Classifications

• • 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
  • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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 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.
• synthesis gas i.e. a mixture of predominantly hydrogen and carbon monoxide
• Fischer-Tropsch-derived gasoil feedstocks Due to their synthetic origin, these Fischer-Tropsch-derived gasoil feedstocks have very low levels of aromatics, naphthenics and impurities compared to their crude oil derived counterparts. In addition, the Fischer-Tropsch-derived gasoil feedstocks have properties that provide advantages in solvent and functional fluid applications with low viscosity requirements.
• US 2004/164000 describes a method of preparing high linear paraffin or high end-chain monomethyl content hydrocarbon products, wherein a Fischer-Tropsch feedstock with n-paraffin content of greater than 50 wt % is pre-treated to remove oxygenates and subsequently fractionated.
• a Fischer-Tropsch-derived solvent is disclosed with a boiling range from approximately 160 to 370° C. According to U.S. Pat. No. 5,906,727, the solvent has a low odor and is colorless (Saybolt color number of +30).
• the present invention provides for a process for preparing a high purity Fischer-Tropsch gasoil fraction. It has been found that, when a Fischer-Tropsch-derived gasoil feedstock 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 discoloration. These disadvantageous side-effects encountered when fractionating virtually odorless and colorless Fischer-Tropsch-derived gasoil feedstock were till now unknown. It has now been found that this problem can be resolved by the process according to the present invention.
• the present invention provides a process for preparing a purified Fischer-Tropsch gasoil fraction, comprising:
• the process according to the invention allows for the preparation of purified Fischer-Tropsch gasoil fractions, having applicability as solvents, diluents and functional fluids, which have a boiling point range that is narrower than the Fischer-Tropsch-derived gasoil feedstock (also referred to as Fischer-Tropsch-derived gasoil feedstock) feedstock it was prepared from.
• Fischer-Tropsch-derived gasoil feedstock also referred to as Fischer-Tropsch-derived gasoil feedstock
• 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 relatively straightforward, cheap and safe absorption method.
• the process according to the invention further allows for the removal of both those contaminates that are carried over and accumulate in the fractions essentially unchanged, as well as those contaminants that may react to further contaminants when subjected to the fractionation conditions.
• the invention provides for the use of a purified Fischer-Tropsch gasoil fraction produced by the process according to the present invention as a solvent, diluent or functional fluid.
• the present invention provides for a process for preparing purified Fischer-Tropsch gasoil fractions.
• Fischer-Tropsch gasoil fractions are particularly suitable for use as solvents, diluents and functional fluids, in particular for the applications as mentioned herein.
• Fischer-Tropsch-derived gasoil is a synthetic gasoil derived from a Fischer-Tropsch process.
• Fischer-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.
• the 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 conditions over a, preferably, bifunctional, catalyst, or catalyst containing a metal, or metals, hydrogenation component and an acidic oxide support component active in producing both hydrocracking and hydroisomerization reactions.
• a least part of the resulting hydrocracked/hydroisomerized Fischer-Tropsch product may be provided as the Fischer-Tropsch-derived gasoil feedstock.
• 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 feedstock having a similar volatility and flashpoint. Notwithstanding the above, 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.
• the different characteristics of the Fischer-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.
• Fischer-Tropsch-derived 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 discoloration. A Saybolt number lower than 25 already indicates the presence of a visually observable discoloration. 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-derived gasoil by fractionating the Fischer-Tropsch-derived gasoil feedstock 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.
• Fischer-Tropsch gasoil fractions also referred to as Fischer-Tropsch gasoil fractions
• the viscosity, pour point, density and flash point characteristics of the Fischer-Tropsch-derived gasoil fractions may be change, beyond the change that would be expected on the basis of a fractionation based on boiling ranges alone.
• Contaminants herein are non-paraffinic, non naphthenic compounds.
• the term contaminant herein refers to compounds selected from the group consisting of oxygenate compounds, unsaturated hydrocarbon compounds, sulphur containing compounds and nitrogen containing compounds.
• oxygenate compounds herein refers to oxygen-containing hydrocarbonaceous compounds.
• oxygenates include, but are not limited to alcohols, ketones, aldehydes, ethers, epoxides and acids.
• unsaturated hydrocarbon compounds herein refers to compounds having one or more unsaturated bonds, including unsaturated aliphatic hydrocarbon compounds and aromatics.
• 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, unsaturated aliphatic hydrocarbon compounds, and aromatics, as these compounds are believed to provide the most significant contribution to the odor and discoloration if they accumulate in any resulting Fischer-Tropsch gasoil fractions.
• oxygenate compounds are believed to provide the most significant contribution to the odor and, to a lesser extent, discoloration of the contaminant-enriched Fischer-Tropsch gasoil fractions.
• Aromatics compounds are believed to provide the most significant contribution to the discoloration and odor of the contaminant-enriched Fischer-Tropsch gasoil fractions.
• contaminant concentration herein refers to a contaminant concentration expressed in ppmw, unless expressly indicated differently, and calculated on the basis of the total Fischer-Tropsch-derived gasoil feedstock, purified Fischer-Tropsch gasoil, or purified Fischer-Tropsch gasoil fraction and the total weight of the contaminants.
• the Fischer-Tropsch-derived gasoil feedstock may contain one or more contaminant selected from the group consisting of oxygenate compounds, unsaturated aliphatic hydrocarbon compounds and aromatics.
• the, albeit low level of, contaminants present in the Fischer-Tropsch-derived gasoil feedstock are exposed to elevated temperatures, optionally in the presence of oxygen or oxygen-comprising compounds.
• undesired side-reactions may take place during fractionation, whereby one or more of the contaminants present in the Fischer-Tropsch-derived gasoil feedstock may be converted in-situ to other contaminants, which in-situ formed contaminants may exhibit more distinct odor and color inducing characteristics.
• Oxidation herein refers to reactions with oxygen during the fractionation.
• the oxygen may be present in the fractionation unit.
• Oxygen may be introduced in the process in the form of air that is present in the fractionation units.
• Another particular side-reaction that may take place is the thermal dehydrogenation of one or more of the contaminants in the Fischer-Tropsch-derived gasoil feedstock to unsaturated and/or multiple-unsaturated contaminants, including unsaturated aliphatic hydrocarbon and aromatics.
• the thermal dehydrogenation of one or more of the hydrocarbon contaminants may lead to a wide range of subsequent or further side-reactions, including but not limited to oxidation, isomerization, oligomerization, cracking, alkylation and aromatization side reactions.
• oxidation and, or a lesser extent, aromatization and/or dehydro-aromatization reactions may result in the formation of oxygenate and aromatic contaminants as by-products.
• the presence of metal surfaces in fractionation units, in particular distillation units may catalyze the dehydrogenation and subsequent reactions.
• an effect of the increased concentration of contaminants in the Fischer-Tropsch gasoil fractions that are prepared may be that the Saybolt number of the Fischer-Tropsch gasoil fractions is lowered, i.e. the fraction is colored. This undesired discoloration is particularly observed in the higher boiling Fischer-Tropsch gasoil fractions.
• a further effect of the increased concentration of contaminants in the Fischer-Tropsch gasoil fractions 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.
• Fischer-Tropsch-derived gasoil feedstocks 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 gasoil feedstocks 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 gasoil feedstocks or paraffins.
• This difference in odor can be characterized by comparing the odor of a Fischer-Tropsch gasoil fraction, optionally containing an increased concentration of contaminants, 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 process according to the present invention provides for a pre-treatment of the Fischer-Tropsch-derived gasoil feedstock prior to fractionating the Fischer-Tropsch-derived gasoil feedstock.
• the pretreatment may be any pretreatment suitable to remove the contaminants or reduce the contaminant concentration in the Fischer-Tropsch-derived gasoil feedstock.
• suitable pretreatments include, absorption, hydrotreating and acid treatment.
• the preferred pretreatment is an absorption treatment wherein the Fischer-Tropsch-derived gasoil feedstock is contacted with at least one absorbent material.
• This process is relatively straightforward and less expensive compared to for instance a hydrotreating step and does not require introducing hazardous and reactive compounds such as e.g. acids into the Fischer-Tropsch-derived gasoil feedstock.
• the Fischer-Tropsch-derived gasoil feedstock comprising one or more contaminants is provided to a pretreatment zone and pretreated to remove at least part of the one or more contaminants and a purified Fischer-Tropsch gasoil is retrieved from the pretreatment zone.
• the Fischer-Tropsch-derived gasoil feedstock is provided to a pretreatment zone that is an absorption zone comprising at least one absorbent material and the pretreatment comprises contacting the Fischer-Tropsch-derived gasoil feedstock with the absorbent material to absorb at least part of the one or more contaminants.
• the absorption zone comprises at least one absorbent material selected from the group consisting of magnesium silicate and molecular sieve materials including 4A or 5A molecular sieve, zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite omega.
• absorbent material selected from the group consisting of magnesium silicate and molecular sieve materials including 4A or 5A molecular sieve, zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite omega.
• 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 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, mordenite, zeolite beta, zeolite L, zeolite omega, more preferably zeolite X, zeolite 13X, zeolite Y, dealuminized zeolite Y, ultrastable Y, ZSM-12, mordenite, zeolite beta, zeolite L, zeolite omega, even more preferably the absorbent material is zeolite 13X, which is the sodium form of Zeolite X.
• zeolite 13X which is the sodium form of Zeolite X.
• 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, unsaturated aliphatic hydrocarbon compounds 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 particles.
• 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 Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock 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 an undesirable decrease of the diffusion rate of the contaminants from the Fischer-Tropsch-derived gasoil feedstock to the absorbent material.
• the contact temperature is increased, i.e. above 0° C., the rate of diffusion may increase.
• the formation of by-products is reduced. This is important as these by-products may remain in the purified Fischer-Tropsch gasoil and consequently carry over into the fractions and therefore may have an undesirable effect on the applicability of the resulting Fischer-Tropsch gasoil fraction.
• the Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock may contacted with the absorbent material batch-wise or in a continuous mode. It is preferred that the Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock is contacted with the absorbent material under continuous stirring or induced mixing, this is particularly preferred in case of a batch-wise operation.
• Fischer-Tropsch-derived gasoil feedstock is contacted with the absorbent material in the absorption zone at for a time sufficient to absorb at least part of the contaminants.
• the Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock may be contacted with the absorbent material in a volume ratio of Fischer-Tropsch-derived gasoil feedstock over absorbent material of in the range of from 0.5 to 200, more preferably of from 1 to 175, even more preferably 5 to 125.
• the Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock 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 two or more absorption sections in parallel, preferably comprising the same absorbent material.
• inventions may include both parallel as well as in-series aligned absorption zones.
• 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 regenerated.
• 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.
• a purified Fischer-Tropsch gasoil is retrieved from the pretreatment zone.
• the purified Fischer-Tropsch gasoil retrieved from the absorption zone is contaminant-depleted, i.e. the purified Fischer-Tropsch gasoil comprises a contaminant concentration that is lower than the contaminant concentration of the Fischer-Tropsch-derived gasoil feedstock.
• at least one of the aromatic, unsaturated aliphatic hydrocarbon compound and oxygenate concentrations of the purified Fischer-Tropsch gasoil is lower the corresponding concentrations of the Fischer-Tropsch-derived gasoil feedstock.
• At least two of the aromatic, unsaturated aliphatic hydrocarbon compound and oxygenate concentrations of the purified Fischer-Tropsch gasoil is lower the corresponding concentrations of the Fischer-Tropsch-derived gasoil feedstock. Still more preferably, Preferably, all of the aromatic, unsaturated aliphatic hydrocarbon compound and oxygenate concentrations of the purified Fischer-Tropsch gasoil is lower the corresponding concentrations of the Fischer-Tropsch-derived gasoil feedstock.
• the purified Fischer-Tropsch gasoil according to the present invention comprises:
• the purified Fischer-Tropsch gasoil is subsequently provided to a fractionation zone and fractionated.
• the Fischer-Tropsch-derived gasoil feedstock is preferably fractionated by distillation, wherein the Fischer-Tropsch-derived gasoil feedstock is fractionated, i.e. distilled, by heating part or all of the Fischer-Tropsch-derived gasoil feedstock to temperatures in the range of from 150 to 500° C.
• the purified Fischer-Tropsch gasoil is fractionated into two or more purified Fischer-Tropsch gasoil fractions, each having a different boiling point range.
• the purified Fischer-Tropsch gasoil is fractionated into three or more, more preferably four or more, Fischer-Tropsch gasoil fractions each having a different boiling point range.
• at least one, more preferably at least two, of the purified 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 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.
• 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.
• At least one of the purified Fischer-Tropsch gasoil fractions obtained in step (d) may be a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a purified Fischer-Tropsch gasoil fraction a final boiling point of at most 180° C., preferably at most 170° C., (2) a purified 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., and (3) a purified 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 atmospheric conditions, as determined using ASTM D86.
• At least one of the purified Fischer-Tropsch gasoil fractions obtained in step (d) is a purified Fischer-Tropsch gasoil fraction selected from the group consisting of (2) a purified 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 purified 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 atmospheric conditions, as determined using ASTM D86.
• At least one of the purified Fischer-Tropsch gasoil fractions obtained in step (d) has an initial boiling point of more than 260° C., preferably more than 300° C., more preferably more than 310° C.
• at least one of the purified Fischer-Tropsch gasoil fractions is a Fischer-Tropsch gasoil fraction selected from the group consisting of (1) a purified Fischer-Tropsch gasoil fraction an initial boiling point of more than 260° C., preferably at least 270° C.
• a purified 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 purified Fischer-Tropsch gasoil fractions obtained in step (d) 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.
• At least one of the purified Fischer-Tropsch gasoil fractions obtained in step (d) has an i/n ratio of in the range of from 2 to 6.
• the majority, i.e. more than half, of the purified Fischer-Tropsch gasoil fractions obtained in step (d) has a has an i/n ratio of in the range of from 2 to 6.
• a high i/n ratio may advantageously effect on amongst others the viscosity of the purified Fischer-Tropsch gasoil fractions. Increasing the relative concentration of isoparaffin may lower the overall viscosity of the purified Fischer-Tropsch gasoil fractions.
• At least one of the purified Fischer-Tropsch gasoil fractions obtained in step (d) comprises in the range of from 30 to 75 wt %, more preferably of from 35 to 70 wt %, more preferably of from 35 to 60 wt % of mono-methyl branched isoparaffins, based on the total weight of isoparaffins in the purified Fischer-Tropsch gasoil fraction.
• the majority, i.e. more than half, of the purified Fischer-Tropsch gasoil fractions obtained in step (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 purified Fischer-Tropsch gasoil fraction.
• at least one of the purified Fischer-Tropsch gasoil fractions obtained in step (d) comprises a higher weight percentage of mono-methyl branched isoparaffins, based on the total weight of isoparaffins than the purified Fischer-Tropsch-derived gasoil feedstock.
• At least two, still more preferably three, of the purified Fischer-Tropsch gasoil fractions obtained in step (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.
• Mono-methyl branched isoparaffins exhibit desirable bio degradation characteristic compared to other isoparaffins.
• a relative high concentration of mono-methyl isoparaffins to other isoparaffins may advantageously effect amongst others the bio degradation characteristics of the Fischer-Tropsch gasoil fractions.
• Increasing the relative concentration of mono-methyl isoparaffin to other isoparaffins may improve the bio degradation characteristics of the purified Fischer-Tropsch gasoil fractions beyond the bio degradation characteristics of the Fischer-Tropsch-derived gasoil feedstock.
• the purified Fischer-Tropsch gasoline fraction prepared by the process according to the invention 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 production, process oils, agro chemicals, process chemicals, construction industry, food and related industries, paper, textile and leather, and various household and consumer products.
• the type of 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.
• Typical solvent, diluent and functional fluid applications are for example described in “The Index of Solvents”, Michael Ash, Irene Ash, Gower publishing Ltd, 1996, ISBN 0-566-07884-8 and in “Handbook of Solvents”, George Wypych, Willem Andrew publishing, 2001, ISBN 0-8155-1458-1.
• An advantage of the use of the purified Fischer-Tropsch gasoil fraction as solvents, diluents or in functional fluid formulations is that the purified Fischer-Tropsch gasoil fraction has a low viscosity, low pour point while having a high flash point. This combination of physical characteristics of the purified Fischer-Tropsch gasoil fraction is highly desirable for its use in functional fluid formulations with low viscosity requirements.
• 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 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-Tropsch-derived gasoil feedstock.
• Fischer-Tropsch gasoil fraction The specific use of a particular purified Fischer-Tropsch gasoil fraction may be dependent on the exact composition and characteristics of that particular Fischer-Tropsch gasoil fraction.
• the Fischer-Tropsch-derived gasoil feedstock 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 gasoil feedstocks 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.
• Fischer-Tropsch-derived gasoil feedstocks have a different molecular composition and have significantly different properties compared to crude oil-derived gasoil feedstock. Therefore, Fischer-Tropsch-derived gasoil feedstocks can be clearly distinguished from crude oil-derived gasoil feedstocks.
• a number of preferred properties of the Fischer-Tropsch-derived gasoil feedstocks are provided herein.
• the Fischer-Tropsch-derived gasoil feedstock comprises more than 70 wt % of iso-paraffins, still preferably more than 80 wt %.
• Fischer-Tropsch-derived gasoil feedstocks have a 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 feedstock comprises in the range of from 20 to 40 wt %, preferably of from 21 to 37 wt %, more preferably of from 23 to 37 wt % of mono-methyl branched isoparaffins, based on the total weight of isoparaffins in the Fischer-Tropsch-derived gasoil feedstock.
• the Fischer-Tropsch-derived gasoil feedstock 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 feedstock 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.
• initial boiling points, final boiling points and boiling ranges as determined by ASTM D86 for the whole of the Fischer-Tropsch-derived gasoil feedstock do not exclude the presence of compounds or fractions that have a true boiling temperature below or above the respective ASTM D86-based initial boiling point and ASTM D86-based final boiling point of the whole of the Fischer-Tropsch-derived gasoil feedstock.
• 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 conditions.
• boiling points at atmospheric conditions is meant atmospheric boiling points, which boiling points are determined by ASTM D86.
• the Fischer-Tropsch-derived gasoil feedstock is a fluid comprising paraffins, including iso-paraffins and normal paraffins, with alkyl chain lengths in the range of from 7 to 30 carbon atoms, preferably comprising paraffins having from 9 to 25 carbon atoms;
• the Fischer-Tropsch-derived gasoil feedstock 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 Fischer-Tropsch-derived gasoil feedstock preferably has a density at 15° C. according to ASTM D4052 of from 774 kg/m 3 to 782 kg/m 3 , more preferably of from 775 kg/m 3 to 780 kg/m 3 , and even more preferably of from 776 kg/m 3 to 779 kg/m 3 .
• the kinematic viscosity at 40° C. according to ASTM D445 of the Fischer-Tropsch-derived gasoil feedstock 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 feedstock 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 feedstock 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 preferably above ⁇ 40° C.
• the flash point of the Fischer-Tropsch-derived gasoil feedstock 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 feedstock has a smoke point according to ASTM D1322 of more than 50 mm.
• the Fischer-Tropsch-derived gasoil feedstock used in the present invention contains one or more contaminants.
• the Fischer-Tropsch-derived gasoil feedstock provided as feedstock to the process according to the present invention contains:
• the Fischer-Tropsch-derived gasoil feedstock provided as feedstock to the process according to according to the present invention comprises:
• the Fischer-Tropsch-derived gasoil feedstock preferably comprises less than 300 ppmw of polycyclic aromatic hydrocarbons, more preferably less than 25 ppmw polycyclic aromatic hydrocarbons and most preferably less than 1 ppmw polycyclic aromatic hydrocarbons, based on the weight of the Fischer-Tropsch-derived gasoil feedstock.
• the Fischer-Tropsch-derived gasoil feedstock comprises n-paraffins and may comprise cyclo-alkanes.

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• 2015
  • 2015-05-18 BR BR112016025455A patent/BR112016025455A2/pt not_active Application Discontinuation
  • 2015-05-18 KR KR1020167034025A patent/KR20170010784A/ko unknown
  • 2015-05-18 US US15/311,895 patent/US20170218282A1/en not_active Abandoned
  • 2015-05-18 EP EP15724229.8A patent/EP3146020A1/en not_active Withdrawn
  • 2015-05-18 JP JP2016566787A patent/JP2017519855A/ja active Pending
  • 2015-05-18 CN CN201580023308.0A patent/CN106459775A/zh active Pending
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