WO2014168403A1 - Method of producing lube base oil by alkylation of hydrocarbons - Google Patents

Method of producing lube base oil by alkylation of hydrocarbons Download PDF

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Publication number
WO2014168403A1
WO2014168403A1 PCT/KR2014/003045 KR2014003045W WO2014168403A1 WO 2014168403 A1 WO2014168403 A1 WO 2014168403A1 KR 2014003045 W KR2014003045 W KR 2014003045W WO 2014168403 A1 WO2014168403 A1 WO 2014168403A1
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isoparaffin
base oil
lube base
peroxide
fraction
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PCT/KR2014/003045
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English (en)
French (fr)
Inventor
Jae Wook Ryu
Yong Woon Kim
Do Woan Kim
Myoung Han Noh
Wan Seop KWON
Jin Hee Ok
Jin Heong LIM
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Sk Innovation Co., Ltd.
Sk Lubricants Co., Ltd.
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Publication of WO2014168403A1 publication Critical patent/WO2014168403A1/en

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    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/0206—Well-defined aliphatic compounds used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/022—Well-defined aliphatic compounds saturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to a method of producing lube base oil by alkylation of hydrocarbons. More particularly, the present invention relates to a method of producing high-quality lube base oil by alkylating an isoparaffin-containing hydrocarbon feedstock using peroxide as a radical initiator without the addition of olefins.
  • lube base oil having a high viscosity index and low pour point can be produced by reacting an isoparaffin-containing fraction (for example, a fraction having a middle distillate boiling point) with an olefin-containing fraction.
  • the alkylation reaction between isoparaffin and olefin having a long chain is extremely restrictive, and the lube base oil produced thereby has relatively low viscosity although it is somewhat improved in terms of viscosity index, so this lube base oil has a limitation in being applied to the fields requiring high viscosity characteristics (for example, engine oil, gear oil and the like for automobiles; and hydraulic oil, oil, machine oil, compressor oil and the like for industries).
  • the final lube base oil obtained has a viscosity index of about 100, which is insufficient to meet the recently required high viscosity index specifications.
  • the present invention intends to provide a method of producing high value-added lube base oil having high kinematic viscosity and a high viscosity index by the alkylation reaction of long-chain isoparaffins of 5 or more carbon atoms in a feedstock using a specific radical initiator (peroxide) without the addition of olefins.
  • a first aspect of the present invention provides a method of producing lube base oil, including the steps of: a) providing at least one isoparaffin-containing feedstock selected from the group consisting of (i) an isomerized fraction of biomass-derived diesel, (ii) a group II or group III lube base oil fraction produced from the isomerization reaction of unconverted oil derived from the hydrocracking of fuel oil, (iii) a naphtha fraction, (iv) a diesel fraction and (v) a group I lube base oil fraction; b) adding peroxide to the isoparaffin-containing feedstock in an amount of 5 to 35 wt% based on a total amount of reactants to perform an alkylation reaction at a pressure of 1 to 100 bar and a temperature of 10 to 200°C; and c) recovering lube base oil from the alkylation reaction product, wherein the step b) is performed without the addition of olefins.
  • the lube base oil may have a boiling point of 300 to 700°C, a viscosity index of 90 to 150, a kinematic viscosity of 2 to 30 cSt (100°C) and a pour point of -36 to 0°C.
  • the lube base oil may have a boiling point of 400 to 700°C, a viscosity index of 90 to 150, a kinematic viscosity of 6 to 60 cSt (100°C) and a pour point of -40 to 0°C.
  • a second aspect of the present invention provides a method of producing lube base oil, including the steps of: a1) continuously introducing at least one isoparaffin-containing feedstock selected from the group consisting of (i) an isomerized fraction of biomass-derived diesel, (ii) a group II or group III lube base oil fraction produced from the isomerization reaction of unconverted oil derived from the hydrocracking of fuel oil, (iii) a naphtha fraction, (iv) a diesel fraction and (v) a group I lube base oil fraction into an alkylation reaction region; b1) adding peroxide to the isoparaffin-containing feedstock in an amount of 5 to 35 wt% based on a total amount of reactants to perform an alkylation reaction at a pressure of 1 to 100 bar, a temperature of 10 to 200°C and a weight hourly space velocity (WHSV) of 0.2 to 2 hr -1 ; b2) separating alkylate, unreacted feedstock and ureacted per
  • the lube base oil produced by the method of producing lube base oil according to the present invention has high viscosity and a high viscosity index compared to conventional lube base oil obtained by the alkylation reaction of isoparaffin and olefins.
  • the method of producing lube base oil according to the present invention is advantageous in that a single hydrocarbon feedstock is used, so side reactions occurring when an olefin is used can be prevented, and a separation procedure can be simplified, thereby easily realizing commercially-advantageous continuous processes.
  • FIG. 1 is a schematic view showing a process of producing biodiesel as a feedstock for an alkylation reaction according to an embodiment of the present invention
  • FIG. 2 is a schematic view showing a process of producing a lube base oil fraction as a feedstock for an alkylation, wherein the lube base oil fraction is prepared from the isomerization reaction of unconverted oil derived from the hydrocracking of fuel oil, according to an embodiment;
  • FIG. 3 is a schematic block diagram showing a continuous process including the steps of alkylation reaction, separation and peroxide regeneration according to an embodiment of the present invention
  • FIG. 4 is a SIMIDIS graph of an alkylation product obtained in Example 1;
  • FIG. 5 is a SIMIDIS graph of alkylation products obtained in Example 2 and Comparative Example 1;
  • FIG. 6 is a SIMIDIS graph of alkylation products obtained in Example 3 and Comparative Example 2.
  • VGO vacuum gas oil
  • alkylation reaction means a reaction for adding an organic molecule with an alkyl group, specifically, a reaction for bonding isoparaffins in a feedstock.
  • isoparaffin means a non-straight-chain, that is, branched paraffin having a carbon number of 5 or more (specifically, 5 to 30, and more specifically 10 to 25).
  • isoparaffin-containing feedstock means a feedstock containing isoparaffin in an amount of 10 wt% or more, specifically 20 wt% or more, and more specifically 50 wt% or more.
  • lube base oil means a hydrocarbon fraction having a boiling point of 300°C or higher (specifically, 340 to 700°C) and a viscosity of 1 cSt or more at 100°C.
  • unconverted oil means an unconverted bottom fraction remaining after separating fuel oils (gasoline, kerosene and diesel) from vacuum gas oil using a hydrocracking reactor.
  • fraction of biomass-derived diesel means an arbitrary fuel equal to diesel, obtained from a renewable biological source, in a wide sense, specifically, a fuel satisfying the standard ASTM D6751.
  • fraction of biomass-derived diesel means a fraction prepared by isomerizing a diesel obtained by converting triglyceride and/or aliphatic acid in biomass into paraffin through hydrodeoxygenation (hydrodecarbonylation or hydrodecarboxylation).
  • lube base oils may be classified as given in Table 1 below according to the mechanical and chemical property standards prescribed in the API.
  • an isoparaffin-containing feedstock can be obtained from various sources.
  • feedstock Typically, as the feedstock, (i) an isomerized fraction of biomass-derived diesel and (ii) a group II or group III lube base oil fraction produced from the isomerization reaction of unconverted oil derived from the hydrocracking of fuel oil may be selected. These fractions may be used independently or in a combination thereof.
  • the content of olefin in the isoparaffin-containing feedstock may be less than 1 wt%, specifically, less than 0.1 wt%.
  • the feedstock may not substantially contain an olefin. If the content of olefin reaches or exceeds a predetermined level, the reaction between isoparaffin and olefin or the reaction between olefins is favored in comparison to the reaction between isoparaffins, thus deteriorating the characteristics of a final alkylation product and causing a side reaction.
  • biomass used in preparing the isomerized fraction of biomass-derived diesel may include animal oils and plant oils.
  • animal oils may include fish oil, cow oil, hog oil, sheep oil, butter, and the like.
  • plant oils may include sunflower oil, canola oil, coconut oil, corn oil, cottonseed oil, linseed oil, safflower seed oil, oat oil, olive oil, palm oil, peanut oil, apricot seed oil, almond oil, avocado oil, camellia oil, rice bran oil, walnut oil, rapeseed oil, flaxseed oil, sesame oil, soybean oil, castor oil, cocoa butter, palm kernel oil, and the like. These oils may be used independently or in a combination thereof.
  • the biomass of the present invention is not limited thereto.
  • FIG. 1 shows a process of producing biodiesel as a feedstock for an alkylation reaction.
  • palm oil as plant oil, is introduced into a reactor (HBD&HDS reactor) together with hydrogen to conduct a hydrodeoxygenation reaction.
  • HBD&HDS reactor a reactor
  • oxygen in a feed is converted into water, and paraffin components are obtained.
  • the water is discharged through the bottom of a separator, and the by-product gas is discharged through the top of a separator.
  • a part of the discharged by-product gas (containing unreacted hydrogen) is combined with new hydrogen, and then returns to the reactor.
  • the paraffin separated from the separator is transferred to a distillation tower to separate wax components and obtain paraffin components (particularly, biodiesel).
  • general hydrogenation catalysts for example, a catalyst including an inorganic oxide support (alumina, silica, silica-alumina, zirconia, titania or the like) supported with VIB group metal and/or VIII group metal, a VIB group metal and/or VIII group metal phosphide catalyst, or the like may be used.
  • a catalyst including an inorganic oxide support alumina, silica, silica-alumina, zirconia, titania or the like
  • VIB group metal and/or VIII group metal a VIB group metal and/or VIII group metal phosphide catalyst, or the like
  • the paraffin components obtained may include n-paraffin and iso-paraffin.
  • an isomerization reaction is additionally performed to convert n-paraffin into iso-paraffin (that is, isomerized fraction of biomass-derived diesel).
  • the iso-paraffin in the product may have a carbon number of 10 to 25, specifically, 15 to 18; a boiling point of 170 to 400°C, specifically, 270 to 320°C; and a kinematic viscosity (at 100°C) of 2 cSt or less, specifically, 1 to 2 cSt.
  • FIG. 2 is a schematic view showing a process of producing a lube base oil fraction as a feedstock for an alkylation, wherein the lube base oil fraction is prepared from the isomerization reaction of unconverted oil derived from the hydrocracking of fuel oil.
  • a fuel oil hydrocracking process is a process of hydrocracking vacuum gas oil (VGO) obtained by the vacuum distillation process (V1) of an atmospheric residue, that is, a heavy hydrocarbon mixture.
  • VGO vacuum gas oil
  • a hydrotreatment process (R1) which is a pretreatment process for removing heterocompounds containing impurities such as sulfur, nitrogen, oxygen and the like and metal components from vacuum gas oil (VGO) is conducted in order to protect a catalyst for a hydrocracking process (R2) (main process).
  • the hydrocracking process (R2) as a main process, is conducted.
  • unsaturated hydrocarbons such as aromatic compounds, olefin compounds and the like, included in vacuum gas oil (VGO) is hydrogenated to be converted into saturated hydrocarbons, such as naphthene compounds, paraffin compounds and the like.
  • saturated hydrocarbons such as naphthene compounds, paraffin compounds and the like.
  • some of the naphthene compounds, which are cyclic saturated hydrocarbons may be converted into paraffin compounds, which are straight-chain hydrocarbons, by a ring-opening reaction. Further, these compounds may be decomposed into smaller compounds.
  • hydrocracking Such a series of procedures is referred to as hydrocracking , and these compounds are converted into a light hydrocarbon mixture, that is, a light fuel distillate.
  • Oil and hydrogen, having passed the hydrocracking process (R2), are recycled after hydrogen is removed via a separator, and various kinds of converted light fuel distillates and gases are fractionated through a first fractional distillation process (Fs1) and made into products.
  • the conversion ratio of vacuum gas oil (heavy oil fraction) into a light fuel distillate is generally designed such that a reactor per pass conversion is 50 to 90%. Since it is substantially impossible to perform an operation at a reactor per pass conversion of 100%, unconverted oil (UCO) is produced in the final fractional distillation process.
  • the unconverted oil (UCO) is treated by a once-through mode for directly transferring UCO to a tank or by a recycle mode for recycling UCO to the hydrocracking process to increase the total conversion ratio.
  • the unconverted oil (UCO) which is not converted into a light fuel distillate in the hydrocracking process, includes a small amount of aromatic and heterocyclic compounds not preferable to lube base oil, and has viscosity suitable for lube base oil.
  • the unconverted oil (UCO) includes a large amount of straight-chain paraffin, that is, n-paraffin
  • straight-chain hydrocarbons are converted into branched hydrocarbons by an isomerization process, and then the branched hydrocarbons may be used as an isoparaffin-containing feedstock.
  • the isomerization process may be performed in the presence of an isomerization catalyst known in the related field, for example, a catalyst including mesopore zeolite (for example, EU-1, ZSM-35, ZSM-11, ZSM-57, NU-87, ZSM-22, EU-2, EU-11, ZBM-30, ZSM-48, ZSM-23 or a combination thereof) supported with VIII metals (for example, precious metals, such as platinum, palladium and the like) independently or in a combination thereof.
  • the isomerization reaction temperature may range from 300 to 400°C (specifically, 310 to 380°C)
  • the isomerization reaction pressure may range from 50 to 200 bar (specifically, 80 to 180 bar).
  • the isomerized unconverted oil (UCO) is selectively hydrofinished to remove aromatic and/or olefin components therefrom, thereby improving stability (not shown). Meanwhile, the unconverted oil (UCO) may be separated and recovered according to viscosity through a subsequent vacuum distillation process (not shown), and, in this case, this separated fraction having specific viscosity characteristics may be used as a feedstock for an alkylation reaction.
  • unconverted oil-derived lube base oil fraction as a feedstock for an alkylation reaction, may have a boiling point of 260 to 460°C, specifically, 290 to 430°C and a kinematic viscosity (at 100°C) of 8 cSt or less, specifically, 2 to 8 cSt. More specifically, the unconverted oil-derived lube base oil may have a carbon number of 14 to 30 (specifically, 16 to 28), and may have characteristics of group II or III metals.
  • Table 3 The exemplified characteristics of the unconverted oil-derived lube base oil are given Table 3 below.
  • fractions may be selectively used as a feedstock for an alkylation reaction during an oiling refining process.
  • these fractions may include a naphtha fraction, a diesel fraction and/or a group I lube base oil fraction.
  • a naphtha fraction having a boiling point of 38 to 140°C particularly, a paraffin-based naphtha fraction discharged from an atmospheric distillation tower includes a large amount of paraffins, and also includes a large amount of iso-paraffin.
  • a naphtha fraction particularly, full range naphtha includes paraffins (n-paraffin and iso-paraffin) in an amount of 60 to 90 wt%, and, particularly, includes iso-paraffin in an amount of 50 wt% or more. Therefore, this naphtha fraction may be used as a feedstock for an alkylation reaction without additional treatment, but, if necessary, may be subsequently isomerized to include a desired amount of iso-paraffin.
  • a diesel fraction (or middle distillate) may also be used as a feedstock for an alkylation reaction as long as it has a boiling point (for example, 200 to 380°C) similar to that of the above-mentioned biomass-derived diesel isomerized fraction and includes a predetermined amount or more of iso-paraffin. If the content of iso-paraffin in the diesel fraction is below the predetermined amount, the content thereof will be increased through an isormerization process.
  • the group I lube base oil which is lube base oil obtained by treating hydrocarbons through solvent refining, solvent dewaxing, finishing or the like, includes a considerable amount of paraffins. Therefore, as in the embodiment, the group I lube base oil may be used in an alkylation reaction as long as it includes a predetermined amount or more of isoparaffin. If necessary, the group I lube base oil is selectively isomerized to increase the content of isoparaffin therein.
  • the peroxide used in an alkylation reaction is a radical initiator, and is represented by Formula 1 below:
  • R and R' are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms (specifically, an alkyl group of 1 to 4 carbon atoms) or an acetyl group of 1 to 10 carbon atoms (specifically, an acetyl group of 1 to 6 carbon atoms).
  • the peroxide may include hydrogen peroxide, dimethyl peroxide, diethyl peroxide, di-t-butyl peroxide, benzoyl peroxide, and the like. It is particularly advantageous that di-t-butyl peroxide be used as the peroxide in terms of characteristics of an isoparaffin-containing feedstock as a reactant.
  • the peroxide may be introduced into a reaction system together with an isoparaffin-containing feedstock, and may also be separately introduced into the reaction system.
  • the used amount of peroxide may be 5 to 35 wt%, specifically 15 to 30 wt%, and more specifically 20 to 30 wt%, based on the total amount of reactants.
  • the degree of alkylation also increases.
  • the amount of peroxide be suitably adjusted within the above-mentioned range in consideration of the characteristics of paraffin in the isoparaffin-containing feedstock.
  • an alkylation reaction may be performed using peroxide without additional catalysts (for example, an acid catalyst, specifically, a zeolite catalyst).
  • the alkylation reaction may be performed under the conditions of a temperature of 10 to 200°C, specifically 120 to 180°C, and more specifically 150 to 180°C, and a pressure of 1 to 100 bar, specifically 3 to 10 bar, and more specifically 3 to 8 bar.
  • olefin components are not intentionally used during the alkylation reaction.
  • olefin there is a limitation in increasing the viscosity index of the final lube base oil product, which is a major characteristic index thereof, to 120 or more (group III standard), and it is difficult to obtain lube base oil having high viscosity.
  • group III standard group III standard
  • the unreacted olefin is inevitably included in a reaction product because the conversion ratio of olefin does not reach 100%.
  • a hydrofinishing process is required.
  • dimmers or oligomers may be formed due to the reaction between olefins. These dimmers or oligomers function as a factor deteriorating the characteristics of lube base oil.
  • the alkylation reaction may be performed by a batch mode or a continuous mode.
  • reaction time may be 0.5 to 5 hr, specifically 0.5 to 4 hr, and more specifically 1 to 2 hr.
  • weight hourly space velocity (WHSV) may be adjusted within the range of 0.2 to 2 hr -1 , specifically 0.25 to 2 hr -1 , and more specifically 0.5 to 1 hr -1 .
  • the conversion ratio in the alkylation reaction may be 20 to 50%, specifically, 30 to 40%.
  • FIG. 3 is a schematic block diagram showing a continuous process including the steps of alkylation reaction, separation and peroxide regeneration.
  • an isoparaffin-containing feedstock is introduced into an alkylation reaction unit through a line 1, and, at this time, the regenerated and recycled peroxide is mixed with the feedstock through a line 5. Further, the unreacted feedstock separated by a separator is recycled through a line 3 to be mixed with the feed stock.
  • the alkylation reaction product includes alkylate, ureacted feedstock and/or alcohol (alcohol produced by the side-reaction between hydrocarbons and peroxide). Therefore, after the alkylation reaction is completed, the reaction product stream is transferred to a separator. In this case, alcohol and the like, which are by-products, may be removed by a phase-separation method (not shown), and the alkylation product may be separated from unreacted feedstock at 200 to 450°C under an atmospheric pressure.
  • the alcohol is transferred to a peroxide regeneration unit through a line 4 to be regenerated into peroxide.
  • a peroxide regeneration unit for example, when di-t-butyl peroxide is used, t-butyl alcohol produced therefrom reacts with hydrogen peroxide in the presence of an acid catalyst to be converted into di-t-butyl peroxide.
  • Alkylate prepared by an alkylation process according to an embodiment of the present invention, satisfies basic boiling point conditions of lube base oil, and exhibits high viscosity and a high viscosity index. Therefore, this alkylate can be successfully used as lube base oil.
  • lube base oil when an isomerized fraction of biomass-derived diesel is used as a feedstock, lube base oil may exhibit a boiling point (ASTM D2887) of 300 to 700°C (specifically, 320 to 600°C), a viscosity index of 90 to 150 (specifically, 100 to 140), a kinematic viscosity (at 100°C) of 2 to 30 cSt (specifically, 3 to 20 cSt) and a pour point of -36 to 0°C (specifically, -30 to -20°C).
  • lube base oil may exhibit a boiling point (ASTM D2887) of 400 to 700°C (specifically, 440 to 600°C), a viscosity index of 90 to 150 (specifically, 100 to 140), a kinematic viscosity (at 100°C) of 6 to 60 cSt (specifically, 6 to 40 cSt) and a pour point of -40 to 0°C (specifically, -30 to -20°C).
  • a 500 mL high-pressure reactor (autoclave) was maintained under a nitrogen atmosphere.
  • 104.25 g of isoheptadecane (C 15-18 ) having an average carbon number of 17 and 26.06 g of di-t-butyl peroxide (radical initiator) were mixed at a weight ratio of 80: 20, and the mixture was introduced into the high-pressure reactor using nitrogen stream.
  • the high-pressure reactor was sealed, and then the mixture was stirred at a pressure of 5 atm. (5.07 bar) and a temperature of 150°C for 120 min at a rotation speed of 100 rpm to be reacted.
  • the high-pressure reactor was cooled to room temperature, and then its pressure was reduced to the atmospheric pressure, and a transparent liquid reaction product was transferred from the reactor to a 500 mL round-bottom flask.
  • the liquid reaction product was washed with ethanol and distilled water, and then phase-separated for 1 day using a separatory funnel. Pressure was reduced at 50°C to remove residual peroxide and water from the phase-separated reaction product, thereby finally obtaining transparent liquid alkylate.
  • Transparent liquid alkylate was obtained in the same manner as in Example 1, except that 117 g of isooctadecane and 29.13 g of di-t-butyl peroxide were used instead of isoheptadecane having an average carbon number of 17.
  • the physical properties of the obtained alkylate are given in Table 5 below, and the SIMDIS graph thereof is shown in FIG. 5.
  • Yellow alkylate was obtained in the same manner as in Example 1, except that 127.62 g of isotricosane having an average carbon number of 23 and 30.40 g of tertiary-butyl peroxide were used instead of isoheptadecane having an average carbon number of 17.
  • the physical properties of the obtained alkylate are given in Table 5 below, and the SIMDIS graph thereof is shown in FIG. 6.
  • a 500 mL high-pressure reactor (autoclave) was maintained under a nitrogen atmosphere.
  • 42 g of isooctadecane, 14 g of 2-pentene (an olefin) and 14 g of di-t-butyl peroxide (radical initiator) were mixed at a weight ratio of 60: 20: 20, and the mixture was introduced into the high-pressure reactor using nitrogen stream.
  • the high-pressure reactor was sealed, and then the mixture was stirred at a pressure of 5 atm. (5.07 bar) and a temperature of 150°C for 120 min at a rotation speed of 100 rpm to be reacted.
  • the high-pressure reactor was cooled to room temperature, and then its pressure was reduced to the atmospheric pressure, and a reaction product was transferred from the reactor to a 500 mL round-bottom flask.
  • pressure was reduced at room temperature to obtain a transparent liquid reaction product.
  • this liquid reaction product was washed with ethanol and distilled water, and then phase-separated for 1 day using a separatory funnel. Pressure was reduced at 50°C to remove residual peroxide and water from the phase-separated reaction product, thereby finally obtaining transparent liquid alkylate.
  • the physical properties of the obtained alkylate are given in Table 5 below, and the SIMDIS graph thereof is shown in FIG. 5.
  • Yellow alkylate was obtained in the same manner as in Example 1, except that 42 g of isotricosane having an average carbon number of 23 was used instead of isooctadecane.
  • the physical properties of the obtained alkylate are given in Table 5 below, and the SIMDIS graph thereof is shown in FIG. 6.
  • Example 2 the alkylation reaction was conducted using isoparaffin having a long chain and peroxide without the addition of olefins.
  • isooctadecane was used as isoparaffin (Example 2)
  • the kinematic viscosity of the produced alkylate at 100°C was increased to about 186.2% compared to that of a reactant.
  • Example 3 when isotricosane having an average number of 23 was used as isoparaffin (Example 3), the kinematic viscosity of the produced alkylate at 100°C was increased to about 225.9% compared to that of a reactant, and the viscosity index thereof was increased to about 119.2% compared to that of a reactant.

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PCT/KR2014/003045 2013-04-09 2014-04-08 Method of producing lube base oil by alkylation of hydrocarbons WO2014168403A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9822046B1 (en) 2016-05-19 2017-11-21 Chevron U.S.A. Inc. Farnesane alkylation
US10093594B2 (en) 2016-05-19 2018-10-09 Chevron U.S.A. Inc. High viscosity index lubricants by isoalkane alkylation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102026330B1 (ko) 2018-09-27 2019-09-27 에스케이이노베이션 주식회사 저온 성능이 개선된 광유계 윤활기유 및 이의 제조 방법, 및 이를 포함하는 윤활유 제품
KR102213789B1 (ko) 2019-09-20 2021-02-08 에스케이이노베이션 주식회사 디젤 분획을 포함하는 공급원료로부터 윤활기유를 제조하는 방법, 및 이에 의해 제조되는 윤활기유

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4594172A (en) * 1984-04-18 1986-06-10 Shell Oil Company Process for the preparation of hydrocarbons
US4990713A (en) * 1988-11-07 1991-02-05 Mobil Oil Corporation Process for the production of high VI lube base stocks
US5037528A (en) * 1985-11-01 1991-08-06 Mobil Oil Corporation Lubricant production process with product viscosity control
US20080253936A1 (en) * 2007-04-16 2008-10-16 Ramin Abhari Process for producing synthetic petroleum jelly
US20110124537A1 (en) * 2008-06-13 2011-05-26 Thomas Kilthau Lubricant composition based on natural and renewable raw materials

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090001330A1 (en) 2007-06-28 2009-01-01 Chevron U.S.A. Inc. Electrical Insulating Oil Compositions and Preparation Thereof
JP5525786B2 (ja) 2009-08-31 2014-06-18 Ｊｘ日鉱日石エネルギー株式会社 航空燃料油基材の製造方法及び航空燃料油組成物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4594172A (en) * 1984-04-18 1986-06-10 Shell Oil Company Process for the preparation of hydrocarbons
US5037528A (en) * 1985-11-01 1991-08-06 Mobil Oil Corporation Lubricant production process with product viscosity control
US4990713A (en) * 1988-11-07 1991-02-05 Mobil Oil Corporation Process for the production of high VI lube base stocks
US20080253936A1 (en) * 2007-04-16 2008-10-16 Ramin Abhari Process for producing synthetic petroleum jelly
US20110124537A1 (en) * 2008-06-13 2011-05-26 Thomas Kilthau Lubricant composition based on natural and renewable raw materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9822046B1 (en) 2016-05-19 2017-11-21 Chevron U.S.A. Inc. Farnesane alkylation
US10093594B2 (en) 2016-05-19 2018-10-09 Chevron U.S.A. Inc. High viscosity index lubricants by isoalkane alkylation
US10246384B2 (en) 2016-05-19 2019-04-02 Chevron U.S.A. Inc. Alkylate base oil of biological origin
US10435337B2 (en) 2016-05-19 2019-10-08 Chevron U.S.A. Inc. Composition of isoalkane alkylate base oil

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