EP0376637B1 - Procédé de préparation au lubrifiants polyoléfiniques à partir de résidus de craquage thermique contenant du soufre - Google Patents

Procédé de préparation au lubrifiants polyoléfiniques à partir de résidus de craquage thermique contenant du soufre Download PDF

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EP0376637B1
EP0376637B1 EP19890313478 EP89313478A EP0376637B1 EP 0376637 B1 EP0376637 B1 EP 0376637B1 EP 19890313478 EP19890313478 EP 19890313478 EP 89313478 A EP89313478 A EP 89313478A EP 0376637 B1 EP0376637 B1 EP 0376637B1
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olefins
olefin
sulfur
components
separation
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EP0376637A1 (fr
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Frank Joung-Yei Chen
Ramon Luis Espino
Alexis Alexander Oswald
Kuo Liang Peng
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms

Definitions

  • the present invention relates to a multistep process for the conversion of the olefinic components of thermally cracked petroleum residua to paraffin products useful as synthetic lubricants.
  • the present invention provides a multistep process for the manufacture of polyolefin lubricants, derived mostly from C8 to C24 linear olefin components of coker distillate fractions containing more than 0.1 wt.% sulfur which are produced by the high temperature thermal cracking of petroleum residua, comprising the following three steps:
  • the enrichment of the coker distillate in 1-n-olefins and n-paraffins may include either their separation as urea adducts or the crystallization of these components.
  • the oligomerization of C8 to C24 olefin components of an enriched coker distillate fraction may be carried out in the presence of a cationic catalyst.
  • the hydrogenation of the sulfur-containing polyolefins may be carried out in the presence of transition metal sulfide catalysts.
  • the oligomerization of the C8 to C24 olefin components of an enriched coker distillate fraction may be effected in the presence of a Friedel-Crafts catalyst.
  • the oligomerization of the C8 to C24 olefin components may be carried out in the presence of a BF3 complex catalyst.
  • the preferred feed is produced by the high temperature thermal cracking of vacuum resids, particularly by Fluid-coking and Flexicoking.
  • the distillate products of these processes contain high percentages of the desired linear olefin reactants. Due to the presence of relatively high amounts of sulfur these distillates are below liquid fuel value.
  • One feature of the process of the invention is the types of compounds produced by the thermal cracking of petroleum resids.
  • the desired 1-n-olefin and linear internal olefin components of light gas oil distillates derived by cracking vacuum resids in fluidized bed processes, have been particularly investigated. They were found to be characterized by a combination of high resolution capillary gas chromatography (GC), mass spectrometry (MS) and nuclear magnetic resonance spectroscopy (NMR).
  • GC capillary gas chromatography
  • MS mass spectrometry
  • NMR nuclear magnetic resonance spectroscopy
  • Another feature of the process of the invention is the separation of the desired linear olefin components of cracked petroleum distillates.
  • the separation via urea adduction and by crystallization of mixtures of 1-n-olefins and n-paraffins is particularly taught herein.
  • Appropriate carbon range fractions of such mixtures can be used as a feed for oligomerization reactions without prior paraffin separation.
  • Extraction of the coker distillate feed can be used for the removal of the aromatic components, including most of the sulfur compounds.
  • Membrane separation can result in an aliphatic and an aromatic hydrocarbon rich fraction.
  • a key aspect of the invention is the oligomerization of the linear olefin mixtures derived from cracked petroleum distillates to provide intermediates for synthetic lubricants.
  • the dimers, trimers and tetramers derived from C10 to C17 1-n-olefins are particularly described.
  • the final step in the production of the isoparaffin lubricants via the process is the hydrogenation of the polyolefin intermediates in the presence of known hydrogenation catalysts.
  • the elimination of the unsaturation of polyolefins is a necessary step in producing synthetic lubricants of outstanding stability.
  • Another feature of the present invention relates to the unique structure and lubricant properties of the products of the process. In this respect branching and molecular weight of the isoparaffin products and their viscosity and low temperature properties are particularly discussed.
  • 1-decene based synthetic hydrocarbon lubricants have excellent quality, their economics of manufacture are unfavorable.
  • 1-Decene is only one of the products of ethylene oligomerization. Therefore, its availability is limited and its price is very high. There is a great need for other synthetic hydrocarbon lubricants of greater availability and lesser cost.
  • isoparaffins in the C25 to C60 carbon range per molecule are good lubricant candidates, if they have 1 to 3 alkyl side chains of medium chain length on the n-alkane carbon skeleton as close to the center of the molecule as possible.
  • Heckelsberg produces an internal olefin, preferably via metathesis of an ⁇ -olefin.
  • the internal olefin is codimerized with an ⁇ -olefin.
  • 1-dodecene is converted to a 11-docosene which is then isolated and codimerized with 1-dodecene to provide C34 isoolefins: U.S. patent 4,319.064 by Heckelsberg et. al.
  • U.S. Patent 3,156,736 assigned to Shell also utilized cracked wax olefins for producing lubricants.
  • C9 to C17 cracked wax olefins are first separated by urea clathration. Then they are purified by percolation over silica gel. The pure olefins are polymerized using an aluminum trialkyl - titanium tetrachloride catalyst system. The C30 and higher distillate product fraction is hydrogenated to provide the lubricant product.
  • Another U.S. Patent to Shell, No. 2,051,612 describes a process for the preparation of a suitable olefin feed for lube oil manufacture. According to this patent a paraffinous oil provides the desired olefins in a two stage cracking process.
  • Patent 3,382,291 by Brennan to Mobil describes a process for the oligomerization of C5 to C20 ⁇ -olefins, preferably 1-decene in the presence of BF3 plus a 1:1 BF3 complex of water, alcohol, acids, ethers, esters, aldehydes, and ketones.
  • Another Mobil patent i.e. U.S. Patent 3,769,363, specifically claims the oligomerization of C6-C12 olefins with BF3 pentanoic acid complexes.
  • U.S. Patent 4,213,001 by Madgavkar et. al.
  • Patent 4,420,646 by Darden, Walts and Marquis of Texaco, discloses the use of a promoted BF3 catalyst at elevated temperature.
  • U.S. Patent 4,417,082 also from Texaco, describes the cooligomerization of C3-C5 and C8-C18 ⁇ -olefins with a similar catalyst system at close to ambient temperature.
  • linear olefin feeds for lubricant synthesis of the prior art were mostly derived via ethylene polymerization. These feeds did not require the application of olefin separation processes. The only relatively complex feeds employed were cracked distillates. These contained a mixture of mostly linear olefins but no aromatics and sulfur compounds. As it will be discussed the linear olefin and paraffin components of cracked wax were separated via urea adduction to produce feeds for synthetic lubricants. Urea adduction is also applicable to the thermally cracked, residua derived feeds of the present process.
  • Standard Oil Co. (Indiana) operated a dewaxing unit for the production of lubricating oil.
  • the chemical basis of this unit has been described by Zimmer Kunststoff and coworkers in Ind. Eng. Chem., Vol. 42, pages 1300-1396 in 1950.
  • inhibitors e.g. sulfur compounds etc.
  • probably methanol was used as an activator solvent.
  • Shell Oil Co. developed a process applicable for the separation of the ⁇ -olefin and n-paraffin components of cracked wax which was described by the earlier quoted Bailey et. al., paper in Ind. Eng. Chem., a paper in the Proceedings of the 2nd World Petr. Congr., Hague, Sect. III, pages 161-171 also by Bailey et. al. and another paper by Goldsbrough which was also referenced earlier.
  • This process employs both an organic solvent, methyl i-butyl ketone, and water and obtains the urea adducts by phase separation rather than filtration.
  • Societe Francais des Petroles also developed a process based on the same phase separation principle.
  • European Patent Application 164,229 by Atsushi et. al. assigned to Nippon Petrochemicals Company disclosed a method of upgrading to paraffins thermally cracked distillate products derived from petroleum residua. Acccording to this method, the olefin components of the distillate are reacted with the aromatic components to produce alkylaromatic compounds in the presence of an acid catalyst in the first step. The unreacted, paraffin rich components of the feed are then separated by distillation from the reaction mixture in the second step. The n-paraffins could then be isolated via urea adduction or by molecular sieve.
  • Patent 3,767,724 by Tan Hok Gouw disclosed the selective crystallization of paraffins from CO2 solutions of olefin-paraffin mixtures.
  • a journal publication by Von Horst Gundermann, Josef Weiland and Bernd Speckelsen [Erdoel and Kohle-Erdgas, Vol 24, No. 11, pages 696 to 701, (1971)] described the crystallization of C16 - C20 n-olefin plus n-paraffin mixtures from methylnaphthalene. The formation of n-paraffin crystals was reported. The authors concluded that for the crystallization of n-olefins always significantly lower temperatures are required than for that of the corresponding n-paraffins. Thus, this paper also taught away from the cocrystallization of these components.
  • the gasoline range feed of the present invention has a relatively low percentage of aromatics and high percentage of straight chain aliphatic hydrocarbons, largely 1-n-olefins. While the process of the prior art was simply directed to BTX production, aliphatic hydrocarbons, particularly olefins, are important co-products of the present process. These aliphatic hydrocarbon rich fractions are for example advantageously used as feeds in the urea adduction process.
  • Eluent chromatography using highly polar solids such as silica gel was employed widely in petroleum chemistry as an analytical method for determining the types of compounds present.
  • the analysis of olefin-paraffin and aromatic hydrocarbon mixtures derived by wax cracking is described using such a method by E. Kh. Kurashova, I.A. Musayev, P. I. Sanin and A.N. Rumyantsev in Neftekhimiya, Vol. 7, No. 4, pages 519 to 529 in 1967.
  • these applications were analytical rather than methods for producing components for industrial utilization.
  • the present invention starts with linear olefinic products of the high temperature thermal cracking of petroleum residua, separates the straight chain hydrocarbons of such cracked distillates and oligomerizes the linear olefin components to liquid polyolefin lubricant intermediates.
  • the final step in synthetic lubricant manufacture is the hydrogenation of polyolefins. Since the polyolefin intermediates of the prior art contained no sulfur compounds as impurities, generally sulfur sensitive metal catalysts of hydrogenation were employed. For example, the previously discussed U.S. Patent 4,420,646 by Darden et. al. particularly prefers a nickel-copperchromium hydrogenation catalyst described in U.S. Patent 3,152,998.
  • the hydrogenation step of the present process is preferably carried out in the presence of sulfur insensitive catalysts.
  • Transition metal sulfide based catalysts are particularly preferred.
  • a CoS/MoS catalyst is used to advantage.
  • such catalysts result in the conversion of the sulfur compound impurities and their removal as hydrogen sulfide.
  • Figure 1 illustrates by capillary gas chromatograms the composition of light Fluid-coker gas oil feeds containing major amounts of 1-n-olefins and n-paraffins plus various sulfur compounds.
  • Figure 2 illustrates by capillary gas chromatograms the composition of mixtures of 1-n-olefins and paraffins separated from light Fluid-coker gas oils.
  • Figure 3 illustrates by 1H nuclear magnetic resonance spectrum of the vinylic region the amounts of various types of olefins separated from light Fluid-coker gas oils.
  • Figure 4 illustrates by 13C nuclear magnetic resonance spectrum the chemical structure of the main 1-n-olefin and n-paraffin components of the product separated from light Fluid-coker gas oils.
  • the multistep process of the present invention provides a less expensive route for the manufacture of polyolefin liquid lubricants, i.e., isoparaffins derived via the oligomerization of C8 to C24 linear olefins.
  • Such lubricants in the past were optimally prepared via the trimerization 1-n-decene.
  • the high cost and limited availability of 1-n-decene is a major factor in limiting the use of poly- ⁇ -olefin (PAO) synthetic lubricants.
  • PAO poly- ⁇ -olefin
  • Synthetic lubricants can be also derived from C10 to C24 internal olefins. However, the ultimate starting materials for these poly-internal olefins are also ⁇ -olefins.
  • sulfur- containing petroleum distillate of high a-olefins content are employed as the feed.
  • These distillate:, hereafter defined as coker distillate:, are derived by the high temperature thermal cracking of petroleum residua, i.e. vacuum resids.
  • Preferred processes producing such coker distillates are Fluid-coking and Flexicoking.
  • the coker distillates feeds of the present process preferably contain major amounts of 1-n-olefins, n-paraffins and greater than 0.1% concentration of sulfur, mostly in the form of aromatic, thiophene type, sulfur compounds. There may also be significant amounts of conjugated dienes present.
  • Fractional distillation of the cracked coker product in the refinery usually provides heavy coker naphtha and/or light coker gas oil fractions. This may suffice to provide appropriate molecular weight range feeds as part of the coking process. Additional fractional distillation may be needed to obtain narrower carbon range feeds, e.g. a C9 to C13 cut or a C10 cut. Thus, the present coker distillate feeds are obtained either by simple refinery distillation or additional fractional distillation.
  • the first step of the present process is the enrichment in straight chain aliphatic hydrocarbon components, particularly 1-n-olefins, of the coker distillate feed. This is accomplished by one or more of several separation processes.
  • a preferred separation process is urea adduction. Urea forms reversible, crystalline complexes with the 1-n-olefin and n-paraffin components of the feed. These complexes are then separated by filtration and decomposed to give an enriched feed.
  • a preferred alternative to urea adduction is crystallization. It was surprisingly found that cooling broad distillate fractions of higher olefins containing three or more different carbon atoms results in the separation of crystalline mixtures of 1-n-olefins and n-paraffins.
  • separation methods include liquid-liquid extraction, membrane separation and adsorption on solids such as silica gel and zeolites. These methods can be used alone or as the first step in a two step separation process. For example, extraction or membrane separation may be used to reduce the aromatics content, prior to the separation of 1-n-paraffins by crystallization.
  • the second step of the instant process is the polymerization, i.e. selective oligomerization of the linear olefin components of the enriched feed containing sulfur compounds to produce appropriately branched polyolefins.
  • the polyolefin products of this step are mixtures of dimers, trimers, tetramers and pentamers.
  • the oligomerization is preferably carried out in the presence of acid, i.e. cationic, catalysts.
  • a specifically preferred type of catalysts is the Friedel-Crafts type such as BF3 and AlCl3.
  • the oligomerization can be carried out in one or two steps. In a two step process, olefin dimers may be produced in the first step. These dimers may be then codimerized with ⁇ -olefins in the second step.
  • the third and final step of the instant process is the hydrogenation of the sulfur containing polyolefin product of the second step, preferably in the presence of transition metal sulfide catalysts.
  • This hydrogenation results in a sulfur free isoparaffin product of appropriate branchiness.
  • Such an isoparaffin has a high viscosity index, good low temperature flow properties and an outstanding high temperature stability, i.e. the desired characteristics of a polyolefin derived synthetic lubricant.
  • the polyolefin precursor of the synthetic lubricant produced via the present multistep process is a copolymer of major amounts of 1-n-olefins, i.e. ⁇ -olefins, including even and uneven numbered carbon compounds.
  • minor components such copolymers also contain units derived from linear internal olefins and methyl branched olefins. The incorporation of these minor comonomers into the present isoparaffin lubricants results in a unique balance of properties desirable in various lube applications.
  • the multistep process of the present invention is to manufacture polyolefin type synthetic lubricants, derived mostly from C8 to C24 linear olefin components of coker distillate fractions containing more than 0.1% sulfur. These coker distillates are produced by the high temperature thermal cracking of petroleum residua.
  • the process comprises the following three steps:
  • the coker distillates of the present invention contain 1-n-olefins as the major type of olefin components.
  • the percentage of the Type I olefins is preferably more than 30% of the total olefins.
  • the preferred distillates contain organic sulfur compounds in concentrations exceeding 0.5 wt.% sulfur equivalent.
  • the coker distillate feed is enriched in 1-n-olefin and n-paraffin components.
  • preferred separation processes for enrichment include the urea adduction and crystallization of these components.
  • the C8 to C24 olefin components of an enriched coker distillate fraction are oligomerized to sulfur containing C30 to C60 polyolefins, preferably in the presence of a Friedel-Crafts catalyst, most preferably in the presence of a boron trifluoride complex catalyst.
  • the sulfur containing polyolefins are hydrogenated to isoparaffins with the simultaneous removal of sulfur as hydrogen sulfide in the presence of transition metal sulfide catalysts.
  • the present invention also covers a novel polyolefin type synthetic lubricant composition derived mostly from C8 to C24 linear olefins, preferably C9 to C13 1-n-olefin rich linear olefins wherein said olefins contain 1-n-olefins as major components and internal n-olefins and methyl branched components as minor components, and said olefin mixture is separated from a coker distillate feed containing 1-n-olefins and n-paraffins as major components, and oligomerized in the presence of acid catalysts to a polyolefin comprising 2 to 6 monomer units, said polyolefin product mixture containing n-paraffins then being hydrogenated to provide a mixture of isoparaffin lubricants and unconverted n-paraffins from which the paraffins are then removed preferably by distillation or said mixture of n-olefins and n-paraffins is first subjected to distill
  • the preferred hydrocarbon feeds of the present invention contain major amounts of olefins, paraffins and aromatic compounds. More preferably the feeds also contain significant amount of sulfur compounds.
  • the olefinic feed of the present process is a critical factor in producing the polyolefin lubricants of the present invention at a low cost.
  • Such a feed is produced by high temperature thermal cracking of petroleum residua.
  • the percentages of 1-n-olefin and other olefin components of petroleum distillates generally increase with the temperature of cracking.
  • Thermal cracking processes produce hydrocarbons of more linear olefinic character than catalytic cracking.
  • the presence of linear olefin components, particularly 1-n-olefins, in the cracked distillates is important in producing an olefin-paraffin mixture of high 1-n-olefin content in the separation step.
  • 1-n-Olefins are more readily oligomerized than internal n-olefins. They lead to polyolefins and, in turn, isoparaffins containing longer alkyl branches than the corresponding internal linear olefins. An appropriate number and length of alkyl chains is critical for the high performance of isoparaffin products.
  • Suitable distillate feeds can be also prepared in thermal processes employing a plurality of cracking zones at different temperatures. Such a process is described in U.S. Patents 4.477.334 and 4,487,686. Each of these thermal cracking processes can be adjusted to increase the olefin content of their products. Heavy gas oil distillates can be further cracked to increase the amount of lower molecular weight olefins.
  • the coker distillate feeds of the present invention are preferably in the C8 to C24 carbon range where the linear olefins and n-paraffins can be separated via urea adduction or crystallization.
  • Light coker gas oil refinery fractions are usually in that carbon range. The preference for fractions within this range depends on the specific use requirements of the polyolefin lubricants to be produced.
  • the preferred cracked distillates of the present feed contain relatively high amounts of organic sulfur compounds.
  • the sulfur concentration is preferably greater than 0.1% (1000 ppm), more preferably greater than 1% (10,000 ppm).
  • the prevalent sulfur compounds in these feeds are aromatic, mainly thiophenic. Most preferably the aromatic sulfur compounds represent more than 90% of the total. This finding is important for the present process since thiophenes, benzothiophenes and similar aromatic sulfur compounds do not inhibit the separation of the desired 1-n-olefins.
  • the olefin containing distillate fractions of thermal cracking processes may be employed as feeds in the process of the invention without prior purification. However, these distillate fractions may optionally be treated prior to their use to reduce the concentrations of aromatic hydrocarbons conjugated dienes, sulfur and nitrogen compounds if so desired.
  • aromatic hydrocarbons and sulfur compounds can be selectively extracted from the olefin containing fraction by polar solvents. A similar separation of aromatics from aliphatic compounds can be achieved using membranes. Shape selective zeolite adsorbents can be also used for the separation of n-olefins plus n-paraffins.
  • Nitrogen and sulfur compounds in general can be removed by use of absorption columns packed with polar solids such as silica, Fuller's earth, bauxite and the like.
  • Sulfur compounds can be also removed by acid treatment.
  • treatment with BF3 complexes can result in the alkylation of thiophene type sulfur compounds by the conjugated diene and branched olefin components of the feed.
  • the conjugated olefin components of the present feeds may also be removed by prior mild hydrogenation to monoolefins.
  • the light coker gas oil (LKGO) feed from the refinery is preferably further fractionated prior to use in the present process. It is preferred to distill a present fraction of LKGO up to C17 and use it in the present process. Narrow gas oil fractions, containing aliphatic hydrocarbons having as low as three different carbon atoms, such as C9 to C11, can be also employed. However, single carbon LKGO fractions cannot be utilized for linear olefin plus n-paraffin separation by crystallization. The separation of single carbon LKGO fractions such as an olefinic C10 fraction is though possible via urea adduction.
  • the olefin content of the present cracked distillate feeds is above 30%.
  • the 1-n-olefins are the major type components.
  • R hydrocarbyl, preferably non-branched alkyl
  • the R groups in the formulas of the various types of olefins can be straight chain or branched alkyl groups.
  • the alkyl groups of the preferred coker olefins of Type I and Type II are predominantly either straight chain or monomethyl branched.
  • the Type III and Type IV olefin components of these preferred feeds predominantly possess a methyl group as one of the alkyl groups on the completely substituted vinylic carbon.
  • NMR also indicated the presence of minor amounts of conjugated dienes ranging from 2 to 10% concentration.
  • the concentration of the various olefins generally decreases with their molecular weight, i.e. carbon number. Therefore, coker distillates having more than 24
  • the paraffin components of the preferred coker distillate feeds are present in concentrations similar to but smaller than the olefin components.
  • the n-paraffins are the major single types of paraffins present.
  • the branched paraffins are largely methyl branched. Monomethyl branched paraffins are prevalent.
  • the aromatic hydrocarbons of the present feeds have a concentration range from about 6% to about 50%.
  • the percentage of the aromatic components increases with the carbon number of the distillate fractions. Of course the percentages of olefins and paraffins decrease accordingly.
  • the concentration of aromatics is between 10 and 50%.
  • the aromatic hydrocarbon components of these feeds are predominantly unsubstituted parent compounds such as benzene or substituted with methyl groups such as toluene.
  • concentration of ethyl substituted compounds is much smaller.
  • Propyl substituted aromatics are present in insignificant amounts.
  • Up to 12 carbon atoms, the aromatics are benzenoid hydrocarbons. From C12 to C15 most aromatics are of the naphthalene type. Among the higher carbon number hydrocarbons most aromatics are three member fused ring compounds such as anthracenes and phenanthrenes.
  • the concentration and type of sulfur compounds in the preferred coker distillates depend on their carbon number.
  • the sulfur concentrations range from 0.1% to 3%. In general, sulfur concentrations increase with the carbon number to 3%.
  • the C5 to C7 carbon range there are major amounts of thiols present.
  • the C8 and higher fractions contain mostly aromatic sulfur compounds, mostly of the thiophene type.
  • the structure of aromatic thiol components is similar to those of the aromatic hydrocarbons. Methyl and ethyl substituted thiophenes are present in decreasing amounts.
  • Alkylthiophenes are the major sulfur compounds in the C8 to C11 range. Benzothiophenes are mostly present in the C12 to C13 range. In higher boiling fractions dibenzothiophenes are the major sulfur compounds.
  • methanol is used as an activator solvent for urea.
  • Another method employs an aqueous urea solution as a reactant for cracked distillates.
  • crystalline urea reactant is employed.
  • urea such as aqueous isopropanol and aqueous methyl i-butyl ketone.
  • the choice of solvent or solvent mixture is influenced by the solvent's characteristics and cost plus the ease of urea and solvent recycle after the decomposition of the complex. It is desirable to have a volatile solvent or solvent mixture which is not only a good solvent for urea but also has some miscibility with the cracked hydrocarbon feed.
  • contacting the urea solution reactant with the hydrocarbon feed results in the formation of a solid urea adduct precipitate and a liquid unconverted feed - excess reactant mixture from which the reactant is readily separated e.g. by distillation and water extraction.
  • the urea reactant is employed in several fold molar excess over the 1-n-olefin plus n-paraffin components of the feed.
  • the molar ratio of urea to the 1-n-olefin plus n-paraffin compounds is preferably 5 or more. Increased ratios result in increased amounts of adduct precipitate. However, the ratio of urea to the n-aliphatic hydrocarbons in such adducts increases. Thus the yield of separated aliphatic hydrocarbon product per weight of urea decreases.
  • the solid urea adducts formed are separated preferably by filtration.
  • the filtered adduct is voluminous and is advantageously washed with a C5 to C8 hydrocarbon solvent, preferably isooctane, to remove the occluded feed and reactant solution.
  • the separated urea adducts are decomposed, preferably by heating, to recover a mixture 1-n-olefins and n-paraffins.
  • the adduct is added to a hot, stirred water which dissolves the urea by-product of decomposition.
  • the 1-n-olefin - n-paraffin product mixture is insoluble in the water and as such separates as a top hydrocarbon phase.
  • the hydrocarbon product consists mainly of 1-n-olefins and n-paraffins.
  • the combined percentage of 1-n-olefins and n-paraffins is preferably greater than 75%.
  • the ratio of the 1-n-olefin versus n-paraffin components depends on their ratio in the feed and the extent of adduct formation in the complexing step. With increasing amounts of adducts formed increasing amounts of the more soluble 1-n-olefin complexes precipitate.
  • the ratio of 1-n-olefins to n-paraffins is preferably from about 0.4 to about 1.5. With the more preferred C10 to C19 Flexicoker feeds, ratios ranging from about 0.6 to about 1.2 were found.
  • a preferred method of separation employs selective crystallization of the distillate feed, preferably from solution.
  • This process comprises the separation by crystallization of a petroleum distillate fraction, containing major amounts of 1-n-olefins and n-paraffins with at least two preferably at least three different carbon numbers per molecule, to obtain crystals mostly consisting of 1-n-olefins and n-paraffins.
  • the feed Prior to separation by crystallization the feed is preferably diluted with a volatile solvent.
  • Preferred solvents are selected from the group of hydrocarbons, oxygenated solvents and CO2.
  • Exemplary solvents are propylene and methyl ethyl ketone. Crystallization is effected by cooling the feed. The crystals formed are separated, for example by filtration using techniques developed for lube oil dewaxing and p-xylene separation.
  • crystals containing n-paraffins and 1-n-olefins are preferably modified by additives.
  • Additives developed for wax crystal modifications are effective.
  • a copolymer of ethylene and vinyl acetate, Paranox 25, and the like can be used.
  • Such additives control crystal growth.
  • the washcrystal method is particularly suited. Using this method the paraffin-olefin crystals are washed with the melt of the same to remove impurities.
  • Another preferred method of separation in the present process employs liquid-liquid extraction.
  • This process comprises the separation by extraction with a polar solvent of a petroleum distillate fraction derived via the high temperature thermal cracking of petroleum residua, i.e. a feed containing major amounts of 1-n-olefins, n-paraffins and greater than 0.1% sulfur to provide an extract enriched in aromatic hydrocarbon and sulfur components.
  • the polar solvents are preferably selected from the group consisting to organic nitrogen, oxygen, sulfur and phosphorus compounds.
  • organic nitrogen compounds are amines, amides and nitriles such as triethanolamine, N-methylpyrrolidone, dimethylformamide, acetonitrile, ⁇ , ⁇ - oxydipropionitrile, 1,2,3- tris-(2-cyanoethoxy) propane.
  • organic oxygen, sulfur and phosphorus compounds are ethylene carbonate, diethylene glycol, tetraethylene glycol, butyrolactone, methanol, sulfolane, diethyl sulfone, trimethylphosphate. The selectivity of most of these polar organic compounds can be enhanced by the addition of appropriately minor amounts of water.
  • the suitability of a solvent is mainly determined by its group selectivity. This is directly related to the polarity of the solvent.
  • the groups of interest are aromatic compounds including sulfur containing aromatics on one olefins and paraffins on the other.
  • Group selectivity changes with increasing boiling ranges of the feed since the character of the aromatic components changes from mononuclear to dinuclear compounds, etc. With an increasing number of fused aromatic rings, the polarity of the present feed components increases. Thus the selectivity is also increased.
  • solvent power determines the amount of solute contained in the solvent phase. As such, it affects the economy of a given solvent.
  • the third basic factor is solvent selectivity for low versus high boiling components, e.g. light-heavy selectivity. This selectivity factor should be usually at a minimum. However, since the feed of the present invention is preferably a narrow distillate cut, the value of this factor has often no effect on the separation.
  • the solvent is usually higher boiling than the coker distillate feed.
  • the extracted distillate components can be recovered by fractional distillation and the solvent recycled.
  • the solvent can be much lower boiling.
  • the solvent is recovered as a distillate and the extract remains as a residual product.
  • the solvent can be also recovered from the extract by membrane separation. For example, acetonitrile is a highly suitable solvent for recovery by the membrane technique.
  • Another preferred method of separation employs a solid adsorbent such as clay, alumina, alumino-silicates, fullers earth, silica gel.
  • a solid adsorbent such as clay, alumina, alumino-silicates, fullers earth, silica gel.
  • adsorbents consists of highly polar materials. They are highly polar solids such as silica gel or solids covered by a highly polar stationary phase such as polyethylene glycol on a solid carrier. Such solids effect chromatographic separation. When in contact with the present feed they retain the components of the present feed in proportion to their polarity. Using a narrow distillate fraction as a feed, the paraffin components are eluted at first followed by the olefins and then by the mononuclear and binuclear aromatics, etc.
  • separation process steps of the present invention can be advantageously combined with each other or with selective chemical conversion processes to provide single types of chemicals based on Flexicoker distillates. In the following these combinations will be discussed in some detail.
  • the separation by crystallization of 1-n-olefin-n-paraffin mixtures can be combined with their further separation using molecular sieves to provide 1-n-olefins containing both even and uneven numbers of carbons per molecule.
  • the mixtures can be first distilled to obtain single carbon fractions.
  • the n-paraffins can then be selectively crystallized and separated from the n-olefin rich liquid phase.
  • the 1-n-olefin components of these mixtures of 1-n olefins and n-paraffins are preferably reacted selectively leaving unconverted n-paraffins behind.
  • the 1-n-olefins can be hydroformylated, i.e. reacted with CO nd H2, to provide aldehydes and/or alcohols of high linearity. They can be reacted with aromatics such as phenol to produce via alkylation the corresponding linear alkylaromatic compounds, i.e. alkylphenols.
  • the 1-n-olefins can be also oligomerized, preferably by acid catalysts, to provide low molecular weight polyolefins.
  • the aliphatic raffinate can also be reacted selectively to convert to olefinic components and leave a mixture of paraffins unconverted. Selective reactions for olefin conversion are the same as discussed above.
  • the aromatic extract can be further separated for example by crystallization. E.g. p-xylene, durene and naphthalene can thus be separated. Alternatively, the aromatic extract can be selectively hydrogenated to remove the sulfur compounds present.
  • the aromatic compounds in the presence and in the absence of thiophenic sulfur compounds can be alkylated with olefins to provide alkylaromatic products with or without sulfur. The alkylation of dinuclear aromatics with higher olefins, preferably in the C15-C30 range, is preferred to provide nonvolatile solvents.
  • n-olefin plus n-paraffin mixtures obtained in the present separation process are advantageously converted to higher boiling derivatives and then separated from the unreacted n-paraffins.
  • These conversions generally comprise known chemical reactions and processes.
  • the preferred conversions are oligomerization, alkylation of aromatic compounds and carbonylation of olefins.
  • a preferred aspect of the present invention is a unique comtination of separation via urea adduction or crystallization and selective conversion of n-olefin plus n-paraffin mixtures followed by the separation of the n-paraffin.
  • the preferred mixtures of n-olefins and n-paraffins of the present invention contain 1-n-olefins as the main olefinic components. These 1-n-olefins are the preferred reactants in numerous types of conversions which are more specifically polymerization, particularly oligomerization, alkylation, carbonylation and various other olefin conversions. In the following, mainly the conversion of 1-n-olefins to oligomers will be discussed. Internal n-olefins generally undergo similar conversions at a lower rate.
  • the acid catalyzed and free radical oligomerization of 1-n-olefins is widely known.
  • acid catalysed oligomerization in the liquid phase is preferred.
  • the catalysts are generally strong acids such as phosphoric acid, sulfonic acid, aluminum chloride, alkylaluminum dichloride and boron trifluoride complexes.
  • Boron trifluoride complexes are preferably those of protic compounds such as water, alcohols, and protic acids. Using BF3 complexes, cracking side reactions are avoided.
  • the oligomerizations are generally carried out in the -100 to 100°C temperature range at atmospheric pressure. Superatmospheric pressure may be used to assure a liquid phase operation.
  • the number of monomer units in the oligomer products is 2 to 30, preferably 2 to 6.
  • the n-olefin components of a mixture of n-olefins and n-paraffins are converted into oligomers by reacting them in the presence of an acid or a free radical catalyst, preferably an acid catalyst.
  • oligomers containing an average of 3 to 4 monomer units i.e. trimers and tetramers, are produced by reacting a mixture rich in C9 to C13 1-n-olefins and n-paraffins, in the presence of a boron trifluoride complex.
  • the 1-n-olefin and internal normal olefin components of a C13 to C17 mixture of n-olefins and n-paraffins are cooligomerized to produce oligomers containing an average of 2 to 3 monomer units.
  • Another preferred acid catalysed oligomerization of n-olefins produces polyolefins in the C16 to C50 carbon range. These are subsequently used to alkylate benzene to produce C16 to C30 alkylbenzene intermediates for the synthesis of oil soluble Ca and Mg alkylbenzene sulfonate detergents.
  • the preferred alkylating agents are dimers.
  • the unconverted paraffin components of the n-olefin oligomer product mixture are removed preferably by distillation.
  • the distillation is performed either right after the oligomerization or subsequent to the next conversion step comprising hydrogenation to isoparaffins.
  • the filtrate of the reaction mixture separated into a lower oily phase (about 10%) and an upper methanolic phase (about 90%).
  • the adduct was dried in vacuo overnight to remove the residual i-octane (about 65%) and methanol (about 35%).
  • the remaining dry adduct, 213g. was added to 1800 ml of water and stirring.
  • the stirred mixture was heated to 70°C to complete the decomposition of the adduct and then allowed to cool to room temperature. This resulted in the separation of 44g of an upper hydrocarbon phase.
  • the lower, hazy water phase yielded an additional 1.8g of hydrocarbons on extraction with 600 ml of hexane.
  • the total yield was 9 wt/wt% based on the feed.
  • FIG. 1 shows the gas chromatogram recorded by a Flame Ionization Detector of the organic compounds in general.
  • the tall doublet peaks indicate the presence of 1-n-olefin - n-paraffin pairs of the same carbon number in the C10 to C26 range. These are the largest single compound components of the mixture.
  • the 1-n-olefin component is always of a shorter retention time than the corresponding paraffin.
  • the 1-n-olefin componemts are present in a larger concentration than the n-paraffins.
  • the unresolved hump of the figure indicates the presence of an extremely high number of individual components present.
  • FIG. 1 shows the corresponding chromatogram for sulfur compounds. It is noted that the sulfur detector had a near to square response to sulfur concentration. A comparison of the peak heights of the sulfur compound components with that of a standard sulfur compound containing 100 ppm sulfur indicates the presence of numerous sulfur compounds at greater than 100 ppm sulfur concentration.
  • Figure 2 shows the FID chromatogram of the 1-n-olefin - n-paraffin mixture separated from the light Flexicoker gas oil feed of Figure 1.
  • the tall 1-n-olefin -n-paraffin doublet peaks of this figure represent more than 90% of this mixture.
  • Combined gas chromatography mass spectrometry showed that minor distinguishable components of the mixture are 2- and 3-olefins, 2-methyl substituted 1-olefins and 2- plus 3-methyl sutstituted n-alkenes.
  • the lower part of Figure 2 similarly shows the S specific gas chromatogram of the hydrocarbons separated via urea adduction.
  • a comparison with the S specific GC of the feed in Figure 1 shows a tremendous reduction of sulfur content.
  • All the remaining sulfur compounds of Figure 2 are present in concentrations equivalent to or less than 100 ppm sulfur. It is also apparent that the remaining sulfur compounds are not the main sulfur compounds of the feed.
  • the main sulfur compounds of the feed are aromatics such as benzothiophenes and dibenzothiophenes.
  • the main sulfur compounds remaining in the product appear to be homologous n-alkyl mercaptans.
  • the 1H NMR spectrum showed the presence of methylene, methine and methyl protons plus the vinylic protons of the olefinic groups. Aromatic protons were essentially absent.
  • Type I olefins include 1-n-olefins, one of the most common type of compounds of the present mixture according to GC.
  • the final reaction mixture was worked up in a manner described in Example 1.
  • the amount of dry urea adduct obtained was 506g.
  • 106g of ⁇ -olefin -n-paraffin mixture separated as a top phase.
  • Hexane extraction of the aqueous phase and subsequent removal of the hexane by film evaporation resulted in the recovery of another 4.5g product.
  • the total yield of the product was 110.5g (6.9%).
  • Table I The composition of the product was determined by capillary GC and is shown by Table I.
  • Table I shows the percentages of the 1-n-olefin and n-paraffin components of different carbon numbers.
  • the total percentage of the ⁇ -olefins is 43%. Most of these olefins (36.4%) are in the C13 to C17 range. The overall ratio of ⁇ -olefins to n-olefins is close to one (0.95).
  • the dry weight of the urea adduct in thie example was 6.4 times greater than that of the final product.
  • the adduct to produce weight ratio was ranging from 4.7 to 5.4. This indicates that the excess urea reactant may crystallize from the reactant solution without adversely affecting the separation process.
  • a 2 to 1 ethanol/methanol mixture was used as a solvent for the urea reactant because it contains sufficient amounts of ethanol for miscibility with the light Flexicoker gas oil.
  • a nearly saturated solution of 25.5 g urea in 100 ml of this solvent mixture was added to 45 ml (35.9g) of LKGO with stirring. Stirring of the reaction mixture was continued for 30 minutes.
  • the urea adduct was then separated by filtration, washed three times with 15 ml isooctane and dried. The dry adduct was then reacted with hot water. This resulted in the separation of 4.6g (11.6%) of oil product having a composition similar to that of the previous example.
  • the adduct was added to 3600 mL of hot (70°C) stirred water to liberate the n-decenes-n-decane mixture which was successively extracted from the water by 500 ml n-hexane and 500 mL ether.
  • the hydrocarbon extract was a stable emulsion).
  • the combined extracts were washed with 200 mL water and the solvent stripped off to provide 73 g of the residual product. Cooling the filtrate of the reaction mixture to -20°C resulted mostly in urea crystallization.
  • the composition of the product is illustrated by the capillary gas chromatogram of Figure 2.
  • the quantitative GC data show the presence of 44.8% 1-n-decene and 36.8% n-decane in the product. Based on these data 48% of the starting 1-n-decene was recovered from the starting Flexicoker distillate. The remaining minor components of the separated product mixture are mainly linear internal decenes: cis-and trans-2-decene 3-, 4- amd 5-decenes. 2-Methyl-1-nonene and 2-methyl-nonane were also present in small quantities as indicated by the Figure. The small amounts of 1-n-nonene and n-nonane present in the feed were also isolated with the main n-C10 aliphatic hydrocarbon components.
  • BF3 gas was introduced into the reaction mixture until saturation for 10 minutes with continued stirring. This resulted in a greater exotherm, up to 40°C.
  • the composition of the mixture was again determined by GC. It was found that most of the olefin components were reacted to form dimers and trimers. According to packed GC the upper product phase consisted of about 44% C12 feed, 11% of C20 dimer and 45% C30 trimer. Capillary GC showed that 95% of the unconverted C10 feed was paraffinic. The percentages of n-undecane and n-dodecane were 18.6% and 69.1%, respectively. After stirring the reaction mixture over the weekend, all the olefins were reacted.
  • the lower catalyst phase of the reaction mixture was separated. It was 4 g, double the amount of the initially added catalyst.
  • Sulfur specific capillary GC showed that most of the sulfur compounds of the C12 feed were converted to higher molecular weight species: The presence of a thiolester among the neopentanoates and several sulfur compounds presumably thiethers in The dimer range were indicated.
  • Example 6 The distillate fractions of Example 6 --which were obtained by the fractional distillateion of the n-olefin - n-paraffin mixtures separated via urea adduction from light Flexicoker gas oil in Example 1 to 6 -- were used as feeds for oligomerization in the present example.
  • the composition of these feeds is listed Table II of Example 6.
  • the C15 reactant was fraction VIII.
  • the C16 reactant was fraction IX.
  • As the C17 reactant fraction XI was employed.
  • n-Olefin - n-paraffin reactant mixtures of the composition shown in Table III were added into the reaction flask. Their quantities ranged from 19 to 84 grams.
  • the amount of the ethylaluminum dichloride (EADC) catalyst employed was 4 mole % (4 m EADC per 100 moles olefin). The EADC was added to the stirred olefin as a 26% heptane solution at once at ambient temperature.
  • EADC ethylaluminum dichloride
  • reaction mixtures were allowed to cool and then treated with excess water to hydrolyze the catalyst. This usually resulted in the formation of an emulsion which was treated with an about 30% aqueous sodium hydroxide solution to break it.
  • the hazy organic phase was then filtered through a Celite 512 to get clear liquid products. These products were then stripped at reduced pressure while heated to remove any volatile components, i.e. hydrocarbons having less than 20 carbon atoms per molecule.
  • the data of the table show that the olefin components of all the various olefin paraffin mixtures were oligomerized but to varying degrees.
  • the decenes of the C10 feed were converted to oligomers of a broad molecular weight distribution, ranging from C20 dimers to C60 hexamers.
  • the main products were trimers and tetramers. Only about 1.4% unconverted decenes were present in the reaction mixture.
  • the C13 to C17 olefins of the other four reaction mixtures were mainly converted to dimers and trimers. From 24 to 37% of the olefins remained unconverted.
  • the composition of the residual products of the C13 to C17 olefins on the right side of the table shows that the main components were dimers.
  • the key properties of the polyolefin lubricants were studied using the oligomeric products of the previous example. These properties, the magnitude and temperature dependence of viscosity and low temperature flow, are similar for the polyolefins and their hydrogenated isoparaffin derivatives. Both properties depend on the molecular weight, branchiness and n-alkyl side chain length.
  • the molecular weight distribution of the residual products was further studied by gel permeation chromatography i.e. GPC. (Product components having more than 60 carbons per molecule could not be determined by GC). As it is shown by the data of Table IV, the number average molecular weights of the products (Mn) decreased with the increasing carbon number of monomers, indicating a definite decrease in the degree of polymerization. The residual products of decene and heptadecene oligomerization had a relatively larger percentage of trimers, thus a higher molecular weight, apparently as a consequence of the prior removal of some of the dimers (see Table III of the previous example).
  • the prevalence of dimers in products of higher olefins in the C14 to C17 range is desirable for producing isoparaffins in the C30-C40 range.
  • a combination of ⁇ -olefin isomerization plus ⁇ -olefin - internal n-olefin codimerization is a preferred route to such dimers, e.g.
  • the molecular weight distribution of the residual product as defined by the ratio of number average and weight average values (Mw/Mn) is generally broad. Only the pentadecene oligomer, from which the monomer and paraffin were completely removed, has a narrow molecular weight distribution. While the pure trimer derived from 1-n-decene has ideal lubricant properties for many applications, appropriate mixtures of oligomers of broad molecular weight distribution in the dimer to hexamer range possess balanced properties, particularly suited for some applications.
  • the residual olefin oligomers exhibit varying kinematic viscosities at 40°C and 100°C. These viscosities increase in case of the oligomers of C13 to C16 olefins even though their molecular weights do not change much. More importantly, the viscosity index of these oligomers remains high indicating that their viscosity is relatively little affected by temperature changes.
  • Table IV also shows the pour points of the residual products according to ASTM.D97-66. This is a measure of low temperature properties; low pour point indicates good low temperature flow.
  • the data of the table indicate that with increasing chain lengths of the olefin feeds, the oligomer products have higher pour points i.e. poorer low temperature properties.
  • the decene oligomer has a low pour point. Both its low temperature flow properties and high temperature viscosity characteristics match those of the oligomer similarly derived from pure 1-n-decene. With increasing monomer carbon numbers, the low temperature lubricant properties decline due to the presence longer n-alkyl chains. However, at the same time the viscosity becomes less dependent on the temperature as indicated by the increased viscosity indices. The desired compromise between high pour point and high VI apparently depends on the temperature of the desired lubricant application.
  • Part of the polydecene residual product of Example 10 is hydrogenated in the presence of a sulfided cobalt-nickel catalyst under 1500 psi hydrogen pressure in the 140 to 220°C range at a temperature sufficient not only for adding hydrogen to the olefinic unsaturation of the oligomeric feed but for the conversion to hydrogen sulfide of the sulfur compound impurities. Higher temperatures are avoided because they may result in the sulfuration of the isoparaffin product by the sulfided catalyst.
  • the crude isoparaffin product is purged in vacuo with heating under nitrogen to remove all the volatile by-products, mostly paraffins, having less than 25 carbon atoms per molecule.

Claims (7)

  1. Procédé multiétape pour la fabrication de lubrifiants polyoléfiniques, dérivés pour la plupart de composants oléfiniques linéaires en C8 à C24 de fractions de distillats de cokéfacteur contenant plus de 0,1% en poids de soufre qui sont produits par le craquage thermique àtempérature élevée de résidus de pétrole, comprenant les trois étapes suivantes consistant:
    (a) à enrichir une fraction ou une alimentation de distillat de cokéfacteur en composants 1-n-oléfiniques et n-paraffiniques par un ou plusieurs procédés de séparation;
    (b) à oligomériser les composants oléfiniques en C8 à C24 d'une fraction enrichie de distillat de cokéfacteur pour produire des polyoléfines en C30 à C60 contenant du soufre;
    (c) à hydrogéner les polyoléfines contenant du soufre en isoparaffines avec l'élimination simultanée de soufre.
  2. Procédé selon la revendication 1, dans lequel lesdites fractions d'alimentation de distillat de cokéfacteur extraites du craquage thermique de résidus de pétrole, contiennent des 1-n-oléfines comme type principal de composants d'oléfine, le pourcentage des oléfines de type 1 (de formule R-CH=CH2) étant supérieur à 30% en poids des oléfines totales, et les composés de soufre organique sont présents en concentrations dépassant 0,5% en poids de soufre équivalent.
  3. Procédé selon la revendication 1 ou 2, dans lequel l'enrichissement du distillat de cokéfacteur en 1-n-oléfines et n-paraffines comprend soit leur séparation sous forme de produit d'addition d'urée, soit la cristallisation de ces composants.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel l'oligomérisation des composants oléfiniques en C8 à C24 de la fraction de distillat de cokéfacteur enrichie est effectuée en présence d'un catalyseur cationique.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel l'hydrogénation des polyoléfines contenant du soufre est effectuée en présence de catalyseurs à base de sulfure de métal de transition.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel l'oligomérisation des composants oléfiniques en C8 à C24 d'une fraction de distillat de cokéfacteur enrichie est effectuée en présence d'un catalyseur Friedel-Crafts.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel l'oligomérisation des composants oléfiniques en C8 à C24 est effectuée en présence d'un catalyseur à base de complexe BF3.
EP19890313478 1988-12-29 1989-12-21 Procédé de préparation au lubrifiants polyoléfiniques à partir de résidus de craquage thermique contenant du soufre Expired - Lifetime EP0376637B1 (fr)

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BR9400079A (pt) * 1994-01-12 1995-09-26 Petroleo Brasileiro Sa Processo para a produção de óleos lubrificantes sintéticos e óleos lubrificantes sintéticos
IT1276997B1 (it) * 1995-11-30 1997-11-04 Enichem Augusta Spa Basi per olii lubrificanti e procedimento per la loro preparazione
AU2004297557B2 (en) * 2003-12-05 2009-12-24 Exxonmobil Research And Engineering Company A process for the acid extraction of hydrocarbon feed
CN100390256C (zh) * 2004-11-26 2008-05-28 三井化学株式会社 合成润滑油和润滑油组合物
US7880047B2 (en) * 2008-05-06 2011-02-01 Chemtura Corporation Polyalphaolefins and processes for forming polyalphaolefins
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JP5735017B2 (ja) * 2013-01-15 2015-06-17 Ｊｘ日鉱日石エネルギー株式会社 潤滑油基油及び潤滑油組成物
WO2019189446A1 (fr) * 2018-03-27 2019-10-03 Ｊｘｔｇエネルギー株式会社 Huile isomérisée à la cire et procédé de production
WO2021028877A1 (fr) * 2019-08-14 2021-02-18 Chevron U.S.A. Inc. Procédé pour améliorer les performances d'un moteur avec des compositions lubrifiantes renouvelables

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US4124650A (en) * 1977-07-22 1978-11-07 Exxon Research & Engineering Co. Process for the production of low pour point synthetic oils
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