WO2019123237A1 - Procédé de réduction de la teneur en asphaltènes et en composés aromatiques polynucléaires non substitués d'hydrocarbures lourds - Google Patents

Procédé de réduction de la teneur en asphaltènes et en composés aromatiques polynucléaires non substitués d'hydrocarbures lourds Download PDF

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WO2019123237A1
WO2019123237A1 PCT/IB2018/060236 IB2018060236W WO2019123237A1 WO 2019123237 A1 WO2019123237 A1 WO 2019123237A1 IB 2018060236 W IB2018060236 W IB 2018060236W WO 2019123237 A1 WO2019123237 A1 WO 2019123237A1
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Prior art keywords
hydrocarbon feed
heavy hydrocarbon
content
fluid medium
asphaltene
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PCT/IB2018/060236
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English (en)
Inventor
Mayuresh Arun SAHASRABUDHE
Sumit KHANDALKAR
Ramachandra Krishnamurthy CHAKRAVARTHY
Anilkumar Haribhai SAVALIA
Chandra Saravanan
Madhukar Onkarnath Garg
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Reliance Industries Limited
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Publication of WO2019123237A1 publication Critical patent/WO2019123237A1/fr

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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
    • C10G21/003—Solvent de-asphalting
    • 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
    • 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
    • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
    • 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
    • C10G21/08—Inorganic compounds only
    • 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
    • C10G21/14—Hydrocarbons
    • 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
    • C10G21/28—Recovery of used solvent
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
    • 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
    • C10G2300/1033—Oil well production fluids
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • C10G2300/206—Asphaltenes
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/208—Sediments, e.g. bottom sediment and water or BSW

Definitions

  • the present disclosure relates to a process for reducing the content of asphaltene and unsubstituted polynuclear aromatics of heavy hydrocarbons.
  • heavy hydrocarbons such as heavy coker gas oil (HCGO), vacuum gas oil (VGO), heavy vacuum gas oil (HVGO), and heavy atmospheric gas oil (HAGO) can be converted to lighter feedstocks by hydrotreating or fluidized catalytic cracking (FCC).
  • Lighter feedstocks are easy to crack and require less capital input for refining.
  • Heavy hydrocarbons comprise paraffins, substituted polynuclear aromatics (substituted PNAs), unsubstituted polynuclear aromatics (unsubstituted PNAs), as well as coke precursors such as asphaltene. Paraffins, and substituted polynuclear aromatics (substituted PNAs) can be converted to useful lower hydrocarbons.
  • the present disclosure relates to a process for reducing content of asphaltene and unsubstituted polynuclear aromatics in a heavy hydrocarbon feed.
  • the present disclosure provides a two stage process comprising reducing the asphaltene content of heavy hydrocarbon feed using a hydrocarbon fluid medium; followed by separating from heavy hydrocarbon feed with/ without reduced asphaltene content, an aromatic fraction containing unsubstituted polynuclear aromatics to obtain the heavy hydrocarbon feed with the reduced content of asphaltene and unsubstituted polynuclear aromatics.
  • the step of separating an aromatic fraction from heavy hydrocarbon feed either follows or precedes process step of reducing the asphaltene content of heavy hydrocarbon feed.
  • the heavy hydrocarbon feed in step is hydrocarbon feed with/ without reduced content of unsubstituted polynuclear aromatics.
  • the heavy hydrocarbon feed is mixed with the hydrocarbon fluid medium in a mixer to obtain a first resultant mixture.
  • the first resultant mixture is introduced in a settler and allowed to settle to obtain a first biphasic mixture comprising a hydrocarbon phase comprising heavy hydrocarbon feed with reduced asphaltene content and the solid phase comprising asphaltene.
  • the solid phase is separated from the first biphasic mixture to obtain the hydrocarbon phase comprising the heavy hydrocarbon feed with reduced asphaltene content.
  • the heavy hydrocarbon feed is mixed with a polar fluid medium to obtain a second resultant mixture.
  • the second resultant mixture is introduced in a settler and allowed it to settle to obtain a second biphasic mixture comprising an upper layer comprising a paraffin fraction with reduced content of aromatics, and the lower layer comprising an aromatic fraction containing unsubstituted polynuclear aromatics.
  • the upper layer is separated from the second biphasic mixture to obtain the paraffin fraction with reduced aromatics content and the aromatic fraction containing unsubstituted polynuclear aromatics.
  • the paraffin fraction is mixed with water and allowed to settle to obtain a third biphasic mixture comprising a first organic phase containing paraffins and a first aqueous phase containing polar fluid medium and water.
  • the aromatic fraction is mixed with water and allowed to settle to obtain a fourth biphasic mixture comprising a second organic phase containing aromatics and a second aqueous phase containing polar fluid medium and water.
  • the process of the present disclosure improves a compositional quality of the heavy hydrocarbon feed, which further helps in improving yield of FCC unit and life of hydro-treating catalyst.
  • Figure 1 is a schematic representation of a process for reducing asphaltene content of a heavy hydrocarbon in accordance with the present disclosure.
  • Figure 2 is a schematic representation of a process for reducing the content of unsubstituted polynuclear aromatics (unsubstituted PNAs) of a heavy hydrocarbon in accordance with the present disclosure.
  • Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
  • first, second, third, etc. should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
  • the present disclosure therefore, discloses a two stage process for reducing content of asphaltene and unsubstituted polynuclear aromatics of heavy hydrocarbon feed.
  • the present disclosure provides a two stage process comprising reducing the asphaltene content of heavy hydrocarbon feed using a hydrocarbon fluid medium; followed by separating from heavy hydrocarbon feed with/ without reduced asphaltene content, an aromatic fraction containing unsubstituted polynuclear aromatics to obtain the heavy hydrocarbon feed with the reduced content of asphaltene and unsubstituted polynuclear aromatics.
  • the step of separating an aromatic fraction from heavy hydrocarbon feed either follows or precedes process step of reducing the asphaltene content of heavy hydrocarbon feed.
  • the heavy hydrocarbon feed in step is hydrocarbon feed with/ without reduced content of unsubstituted polynuclear aromatics.
  • the heavy hydrocarbon feed is mixed with the hydrocarbon fluid medium in a mixer to obtain a first resultant mixture.
  • the first resultant mixture is introduced in a settler and allowed to settle to obtain a first biphasic mixture comprising a hydrocarbon phase comprising heavy hydrocarbon feed with reduced asphaltene content and the solid phase comprising asphaltene.
  • the solid phase is separated from the first biphasic mixture to obtain the hydrocarbon phase comprising the heavy hydrocarbon feed with reduced asphaltene content.
  • the heavy hydrocarbon feed is mixed with a polar fluid medium to obtain a second resultant mixture.
  • the second resultant mixture is introduced in a settler and allowed it to settle to obtain a second biphasic mixture comprising an upper layer comprising a paraffin fraction with reduced content of aromatics, and the lower layer comprising an aromatic fraction containing unsubstituted polynuclear aromatics.
  • the upper layer is separated from the second biphasic mixture to obtain the paraffin fraction with reduced aromatics content and the aromatic fraction containing unsubstituted polynuclear aromatics.
  • the paraffin fraction is mixed with water and allowed to settle to obtain a third biphasic mixture comprising a first organic phase containing paraffins and a first aqueous phase containing polar fluid medium and water.
  • the aromatic fraction is mixed with water and allowed to settle to obtain a fourth biphasic mixture comprising a second organic phase containing aromatics and a second aqueous phase containing polar fluid medium and water.
  • the process further comprises mixing the first aqueous phase and the second aqueous phase and introducing the combined aqueous phase to a distillation unit for recovery of the polar fluid medium.
  • the heavy hydrocarbon feed is at least one selected from the group consisting of heavy coker gas oil (HCGO), vacuum gas oil (VGO), heavy vacuum gas oil (HVGO) and heavy atmospheric gas oil (HA GO).
  • HCGO heavy coker gas oil
  • VGO vacuum gas oil
  • HVGO heavy vacuum gas oil
  • HA GO heavy atmospheric gas oil
  • the heavy hydrocarbon feed is heavy coker gas oil (HCGO).
  • the present disclosure provides a process for reducing the content of asphaltene in a heavy hydrocarbon.
  • the process is described with the help of Figure-1, which depicts a schematic representation of the process for reducing asphaltene content of a heavy hydrocarbon in accordance with the present disclosure.
  • a heavy hydrocarbon feed (102) is mixed with a hydrocarbon fluid medium (104) in a first mixer (106) to obtain a first resultant mixture (108).
  • the first resultant mixture (108) is then introduced in a first settler (110) and allowed to settle to obtain a first biphasic mixture comprising a hydrocarbon phase comprising heavy hydrocarbons with reduced asphaltene content and the solid phase comprising asphaltene.
  • the solid phase (114) is separated from the first biphasic mixture to obtain the hydrocarbon phase comprising the heavy hydrocarbons with reduced asphaltene content (112).
  • the step of separation involves filtration to remove suspended asphaltene particles.
  • the hydrocarbon fluid medium is at least one selected from the group consisting of n-propane, n-pentane, n-hexane, n-heptane and light coker naphtha and de-iso-pentanizer side draw.
  • the hydrocarbon fluid medium is n-pentane.
  • the step of reducing the asphaltene content of heavy hydrocarbon feed is carried out at a temperature in the range of 50 °C to 250 °C, and the pressure in the range of 2 to 20 MPa.
  • the asphaltene content of the heavy hydrocarbon is reduced by an amount in the range of 80 weight% to 99.9 weight% by the process of the present disclosure.
  • the hydrocarbon fluid medium is recovered and reused, thereby providing economical and eco-friendly process.
  • the present disclosure provides a process for reducing the content of unsubstituted polynuclear aromatics (unsubstituted PNAs) of a heavy hydrocarbon.
  • the process is described with the help of Figure-2, which is a schematic representation of the process for reducing the content of unsubstituted polynuclear aromatics (unsubstituted PNAs) of a heavy hydrocarbon in accordance with the present disclosure.
  • a heavy hydrocarbon feed (202) is mixed with a polar fluid medium (204) in a second mixer (206) to obtain a second resultant mixture (208).
  • the second resultant mixture (208) is introduced in a second settler (210), and is allowed to settle to obtain a second biphasic mixture comprising an upper layer containing a paraffin fraction with reduced content of aromatics, and the lower layer comprising an aromatic fraction containing unsubstituted polynuclear aromatics, and polar fluid medium.
  • the upper layer is separated from the second biphasic mixture to obtain the paraffin fraction with reduced content of aromatics (212).
  • the separated upper layer contains a small fraction of the polar fluid medium, which is separated with the help of water.
  • a typical procedure for separating water is provided herein below.
  • the separated upper layer (212) is mixed with water (216) with the help of a third mixer (218) to obtain a first admixture (220).
  • the first admixture is introduced in a third settler (222), and is allowed to settle to obtain a third biphasic mixture comprising a first organic phase containing paraffins and substituted PNAs and the first aqueous phase containing water and the trace amount of the polar fluid medium.
  • the first aqueous phase (228) is separated from the third biphasic mixture to obtain the first organic phase (226).
  • the lower layer comprising an aromatic fraction containing unsubstituted polynuclear aromatics is admixed with water (234) with the help of a fourth mixer (236) to obtain a second admixture (238).
  • the second admixture is introduced in a settler (240) and allowed to settle to obtain a fourth biphasic mixture comprising a second organic phase containing unsubstituted PNAs and the second aqueous phase containing the polar fluid medium and water.
  • the second organic phase (242) is separated from the fourth biphasic mixture to obtain the second organic phase (242) and the second aqueous phase (244).
  • the first aqueous phase (228) and the second aqueous phase (244) are combined and the combined aqueous phase (246) can be introduced in a distillation unit (248).
  • the combined aqueous phase can be distilled to obtain a top fraction comprising water (250) and a bottom fraction containing the polar fluid medium (252).
  • the polar fluid medium is at least one selected from the group consisting of furfural, N-methyl-2-pyrrolidone (NMP), sulfolane, dimethyl formamide (DMF), dimethyl sulphoxide (DMSO), water and combinations thereof.
  • the polar fluid medium is N-methyl-pyrrolidone (NMP).
  • NMP N-methyl-pyrrolidone
  • the polar fluid medium is a combination of N-methyl-pyrrolidone (NMP) and water.
  • the step of separating heavy hydrocarbon feed into paraffin fraction and aromatic fraction is carried out at a temperature in the range of 50 °C to 250 °C, and the pressure in the range of 2 to 20 MPa.
  • the lower layer (214) obtained from the second biphasic mixture comprises majority of the polar fluid medium.
  • the polar fluid medium is recovered reused.
  • the unsubstituted PNAs obtained in the process of the present disclosure may further be converted to useful lower hydrocarbons.
  • the second organic phase (242) comprising unsubstituted PNAs can be hydrotreated to obtain reduced products.
  • the reduced products so obtained can be subjected to ring opening reactions to obtain a mixture comprising paraffins.
  • This mixture can be cracked to obtain useful lower hydrocarbons.
  • this mixture can be mixed with the heavy hydrocarbon with reduced content of asphaltene and unsubstituted PNAs, and the combined mixture can be cracked.
  • the polar fluid medium is recovered and reused, thereby providing economical and eco-friendly process.
  • the process involves separating heavy hydrocarbon feed into paraffin fraction with reduced content of unsubstituted polynuclear aromatics and aromatic fraction, followed by reducing the asphaltene content of the aromatic fraction using a hydrocarbon fluid medium to obtain heavy hydrocarbon with reduced asphaltene content.
  • the step of reducing the asphaltene content of heavy hydrocarbon feed is carried out first, it can be carried out at ambient temperature as dissolved paraffins will be in liquid state and paraffin will not solidify at ambient conditions.
  • coke particle and other inorganic particles will be discarded first, and viscosity of mixture will be reduced drastically which will improve feed filters performance.
  • the disadvantages come from handling higher amount of hydrocarbon fluid medium.
  • step of reducing the asphaltene content of heavy hydrocarbon feed is carried out after separation of paraffin fraction and aromatic fraction, process will have to be carried out at greater than congealing temperature of VGO. Further, asphaltenes separation will require additional capex for handling of hydrocarbon fluid medium and it’s separation and recovery. But this process will discard asphaltenes and reduce catalyst deactivation by metals and coking. It will also reduce or mitigate the VGOHT feed filter problems.
  • the reduction in the content of asphaltene and unsubstituted PNAs of the heavy hydrocarbon leads to an increase in the life of the hydrotreating catalyst and FCC catalyst which are contacted with the heavy hydrocarbon.
  • the FCC process with the hydrocarbon steam having reduced asphaltene content and enriched with paraffins and substituted PNAs have higher yield of useful lower hydrocarbons.
  • the unsubstituted PNAs can be subjected to hydrotreatment, followed by ring opening reaction to obtain paraffins.
  • the loss of heavy hydrocarbon in the form of unsubstituted PNAs is prevented, thereby leading to high the gross refinery margin (GRM).
  • HCGO was mixed with n-pentane to obtain a first resultant mixture.
  • the so obtained first resultant mixture was then introduced in a first settler and allowed to settle to obtain a first biphasic mixture comprising a hydrocarbon phase, and a solid phase.
  • the solid phase was separated from the first biphasic mixture by filtration to obtain a separated hydrocarbon phase with reduced asphaltene content and the solid phase comprising asphaltene.
  • the comparison between the heavy hydrocarbon feed and separated hydrocarbon phase with reduced asphaltene content is given below in Table 2.
  • Table 2 Composition of heavy hydrocarbon feed and separated hydrocarbon phase
  • the hydrocarbon phase was mixed with N-methyl pyrrolidone (NMP) to obtain a second resultant mixture.
  • NMP N-methyl pyrrolidone
  • the second resultant mixture was introduced in a second settler and allowed to settle to obtain a second biphasic mixture comprising an upper layer comprising paraffin fraction and a lower layer comprising aromatic fraction.
  • the upper layer was separated from the second biphasic mixture to obtain paraffin fraction with reduced content of aromatics and the aromatic fraction comprising unsubstituted polynuclear aromatics and polar fluid medium.
  • Table 3 Composition of heavy hydrocarbon feed, aromatic fraction and paraffin fraction
  • paraffin layer also comprises small amount of mono, di- aromatics with long paraffin chain. Due to presence of long paraffin chain, these molecules behave like paraffin and are rejected by solvent. However, these types of molecules are useful in FCC as these molecules can undergo cracking.
  • the present disclosure described herein above has several technical advantages including, but not limited to, the realization of: a process for reducing asphaltene content in a heavy hydrocarbon feed; a process for reducing unsubstituted PNA content in a heavy hydrocarbon feed; and - increase in the life of the hydrotreating catalyst and FCC catalyst which are contacted with the heavy hydrocarbon feed for cracking.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de réduction de la teneur en asphaltènes et en composés aromatiques polynucléaires non substitués d'une charge d'hydrocarbures lourds. La présente invention concerne un procédé en deux étapes comprenant la réduction de la teneur en asphaltènes d'une charge d'hydrocarbures lourds à l'aide d'un milieu fluide hydrocarboné ; suivi par la séparation d'une charge d'hydrocarbures lourds en une fraction de paraffine avec une teneur réduite en composés aromatiques polynucléaires non substitués et une fraction aromatique. Le procédé de la présente invention améliore une qualité de composition de la charge d'hydrocarbures lourds, ce qui aide en outre à améliorer le rendement de l'unité FCC et la durée de vie du catalyseur de traitement hydraulique.
PCT/IB2018/060236 2017-12-18 2018-12-18 Procédé de réduction de la teneur en asphaltènes et en composés aromatiques polynucléaires non substitués d'hydrocarbures lourds WO2019123237A1 (fr)

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IN201721045417 2017-12-18
IN201721045417 2017-12-18

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WO2019123237A1 true WO2019123237A1 (fr) 2019-06-27

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500757A (en) * 1947-03-12 1950-03-14 Texaco Development Corp Removal of asphaltic constituents from hydrocarbon oil
US3321394A (en) * 1964-10-05 1967-05-23 Phillips Petroleum Co Method for rendering an asphalt or asphaltene product collected in the separation zone of a solvent extraction apparatus free flowing by dispersing an immiscible liquid therewith
CA1085334A (fr) * 1976-05-05 1980-09-09 Bruce M. Sankey Procede d'extraction et de deasphaltage simultanes
US4493765A (en) * 1983-06-06 1985-01-15 Exxon Research And Engineering Co. Selective separation of heavy oil using a mixture of polar and nonpolar solvents
US4784753A (en) * 1985-10-17 1988-11-15 Institut Francais Du Petrole Deasphalting process comprising power recovery from the stage of separating deasphalted oil from the deasphalting solvent
US4859284A (en) * 1986-03-25 1989-08-22 Intevep, S.A. Combined process for the separation and continuous coking of high softening point asphaltenes
WO2014096592A1 (fr) * 2012-12-18 2014-06-26 IFP Energies Nouvelles Procede de desasphaltage selectif de charges lourdes
US20150353847A1 (en) * 2014-06-10 2015-12-10 Saudi Arabian Oil Company Integrated Systems And Methods For Separation And Extraction Of Polynuclear Aromatic Hydrocarbons, Heterocyclic Compounds, And Organometallic Compounds From Hydrocarbon Feedstocks

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500757A (en) * 1947-03-12 1950-03-14 Texaco Development Corp Removal of asphaltic constituents from hydrocarbon oil
US3321394A (en) * 1964-10-05 1967-05-23 Phillips Petroleum Co Method for rendering an asphalt or asphaltene product collected in the separation zone of a solvent extraction apparatus free flowing by dispersing an immiscible liquid therewith
CA1085334A (fr) * 1976-05-05 1980-09-09 Bruce M. Sankey Procede d'extraction et de deasphaltage simultanes
US4493765A (en) * 1983-06-06 1985-01-15 Exxon Research And Engineering Co. Selective separation of heavy oil using a mixture of polar and nonpolar solvents
US4784753A (en) * 1985-10-17 1988-11-15 Institut Francais Du Petrole Deasphalting process comprising power recovery from the stage of separating deasphalted oil from the deasphalting solvent
US4859284A (en) * 1986-03-25 1989-08-22 Intevep, S.A. Combined process for the separation and continuous coking of high softening point asphaltenes
WO2014096592A1 (fr) * 2012-12-18 2014-06-26 IFP Energies Nouvelles Procede de desasphaltage selectif de charges lourdes
US20150353847A1 (en) * 2014-06-10 2015-12-10 Saudi Arabian Oil Company Integrated Systems And Methods For Separation And Extraction Of Polynuclear Aromatic Hydrocarbons, Heterocyclic Compounds, And Organometallic Compounds From Hydrocarbon Feedstocks

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