EP2867342A1 - Process to prepare middle distillates and base oils - Google Patents

Process to prepare middle distillates and base oils

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Publication number
EP2867342A1
EP2867342A1 EP13732201.2A EP13732201A EP2867342A1 EP 2867342 A1 EP2867342 A1 EP 2867342A1 EP 13732201 A EP13732201 A EP 13732201A EP 2867342 A1 EP2867342 A1 EP 2867342A1
Authority
EP
European Patent Office
Prior art keywords
fraction
middle distillates
boiling
residual
dewaxing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13732201.2A
Other languages
German (de)
English (en)
French (fr)
Inventor
Eduard Philip Kieffer
Marcello Stefano Rigutto
Jelle Rudolf Anne Sietsma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP13732201.2A priority Critical patent/EP2867342A1/en
Publication of EP2867342A1 publication Critical patent/EP2867342A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G73/00Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/42Refining of petroleum waxes
    • C10G73/44Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products

Definitions

  • the present invention relates to a process to prepare a first middle distillates fraction, a second middle distillates fraction, a distillate base oil and a residual base oil.
  • Fischer-Tropsch derived middle distillates fractions typically have a high normal paraffin content (and low degree of isomerisation) .
  • Hydrocracking/hydroisomerization and/or dewaxing of the middle distillates fractions is accordingly desirable, to lower the normal paraffin content.
  • distillates fraction good cold flow properties, such as pour point or cloud point, are desired.
  • WO 2009/080681 discloses a process to prepare a gas oil fraction and a residual base oil fraction, by
  • a problem of the process disclosed in WO 2009/080681 is that although this process delivers a high amount of residual base oil, the overall gas oil yield is low.
  • the cold-flow quality of the gas oil prepared in above process is limited by process design, i.e. the - - quality cannot be improved without negatively impacting the overall residual base oil yield. This is caused by the use of a hydrocracking/hydroisomerization step to control the gas oil quality, which step also affects residual base oil yield.
  • a hydrocracking/hydroisomerization step to control the gas oil quality, which step also affects residual base oil yield.
  • Increasing cracking reactivity of Fischer-Tropsch derived paraffins upon increasing chain length means that the residual fraction will be cracked faster when attempting to increase the gas oil quality according to the process described in WO
  • One of the above or other objects may be achieved according to the present invention by providing a process to prepare a first middle distillates fraction, a second middle distillates fraction, a distillate base oil and a residual base oil, the process at least comprising the steps :
  • step (b) separating the Fischer-Tropsch product stream of step (a) , thereby obtaining at least a low boiling fraction, boiling below a temperature in the range of from 300 to 450°C, and a high boiling fraction, boiling above a temperature in the range of from 300 to 450°C;
  • step (c) subjecting the high boiling fraction of step (b) to a hydrocracking/hydroisomerization step to obtain an at least partially isomerised product stream;
  • step (d) separating the product stream of step (c) , thereby obtaining a first middle distillates fraction, a heavy distillates fraction and a residual fraction, wherein the residual fraction has a T5 wt . % boiling point of between 400 and 650°C;
  • step (e) dewaxing the low boiling fraction of step (b) to obtain a second middle distillates fraction
  • step (d) dewaxing the heavy distillates fraction of step (d) to obtain a distillate base oil
  • step (d) dewaxing the residual fraction of step (d) to obtain a residual base oil.
  • a low boiling fraction boiling below a temperature in the range of from 300 to 450°C at
  • atmospheric conditions preferably comprises a C3 to C30 fraction, more preferably comprising a C3 to C23 fraction.
  • a low boiling fraction comprises Fischer-Tropsch derived middle distillates range products.
  • Another advantage of the present invention is that since the lower boiling fraction is not subjected to a hydrocracking/hydroisomerization step, the required hydrocracking/hydroisomerization unit size can be
  • a Fischer-Tropsch product stream is provided.
  • the Fischer-Tropsch product as provided in step (a) is derived from a Fischer-Tropsch process.
  • Fischer-Tropsch product is known in the art.
  • Fischer-Tropsch product is meant a synthesis product of a Fischer- Tropsch process.
  • synthesis gas is converted to a synthesis product.
  • Synthesis gas or syngas is a mixture of hydrogen and carbon monoxide that is obtained by conversion of a hydrocarbonaceous
  • feedstock Suitable feedstock include natural gas, crude oil, heavy oil fractions, coal, biomass and lignite.
  • Fischer-Tropsch product may also be referred to a GTL (Gas-to-Liquids ) product.
  • GTL Gas-to-Liquids
  • Fischer-Tropsch product of the Fischer-Tropsch process is usually separated into a water stream, a gaseous stream comprising unconverted synthesis gas, carbon dioxide, inert gases and CI to C2, and a C3+ product stream by distillation.
  • a gaseous stream comprising unconverted synthesis gas, carbon dioxide, inert gases and CI to C2
  • C3+ product stream by distillation.
  • Commercially available equipment can be used.
  • the distillation may be carried out at atmospheric pressure, but also reduced pressure may be used.
  • Fischer-Tropsch product stream in step (a) is preferably meant the C3+ product stream.
  • step (b) the Fischer-Tropsch product stream provided in step (a) is separated to obtain at least a low boiling fraction boiling below a temperature in the range of from 300 to 450°C at atmospheric conditions and a high boiling fraction boiling above a temperature in the range of from 300 to 450°C at atmospheric
  • step (b) the Fischer-Tropsch product stream provided in step (a) is separated to obtain at least a low boiling fraction in the distillate range with a T95wt.% atmospheric boiling point in the range of from 300 to 450°C and in a high boiling fraction in the
  • atmospheric residue range with a T5wt.% atmospheric boiling point in the range of from 300 and 450°C.
  • boiling points at atmospheric conditions is meant atmospheric boiling points, which boiling points can be determined using methods such as ASTM D2887 or ASTM D7169.
  • the separation is preferably performed by means of a distillation at atmospheric or slightly elevated pressure conditions . - -
  • the low boiling fraction boiling below a
  • the high boiling fraction boiling above 300 to 450°C at
  • atmospheric conditions preferably comprises a C30 to C200 fraction, more preferably a C2 3 to C2 00 fraction, but may also contain C200+ molecules depending on the Fischer- Tropsch synthesis conditions.
  • step (c) the high boiling fraction of step (b) is subjected to a hydrocracking/hydroisomerization step to obtain an at least partially isomerised product. It has been found that the amount of the isomerised product is dependent on the hydrocracking/hydroisomerization
  • Hydrocracking/hydroisomerization processes are known in the art and therefore not discussed here in detail. Hydrocracking/hydroisomerization and the effect of hydrocracking/hydroisomerization conditions on the amount of isomerised product are for example described in Chapter 6 of "Hydrocracking Science and Technology",
  • step (c) The preparation of the at least partially isomerised feedstock in step (c) has been described in e.g. WO
  • step (d) the isomerised feedstock of step (c) is separated by means of distillation into a middle
  • the middle distillates fraction may preferably be obtained via multiple distillation steps.
  • step (d) the isomerised feedstock of step (c) is initially separated by means of distillation - - into a light fraction, the heavy distillates fraction and the residual fraction.
  • the distillation may be performed in one or more steps .
  • the light fraction may be obtained from the
  • isomerised feedstock by distillation at atmospheric or at near atmospheric conditions.
  • the heavy distillates fraction and the residual fraction may be obtained from the isomerised feedstock by vacuum distillation.
  • this vacuum distillation is performed at a pressure of between 1 and 250 mbar, more preferably between 10 and 100 mbar and most
  • the light fraction typically has a T95wt.% between 200 and 420 C, more in particular between 300 and 400°C.
  • T95wt.% is the temperature corresponding to the
  • a gas chromatographic method such as ASTM D2887 can be used to determine the level of recovery.
  • the light fraction comprises a first middle
  • distillates fraction which middle distillates fraction may be separated by distillation. This may preferably be by atmospheric distillation.
  • the first middle distillates fraction of step (d) preferably has a T10 wt . % boiling point from 150 to
  • the first middle distillates fraction has a cetane number according to ASTM D-613 greater than 70, suitably from 74 to 85. - -
  • International Standard ISO 3015 is preferably below -15°C and more preferably below -20°C.
  • the cold filter plugging point (CFFP) of the first middle distillates fraction of step (d) according to
  • European Standard EN 116 is preferably below -10°C, more preferably below -15°C.
  • the first middle distillates fraction may be further dewaxed to obtain a dewaxed first middle distillates fraction.
  • Preferred dewaxing conditions are the same as those described below for step (e)
  • distillates fraction comprises Fischer-Tropsch derived gas oil and Fischer-Tropsch derived kerosene.
  • the heavy distillate preferably has a T10wt.%
  • the heavy distillate fraction will have an intermediate boiling range. Such a fraction preferably has a T90wt% boiling point between 400 and
  • 650°C preferably between 450 and 600°C.
  • a part of the heavy distillate fraction of step (d) is combined with the high boiling fraction of step (b) before step (c) .
  • at least part of the heavy distillate fraction obtained in step (d) may be recycled to step (c) .
  • step (d) fraction of step (d) is recycled to step (c) , more
  • the residual fraction of step (d) typically has a low pour point of below 150°C, more preferably below - -
  • the residual fraction has a T5wt.% boiling point of between 400 and 650°C, preferably between 450 and 600°C.
  • T5 is the temperature corresponding to the
  • step (e) the low boiling fraction of step (b) is dewaxed to obtain a second middle distillates fraction.
  • dewaxing processes are catalytic dewaxing and solvent dewaxing.
  • Catalytic and solvent dewaxing processes are known in the art and therefore not
  • Dewaxing of the low boiling fraction in step (e) is preferably performed by means of a catalytic dewaxing process.
  • Typical catalytic dewaxing processes are for example described in WO 2009/080681 and WO2012055755.
  • catalytic dewaxing is performed in the presence of a catalyst comprising a molecular sieve and a group VIII metal.
  • Suitable dewaxing catalyst are heterogeneous
  • catalysts comprising molecular sieve, more suitably intermediate pore size zeolites and optionally in
  • the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm.
  • catalytic dewaxing is performed in the presence of a catalyst comprising a molecular sieve and a - - group VIII metal, wherein the molecular sieve is selected from a group consisting of a MTW, MTT, TON type molecular sieve, ZSM-48 and EU-2.
  • a catalyst comprising a molecular sieve and a - - group VIII metal, wherein the molecular sieve is selected from a group consisting of a MTW, MTT, TON type molecular sieve, ZSM-48 and EU-2.
  • the reference to ZSM-48 and EU-2 is used to indicate that all zeolites can be used that belong to the ZSM-48 family of disordered structures also referred to as the *MRE family and described in the Catalog of Disorder in Zeolite Frameworks published in 2000 on behalf of the Structure Commission of the
  • any reference to ZSM-48 zeolite also is a reference to ZBM-30 and EU-11 zeolite.
  • zeolites can be present in the catalyst composition especially if it is desired to modify its catalytic properties. It has been found that it can be advantageous to have present zeolite ZSM-12 which zeolite has been defined in the Database of Zeolite Structures published in 2007/2008 on behalf of the Structure Commission of the International Zeolite Assocation.
  • Suitable Group VIII metals are nickel, cobalt, platinum and palladium.
  • a Group VIII metal is platinum or palladium.
  • the dewaxing catalyst suitably also comprises a binder.
  • the binder can be non-acidic. Examples of
  • binders are clay, silica, titania, zirconia, alumina, mixtures and combinations of the above and other binders known to one skilled in the art.
  • the catalyst comprises a silica or a titania binder.
  • the second middle distillates fraction of step e) preferably has a T10wt.% boiling point from 150 to 250°C, more preferably from 175 to 225°C and a T90wt.% boiling point from 300 to 400°C, more preferably from 330 to 370°C.
  • the second dewaxed middle distillates fraction has a cetane number according to ASTM D-613 greater than 70, suitably from 74 to 85.
  • distillates as obtained in step (e) according to the International Standard ISO 3015 is preferably below -40°C and more preferably below -50°C.
  • the cold filter plugging point (CFFP) of the second middle dewaxed distillates fraction of step (e) according to European Standard EN 116 is preferably below -30°C, more preferably below -40°C.
  • the second middle distillates fraction comprises Fischer-Tropsch derived gas oil and Fischer-Tropsch derived kerosene.
  • C3 to C9 is separated from the second dewaxed middle distillates fraction by distillation, preferably at atmospheric conditions.
  • a C3 to C9 fraction is meant a Fischer-Tropsch derived naphtha fraction .
  • the present process suitably comprises a further step (h) wherein prior to performing step (e) , the first middle distillates
  • fraction of step (d) or part of it is combined with the low boiling fraction of step (b) to obtain a mixture and wherein this mixture is dewaxed to obtain a third middle distillates fraction.
  • the fraction of the first middle - - distillates that may be combined with the low boiling fraction of step (b) may cover 0-100%.
  • the process of the present invention comprises a further step (i) , wherein the first middle distillates fraction of step (d) or part of it is combined with the second middle distillates fraction of step (e) to obtain a combined middle distillates product.
  • the fraction of the first middle distillates that may be combined with the second middle distillates fraction of step (e) may cover 0-100%.
  • the present invention provides a middle distillate product obtainable by the process according to the present invention.
  • step (f) of the process according to the present invention the heavy distillates fraction of step (d) is dewaxed to obtain a distillate base oil.
  • Dewaxing of the heavy distillates fraction in step (f) is preferably performed by means of a catalytic dewaxing process.
  • Typical catalytic dewaxing processes are for example described in WO 2009/080681 and
  • Preferred catalytic dewaxing conditions are the same as described above for step (e) .
  • the present invention provides a distillate base oil obtainable by the process according to the present invention.
  • a distillate base oil is separated into further base oils by distillation.
  • these further base oils have different
  • the pour point of the distillate base oil according to ASTM D-5950 is below -5°C, preferably below -10°C, and more preferably below -15°C.
  • the distillate base oil has a cloud point according to ASTM D-2500 of below -10°C, more preferably below -
  • step (g) of the process of the present invention the residual fraction of step (d) is dewaxed to obtain a residual base oil.
  • Dewaxing of the residual fraction in step (g) is preferably performed by means of a catalytic dewaxing process.
  • Typical catalytic dewaxing processes are for example described in WO 2009/080681 and WO2012055755.
  • Preferred catalytic dewaxing conditions are the same as described above for step (e) .
  • the present invention provides a residual base oil obtainable by the process according to the present invention.
  • the residual base oil will preferably have a
  • kinematic viscosity at 100°C according to ASTM D-445 of from 15 to 35 mm 2 /s, preferably from 15 to 30 mm 2 /s, more preferably from 20 to 30 mm 2 /s, and most preferably 23 to 26 mm 2 /s .
  • the pour point of the residual base oil according to ASTM D-5950 is below 0°C, preferably below -20°C, more preferably below -40°C and most preferably below -50°C.
  • the residual base oil has a cloud point according to ASTM D-2500 of between -50°C and +80°C.
  • the process of the present invention comprises a further step (j) wherein at least part of the residual fraction of step (d) is combined with the high boiling fraction of step (b) before step - -
  • step (c) at least part of the residual fraction obtained in step (d) may be recycled to step (c) .
  • step (d) between 20 to 70 wt . % of the residual fraction of step (d) is recycled to step (c) , more preferably between 30 to 60 wt . % and most preferably between 30 to 50 wt . % .
  • Figure 1 schematically shows a process scheme of the process scheme of a preferred embodiment of the process according to the present invention.
  • the process scheme is generally referred to with reference numeral 1.
  • Tropsch product stream is obtained (not shown) .
  • This product is separated in a distillation column (not shown) into a fraction 10 boiling below a temperature in the range of from 300 to 450°C at atmospheric conditions and a fraction 20 boiling above a temperature in the range of from 300 to 450°C at atmospheric conditions.
  • the high boiling fraction 20 is fed to a distillation column (not shown)
  • hydrocracking/hydroisomerization reactor 3 wherein part of the components boiling above a temperature in the range of from 300 to 450°C are converted to product boiling below a temperature in the range of from 300 to 450°C.
  • the effluent (not shown) of reactor 3 is distilled in a distillation column (not shown) to recover a first middle distillates fraction 30, a heavy distillates fraction 40 and a residual fraction 50.
  • the middle distillates fraction 30 is distilled in a distillation column 4 to recover a gas oil 60 and kerosene 70.
  • the heavy distillates fraction 40 is fed to a catalytic - - dewaxing reactor 5 to obtain a distillate base oil 80.
  • the effluent 80 of reactor 5 is distilled in distillation column 6 to recover further base oils 90 with different kinematic viscosities at 100°C between 2 and 10 mm 2 /s, preferably between 2 and 8 mm 2 /s.
  • Part of the residual fraction 50 is fed to a catalytic dewaxing reactor 7 to obtain a residual base oil 100 with a kinematic viscosity at 100°C between 15 and 35 mm 2 /s.
  • part of the residual fraction 50A is recycled to reactor 3 by
  • the low boiling fraction 10 is fed to a catalytic dewaxing reactor 8 wherein the low boiling fraction is converted to a second dewaxed middle distillates fraction 110.
  • the middle distillates fraction 110 is distilled in distillation column 9 to recover a gas oil 120 and kerosene 130.
  • part of first middle distillates fraction 30A is fed to catalytic dewaxing reactor 8.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP13732201.2A 2012-06-28 2013-06-28 Process to prepare middle distillates and base oils Withdrawn EP2867342A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13732201.2A EP2867342A1 (en) 2012-06-28 2013-06-28 Process to prepare middle distillates and base oils

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12174121 2012-06-28
PCT/EP2013/063738 WO2014001552A1 (en) 2012-06-28 2013-06-28 Process to prepare middle distillates and base oils
EP13732201.2A EP2867342A1 (en) 2012-06-28 2013-06-28 Process to prepare middle distillates and base oils

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EP2867342A1 true EP2867342A1 (en) 2015-05-06

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US (1) US20150184089A1 (ru)
EP (1) EP2867342A1 (ru)
CA (1) CA2877044A1 (ru)
RU (1) RU2015102594A (ru)
WO (1) WO2014001552A1 (ru)

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US5015359A (en) * 1986-06-30 1991-05-14 Mobil Oil Corporation Hydrodewaxing method with interstate recovery of olefin
MY137259A (en) * 2001-03-05 2009-01-30 Shell Int Research Process to prepare a lubricating base oil and a gas oil.
ATE462775T1 (de) 2002-02-25 2010-04-15 Shell Int Research Gasöl oder gasöl mischkomponente
JP5000296B2 (ja) * 2003-07-04 2012-08-15 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ フィッシャー・トロプシュ合成生成物から基油を製造する方法
US7354507B2 (en) * 2004-03-17 2008-04-08 Conocophillips Company Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons
AU2008297217B2 (en) 2007-09-10 2011-04-28 Shell Internationale Research Maatschappij B.V. A process for hydrocracking and hydro-isomerisation of a paraffinic feedstock
WO2009080681A2 (en) 2007-12-20 2009-07-02 Shell Internationale Research Maatschappij B.V. Process to prepare a gas oil fraction and a residual base oil
EP2231833A2 (en) * 2007-12-20 2010-09-29 Shell Internationale Research Maatschappij B.V. Fuel compositions
US8685231B2 (en) 2009-11-27 2014-04-01 Shell Oil Company Process for conversion of paraffinic feedstock
CN103180043B (zh) 2010-10-25 2016-04-27 国际壳牌研究有限公司 烃转化催化剂组合物

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RU2015102594A (ru) 2016-08-20
CA2877044A1 (en) 2014-01-03
US20150184089A1 (en) 2015-07-02
WO2014001552A1 (en) 2014-01-03

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