EP2338955A1 - Selektives Entfernen von Aromaten - Google Patents

Selektives Entfernen von Aromaten Download PDF

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EP2338955A1
EP2338955A1 EP09252723A EP09252723A EP2338955A1 EP 2338955 A1 EP2338955 A1 EP 2338955A1 EP 09252723 A EP09252723 A EP 09252723A EP 09252723 A EP09252723 A EP 09252723A EP 2338955 A1 EP2338955 A1 EP 2338955A1
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feedstock
compounds
ionic liquid
aromatic compounds
process according
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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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26

Definitions

  • This invention relates to the selective removal of aromatics from a hydrocarbon mixture, more specifically to the selective removal of aromatics from a hydrocarbon mixture additionally comprising olefins.
  • the major sources of benzene and other aromatic compounds in gasoline are refinery streams derived from catalytic reforming, and also naphtha streams derived from fluid catalytic cracking (cracked naphtha).
  • a straight run naphtha i.e. naphtha taken directly from the crude oil distillation unit (CDU) of a refinery
  • CDU crude oil distillation unit
  • a straight run naphtha i.e. naphtha taken directly from the crude oil distillation unit (CDU) of a refinery
  • CDU crude oil distillation unit
  • UOP PlatformingTM process is an example of such a catalytic reforming process ( Platinum Metals Review, 1961, 5 (1), 9-12 ).
  • Other reforming processes are described in the Kirk-Othmer Encyclopaedia of Chemical Technology, Volume 17, third edition, pp 218-221 .
  • a heavy crude oil fraction for example vacuum gas oil
  • a solid acid catalyst typically zeolite Y or USY
  • Aromatic hydrocarbons and olefins are also produced.
  • Catalytic cracking processes are described in Kirk-Othmer Encyclopaedia of Chemical Technology, Volume 17, third edition, pp 205-211 .
  • One process for reducing the concentration of aromatics in a hydrocarbon mixture is by hydrogenation, for example hydrodearomatisation processes in which the aromatic-containing composition and hydrogen are contacted with a catalyst comprising a Group VIB and Group VIII element, for example as described in US 1,965,956 , or a catalyst additionally comprising boron and a carbon support, as described in US 5,449,452 .
  • a catalyst comprising a Group VIB and Group VIII element, for example as described in US 1,965,956 , or a catalyst additionally comprising boron and a carbon support, as described in US 5,449,452 .
  • Another method of removing aromatic compounds is to use distillation.
  • a large distillation column with a large number of trays would be required, which would be highly energy and capital intensive.
  • the formation of azeotropes between some components can limit the extent of separation that is possible by distillation.
  • a further method is to use solvent extraction.
  • Solvent extraction may be performed using a solvent such as N-methyl-2-pyrrolidine, as described by Sergeant et al in Fuel Processing Technology, 41, 1995, 147-157 .
  • Another such solvent is sulfolane (2,3,4,5-tetrahydrothiophene-1,1-dioxide).
  • GB 1,008,921 discloses a process in which sulfolane is used to selectively dissolve aromatic compounds in a hydrocarbon stream.
  • a problem with this process is that the solvent recovery and recycle is energy intensive; see Meindersma et al in Chem. Eng. Res. Design, 86 (2008), 745-752 . Additionally, solvent is continually lost from the process, and therefore requires continuous replenishment.
  • Ionic liquids are non-volatile liquid salts. They have found application in separation technology, for example in the separation of paraffinic molecules from aromatic molecules or olefinic molecules.
  • Meindersma et al in Fuel Processing Technology, 87 (2005), 59-70 describe a process for the separation of C 4 to C 10 aliphatic alkanes and aromatic compounds such as benzene, toluene, ethyl benzene and xylenes using ionic liquids. It was found that the ionic liquids [Mebupy]BF 4 , [Mebupy]CH 3 SO 4 , [BMIM]BF 4 and [EMIM]tosylate can achieve superior toluene/heptane separation compared to sulfolane.
  • EP-A-1 854 786 describes the use of an ionic liquid to extract aromatic compounds from a mixture containing at least one aliphatic hydrocarbon.
  • the ionic liquid comprises a cation having an aromatic nitrogen-containing heterocyclic ring system, in which one of the nitrogens in the aromatic ring is quaternised, and the ring has at least one electron-withdrawing substituent.
  • US 6,623,659 describes a process for separating olefinic from non-olefinic hydrocarbons such as paraffins, cycloparaffins, oxygenates and aromatics using metal ions, in particular copper or silver ions, dissolved in ionic liquids, in which the metal salts are used to form a complex with the olefinic compounds and retain them in the ionic liquid phase.
  • DE 10154052 describes the use of ionic liquids for separating aromatics from other hydrocarbons, and exemplifies benzene/cyclohexene separation using the ionic liquid [EMIM](CF 3 SO 2 ) 2 N.
  • EMIM ionic liquid
  • a process for reducing the concentration of one or more aromatic compounds in a feedstock comprising one or more aromatic compounds and one or more olefinic compounds comprises contacting the feedstock with an ionic liquid comprising an anionic component and a cationic component to produce a product with a higher mole ratio of olefinic compounds to aromatic compounds than the feedstock, and an ionic liquid phase with a lower mole ratio of olefinic compounds to aromatic compounds than the feedstock, wherein the surface charge profile of the cationic component has a maximum value at a charge density value ( ⁇ ) in the range -0.0085 ⁇ ⁇ ⁇ -0.0040 e/ ⁇ 2 , and wherein from 25% to 65% of the molecular surface area of the anionic component has a charge density value ( ⁇ ) in the range -0.0085 ⁇ ⁇ +0.0085 e/ ⁇ 2 , where e represents the charge of an electron.
  • the feedstock comprises one or more aromatic compounds.
  • the one or more aromatic compounds comprise one or more monoaromatic compounds, for example selected from benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, xylenes, ethyltoluenes, trimethylbenzenes, diethylbenzenes, n-butyl benzene and tetramethylbenzenes, and/or one or more compounds with more than one aromatic ring, for example selected from naphthalene, methylnaphthalenes, fluorene, methylfluorenes, phenanthrene, anthracene, methylphenanthrenes, methyl-isopropyl-phenanthrenes, dimethylphenanthrenes, methylanthracenes, fluoranthrene, pyrene, methylpyrenes, benzofluoranthene, cyclopentopyren
  • the feedstock also comprises one or more olefinic compounds.
  • the one or more olefinic compounds are selected from linear, cyclic and branched alkenes, for example selected from C 4 to C 10 olefins such as butenes, pentenes, hexenes, hexadienes, heptenes, octenes, cyclohexene, cyclooctene, and/or larger molecules such as C 11 to C 20 olefins, for example hexadecene or octadecene.
  • the one or more olefinic compounds include 1-hexene.
  • the olefinic compound can have one carbon-carbon double bond or a plurality of carbon-carbon double bonds.
  • Examples of olefinic compounds containing a plurality of carbon-carbon double bonds include 1,3-butadiene and dicyclopentadiene.
  • the feedstock can be a process stream derived from the refining of crude oil, or a mixture of two or more process streams from crude oil refining.
  • the feedstock is predominantly comprised of hydrocarbons, but it may also contain heteroatom-containing organic molecules such as organo-nitrogen and organo-sulphur compounds.
  • Ionic liquids are generally defined as low melting point salts, i.e. compounds having an anionic component and cationic component, and which are typically liquids at temperatures below 150 °C. In the present invention, the ionic liquids are preferably liquid at temperatures below 100 °C. Individual ionic liquids or mixtures of two or more ionic liquids can be used.
  • the surface charge profile of a molecule can be calculated using quantum mechanics calculations, based for example on density functional theory.
  • calculations may be performed using the software "COSMO-RS” (Conductor-like Screening Model for Real Solvents), the principles of which are described in detail by Klamt in "COSMO-RS, From Quantum Chemistry to Fluid Phase Thermodynamics and Drug Design", published by Elsevier (1st Edition, 2005 ).
  • COSMO-RS theory considers all molecular interactions to consist of local pair-wise interactions of segments of molecular COSMO-surfaces.
  • Quantum chemical COSMO calculations provide a discrete surface around a molecule embedded in a virtual conductor.
  • Each segment, i, of the surface is characterised by its area (a i ) and the screening charge density ( ⁇ i ), which takes into account the electrostatic screening of the molecule by its surrounding, and the back-polarization of the molecule.
  • screening is considered to be perfect, and so the ⁇ i value is related predominantly to back-polarization.
  • the total energy of the ideally screened molecule (E cosmo ) is also provided.
  • a liquid is considered to be an ensemble of closely packed ideally screened molecules. Thermodynamic properties of compounds are calculated from statistical averaging in the ensemble of interacting surface segments.
  • ⁇ -profiles The ⁇ -profile of the whole system or mixture, p s ( ⁇ ), is a sum of the ⁇ -profiles of the components X i weighted with the mole fraction in the mixture, x i .
  • the surface charge profile, or ⁇ -profile, of a molecule or ion can be represented graphically with charge density on the abscissa, and a frequency value on the ordinate related to the surface area of the molecule or ion having that charge density.
  • the charge density is often represented by the term sigma ( ⁇ ), and is expressed in units of charge per unit area, for example e/ ⁇ 2 , where e represents the charge of an electron, or the negative of the charge of a proton, otherwise termed the "elementary charge”.
  • the elementary charge is taken to be 1.602176 x 10 -19 C.
  • the surface area of a molecule or ion associated with a particular charge density value can be expressed in a variety of ways, for example as a surface area value itself, i.e. the surface area of the molecule or ion having that charge density, or as a relative value such as the percentage of the total surface area of the molecule or ion having that charge density.
  • the anionic and cationic components of the ionic liquid are preferably selected so as to match the surface charge profile of the one or more aromatic compounds in the feedstock. Matching the surface charge profiles enables better interaction between the ionic liquid components and the one or more aromatic compounds, which improves their solubility in the ionic liquid and provides a more efficient selective removal from the feedstock. Preferably, the surface charge profile differs significantly from that of the one or more olefinic compounds.
  • Examples of cationic components falling within the above definition include imidazolium, pyrrolidinium and pyridinium cations having one, two or three alkyl substituents, the alkyl substituents typically having from 1 to 6 carbon atoms, for example 1 to 4 carbon atoms.
  • the cationic component is selected from dialkyl-substituted imidazolium cations such as 3-butyl-1-methyl-imidazolium [BMIM], dialkyl-substituted pyridinium cations such as 3-methyl-N-butyl pyridinium [3-Mebupy], and dialkyl-substituted pyrrolidinium cations, such as 1-methyl-3-butyl pyrrolidinium [Mebupyrr]. Additional examples include N-containing organic cations with two aromatic rings, for example quinolinium and guanidinium cations and alkyl-substituted analogues thereof. [3-Mebupy] and [BMIM] are particularly effective as the cationic component.
  • anionic components examples include dicyanamide [N(CN) 2 ; DCA], tricyanomethanide [C(CN) 3 ; TCM], SCN and B(CN) 4 .
  • the performance of an ionic liquid in separating aromatic compounds from olefinic compounds in a feedstock can be expressed using two parameters.
  • the distribution coefficient, D, of a component is defined as the ratio of the concentration of that component in the ionic liquid, C IL , compared to the concentration of that component remaining in the product, C Prod .
  • Concentrations can be expressed in any units, for example on a molar basis such as mol/L, on a weight basis (w/w), such as g/g or kg/kg, on a volume basis (v/v), such as L/L or mL/mL, or a weight per volume basis (w/v), such as g/mL or kg/L
  • D arom C arom IL / C arom Prod
  • D olefin C olefin IL / C olefin Prod
  • the D value is high, the relative concentration of the component in the ionic liquid phase is high compared to the product phase, and represents high solubility of that component in the ionic liquid phase.
  • preferred ionic liquids will have a high D arom value, and a low D olefin value. High D values also indicate that the ionic liquid has a high capacity for the relevant component.
  • the selectivity, S, of one component over another can be expressed in terms of the ratio of the distribution coefficients for the two components to be separated.
  • a high S value represents relatively higher aromatic solubility in the ionic liquid compared to olefin.
  • Preferred ionic liquids combine the benefits of high distribution coefficients with high selectivity, i.e. have high D arom and S values.
  • the ionic liquid preferably has an S value greater than 0.75 times that of the corresponding S value for sulfolane, and more preferably has an S value greater than that of the corresponding S value for sulfolane.
  • the S value is greater than 5.25, for example greater than 5.5 or greater than 10, wherein the corresponding D arom and D olefin values are calculated from the respective C IL and C Prod values expressed on a w/w basis, typically g/g.
  • Higher D arom values represent high capacity for an aromatic compound, whereas higher S values are advantageous in that the selectivity towards aromatic separation compared to olefinic separation is greater.
  • high D arom and high S values are preferred, as this may reduce the size of separation vessels and the quantities of ionic liquids required for achieving a sufficient level of separation.
  • high S values may correspond to a reduced quantity of olefin removed from the feedstock, which is beneficial towards products that are used as or in the production of gasoline fuels for maintaining high octane rating, and/or reducing the negative impact on octane rating through removal of the aromatics.
  • the purity of aromatics that can be recovered from the ionic liquid phase may be higher.
  • the volume ratio of ionic liquid to hydrocarbon feedstock fed to the separator is typically in the range of from 10:1 to 0.001: 1.
  • Preferred ionic liquids that have shown particularly good separation activity, in terms of capacity and selectivity, include [3-Mebupy][C(CN) 3 ] , [3-Mebupy][N(CN) 2 ], [BMIM][C(CN) 3 ] and [Mebupyrr][N(CN) 2 ].
  • a feedstock comprising one or more aromatic compounds and one or more olefinic compounds is contacted with an ionic liquid to produce a product with a lower concentration of the one or more aromatic compounds.
  • the ionic liquid and the product typically form separate phases, the ionic liquid generally being denser, for example when the feedstock and product predominantly comprise hydrocarbons.
  • the mole ratio of olefinic compounds to aromatic compounds is higher in the product compared to the initial feedstock, while in the ionic liquid phase the mole ratio is lower than that of the feedstock.
  • the concentration of one or more aromatic compounds in the feedstock is reduced, yielding a product with a lower concentration of aromatic compounds.
  • the net effect of the ionic liquid separation process is a relative decrease in the concentration of aromatic compounds compared to the concentration of olefin compounds in a feedstock, resulting in a product having a lower concentration of aromatic compounds compared to the feedstock, with a lower reduction of the olefin content of the product compared to the feedstock.
  • Preferably more than 10% of the aromatic compounds are removed from the hydrocarbon feedstock, for example in the range of from 10 to 100%.
  • greater than 50% of the aromatic compounds are removed from the hydrocarbon feedstock.
  • a process of the present invention is particularly effective at selective removal of aromatic compounds where their content in the feedstock is low, for example less than 20% by volume. At such concentrations, the D arom exceeds that of sulfolane as a solvent.
  • the ionic liquid and feedstock are both fed to a separation vessel.
  • the ionic liquid and feedstock are fed counter-currently into a static vessel, wherein the denser phase, typically the ionic liquid, is fed to the upper portion of the vessel and the less dense phase, typically the feedstock, is fed to the lower portion of the vessel.
  • the denser phase typically the ionic liquid
  • the less dense phase typically the feedstock
  • the ionic liquid and feedstock are stirred or otherwise agitated in a first separation vessel. They can then be allowed to settle after mixing before portions of each phase are removed from the vessel.
  • the mixed phases can be transferred to a second separation vessel, where the two phases are allowed to separate. This process can also operate continuously, such that a continuous supply of ionic liquid and feedstock can be fed to the first vessel, and the mixed phases can be continuously extracted from the first separation vessel to the non-agitated second separation vessel, the resulting product phase and ionic liquid phase from which can be separately and continuously extracted.
  • the ionic liquid and feedstock are fed to a rotating disc separation column which acts as the separation vessel, in which a series of separation plates are rotated, providing agitating mixing of the ionic liquid and feedstock phases, the ionic liquid being fed towards the top of the column, and the feedstock being fed into the column at a point nearer the base of the column.
  • the extracted product phase which contains a reduced concentration of aromatic compounds, is removed from a point towards the top of the separation column, while ionic liquid with extracted aromatic compounds can be removed from a point towards the bottom of the column.
  • the ionic liquid can be processed to remove the aromatic compounds. This can be achieved by distillation or flash separation techniques, due to the extremely low volatility of the ionic liquid.
  • the aromatic compounds can then be used for chemicals manufacture, for example in toluene or xylene production. Alternatively, they can be hydrogenated to produce cyclic alkanes, typically naphthenes such as cyclohexane, alkylcyclohexanes and polycyclic naphthenes.
  • Aromatic hydrogenation can be achieved, for example, by contacting the aromatic-containing composition and hydrogen with a catalyst comprising a Group VIB and Group VIII element, for example as described in US 1,965,956 or US 5,449,452 , the latter of which involves the use of a catalyst additionally comprising boron and a carbon support.
  • a catalyst comprising a Group VIB and Group VIII element, for example as described in US 1,965,956 or US 5,449,452 , the latter of which involves the use of a catalyst additionally comprising boron and a carbon support.
  • Pressures of 3 MPa or more are typically employed, for example in the range of from 10 to 25 MPa, and temperatures are typically in the range of from 200 to 450 °C.
  • the hydrogenated aromatics can be added to the product of the initial ionic liquid extraction process, i.e. the product with reduced aromatics content.
  • the product is a gasoline or can be used in the production of gasoline.
  • the naphthenes (cyclic alkanes) from the aromatics hydrogenation process can be useful components of gasoline fuel, and do not suffer the same toxicity and regulatory constraints of the corresponding aromatic compounds from which they can be produced. By adding them to the initial product of the extraction, fuel yields may be improved.
  • the product with reduced aromatic content after the ionic liquid extraction, can be used as a fuel, for example diesel or gasoline depending on the boiling point of the product.
  • Gasoline is produced from hydrocarbon mixtures that typically boil within the range of from 40 to 200 °C.
  • sources of gasoline blending stock include straight run light or heavy naphtha, isomerised straight run naphtha, cracked naphtha, pyrolysis gasoline, and products of catalytic reforming and alkylation processes.
  • the feedstock of the present invention may comprise one or more of these refinery streams.
  • the feedstock can be a fuel formulation, for example a gasoline fuel or a diesel fuel, that requires a reduction in aromatic concentration.
  • the process of the present invention can be applied in the selective removal of aromatics in the production of diesel fuel.
  • Typical refinery streams used in the production of diesel include straight run middle distillate, light cycle oils, heavy cycle oils, vacuum gas oils and cracked gas oils, any one or more of which can be used as a feedstock in the process of the present invention.
  • suitable process streams for diesel fuels boil within the range of from 150 to 400 °C.
  • Refinery process streams used in the production of diesel fuel typically comprise higher concentrations of aromatics with more than one aromatic ring, compared to streams used for gasoline production for example.
  • Aromatic concentrations in a diesel fuel are regulated, and are preferably less than 11% by volume in the final fuel, more preferably less than 8% by volume.
  • One source of aromatics in diesel fuels is light cycle oil, produced from fluidised catalytic cracking, and in one embodiment the process is used in the production of diesel fuel, or a product that can be blended with diesel, and the feedstock is or comprises light cycle oil.
  • the ionic liquid is also capable of removing heteroatom-containing organic compounds that may be present in the feedstock.
  • the product phase that is produced will have a lower concentration of one or more heteroatom-containing organic compounds compared to the feedstock.
  • the olefin to heteroatom-containing organic compound molar ratio will be higher in the product phase compared to the feedstock, and the olefin to heteroatom-containing organic compound molar ratio will be lower in the ionic liquid phase compared to the feedstock.
  • the ionic liquid may be used to separate aromatics and heteroatom-containing compounds from a hydrocarbon feedstock.
  • Heteroatom-containing compounds typically include sulphur and/or nitrogen-containing compounds, such as organo-amines and organo-sulphides, for example heterocyclic compounds or compounds comprising one or more alkyl and/or aryl groups.
  • sulphur and/or nitrogen-containing compounds such as organo-amines and organo-sulphides, for example heterocyclic compounds or compounds comprising one or more alkyl and/or aryl groups.
  • the feedstock comprises sulphur-containing organic compounds.
  • Typical sulphur-containing organic compounds associated with refining include mercaptans, sulphides, di-sulphides, thiophenes, benzothiophenes and dibenzothiophenes, at least a portion of which are extracted in the ionic liquid phase during the extraction process.
  • the product comprises reduced concentrations of sulphur-containing compounds and aromatic compounds, and can be used as, or in the production of, low sulphur and low aromatic fuels, such as gasoline or diesel.
  • the ionic liquid is removed from the separation vessel, and the separated compounds from the feedstock are separated, for example by flash separation or distillation.
  • the extracted compounds may then be subjected to a desulphurisation reaction, for example a hydrodesulphurisation reaction.
  • a desulphurisation reaction for example a hydrodesulphurisation reaction.
  • hydrodesulphurisation reaction involve the use of temperatures in the range of from 200 to 430 °C, for example 230 to 400 °C or 280 to 400 °C, and pressures in the range of from 20 to 200 bara (2 to 20 MPa), for example 25 to 130 bara (2.5 to 13 MPa).
  • the desulphurisation preferably takes place before any benzene hydrogenation stages, as sulphur can act as a catalyst poison for some aromatic hydrogenation catalysts.
  • a suitable desulphurisation process is described in US 2007/0227948 , the contents of which are incorporated herein by reference.
  • the feedstock comprises nitrogen-containing organic compounds.
  • Typical nitrogen-containing organic compounds associated with refining include heterocyclic aromatic compounds such as pyridines, quinolines and pyrroles. Their removal, for example by hydrodenitrification, tends to require more hydrogen compared to sulphur removal. Conditions similar to those of hydrodesulphurisation reactions can be used. For example, temperatures in the range of from 200 to 430 °C, such as 230 to 400 °C or 280 to 400 °C, and pressures in the range of from 20 to 200 bara (2 to 20 MPa), for example 25 to 130 bara (2.5 to 13 MPa) may be used.
  • the resulting composition can be added to the product from the initial extraction, which reduces any loss in yield of products such as fuels from the feedstock.
  • the feedstock is a coker naphtha.
  • Coker naphtha derives from coking processes such as delayed coking, which are typically carried out on a vacuum residue, i.e. the residue remaining after vacuum distillation.
  • the aromatics content of coker naphtha depending on the boiling point, is typically in the range of from 1 to 50% by volume, and the olefins content is typically in the range of from 15 to 50 % by volume. Removing aromatics from a coker naphtha leaves an olefin-rich product, which can be oligomerised to produce hydrocarbons that can be used as or in the production of fuels such as gasoline, diesel or aviation fuel, in particular diesel fuel.
  • coker naphtha is typically quite rich in heteroatom-containing compounds, such as sulphur- or nitrogen-containing compounds, which can also be removed by the ionic liquid during extraction, then the removal of aromatics and heteroatom-containing compounds can be achieved in a single processing step.
  • heteroatom-containing compounds such as sulphur- or nitrogen-containing compounds
  • Figure 1 illustrates a process for producing gasoline, in which an ionic liquid 1 and a full range naphtha feedstock 2 comprising aromatic compounds, olefinic compounds and sulphur-containing compounds is fed to an extraction vessel 3. The resulting mixture 4 is then fed to separation/recovery vessel 5, where an olefin-rich product stream 6 with reduced aromatic and sulphur content is obtained. Regenerated ionic liquid 7 and a process stream 8 that is rich in aromatic and sulphur-containing compounds are also obtained.
  • the olefin-rich product stream 6 is fed to a sulphur removal unit 9.
  • the sulphur content of the olefin-rich product stream may be less than 1000 ppm expressed as elemental sulphur, more preferably less than 200 ppm.
  • the sulphur removal unit may comprise an adsorbent, such as zinc oxide, which adsorbs the sulphur-containing compounds.
  • a suitable desulphurisation process is described in US 2007/0227948 .
  • the resulting product stream 10 has a sulphur content of less than 50 ppm sulphur, expressed as elemental sulphur.
  • the reduced sulphur product stream 10 is then fractionated in fractionator 11 to produce ultra low sulphur gasoline fraction 12 and ultra low sulphur aviation fuel fraction 13. Alternatively, the whole product can be used to produce gasoline.
  • the regenerated ionic liquid 7 is removed from the base of separation/recovery vessel 5 and recycled to separation vessel 2.
  • Process stream 8 that is rich in aromatic and sulphur-containing compounds is fed to a hydrodesulphurisation unit 14 to reduce the sulphur concentration therein, typically to a value less than 200 ppm, and more preferably less than 50 ppm.
  • the resulting desulphurised stream 15 is then fed to a hydrodearomatisation unit 16, where it is contacted with hydrogen in the presence of a hydrodearomatisation catalyst.
  • the resulting dearomatised stream 17 comprising cyclic alkanes is then fed to a fractionator 18 to remove any unconverted aromatics 19.
  • the resulting low sulphur dearomatised product stream 20, comprising mainly cyclic alkanes may then be blended with the ultra low sulphur gasoline fraction 12, thereby enhancing the gasoline yield.
  • Figure 2 illustrates another process according to the present invention, in which a coker naphtha feedstock 1 and ionic liquid 2 are fed to a separation vessel 3.
  • a product stream 4 comprising high olefin content, and reduced sulphur, nitrogen and aromatics levels, is removed from separation vessel 3.
  • the olefins optionally after further separation or purification, may then be used as a feedstock for an oligomerisation process, to produce hydrocarbons that can be used as, or used in the production of diesel fuel.
  • An ionic liquid phase 5 containing extracted aromatics and nitrogen- and sulphur-containing compounds is also removed from the base of separation vessel 3. This phase is then fed to an ionic liquid recovery column 6, where the extracted components 7 are separated from the ionic liquid by distillation and, if desired, subjected to further processing. The extracted components 7 and the ionic liquid 8 are removed from the recovery column, and the ionic liquid is recycled to the separation vessel 3.
  • Figure 3 shows the surface charge profiles of toluene and 1-hexene, together with some other aromatic compounds.
  • the aromatic compounds there are two distinct peaks on the charge profile, relating to the negatively charged ⁇ -electron density above and below the aromatic ring, which corresponds to the peak at positive ⁇ values, and the positively charged portion of the molecular surface in the plane of the ring, around the hydrogen atoms, with a peak at negative ⁇ values.
  • Preferred cations include those based on pyridinium and imidazolium ions.
  • Figure 5 shows the surface charge profiles for a toluene, 1-hexene and a number of ionic liquid anions.
  • the anions generally have between 25 and 65% of their surface area with a charge density ⁇ in the range of from -0.0085 to +0.0085.
  • DCA, TCM, B(CN) 4 , SCN and CH 3 SO 4 It has been found that the extraction performance of ionic liquids for aromatics from olefins with these anions follows the order B(CN) 4 ⁇ TCM > DCA > SCN > CH 3 SO 4 . Improved extraction is correlated to a larger overlap of the anion surface charge profile with the whole toluene surface charge profile.
  • the superior extraction performance of B(CN) 4 and TCM is in agreement with the fact that the largest relative part of the surface charge area overlaps, which corresponds to increased interaction and therefore a higher distribution coefficient.
  • Performance results (in the form of distribution coefficients and selectivities) for these ionic liquids and sulfolane in relation to benzene / 1-hexene and toluene/1-hexene separations are shown in Table 1.
  • the units of the distribution coefficients are expressed on a weight basis, in g aromatic or olefin per g solvent or ionic liquid.
  • Mebupy- and BMIM-containing ionic liquids show significant advantages in terms of D arom values, and hence have a high capacity for aromatic compounds. Their selectivities are also significantly higher than the reference solvent sulfolane and the S222 and N1888 cations. Thus, compared with e.g. sulfolane, these ionic liquids selectively increase the distribution coefficient of benzene as well as toluene while leaving the distribution coefficient of 1-hexene nearly unaffected. As a result the extraction selectivity for both aromatics over 1-hexene is significantly higher compared with sulfolane.
  • Mebupyrr also confers significant advantages in terms of selectivity towards aromatics, as it has very low D olefin values and therefore high S-values, significantly higher than the sulfolane reference and the S222 and N1888 cations. This is due, in part, to its comparatively much lower D olefin value.
  • Ionic liquids comprising Mebupy, BMIM and Mebupyrr also exhibited higher extraction selectivity for aromatics from a synthetic FCC-derived gasoline feed comprising 1 wt% benzene, 3 wt% toluene, 40 wt% 1-hexene and 56 wt% hexane compared to sulfolane.
  • ionic liquids were used to extract aromatics at low aromatic concentrations.
  • 20 ml of a toluene/1-hexene mixture containing various concentrations of toluene was contacted for 15 min at 30 °C in a stirred glass vessel with 20 ml of solvent.
  • Sulfolane was used as the solvent.
  • the two phases were allowed to settle for 1h.
  • Samples were taken from both phases and analyzed by gas chromatography. The resulting composition data of both phases were used to calculate the distribution coefficient of toluene, D toluene .
  • a model FCC cracked naphtha stream comprising 1wt% benzene, 3wt% toluene, 40wt% 1-hexene and 56wt% hexane was continuously fed to a rotating disc extraction column, together with the ionic liquid [3-Mebupy][N(CN) 2 ].
  • a temperature of 40°C was maintained.
  • the rotating disc apparatus has been described previously by Meindersma et al in Chem. Eng. Res. Design, 86 (2008 ).
  • the extraction column had an internal diameter of 60mm, and was 3.8m tall.
  • the rotating element comprised numerous discs, and was rotated at 700rpm.
  • the top and bottom of the extraction column comprised settlers to ensure good phase separation.
  • Stators were present on the inner wall of the extraction columns. 16.8 kg/h of the model cracked naphtha feedstock was fed towards the top of the column. Ionic liquid and hydrocarbon product were continually removed from the column. Gas chromatography was used to analyse the hydrocarbon product removed from the extraction column. 86% of the benzene initially present in the feedstock had been removed, together with 64% of the toluene. Only 5% of the 1-hexene initially present was extracted by the ionic liquid.
  • a conversion model based upon the process scheme illustrated in Figure 1 was derived using Aspen Plus® software.
  • the model was based upon a full range naphtha composition comprising, by weight, 3% paraffins, 21% isoparaffins, 10% naphthenes, 30% olefins, 31% aromatics, and 5% high boilers (i.e. non-aromatic components having 12 or more carbon atoms).
  • the flow rate of the naphtha feedstock to the process was 100,000 barrels per day (100 kbpd), where one barrel is equal to 158.9873 litres.
  • the separation characteristics of the ionic liquid were taken to be those of [3-mebupy][N(CN) 2 ], which resulted in a calculated hydrocarbon product after extraction as comprising (by weight) 3.9% paraffins, 26.5% isoparaffins, 12.6% naphthenes, 37.7% olefins, 13.0% aromatics, 6.4% high boilers, and 300 ppm total sulphur. After sulphur absorption, the sulphur content is reduced to 10 ppm.
  • the hydrocarbons extracted in the ionic liquid phase comprise (by weight) 0.5% paraffins, 4.5% isoparaffins, 2.0% naphthenes, 8.3% olefins, 83.6% aromatics, 1.0% high boilers, and 1231ppm total sulphur. After hydrodesulphurisation, the sulphur content is reduced to 10ppm.
  • the hydrocarbon product of the ionic liquid separation process has improved motor octane number (MON) and research octane number (RON) compared to the initial full range naphtha feed, even though it is low in sulphur and low in aromatics, at least in part because the olefins content has not been reduced after the ionic liquid extraction process.
  • MON motor octane number
  • RON research octane number
  • the hydro-desulphurised and dearomatised composition produced from the components extracted with and subsequently recovered from the ionic liquid is blended with the ultra low sulphur (ULS) gasoline product, to produce a gasoline product with low aromatics and sulphur content, but with comparable MON and RON characteristics to the naphtha feed.
  • ULS ultra low sulphur

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KR20140064823A (ko) * 2011-07-29 2014-05-28 사우디 아라비안 오일 컴퍼니 선택적 단일-단계 수소화처리 시스템 및 방법
CN104049056A (zh) * 2014-06-25 2014-09-17 川渝中烟工业有限责任公司 烟气总粒相物中苯并[α]芘含量的测定方法
US9169446B2 (en) 2013-12-30 2015-10-27 Saudi Arabian Oil Company Demulsification of emulsified petroleum using carbon dioxide and resin supplement without precipitation of asphaltenes
WO2015191244A1 (en) * 2014-06-10 2015-12-17 Saudi Arabian Oil Company Integrated systems and methods for separation and extraction of polynuclear aromatic hydrocarbons, heterocyclic compounds, and organometallic compounds from hydrocarbon feedstocks
US9394489B2 (en) 2013-12-16 2016-07-19 Saudi Arabian Oil Company Methods for recovering organic heteroatom compounds from hydrocarbon feedstocks
RU2598383C2 (ru) * 2011-12-15 2016-09-27 Юоп Ллк Экстрагирование полициклических ароматических соединений из нефтяного сырья с использованием ионных жидкостей
RU2652406C2 (ru) * 2014-02-07 2018-04-27 Сауди Бейсик Индастриз Корпорейшн Удаление ароматических примесей из потока алкенов при помощи кислотного катализатора, такого как кислота льюиса
US10144685B2 (en) 2014-02-07 2018-12-04 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst
KR101945568B1 (ko) 2011-07-29 2019-02-07 사우디 아라비안 오일 컴퍼니 선택적 2-단계 수소화처리 시스템 및 방법
KR101945570B1 (ko) 2011-07-29 2019-02-07 사우디 아라비안 오일 컴퍼니 선택적 직렬-흐름 수소화처리 시스템 및 방법
KR101947849B1 (ko) 2011-07-29 2019-02-13 사우디 아라비안 오일 컴퍼니 선택적 직렬-흐름 수소화처리 시스템 및 방법
KR101947850B1 (ko) 2011-07-29 2019-02-13 사우디 아라비안 오일 컴퍼니 선택적 2-단계 수소화처리 시스템 및 방법
RU2686693C2 (ru) * 2014-02-07 2019-04-30 Сауди Бейсик Индастриз Корпорейшн Удаление ароматических примесей из потока алкенов при помощи кислотного катализатора, такого как кислотная ионная жидкость

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KR101945568B1 (ko) 2011-07-29 2019-02-07 사우디 아라비안 오일 컴퍼니 선택적 2-단계 수소화처리 시스템 및 방법
KR101945569B1 (ko) 2011-07-29 2019-02-07 사우디 아라비안 오일 컴퍼니 선택적 단일-단계 수소화처리 시스템 및 방법
KR20140064823A (ko) * 2011-07-29 2014-05-28 사우디 아라비안 오일 컴퍼니 선택적 단일-단계 수소화처리 시스템 및 방법
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RU2598383C2 (ru) * 2011-12-15 2016-09-27 Юоп Ллк Экстрагирование полициклических ароматических соединений из нефтяного сырья с использованием ионных жидкостей
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RU2652406C2 (ru) * 2014-02-07 2018-04-27 Сауди Бейсик Индастриз Корпорейшн Удаление ароматических примесей из потока алкенов при помощи кислотного катализатора, такого как кислота льюиса
US10144685B2 (en) 2014-02-07 2018-12-04 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst
RU2686693C2 (ru) * 2014-02-07 2019-04-30 Сауди Бейсик Индастриз Корпорейшн Удаление ароматических примесей из потока алкенов при помощи кислотного катализатора, такого как кислотная ионная жидкость
US10519080B2 (en) 2014-02-07 2019-12-31 Saudi Basic Industries Corporation Removal of aromatic impurities from an alkene stream using an acid catalyst, such as an acidic ionic liquid
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US9688923B2 (en) 2014-06-10 2017-06-27 Saudi Arabian Oil Company Integrated methods for separation and extraction of polynuclear aromatic hydrocarbons, heterocyclic compounds, and organometallic compounds from hydrocarbon feedstocks
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