization conditions in contact with an oliogmerization catalyst comprising a reduced valence state Group VIB metal catalyst on a porous support, the product having a regio-irregularity of at least 20 percent.
18. A liquid composition according to claim 17 in which the regio-irregularity is from 20 to 60 percent.
19. A liquid composition according to claim 17 or 18 in which the l-olefin comprises l-propylene or l-butene or l-pentrene.
20. A liquid composition according to claim 17 in which the liquid is the product of oligomerization of at least one C3 to C5 1-olefin with ethylene.
21. A liquid composition according to claim 20 in which the l-olefin comprises 1-propylene and the molar ratio of propylene to ethylene is from 10:1 to 1:1.
22. A liquid composition according to claim 17 in which the liquid is the product of oligomerization of at least one C3 to C5 l-olefin produced at an oligomerization temperature from 90° to 250°C.
23. A liquid composition according to claim 17 in which the liquid is the product of oligomerization of at least one C3 to C5 1-olefin with ethylene produced at an oligomerization temperature from 0° to 250°C.
24. A liquid composition according to claim 17 which has a viscosity between 3mm2/s and 5000mm2/s, measured at 100°C.
25. A liquid composition according to claim 17 which has been hydrogenated after formation of the olefin oligomer.
26. A liquid composition according to claim 17 in which the liquid oligomer product comprises at least 40 wt. percent C30+ lubricant range oligomers.
27. A liquid composition according to claim 17 in which the catalyst comprises reduced chromium metal oxide on a porous support.
28. A liquid composition according to claim 27 in which the support comprises silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002034687A CA2034687A1 (en) | 1989-04-28 | 1991-01-22 | C2-c5 olefin oligomerization by reduced chromium catalysis |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/345,061 US4990709A (en) | 1989-04-28 | 1989-04-28 | C2-C5 olefin oligomerization by reduced chromium catalysis |
| CA002034687A CA2034687A1 (en) | 1989-04-28 | 1991-01-22 | C2-c5 olefin oligomerization by reduced chromium catalysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2034687A1 true CA2034687A1 (en) | 1992-07-23 |
Family
ID=25674451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002034687A Abandoned CA2034687A1 (en) | 1989-04-28 | 1991-01-22 | C2-c5 olefin oligomerization by reduced chromium catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2034687A1 (en) |
-
1991
- 1991-01-22 CA CA002034687A patent/CA2034687A1/en not_active Abandoned
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