WO2015177067A1 - Procédé de préparation d'une fraction de gasoil de fischer-tropsch de grande pureté - Google Patents

Procédé de préparation d'une fraction de gasoil de fischer-tropsch de grande pureté Download PDF

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Publication number
WO2015177067A1
WO2015177067A1 PCT/EP2015/060842 EP2015060842W WO2015177067A1 WO 2015177067 A1 WO2015177067 A1 WO 2015177067A1 EP 2015060842 W EP2015060842 W EP 2015060842W WO 2015177067 A1 WO2015177067 A1 WO 2015177067A1
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Prior art keywords
fischer
tropsch
contaminant
gasoil fraction
fraction
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PCT/EP2015/060842
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English (en)
Inventor
Johannes Bernardus Wilhelmus Morsink
Robert RIEMERSMA
Johannes TURFBOER
Rendert Jan Wiersma
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Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP15724226.4A priority Critical patent/EP3146022A1/fr
Priority to US15/311,867 priority patent/US20170137723A1/en
Priority to KR1020167034023A priority patent/KR20170010782A/ko
Priority to JP2016568596A priority patent/JP2017519857A/ja
Priority to CN201580026447.9A priority patent/CN106459785A/zh
Publication of WO2015177067A1 publication Critical patent/WO2015177067A1/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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/165—Natural alumino-silicates, e.g. zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • 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
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/06—Gasoil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/18—Solvents

Definitions

  • the present invention relates to a process for preparing a high purity Fischer-Tropsch gasoil fraction and use thereof as a solvent or functional fluid.
  • Such synthetic paraffinic products are for instance produced by so-called Fischer-Tropsch processes, wherein synthesis gas, i.e. a mixture of predominantly hydrogen and carbon monoxide, is converted into higher hydrocarbon compounds including paraffins .
  • Fischer-Tropsch-derived gasoils Due to their synthetic origin, these Fischer-Tropsch-derived gasoils have very low levels of aromatics, naphthenics and impurities compared to their crude oil derived
  • Fischer-Tropsch-derived gasoils have properties that provide advantages in solvent and functional fluid applications with low viscosity requirements .
  • US 2012/0048775 describes a process for producing middle distillates from a paraffinic feed produced by Fischer-Tropsch synthesis, wherein an intermediate fraction with an initial boiling point in the range 150
  • 2004/152793 describes a process for preparing an olefinic naphtha, wherein an olefinic naphtha stream is isolated from a Fischer-Tropsch hydrocarbon stream and purified over a metal oxide at elevated temperatures . It is disclosed in US 2004/152793 that the paraffins of the non-olefinic component of the naphtha are predominantly n-paraffins. In US5906727, a Fischer-Tropsch-derived solvent is disclosed with a boiling range from
  • the solvent has a low odor and is colorless (Saybolt color number of +30) .
  • Fischer- Tropsch-derived solvents that have more narrow boiling point range compared to the solvent disclosed in
  • the present invention provides for a process for preparing a purified Fischer-Tropsch gasoil fraction. It has been found that, when a Fischer-Tropsch-derived gasoil having a relatively broad boiling point range, e.g. within a range of from approximately 150 to 450°C, is fractionated into two or more fractions that have a more narrow boiling point range, at least one of the fractions exhibits an increased odor and/or
  • the present invention provides a first process for preparing a purified Fischer-Tropsch gasoil fraction, comprising: a) providing a Fischer-Tropsch-derived gasoil
  • Fischer-Tropsch-derived gasoil is a fluid
  • paraffins including isoparaffins and normal paraffins, with alkyl chain lengths in the range of from
  • the process according to the invention allows for the preparation purified Fischer-Tropsch gasoil
  • the process according to the invention further allows for the preparation of purified Fischer-Tropsch gasoil fractions, having applicability as solvents, diluents and functional fluids, which have desired odor properties and/or color specifications.
  • the process according to the invention further allows for the removal of contaminants using a
  • the invention provides a second process for preparing a purified Fischer-Tropsch gasoil fraction, comprising:
  • contaminant-comprising Fischer-Tropsch gasoil fraction having a final boiling point of no more than 260°C and wherein said Fischer-Tropsch gasoil fraction comprises more than 50 wt% of isoparaffins , to an absorption zone comprising an absorbent material and contacting the contaminant-comprising Fischer-Tropsch gasoil fraction with the absorbent material to absorb at least part of contaminant;
  • Fischer-Tropsch gasoil fraction as high purity Fischer- Tropsch gasoil fraction, which purified Fischer-Tropsch gasoil fraction is contaminant-depleted with respect to the contaminant-comprising Fischer-Tropsch gasoil fraction.
  • the invention provides a third process for preparing a high purity Fischer- Tropsch gasoil fraction, comprising: v) providing a contaminant-comprising Fischer-Tropsch gasoil fraction, having an initial boiling point of more than 260°C, to an absorption zone comprising an
  • the invention provides for the use of a purified Fischer-Tropsch gasoil fraction produced by a process according to the present invention as a solvent, diluent or functional fluid.
  • the present invention provides for a first process for preparing purified Fischer-Tropsch gasoil fractions.
  • These Fischer-Tropsch gasoil fractions are particularly suitable for use as solvents, diluents and functional fluids, in particular for the applications as mentioned herein.
  • the fractions are prepared by providing and fractionating a Fischer-Tropsch-derived gasoil.
  • Fischer-Tropsch-derived gasoil according to the present invention is a synthetic gasoil derived from a Fischer-Tropsch process.
  • Tropsch-derived gasoil is known in the art.
  • Fischer-Tropsch-derived is meant that the gasoil, is, or is derived from, a synthesis product of a Fischer- Tropsch process.
  • synthesis gas is converted to a synthesis product.
  • Synthesis gas or syngas is a mixture of predominantly hydrogen and carbon monoxide that is obtained by conversion of a hydrocarbonaceous feedstock. Suitable feedstocks include natural gas, crude oil, heavy oil fractions, coal, biomass or lignocellulosic biomass and lignite and lignite.
  • a Fischer-Tropsch-derived gasoil may also be referred to as a GTL (Gas-to-Liquids ) gasoil.
  • GTL Gas-to-Liquids
  • Fischer-Tropsch-derived gasoil is characterized as the product of a Fischer-Tropsch process wherein a synthesis gas, or mixture of predominantly hydrogen and carbon monoxide, is processed at elevated temperature over a supported catalyst comprised of a Group VIII metal, or metals, e.g., cobalt, ruthenium, iron, etc. At least part of the Fischer-Tropsch product is contacted with hydrogen, at hydrocracking/ hydroisomerization
  • hydrocracked/hydroisomerized Fischer-Tropsch product may be provided as the Fischer-Tropsch-derived gasoil.
  • Fischer-Tropsch-derived gasoils are different from crude oil-derived gasoils. Despite having a similar boiling point range, the specific molecular composition of the Fischer-Tropsch-derived gasoils may allow for, amongst others, improved viscosity characteristics, improved pour point characteristics, improved density characteristics and in particular a combination of any of the aforementioned characteristics with specific desired flash point characteristics. For example, Fischer-Tropsch-derived gasoils may combine a low volatility with a high flash point, whereas the
  • viscosity of such Fischer-Tropsch-derived gasoils may be lower than the viscosity of crude oil-derived gasoil having a similar volatility and flashpoint.
  • the Fischer-Tropsch-derived gasoils is a complex mixture of molecules that should not be compared to a pure paraffinic molecule like e.g. pure n-dodecane .
  • Tropsch-derived gasoils compared to the crude oil- derived gasoils, are generally attributed to their particular isoparaffin to normal paraffin weight ratio (i/n ratio), relative amount of mono-methyl branched isoparaffins and the molecular weight distribution of the paraffins, as well as the absence of substantial levels aromatics and naphthenes.
  • a particular advantage of the Fischer-Tropsch- derived gasoils is that these gasoils exhibit very little odor and are almost colorless. Color as used herein is the Saybolt color as measured by its Saybolt number (ASTM D156: Standard Test Method for Saybolt Color of Petroleum Products) . A high Saybolt number, +30, indicates colorless fluids, whereas lower Saybolt numbers, in particular below zero, indicate a
  • Fischer-Tropsch-derived gasoils typically have the highest Saybolt number, i.e. +30.
  • the high purity, low odor and minimal color characteristics, together with the above mentioned improved viscosity, pour point, density and flash point characteristics make the Fischer-Tropsch-derived gasoils highly suitable for solvent, diluent and functional fluid applications.
  • Fischer-Tropsch process for making the Fischer-Tropsch- derived gasoil, wherein the feedstock to the Fischer-
  • Tropsch process comprises little to no sulphur and the process produces very little unsaturates, e.g.
  • Tropsch-derived gasoil by fractionating the Fischer- Tropsch-derived gasoil into two or more fractions having a different boiling point range.
  • isoparaffins and normal paraffins are distributed unevenly over the two or more fractions and Fischer-Tropsch gasoil fractions may be obtained that have an i/n ratio different from the Fischer-Tropsch-derived gasoil feedstock.
  • the relative amount of mono-methyl branched isoparaffins and the molecular weight distribution of the paraffins may be different.
  • the viscosity, pour point, density and flash point characteristics of the Fischer-Tropsch-derived gasoil fractions may change, beyond the change that would be expected on the basis of a fractionation based on boiling ranges alone.
  • a Fischer-Tropsch-derived gasoil feedstock is
  • a fractionation zone Reference herein to a fractionation zone is to one or more separation means for separating the Fischer-Tropsch-derived gasoil feedstock into two or more fractions having a different boiling point range.
  • suitable separating means include, but are not limited to, distillation units.
  • the Fischer-Tropsch-derived gasoil feedstock is fractionated by distillation.
  • the Fischer- Tropsch-derived gasoil feedstock may be fractionated in a single distillation column or in two or more
  • Fischer- Tropsch-derived gasoil feedstock is fractionated in one or more distillation columns.
  • the Fischer-Tropsch-derived gasoil feedstock is fractionated into two or more Fischer-Tropsch-derived gasoil fractions, herein further referred to as Fischer-Tropsch gasoil fractions, each having a different boiling point range.
  • Fischer-Tropsch-derived gasoil feedstock is
  • Fischer-Tropsch gasoil fractions each having a different boiling point range.
  • at least one, more preferably at least two, of the Fischer-Tropsch gasoil fractions has a final boiling point of at most 260°C, preferably at most 250°C, more preferably at most 215°C. Reference herein to the final boiling point is to the higher limit of the boiling point range of a
  • this boiling point range is defined as the range between the initial boiling point and final boiling point measured under atmospheric conditions as determined according to ASTM D86.
  • At least one, more preferably at least two, of the Fischer-Tropsch gasoil fractions has an initial boiling point of more than 260°C, preferably at least 300°C, more preferably at least 310°C.
  • Reference herein to the an initial boiling point is to the lower limit of the boiling point range of a Fischer-Tropsch gasoil fraction, this boiling point range is defined as the range between the initial boiling point and final boiling point measured under atmospheric conditions as determined according to ASTM D86.
  • the, albeit low levels of, contaminants that are present in the Fischer-Tropsch-derived gasoil feedstock are not uniformly distributed over the two or more fractions. It has been observed that in particular the lower molecular weight and/or more volatile contaminants may accumulate in the lower boiling fractions rather than residing in the higher boiling fractions. These contaminants are believed to cause an undesired odor, and optionally a discoloration of the fraction, which was not observed in the Fischer-Tropsch-derived gasoil feedstock .
  • Contaminants herein are non-paraffinic, non
  • contaminant herein refers to compounds selected from the group consisting of oxygenate compounds, unsaturated hydrocarbon compounds, sulphur containing compounds and nitrogen containing compounds .
  • unsaturated hydrocarbon compounds herein refers to compounds having one or more unsaturated bonds, including aromatics.
  • oxygenate compounds herein refers to oxygen-containing hydrocarbonaceous compounds .
  • oxygenates include, but are not limited to alcohols, ketones, aldehydes, ethers, epoxides and acids.
  • aromatics herein refers to aromatic compounds and compounds that comprise one or more aromatic groups, including polycyclic aromatics.
  • term contaminant herein refers to compounds selected from the group consisting of
  • oxygenate compounds and aromatics as these compounds are believed to provide the most significant
  • contaminant concentration herein refers to a contaminant concentration expressed in ppmw, unless expressly indicated differently, and calculated on the basis of the respective total Fischer-Tropsch-derived gasoil, contaminant-enriched Fischer-Tropsch gasoil fraction, or purified Fischer-Tropsch gasoil fraction and the total weight of the contaminants .
  • At least one Fischer-Tropsch gasoil fraction prepared in step (b) is a contaminant-enriched Fischer- Tropsch gasoil fraction, due to the non-uniform
  • contaminant-enriched Fischer-Tropsch gasoil fraction is to a Fischer-Tropsch gasoil fraction that contains a higher concentration of one or more contaminants compared to the Fischer-Tropsch-derived gasoil
  • the contaminant-enriched Fischer-Tropsch gasoil fraction may comprise at least one contaminant selected from the group consisting of oxygenate compounds and aromatics.
  • An effect of the accumulation of contaminants in the contaminant-enriched Fischer-Tropsch gasoil fraction may be that the Saybolt number of the contaminant- enriched Fischer-Tropsch gasoil fraction is lower than the Saybolt number of the Fischer-Tropsch-derived gasoil feedstock, i.e. the coloring of the fraction has increased.
  • This undesired discoloration is particularly observed in the higher boiling Fischer-Tropsch gasoil fractions.
  • contaminants in the contaminant-enriched Fischer-Tropsch gasoil fraction may be an increase of the odor emitted by the Fischer-Tropsch gasoil fraction. This undesired odor is particularly observed in the lower boiling Fischer-Tropsch gasoil fractions. Without wishing to be bound to any particular theory, it is believed that in particular more volatile lower molecular weight
  • Fischer-Tropsch-derived gasoils and in particular Fischer-Tropsch-derived paraffins intrinsically have an odor. Therefore, when herein reference is made to terms like odorless, low odor or little odor, reference is made to an odor that is qualitatively equal to or qualitatively similar to that of the Fischer-Tropsch- derived gasoils or paraffins. Where herein reference is made to terms like an increased odor, a stronger odor, and an undesired odor or similar qualifications, reference is made to an odor that is qualitatively different from to that of the Fischer-Tropsch-derived gasoils or paraffins.
  • This difference in odor can be characterized by comparing the odor of a, optionally contaminant-enriched, Fischer-Tropsch gasoil fraction to the Fischer-Tropsch-derived gasoil feedstock and classifying the difference, i.e. 1 is qualitatively equal to Fischer-Tropsch-derived gasoil feedstock (good odor characteristic) , while 5 is qualitatively very different to Fischer-Tropsch-derived gasoil feedstock (poor odor characteristic).
  • the Fischer-Tropsch-derived gasoil feedstock is fractionated into at least two Fischer- Tropsch gasoil fractions, of which at least two Fischer-
  • Tropsch gasoil fractions at least one is a contaminant- enriched Fischer-Tropsch gasoil fraction having a final boiling point of at most 260°C, preferably at most 250°C, more preferably at most 215°C. Equally
  • the Fischer-Tropsch-derived gasoil feedstock is fractionated into least two Fischer-Tropsch gasoil fractions, of which at least two Fischer-Tropsch gasoil fractions at least one is a contaminant-enriched
  • Fischer-Tropsch gasoil fraction having an initial boiling point of more than 260°C, preferably at least
  • the Saybolt number of the contaminant-enriched Fischer- Tropsch gasoil fraction having an initial boiling point of more than 260°C may be below 30, in particular at least 2, optionally at least 5, lower than the Saybolt number of the Fischer-Tropsch-derived gasoil feedstock.
  • the above described properties of the contaminant-enriched Fischer-Tropsch gasoil fraction may apply to at least one contaminant- enriched Fischer-Tropsch gasoil fraction, however, may apply to other contaminant-enriched Fischer-Tropsch gasoil fractions.
  • the contaminant-enriched Fischer-Tropsch should be further treated to reduce the odor and/or discoloration .
  • the process according to the invention further includes providing the contaminant-enriched Fischer-Tropsch gasoil fraction to an absorption zone.
  • the absorption zone comprises at least one absorbent material, which is suitable to absorb at least part of the contaminants.
  • Reference herein to an absorbent material is to absorbent material and adsorbent
  • Reference herein to absorb is to absorb and adsorb.
  • Reference herein to absorption is to absorption and adsorption.
  • the absorption zone comprises at least one absorbent material selected from the group
  • magnesium silicate and molecular sieve materials including 4A or 5A molecular sieve, zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y,
  • absorbent materials having larger pore sizes i.e. above 0.5 nm (5 Angstrom) or larger, are able to absorb the relative large aromatic compounds in addition to the oxygenates and other contaminants.
  • Absorbent materials having smaller pore sizes absorb predominately the non-aromatic compounds, including in particular oxygenates.
  • the absorption zone comprises at least one absorbent material comprising pores having a pore size of more than 0.5 nm (5 Angstrom), more preferably at least 0.55 nm (5.5 Angstrom), even more preferably at least 0.6 nm (6 Angstrom), still more preferably at least 0.65 nm (6.5 Angstrom) .
  • the absorption zone comprises at least one absorbent material comprising pores having a pore size of more than 0.5 nm (5 Angstrom), more preferably at least 0.55 nm (5.5 Angstrom), even more preferably at least 0.6 nm (6 Angstrom), still more preferably at least 0.65 nm (6.5 Angstrom) .
  • the absorption zone comprises at least one absorbent material comprising pores having a pore size of more than 0.5 nm (5 Angstrom), more preferably at least 0.55 nm (5.5 Angstrom), even more preferably at least 0.6 nm (6 Angstrom), still more preferably at least 0.65 nm (6.5 Angstrom) .
  • the absorption zone comprises at least one
  • At least one absorbent material that is a molecular sieve material selected from the group consisting of, zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12,
  • the absorbent material is zeolite 13X, which is the sodium form of Zeolite X.
  • the absorption zone comprises at least one molecular sieve absorbent material
  • at least one molecular sieve absorbent material has a channel structure in one or more directions having a diameter of more than 0.5 nm (5 Angstrom), more preferably at least 0.55 nm (5.5 Angstrom), even more preferably at least 0.6 nm (6 Angstrom), still more preferably at least 0.65 nm (6.5 Angstrom) .
  • the absorption zone may comprise two or more of absorbent materials, preferably two or more selected from the absorbent materials described hereinabove.
  • a preferred combination of absorbent material may include zeolite 13X and magnesium silicate.
  • Another preferred combination of absorbent material may include zeolite 13X and active coal.
  • the combination of absorbent may be able to more efficiently absorb a broader range of contaminants, for instance both larger and smaller molecular size contaminants, e.g. oxygenates and aromatics, or polar and non-polar contaminants.
  • the molecular sieve used as the absorbent material in the process of the invention is preferably based on an acidic molecular sieve having a framework silica-to- alumina molar ratio less than 100 and more preferably greater than 10, for example 20 to 50.
  • Lower silica materials have more sites for available adsorption sites and therefore may be more effective than the higher silica molecular sieve materials.
  • the absorbent material used in the absorption zone of the process of the invention may be provided in the form of particles, for example extrudate, spheres or pellets.
  • the particles may comprise the absorbent material alone or together with a binder material or filler material to improve the strength of the
  • the binder or filler material may be for instance amorphous metal oxides, including alumina, silica, zirconia, and titania.
  • the binder or filler material is alumina.
  • the contaminant-enriched Fischer- Tropsch gasoil fraction is contacted with the absorbent material in the absorption zone at a temperature in the range of from 0 to 150°C. The lower limit of the temperature range at which the contaminant-enriched
  • Fischer-Tropsch gasoil fraction is contacted with the absorbent material in the absorption zone is related to the fact that the absorption is diffusion limited and temperatures below 0°C would cause a undesirable decrease of the diffusion rate of the contaminants from the contaminant-enriched Fischer-Tropsch gasoil fraction to the absorbent material.
  • the contact temperature is increased, i.e. above 0°C, the rate of diffusion may increase.
  • the temperature below 150°C the formation of by-products is reduced. This is important as these by-products may have an undesirable effect on the applicability of the resulting Fischer- Tropsch gasoil fraction.
  • the contaminant-enriched Fischer- Tropsch gasoil fraction is contacted with the absorbent material in the absorption zone at a temperature in the range of from 10 to 40°C, most preferably in the range of from 10 to 30° C.
  • the contaminant-enriched Fischer- Tropsch gasoil fraction is contacted with the absorbent material in the absorption zone at a pressure in the range of from 1 to 75 bar, preferably of from 1.1 to 50 bar .
  • the contaminant-enriched Fischer-Tropsch gasoil fraction may contacted with the absorbent material batch-wise or in a continuous mode. It is preferred that the contaminant-enriched Fischer-Tropsch gasoil fraction is contacted with the absorbent material under turbulent flow conditions to stimulate the fluid/solid material interaction.
  • the absorption zone may preferably comprise a fixed bed reactor comprising at least one fixed bed of absorbent material.
  • the contaminant-enriched Fischer-Tropsch gasoil fraction is contacted with the absorbent material under continuous or induced mixing, this is particularly preferred in case of a batch-wise operation.
  • the contaminant-enriched Fischer- Tropsch gasoil fraction is contacted with the absorbent material in the absorption zone at for a time sufficient to absorb at least part of the contaminants.
  • the contaminant-enriched Fischer-Tropsch gasoil fraction may be contacted with the absorbent material for any time in the range of from 1 minute to 48 hours, preferably for of from 30 minutes to 24 hours, more preferably of from 60 minutes to 24 hours.
  • the contaminant- enriched Fischer-Tropsch gasoil fraction may be
  • contaminant-enriched Fischer-Tropsch gasoil fraction over absorbent material in the range of from 0.5 to 200, more preferably of from 1 to 175, even more preferably 5 to 125.
  • the contaminant-enriched Fischer-Tropsch gasoil fraction may be contacted with the absorbent material for any time in the range of from 1 minute to 48 hours, preferably for of from 30 minutes to 24 hours, more preferably of from 60 minutes to 24 hours.
  • the contaminant-enriched Fischer-Tropsch gasoil fraction is contacted with the absorbent material in the absorption zone at a LHSV of from 0.0001 to 0.01 s -1 ' more preferably 0.0001 to 0.005 s -1 , still more preferably 0.0001 to 0.003 s _1 .
  • the absorption zone may comprise one or more absorption sections.
  • the absorption zone may comprise two or more absorption sections in- series.
  • the absorption zone may comprise two or more sections, each comprising a separate absorbent. This has the advantage that different contaminants may be separately removed, to the extent required.
  • One example may be a first section comprising Mg silicate or similar absorbent material and a second section comprising zeolite 13X or similar large pore molecular sieve absorbent material. This combination has the advantage that the Mg silicate or similar absorbent material can absorb part of the oxygenates, allowing a larger part of the absorption capacity of the zeolite 13X or similar large pore molecular sieve absorbent material to be used for the aromatic contaminants.
  • the absorption zone may comprise a mixture of two or more absorbent materials.
  • the absorption zone may comprise two or more absorption sections in parallel, preferably comprising the same absorbent material.
  • a purified Fischer-Tropsch gasoil fraction is retrieved from the absorption zone as the high purity Fischer-
  • the purified Fischer-Tropsch gasoil fraction retrieved from the absorption zone is contaminant-depleted, i.e. the purified Fischer-Tropsch gasoil fraction comprises a contaminant concentration that is lower than the contaminant concentration of the contaminant-enriched Fischer-Tropsch gasoil fraction.
  • the aromatic and oxygenate concentrations of the purified Fischer-Tropsch gasoil fraction is lower the corresponding concentrations of the contaminant-enriched Fischer-Tropsch gasoil fraction.
  • the purified Fischer-Tropsch gasoil fraction according to the present invention comprises:
  • the purified Fischer-Tropsch gasoil fraction according to the present invention comprises :
  • nitrogen-containing hydrocarbonaceous compounds is determined on the basis of the weight of the oxygen, sulphur and nitrogen atoms present in the gasoil and not on the weight to the complete molecule comprising those oxygen, sulphur and nitrogen atoms.
  • each contaminant-enriched Fischer-Tropsch gasoil fraction is preferably provided to separate absorption zones with separate absorption material (s) to prepare more than one purified Fischer-Tropsch gasoil fractions. This is particularly relevant when the fractionation and absorption process steps are operated in a continuous mode.
  • Each of such individual more than one purified Fischer-Tropsch gasoil fractions may preferably have its own specific
  • contaminant-comprising absorbent material may be retrieved from the absorption zone.
  • the contaminant- comprising absorbent material may be recycled to the absorption zone or, in particular when the sorption capacity of the absorbent material is reached, the contaminant-comprising absorbent material may be
  • the absorbent material may be regenerated in any suitable manner that will desorb or otherwise remove the contaminants from the absorbent material.
  • the absorbent material may be regenerated either by stripping with a desorbent, such as steam or nitrogen, or by heating the absorbent material in the presence of for example oxygen, oxygen enriched air, air or a hydrogen-containing gas to burn off, or otherwise decompose the absorbed contaminants. After the absorbent material has been regenerated it may be recycled to the absorption zone.
  • Fischer-Tropsch gasoline fractions that are not contaminant-enriched may be prepared in step (b) .
  • Such Fischer-Tropsch gasoline fractions that are not contaminant-enriched are Fischer-Tropsch gasoline fractions can be directly retrieved from the process, i.e. without subjecting these fractions to the absorption step (c) as further Fischer-Tropsch gasoline fractions.
  • Fischer-Tropsch gasoline fraction (step (d) ) may be used, optionally after even further treatment, for a desired application .
  • the present invention provides the use of the purified Fischer-Tropsch gasoil fraction as a solvent, in a functional fluid formulation or a diluent.
  • a functional fluid formulation herein may be a formulation comprising the purified Fischer-Tropsch gasoil fraction, preferably comprising further containing an additive compound.
  • the solvents, functional fluid formulations and diluents may be used in many areas, for instance oil and gas exploration and
  • additives used in the functional fluid formulation according to the present invention is dependent on the type of fluid formulation.
  • Additives for functional fluid formulations include, but are not limited to, corrosion and rheology control products, emulsifiers and wetting agents, borehole stabilizers, high pressure and anti-wear additives, de- and anti-foaming agents, pour point depressants, and antioxidants.
  • Preferred solvent, diluent and/or functional fluid applications using the purified Fischer-Tropsch gasoil fraction obtained in the process according to the present invention as diluent oil or base oil include, but is not limited to, drilling fluids, heating fuels, lamp oil, barbeque lighters, concrete demoulding, pesticide spray oils, paints and coatings, personal care and cosmetics, consumer goods, pharmaceuticals, industrial and institutional cleaning, adhesives, inks, air fresheners, sealants, explosives, water treatment, cleaners, polishes, car dewaxers, electric discharge machining, transformer oils, process oil, process chemicals, silicone mastic, two stroke motor cycle oil, metal cleaning, dry cleaning, lubricants, metal work fluid, aluminum roll oil, explosives, chlorinated paraffins, heat setting printing inks, Timber treatment, polymer processing oils, rust prevention oils, shock absorbers, greenhouse fuels, fracturing fluids and fuel additives formulations.
  • Fischer-Tropsch gasoil fraction has a low viscosity, low pour point while having a high flash point.
  • the temperature of the drilling fluid may decrease which may lead to an increase of the viscosity of the drilling fluid.
  • the high viscosity may be harmful for the beneficial use of the drilling fluid. Therefore, a purified Fischer-Tropsch gasoil fraction obtained from the process according to the present invention with a low viscosity and high flash point is highly desirable for its use in drilling fluid applications .
  • the use of the purified Fischer-Tropsch gasoil fraction as a diluent may include the use as a diluent oil or base oil for solvent and/or functional fluid applications.
  • diluent oil is meant an oil used to decrease viscosity and/or improve other properties of solvent and functional fluid formulations.
  • base oil an oil to which other oils, solvents or substances are added to produce a solvent or functional fluid formulation.
  • the advantages of the use of the purified Fischer- Tropsch gasoil fraction as a diluent oil or base oil for solvent and/or functional fluid formulations are the same as described above for functional fluid formulations comprising the purified Fischer-Tropsch gasoil fraction, further containing an additive compound.
  • the present invention provides the use of a purified Fischer-Tropsch gasoil fraction obtained by the process according to the invention for improving biodegradability and lower toxicity in solvent and/or functional fluid applications.
  • the purified Fischer-Tropsch gasoil fraction has preferably very low levels of aromatics, sulphur, nitrogen compounds and is preferably free from polycyclic aromatic hydrocarbons. These low levels may lead to, but are not limited to, low aquatic toxicity, low sediment organism toxicity, low human and animal toxicity and low terrestrial ecotoxicity of the purified Fischer-Tropsch gasoil fraction.
  • the molecular structure of the purified Fischer-Tropsch gasoil fraction may lead to the readily biodegradability of the Fischer-
  • Fischer-Tropsch gasoil fraction obtained in step (b) of the process that is not contaminant- enriched also may be used in one or more ways as
  • Fischer-Tropsch-derived gasoil as provided in step (a) of the process according to the invention as feedstock is a synthetic gasoil derived from a feedstock other than crude oil, such a methane, coal or biomass, and produced in a Fischer-Tropsch process.
  • the preparation of the Fischer-Tropsch-derived gasoils has been described in e.g.
  • WO02/070628 and WO-A-9934917 (in particular the process as described in Example VII of WO-A-9934917, using the catalyst of Example III of WO-A-9934917) , both of which are hereby incorporated by reference.
  • these Fischer-Tropsch- derived gasoils have a different molecular composition and have significantly different properties compared to crude oil-derived gasoil. Therefore, Fischer-Tropsch- derived gasoils can be clearly distinguished from crude oil-derived gasoils. A number of preferred properties of the Fischer-Tropsch-derived gasoils are provided herein.
  • the Fischer-Tropsch-derived gasoil comprises more than 50wt%, more preferably more than 70 wt% of isoparaffins, still preferably more than 80 wt%.
  • Fischer-Tropsch-derived gasoils have an i/n ratio of at least 2, more preferably at least 2.8, even more preferably at least 3.5, still more preferably at least 3.7, even still more preferably at least 4, yet more preferably at least 4.5.
  • the Fischer-Tropsch-derived gasoil comprises in the range of from 20 to 40wt%, preferably of from 21 to 37wt%, more preferably of from 23 to 37wt% of mono-methyl branched isoparaffins , based on the total weight of isoparaffins in the Fischer-Tropsch-derived gasoil .
  • the Fischer-Tropsch-derived gasoil has an initial boiling point of at least 150°C and a final boiling point of at most 450°C at atmospheric conditions.
  • the Fischer-Tropsch-derived gasoil has an initial boiling point of at least 175°C at atmospheric conditions, as determined using ASTM D86. It is noted herein that the initial boiling points, final boiling points and boiling ranges provided herein when describing the present invention are those initial boiling points, final boiling points and boiling ranges as determined by ASTM D86. It is further noted that the initial boiling points, final boiling points and boiling ranges as determined by ASTM D86 for the whole of the Fischer- Tropsch-derived gasoil do not exclude the presence of compounds or fractions that have a true boiling
  • the Fischer-Tropsch-derived gasoil feedstock preferably has a final boiling point of from 330 to 450°C, more preferably of from 331 to 370°C, even more preferably of from 332 to 365°C 333 to 351°C, still more preferably of from 336 to 348°C and even still more preferably of from 339 to 345°C at atmospheric
  • boiling points at atmospheric conditions is meant atmospheric boiling points, which boiling points are determined by ASTM D86.
  • Fischer-Tropsch-derived gasoil also referred to as Fischer-Tropsch full range gasoil
  • Fischer-Tropsch full range gasoil is a fluid comprising paraffins, including isoparaffins and normal paraffins, with alkyl chain lengths in the range of from
  • the Fischer-Tropsch- derived gasoil comprises preferably at least 70 wt%, more preferably at least 85 wt%, more preferably at least 90 wt%, more preferably at least 95 wt%, and even more preferably at least 98 wt% of Fischer-Tropsch-derived paraffins having 9 to 25 carbon atoms based on the total amount of Fischer-Tropsch-derived paraffins, preferably based on the amount of Fischer-Tropsch-derived paraffins having of from 7 to 30 carbon atoms.
  • the kinematic viscosity at 40°C according to ASTM D445 of the Fischer-Tropsch-derived gasoil is of from 2.3 to 3.0 cSt, preferably of from 2.5 cSt to 2.9 cSt .
  • the pour point of the Fischer-Tropsch- derived gasoil is preferably below -10°C, more preferably below -15°C, more preferably below -17°C, more preferably below -20°C, more preferably below -22°C, and even more preferably below -27°C and preferably above -40°C.
  • the cloud point of the Fischer-Tropsch- derived gasoil is preferably below -10°C, more preferably below -15°C, more preferably below -18°C, more preferably below -20°C, more preferably below -22°C, and most preferably below -27°C and
  • the flash point of the Fischer-Tropsch- derived gasoil according to ASTM D93 is of at least 60°C, more preferably 70°C, even more preferably at least 80°C and still more preferably at least 85°C.
  • the Fischer-Tropsch-derived gasoil has a smoke point according to ASTM D1322 of more than 50 mm.
  • the Fischer-Tropsch-derived gasoil provided as feedstock to the process according to the present invention comprises :
  • sulphur-containing hydrocarbonaceous compounds in the range of from 0 to 3 ppmw, more preferably of from 0 to 1 ppmw, still more preferably of from 0 to 0.2 ppmw, of sulphur-containing hydrocarbonaceous compounds, calculated based on the weight of the elemental sulphur in the sulphur-containing hydrocarbonaceous compounds and the weight of the Fischer-Tropsch-derived gasoil;
  • Tropsch-derived gasoil feedstock i.e. at least one of the above concentrations is not zero.
  • at least one of aromatics and oxygenates is contained in the Fischer-Tropsch-derived gasoil feedstock, i.e. at least one of the above aromatic and oxygenate concentrations is not zero .
  • the Fischer-Tropsch-derived gasoil provided as feedstock to the process according to according to the present invention comprises:
  • sulphur-containing hydrocarbonaceous compounds in the range of from 0 to 3 ppmw, more preferably of from 0 to 1 ppmw, still more preferably of from 0 to 0.2 ppmw, of sulphur-containing hydrocarbonaceous compounds, calculated based on the weight of the elemental sulphur in the sulphur-containing hydrocarbonaceous compounds and the weight of the Fischer-Tropsch-derived gasoil;
  • Fischer-Tropsch-derived gasoil feedstock i.e. at least one of the above aromatic and oxygenate concentrations is not zero.
  • elemental oxygen, elemental sulphur and elemental nitrogen to indicate that the concentration of oxygenates, sulphur- containing hydrocarbonaceous compounds and nitrogen- containing hydrocarbonaceous compounds is determined on the basis of the weight of the oxygen, sulphur and nitrogen atoms present in the gasoil and not on the weight to the complete molecule comprising those oxygen, sulphur and nitrogen atoms .
  • the Fischer-Tropsch-derived gasoil comprises n- paraffins and may comprise cyclo-alkanes .
  • the Fischer-Tropsch-derived gasoil feedstock is fractionated into two or more Fischer-Tropsch gasoil fractions, preferably three or more Fischer-Tropsch gasoil fractions, more preferably four or more Fischer- Tropsch gasoil fractions.
  • the Fischer-Tropsch gasoil fractions in particular a contaminant-enriched Fischer-Tropsch gasoil fraction, obtained in step (b) may exhibits a stronger odor than the Fischer-Tropsch-derived gasoil feedstock.
  • At least one of the Fischer-Tropsch gasoil fractions obtained in step (b) , or ultimately (d) if the Fischer-Tropsch gasoil fraction is provided to step (c), has a final boiling point of at most 260°C, preferably at most 250°C, more preferably at most 215°C.
  • At least one of the Fischer-Tropsch gasoil fractions is a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a Fischer-Tropsch gasoil fraction having a final boiling point of at most 180°C, preferably at most 170°C, (2) a Fischer-Tropsch gasoil fraction an initial boiling point of at least 160°C, preferably at least 170°C, and a final boiling point of at most 200°C, preferably at most 190°C, (3) a Fischer- Tropsch gasoil fraction an initial boiling point of at least 180°C, preferably at least 190°C, and a final boiling point of at most 225°C, preferably at most 215°C, and (4) a Fischer-Tropsch gasoil fraction an initial boiling point of at least 205°C, preferably at least 215°C, and a final boiling point of at most 260°C, preferably at most 250°C, wherein the boiling point is measured at atmospheric conditions, as determined using ASTM D86
  • At least one of the Fischer-Tropsch gasoil fractions obtained in step (b) , or ultimately (d) if the Fischer-Tropsch gasoil fraction is provided to step (c), may be a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a Fischer-
  • Tropsch gasoil fraction a final boiling point of at most 180°C, preferably at most 170°C
  • a Fischer-Tropsch gasoil fraction an initial boiling point of at least 160°C, preferably at least 170°C, and a final boiling point of at most 200°C, preferably at most 190°C
  • a Fischer-Tropsch gasoil fraction an initial boiling point of at least 180°C, preferably at least 190°C, and a final boiling point of at most 225°C, preferably at most 215°C, wherein the boiling point is measured at
  • At least one of the Fischer- Tropsch gasoil fractions obtained in step (b), or ultimately (d) if the Fischer-Tropsch gasoil fraction is provided to step (c), may be a Fischer-Tropsch gasoil fraction selected from the group consisting of (2) a
  • Fischer-Tropsch gasoil fraction an initial boiling point of at least 160°C, preferably at least 170°C, and a final boiling point of at most 200°C, preferably at most 190°C, (3) a Fischer-Tropsch gasoil fraction an initial boiling point of at least 180°C, preferably at least 190°C, and a final boiling point of at most 225°C, preferably at most 215°C, wherein the boiling point is measured at
  • step (b) Preferably, at least one of the above described fractions obtained in step (b) is provided to step (c) as the contaminant-enriched Fischer-Tropsch gasoil fraction.
  • At least one of the Fischer-Tropsch gasoil At least one of the Fischer-Tropsch gasoil
  • fractions in particular a contaminant-enriched Fischer- Tropsch gasoil fraction, obtained in step (b) may exhibit a color that results in a Saybolt number that is lower than the Saybolt number of the Fischer-Tropsch-derived gasoil feedstock.
  • fraction (s) in step (d) will have essentially the same boiling point ranges as the contaminant-enriched Fischer- Tropsch gasoil fraction provided to step (c) to prepare said purified Fischer-Tropsch gasoil fraction.
  • At least one of the Fischer-Tropsch gasoil fractions obtained in step (b) , or ultimately (d) if the Fischer-Tropsch gasoil fraction is provided to step (c), has an initial boiling point of more than
  • At least one of the Fischer- Tropsch gasoil fractions is a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a Fischer-Tropsch gasoil fraction an initial boiling point of more than 260°C, preferably at least 270°C and a final boiling point of at most 320°C, preferably at most 310°C, (2) a Fischer-Tropsch gasoil fraction having an initial boiling point of at least 310°C, preferably at least 330°C, more preferably at least 360 °C, wherein the boiling point is measured at atmospheric conditions, as determined using ASTM D86.
  • At least one of the Fischer-Tropsch gasoil fractions obtained in step (b) , or ultimately (d) if the Fischer-Tropsch gasoil fraction is provided to step (c), may be a Fischer-Tropsch gasoil fraction having an initial boiling point of at least 310°C, preferably at least 330°C, more preferably at least 360°C, wherein the boiling point is measured at atmospheric conditions, as determined using ASTM D86.
  • a contaminant-enriched Fischer-Tropsch gasoil fraction obtained in step (b) and having an initial boiling point that is more than 330°C, particularly more than 360°C, obtained in step (b) may have a Saybolt number that is lower than 28, in particular lower than 27, more in particular lower than 25.
  • step (b) Preferably, at least one of the above described fractions obtained in step (b) is provided to step (c) as the contaminant-enriched Fischer-Tropsch gasoil fraction.
  • fraction (s) in step (d) will have essentially the same boiling point ranges as the contaminant-enriched Fischer- Tropsch gasoil fraction provided to step (c) to prepare said purified Fischer-Tropsch gasoil fraction.
  • Fischer-Tropsch gasoil fraction (s) retrieved in step (d) as the high purity Fischer-Tropsch gasoil fraction has an i/n ratio of in the range of from 2 to 6.
  • the majority, i.e. more than half, of the Fischer-Tropsch gasoil fractions obtained in step (b) or (d) has an i/n ratio of in the range of from 2 to 6.
  • a high i/n ratio may advantageously have an effect on amongst others the viscosity of the Fischer-Tropsch gasoil fractions.
  • fractions may be obtained that have an improved i/n ratio, depending on the particular envisaged application .
  • At least one of the Fischer-Tropsch gasoil fractions obtained in step (b) or (d) comprises in the range of from 30 to 75 wt%, more preferably of from
  • 35 to 70wt% more preferably of from 35 to 60wt% of mono- methyl branched isoparaffins , based on the total weight of isoparaffins in the Fischer-Tropsch gasoil fraction.
  • the majority, i.e. more than half, of the Fischer-Tropsch gasoil fractions obtained in step (b) or (d) comprises in the range of from 30 to 75 wt% of mono-methyl branched isoparaffins , based on the total weight of isoparaffins in the Fischer-Tropsch gasoil fraction.
  • at least one of the Fischer- Tropsch gasoil fractions obtained in step (b) or (d) comprises a higher weight percentage of mono-methyl branched isoparaffins , based on the total weight of isoparaffins than the Fischer-Tropsch-derived gasoil feedstock.
  • At least two, still more preferably three, of the Fischer-Tropsch gasoil fractions obtained in step (b) or (d) comprises a higher weight percentage of mono-methyl branched isoparaffins, based on the total weight of isoparaffins than the Fischer-
  • isoparaffins A relative high concentration of mono- methyl isoparaffins to other isoparaffins may
  • the invention provides for a second process for preparing a purified Fischer-Tropsch gasoil fraction, comprising:
  • step (c) and (d) respectively, of first process
  • step (i), (ii), respectively, of second process according to the invention apply mutatis mutandis to step (i), (ii), respectively, of second process according to the invention.
  • the contaminant is selected from the group consisting of oxygenate compounds and aromatics .
  • the absorbent material is a molecular sieve material, preferably zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite omega, preferably zeolite 13X.
  • the contaminant-comprising Fischer-Tropsch- derived gasoil is contacted with the absorbent material at a temperature in the range of from 0 to 150°C.
  • the contaminant-comprising Fischer-Tropsch gasoil fraction is contacted with the absorbent material in a fixed bed reactor comprising at least one fixed bed of absorbent material.
  • the invention also provides the use of a purified Fischer-Tropsch gasoil fraction obtained in the second process as a solvent, diluent or functional fluid.
  • the invention provides a third process for preparing a purified Fischer-Tropsch gasoil fraction, comprising:
  • Fischer-Tropsch gasoil fraction as high purity Fischer-Tropsch
  • Tropsch gasoil fraction which purified Fischer-Tropsch gasoil fraction is contaminant-depleted with respect to the contaminant-comprising Fischer-Tropsch gasoil fraction .
  • the limiting features described herein above for the first process according to the invention apply mutatis mutandis to the third process according to the invention.
  • the limiting features described herein above for the contaminant-enriched Fischer-Tropsch gasoil fraction of first process according to the invention apply mutatis mutandis to the contaminant-comprising Fischer-Tropsch gasoil fraction of third process according to the invention .
  • step (v) , (vv) respectively, of third process according to the invention.
  • the contaminant is selected from the group consisting of oxygenate compounds and aromatics .
  • the absorbent material is a molecular sieve material, preferably zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite omega, preferably zeolite 13X.
  • the contaminant-comprising Fischer-Tropsch- derived gasoil is contacted with the absorbent material at a temperature in the range of from 0 to 150°C.
  • the contaminant-comprising Fischer-Tropsch gasoil fraction is contacted with the absorbent material in a fixed bed reactor comprising at least one fixed bed of absorbent material.
  • the invention also provides the use of a purified Fischer-Tropsch gasoil fraction obtained in the third process as a solvent, diluent or functional fluid.
  • Example 1 A Fischer-Tropsch-derived gasoil having a boiling range of 185 to 350°C, as determined by ASTM D86, was fractionated by distillation into 7 fractions. The properties of the prepared Fischer-Tropsch gasoil fractions are shown in Table 1. The aromatic content was determined by UV absorption spectrometry. The ratio of isoparaffin over normal paraffin and the concentration of mono-methyl branched isoparaffins were determined using gas chromatography.
  • the odor of the Fischer-Tropsch-derived gasoil feed and the resulting contaminant-enriched and purified fractions were determined by a 4 member panel using the following procedure :
  • the feedstock contains compounds individually boiling below the ASTM D86-based initial boiling point.
  • the feed gasoil has a relatively low odor and relative low aromatic content.
  • Fischer-Tropsch gasoil fraction samples representative of samples GS160, GS170 and GS190 from Example 1, were contacted with an absorbent material in an absorption zone. Each Fischer-Tropsch gasoil fraction was separately contacted with fresh absorbent material. The Fischer-Tropsch gasoil fraction samples were first contacted with an Mg silicate absorbent material and subsequently with zeolite 13X absorbent material. The volume ratio of Fischer-Tropsch gasoil fraction to absorbent material was 82 for the Zeolite 13x and 210 for the Mg silicate. The Fischer-Tropsch gasoil fraction was contacted with the absorbent material at ambient
  • Mg silicate does not significantly remove aromatics from the contaminant- enriched Fischer-Tropsch gasoil fractions. However, an improvement of the odor is observed. This is attributed to the absorption of other contaminants in particular oxygenates. Zeolite 13X does absorb a significant part of the aromatics and a further improvement of the smell is observed .
  • Tropsch gasoil fractions are shown in Table 3. As can be seen in Table 3, both the color and the odor are shown in Table 3.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une fraction de gasoil de Fischer-Tropsch de grande pureté comprenant les étapes consistant à: a) fournir une matière première de gasoil dérivé de Fischer-Tropsch comprenant un ou plusieurs contaminants; b) fournir la matière première de gasoil dérivé de Fischer-Tropsch à une zone de fractionnement et fractionner la matière première de gasoil dérivé de Fischer-Tropsch en deux ou plus de deux fractions de gasoil de Fischer-Tropsch présentant une plage de points d'ébullition différents, au moins une fraction de gasoil de Fischer-Tropsch étant une fraction de gasoil de Fischer-Tropsch enrichie en contaminants, qui est enrichie en un ou plusieurs contaminants par rapport à la matière première; c) fournir la fraction de gasoil de Fischer-Tropsch enrichie en contaminants à une zone d'absorption comprenant au moins un matériau absorbant et mettre en contact la fraction de gasoil de Fischer-Tropsch enrichie en contaminants avec le matériau absorbant pour absorber au moins une partie des contaminants; et d) récupérer à partir de la zone d'absorption une fraction de gasoil de Fischer-Tropsch purifiée, qui est appauvrie en contaminants. L'invention concerne en outre d'autres procédés de préparation d'une fraction de gasoil de Fischer-Tropsch de grande pureté et l'utilisation de la fraction de gasoil de Fischer-Tropsch purifiée.
PCT/EP2015/060842 2014-05-19 2015-05-18 Procédé de préparation d'une fraction de gasoil de fischer-tropsch de grande pureté WO2015177067A1 (fr)

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EP15724226.4A EP3146022A1 (fr) 2014-05-19 2015-05-18 Procédé de préparation d'une fraction de gasoil de fischer-tropsch de grande pureté
US15/311,867 US20170137723A1 (en) 2014-05-19 2015-05-18 Process for preparing a high purity fischer-tropsch gasoil fraction
KR1020167034023A KR20170010782A (ko) 2014-05-19 2015-05-18 고 순도 피셔-트롭쉬 가스유 분획물의 제조 방법
JP2016568596A JP2017519857A (ja) 2014-05-19 2015-05-18 高純度フィッシャー−トロプシュ軽油画分を調製するための方法
CN201580026447.9A CN106459785A (zh) 2014-05-19 2015-05-18 制备高纯度费托气油馏分的方法

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EP14168860 2014-05-19

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WO2015181114A1 (fr) * 2014-05-28 2015-12-03 Shell Internationale Research Maatschappij B.V. Fraction de gazole fischer-tropsch
CN115386395B (zh) * 2021-05-20 2024-06-04 国家能源投资集团有限责任公司 降低费托合成油浊点的方法及络合剂与络合剂的应用

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US20170137723A1 (en) 2017-05-18
JP2017519857A (ja) 2017-07-20
KR20170010782A (ko) 2017-02-01

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