US20150203769A1 - Process to prepare middle distillates and base oils - Google Patents
Process to prepare middle distillates and base oils Download PDFInfo
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- US20150203769A1 US20150203769A1 US14/408,579 US201314408579A US2015203769A1 US 20150203769 A1 US20150203769 A1 US 20150203769A1 US 201314408579 A US201314408579 A US 201314408579A US 2015203769 A1 US2015203769 A1 US 2015203769A1
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining 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
- C10G45/60—Refining 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
- C10G45/62—Refining 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
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining 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
- C10G45/60—Refining 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
- C10G45/64—Refining 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
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment 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
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
- C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
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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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
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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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
- C10G73/44—Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
Definitions
- the present invention relates to a process to prepare a first middle distillates fraction, a second middle distillates fraction, and one or more base oils.
- 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.
- a lower normal paraffin content (and higher degree of isomerisation) has a positive impact on the cloud point and pour point of the middle distillates fraction as described for instance in US2009/0200203 and WO2011/064236.
- WO 2009/080681 discloses a process to prepare a gas oil fraction and a residual base oil fraction, by hydrocracking/hydroisomerization a Fischer-Tropsch derived feedstock, followed by a separation step to obtain a gas oil fraction, a heavy fraction and a residual fraction, which residual fraction is dewaxed to obtain a residual base oil.
- 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. Moreover, 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. 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 2009/080681.
- 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, and one or more base oils, the process at least comprising the steps:
- a low boiling fraction boiling below a temperature in the range of from 300 to 450° C. at atmospheric conditions, preferably comprises a C 3 to C 30 fraction, more preferably comprising a C 3 to C 23 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 reduced.
- 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.
- a Fischer-Tropsch product may also be referred to a GTL (Gas-to-Liquids) product.
- 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 C1 to C2, and a C3+ product stream by distillation.
- a gaseous stream comprising unconverted synthesis gas, carbon dioxide, inert gases and C1 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 conditions.
- 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 T95 wt. % 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 T5 wt. % 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 temperature range of 300 to 450° C. at atmospheric conditions, preferably comprises a C 3 to C 30 fraction, more preferably comprising a C 3 to C 23 fraction.
- 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 conditions. 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”, Julius Scherzer; A. J. Cruia, Marcel Dekker, Inc, New York, 1996, ISBN 0-8247-9760-4.
- step (c) The preparation of the at least partially isomerised feedstock in step (c) has been described in e.g. WO 2009/080681.
- step (d) the isomerised feedstock of step (c) is separated by means of distillation into a middle distillates fraction and a residual fraction.
- 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 and a 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 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 preferably between 10 and 75 mbar.
- the light fraction typically has a T95 wt. % between 200 and 420° C., more in particular between 300 and 400° C.
- T95 wt % is the temperature corresponding to the atmospheric boiling point at which a cumulative amount of 95% of the product is recovered.
- 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 or at slightly elevated pressure conditions.
- the first middle distillates fraction of step (d) preferably has a T10 wt. % boiling point from 150 to 250° C., more preferably from 175 to 225° C. and a T 90 wt. % boiling point from 300 to 400° C., more preferably from 330 to 370° C.
- 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)
- the first middle distillates fraction comprises Fischer-Tropsch derived gas oil and Fischer-Tropsch derived kerosene.
- the residual fraction typically has a relatively low pour point according to ASTM D-5950 of below 40° C., more preferably below 35° C. and even more preferably below 30° C.
- the residual fraction has a T10 wt % boiling point of between 200 and 450° C. and preferably between 300 and 420° C.
- T10 is the temperature corresponding to the atmospheric boiling point at which a cumulative amount of 10% of the product is recovered, determined using for example a gas chromatographic method such as ASTM D7169.
- 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 described here in detail.
- Typical catalytic and solvent dewaxing processes are for example described in Chapter 7 and 8 of “Lubricant base oil and wax processing”, Avilino Sequeira, Jr., Marcel Dekker, Inc, New York, 1994, ISBN 0-8247-9256-4.
- 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 combination a metal having a hydrogenation function, such as the Group VIII metals.
- 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 International Zeolite Association. Even if EU-2 would be considered to be different from ZSM-48, both ZSM-48 and EU-2 can be used in the present invention. Zeolites ZBM-30 and EU-11 resemble ZSM-48 closely and also are considered to be members of the zeolites whose structure belongs to the ZSM-48 family. In the present application, 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 Association.
- 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.
- suitable 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 titania binder.
- the second middle distillates fraction of step e) preferably has a T10 wt. % boiling point from 150 to 250° C., more preferably from 175 to 225° C. and a T90 wt. % 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.
- the cloud point of the second dewaxed middle 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.
- C 3 to C 9 is separated from the second dewaxed middle distillates fraction by distillation, preferably at atmospheric conditions.
- a C 3 to C 9 fraction is meant a Fischer-Tropsch derived naphtha fraction.
- the present process suitably comprising 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 combined middle distillate product obtainable by the process according to the present invention.
- step (f) of the process according to the present invention the residual fraction of step (d) is dewaxed to obtain one or more base oils.
- Dewaxing of the residual 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 WO2012055755.
- Preferred catalytic dewaxing conditions are the same as those described above for step (e).
- the present invention provides one or more base oils obtainable by the process according to the present invention.
- a dewaxed base oil is separated into further base oils by distillation.
- these further base oils have different kinematic viscosities.
- a base oil as obtained in step (f) is separated into at least one light base oil grade and one heavy base oil grade.
- more than one light or heavy base oil grades are obtained by distillation of the dewaxed base oil as obtained in step (f).
- the present invention provides a light base oil grade obtainable by the process according to the present invention.
- a light base oil grade is meant further base oils having a kinematic viscosity at 100° C. according to ASTM D-445 between 2 to 10 mm 2 /s, preferably between 2 to 8 mm 2 /s.
- the pour point of the light base oil grade according to ASTM D-5950 is below ⁇ 5° C., preferably below ⁇ 10° C., and more preferably below ⁇ 15° C.
- the light base oil grade has a cloud point according to ASTM D-2500 of below ⁇ 10° C., more preferably below ⁇ 15° C. and most preferably below ⁇ 20° C.
- the present invention provides a heavy base oil grade obtainable by the process according to the present invention.
- a heavy base oil grade is meant further base oils having a kinematic viscosity at 100° C. according to ASTM D-445 of from 10 to 40 mm 2 /s, preferably from 15 to 35 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 heavy base oil grade 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 heavy base oil grade 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 (c). In this way, 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. %.
- FIG. 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 .
- a Fischer-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 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 and a residual fraction 40 .
- the middle distillates fraction 30 is distilled in a distillation column 4 to recover a gas oil 50 and kerosene 60 .
- the residual fraction 40 is fed to a catalytic dewaxing reactor 5 to obtain a base oil 70 .
- the effluent 70 of reactor 5 is distilled in 6 to recover in one or more distillation steps one or more distillate base oils that can be grouped into light grade base oils 80 , having a kinematic viscosity at at 100° C. between 2 and 10 mm 2 /s and heavy grade base oils 90 , having a kinematic viscosity at 100° C. between 10 and 40 mm 2 /s.
- part of the residual fraction 40 A is recycled to reactor 3 by combining 40 A with the high boiling fraction 20 .
- the low boiling fraction 10 is fed to a catalytic dewaxing reactor 7 wherein the low boiling fraction is converted to a second dewaxed middle distillates fraction 100 .
- the middle distillates fraction 100 is distilled in distillation column 8 to recover a gas oil 110 and kerosene 120 .
- part of first middle distillates fraction 30 A is fed to catalytic dewaxing reactor 7 .
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12174125.0 | 2012-06-28 | ||
EP12174125 | 2012-06-28 | ||
PCT/EP2013/063734 WO2014001550A1 (en) | 2012-06-28 | 2013-06-28 | Process to prepare middle distillates and base oils |
Publications (1)
Publication Number | Publication Date |
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US20150203769A1 true US20150203769A1 (en) | 2015-07-23 |
Family
ID=48746486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/408,579 Abandoned US20150203769A1 (en) | 2012-06-28 | 2013-06-28 | Process to prepare middle distillates and base oils |
Country Status (5)
Country | Link |
---|---|
US (1) | US20150203769A1 (de) |
EP (1) | EP2867344A1 (de) |
CA (1) | CA2877182A1 (de) |
RU (1) | RU2015102627A (de) |
WO (1) | WO2014001550A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108473884A (zh) * | 2015-12-23 | 2018-08-31 | 国际壳牌研究有限公司 | 用于制备浊点降低的基础油的方法 |
CN108779401A (zh) * | 2015-12-23 | 2018-11-09 | 国际壳牌研究有限公司 | 残余基础油 |
US10934496B2 (en) | 2016-12-23 | 2021-03-02 | Shell Oil Company | Fischer-tropsch feedstock derived haze-free base oil fractions |
US11078430B2 (en) | 2016-12-23 | 2021-08-03 | Shell Oil Company | Haze-free base oils with high paraffinic content |
Citations (3)
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US5015359A (en) * | 1986-06-30 | 1991-05-14 | Mobil Oil Corporation | Hydrodewaxing method with interstate recovery of olefin |
US20040079678A1 (en) * | 2001-03-05 | 2004-04-29 | Germaine Gilbert Robert Bernard | Process to prepare a lubricating base oil and a gas oil |
US20060157384A1 (en) * | 2003-07-04 | 2006-07-20 | Adams Nicholas J | Process to prepare base oil from a fisher-tropsch synthesis product |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003210348A1 (en) | 2002-02-25 | 2003-09-09 | Shell Internationale Research Maatschappij B.V. | Process to prepare a catalytically dewaxed gas oil or gas oil blending component |
WO2006067176A1 (en) * | 2004-12-23 | 2006-06-29 | Shell Internationale Research Maatschappij B.V. | Process to prepare a lubricating base oil |
RU2007127901A (ru) * | 2004-12-23 | 2009-01-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | Способ получения двух изо-парафиновых продуктов из сырья, полученного синтезом фишера-тропша |
JP2008525607A (ja) * | 2004-12-28 | 2008-07-17 | 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 |
WO2009034045A1 (en) | 2007-09-10 | 2009-03-19 | 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 |
US20110024328A1 (en) * | 2009-07-31 | 2011-02-03 | Chevron U.S.A. Inc. | Distillate production in a hydrocarbon synthesis process. |
US8685231B2 (en) | 2009-11-27 | 2014-04-01 | Shell Oil Company | Process for conversion of paraffinic feedstock |
CN103180044B (zh) | 2010-10-25 | 2016-05-18 | 国际壳牌研究有限公司 | 烃类转化催化剂组合物 |
-
2013
- 2013-06-28 US US14/408,579 patent/US20150203769A1/en not_active Abandoned
- 2013-06-28 WO PCT/EP2013/063734 patent/WO2014001550A1/en active Application Filing
- 2013-06-28 RU RU2015102627A patent/RU2015102627A/ru not_active Application Discontinuation
- 2013-06-28 CA CA2877182A patent/CA2877182A1/en not_active Abandoned
- 2013-06-28 EP EP13734030.3A patent/EP2867344A1/de not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5015359A (en) * | 1986-06-30 | 1991-05-14 | Mobil Oil Corporation | Hydrodewaxing method with interstate recovery of olefin |
US20040079678A1 (en) * | 2001-03-05 | 2004-04-29 | Germaine Gilbert Robert Bernard | Process to prepare a lubricating base oil and a gas oil |
US20060157384A1 (en) * | 2003-07-04 | 2006-07-20 | Adams Nicholas J | Process to prepare base oil from a fisher-tropsch synthesis product |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108473884A (zh) * | 2015-12-23 | 2018-08-31 | 国际壳牌研究有限公司 | 用于制备浊点降低的基础油的方法 |
CN108779401A (zh) * | 2015-12-23 | 2018-11-09 | 国际壳牌研究有限公司 | 残余基础油 |
US20190002773A1 (en) * | 2015-12-23 | 2019-01-03 | Shell Oil Company | Process for preparing a base oil having a reduced cloud point |
US20190002774A1 (en) * | 2015-12-23 | 2019-01-03 | Shell Oil Company | Residual base oil |
US10844297B2 (en) * | 2015-12-23 | 2020-11-24 | Shell Oil Company | Residual base oil process |
US11142705B2 (en) * | 2015-12-23 | 2021-10-12 | Shell Oil Company | Process for preparing a base oil having a reduced cloud point |
EP3394215B1 (de) * | 2015-12-23 | 2021-11-03 | Shell Internationale Research Maatschappij B.V. | Verfahren zur herstellung eines restbasisöls |
US10934496B2 (en) | 2016-12-23 | 2021-03-02 | Shell Oil Company | Fischer-tropsch feedstock derived haze-free base oil fractions |
US11078430B2 (en) | 2016-12-23 | 2021-08-03 | Shell Oil Company | Haze-free base oils with high paraffinic content |
Also Published As
Publication number | Publication date |
---|---|
CA2877182A1 (en) | 2014-01-03 |
EP2867344A1 (de) | 2015-05-06 |
WO2014001550A1 (en) | 2014-01-03 |
RU2015102627A (ru) | 2016-08-20 |
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Legal Events
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AS | Assignment |
Owner name: SHELL OIL COMPANY, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KIEFFER, EDUARD PHILIP;RIGUTTO, MARCELLO STEFANO;SIETSMA, JELLE RUDOLF ANNE;SIGNING DATES FROM 20150421 TO 20150507;REEL/FRAME:035786/0851 |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |