EP2746367A1 - Procédé pour préparer une huile de base et du gazole - Google Patents

Procédé pour préparer une huile de base et du gazole Download PDF

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Publication number
EP2746367A1
EP2746367A1 EP12197722.7A EP12197722A EP2746367A1 EP 2746367 A1 EP2746367 A1 EP 2746367A1 EP 12197722 A EP12197722 A EP 12197722A EP 2746367 A1 EP2746367 A1 EP 2746367A1
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EP
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Prior art keywords
range
fischer
fraction
base oil
conversion
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EP12197722.7A
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German (de)
English (en)
Inventor
Arend Hoek
Eduard Philip Kieffer
Jelle Rudolf Anne Sietsma
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/18—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only cracking steps

Definitions

  • the invention is directed to a process to prepare base oil and gas oil from a Fischer-Tropsch product.
  • WO02070629A1 describes a process to prepare a gas oil product and a base oil product from a Fischer-Tropsch product by performing hydroconversion/hydroisomeri sation and isolation of a gas oil fraction and a residue from the obtained cracked effluent. The residue is further distilled to obtain a distillate fraction boiling between 370 and 510 °C. This fraction boiling between 370 and 510 °C is subjected to catalytic dewaxing to obtain various base oil grades.
  • US20080314800A1 discloses a process to prepare a base oil product from a Fischer-Tropsch product by performing hydroconversion/hydroisomerisation and distillation.
  • One part of a Fischer-Tropsch product is subjected to hydroconversion/hydroisomerisation at a certain conversion, preferably a conversion between 30 and 60%.
  • Another part of the Fischer-Tropsch product is subjected to hydroconversion/hydroisomerisation at a higher conversion.
  • This conversion is at least 5% higher, and preferably is a conversion between 50 and 95%.
  • both hydroconversions are performed with the same type of catalyst.
  • the conversion level may be adjusted by varying the temperature.
  • WO2006067174A1 describes a process to prepare a gas oil product and a base oil product from a Fischer-Tropsch product by performing hydroconversion/hydroisomeri sation and distillation.
  • a relatively light part of a Fischer-Tropsch product is subjected to hydroconversion/ hydroisomerisation, and a relatively heavy part of a Fischer-Tropsch product is subjected to hydroconversion/hydroisomerisation.
  • This may be performed in two hydroconversion reactors operating in parallel.
  • the reactors Preferably the reactors have the same type of catalyst.
  • the conversion may be the same or different.
  • the conversion preferably is between 50 and 90%.
  • For the heavy part the conversion preferably is between 30 and 60%.
  • the light part of a Fischer-Tropsch product results in a higher gas oil yield and the heavy part results in a higher waxy raffinate yield.
  • the object of the present invention is to optimise the yield to gas oils and the yield to base oils from a Fischer-Tropsch product.
  • the present invention provides a process for preparing gas oil and base oil from a Fischer-Tropsch product, said process comprising the following steps:
  • the present invention provides a process for preparing gas oil and base oil from a Fischer-Tropsch product, said process comprising the following steps:
  • the process of the present invention it is possible to optimize the yield of gas oil as well as the yield of the fraction boiling in the distillate base oil range.
  • the yield of the fraction boiling in the distillate base oil range is optimised also the yield of the base oils, which are obtained after subjecting the fraction boiling in the distillate base oil range to a pour point reducing step, is optimised.
  • the fraction boiling in the distillate base oil range is sometimes referred to as waxy raffinate fraction.
  • the Fischer-Tropsch product which is provided in step (a) may be obtained from a single Fischer-Tropsch reactor in which the Fischer-Tropsch process is performed.
  • the Fischer-Tropsch product which is provided in step a) may be obtained from two or more Fischer-Tropsch reactors in which the Fischer-Tropsch process is performed.
  • the product(s) from the reactor(s) may be entire Fischer-Tropsch product stream(s) or a part thereof. Such a part may, for example, be split off, may be obtained by distillation, or may be obtained after removal of components such as water.
  • step (a) In case Fischer-Tropsch product provided in step (a) is obtained from two or more reactors, the product stream(s) of one or more reactors may be fed to step (b), while the product stream(s) from the other reactor(s) is bed to step (c).
  • the product stream(s) of one or more reactors is heavier than the product stream(s) of the other reactor(s), preferably the lighter product stream(s) is/are fed to step (b), and the heavier product stream(s) is/are fed to step (c).
  • step a) in case Fischer-Tropsch product provided in step a) is obtained from two Fischer-Tropsch reactors, it is possible to feed the product from one reactor to step (b) and the product from the other reactor to step (c).
  • the product of one reactor is heavier than the product of the other reactor, preferably the lighter product is fed to step (b), and the heavier product is fed to step (c).
  • step (a) In case the Fischer-Tropsch product which is provided in step (a) is obtained from a single Fischer-Tropsch reactor, the product may be split after which one part is fed to step (b) and another part is fed to step (c).
  • step (a) In case the Fischer-Tropsch product which is provided in step (a) is obtained from a single Fischer-Tropsch reactor, the product may be distilled after which preferably a lighter fraction is fed to step (b), and a heavier fraction is fed to step (c).
  • step (a) In case the Fischer-Tropsch product which is provided in step (a) is obtained from two or more reactors, at least a part of the product streams of both or all reactors may be combined and in a subsequent step the combined product may be split after which one part is fed to step (b) and another part is fed to step (c).
  • step (a) In case the Fischer-Tropsch product which is provided in step (a) is obtained from two or more reactors, at least a part of the product streams of both or all reactors may be combined and in a subsequent step the combined product may be distilled after which a lighter fraction is fed to step (b), and a heavier fraction is fed to step (c).
  • the Fischer-Tropsch product provided in step (a) is a product directly obtained from a Fischer-Tropsch synthesis reaction, which product may optionally have been subjected to a distillation and/or hydrogenation step only.
  • the Fischer-Tropsch synthesis product can be obtained by well-known processes, for example the so-called commercial Slurry Phase Distillate technology of Sasol, the Shell Middle Distillate Synthesis Process or by the non-commercial "AGC-21" Exxon Mobil process. These and other processes are for example described in more detail in EP-A-776959 , EP-A-668342 , US-A-4943672 , US-A-5059299 , WO-A-9934917 and WO-A-9920720 . Most of these processes are carried out at temperatures between 200 and 280 °C, especially 210-260 °C.
  • the catalyst contains often cobalt or iron, preferably cobalt.
  • the pressure is suitably between 10 and 80 bar, especially between 20 and 65 bar.
  • the reaction is usually carried out in a fix bed reactor or a slurry reactor.
  • a Fischer-Tropsch synthesis product typically comprises hydrocarbons having 1 to 100 and even more than 100 carbon atoms, e.g. up to 200 carbon atoms or occasionally even more.
  • This hydrocarbon product will comprise normal paraffins, iso-paraffins, oxygenated products and unsaturated products.
  • Paraffins and unsaturated product, especially olefins, more especially alpha-olefins, are the main constituents of the Fischer-Tropsch product.
  • the amount of olefins may vary from 5 to 90 wt% of the total feed stream.
  • the amount of iso-paraffins (and iso-olefins) also depends on the actual reaction conditions.
  • the amount of iso-compounds is up to 25 wt% of the total feed stream, suitably between 1 and 20 wt%, especially between 3 and 15 wt%.
  • the amount of oxygenates is usually up till 10 wt% of the total feed stream, suitably between 0.5 and 6 wt%.
  • the Fischer-Tropsch product provided in step (a) suitably is the full C 5 + fraction of the Fischer-Tropsch process, i.e. no heavy compounds have been removed from the fraction.
  • Other suitable products that may be provided in step (a) are the full C 12 + fraction of the Fischer-Tropsch process or the full C 18 + fraction, i.e. the 200 °C plus fraction or the 310 °C plus fraction of the Fischer-Tropsch process.
  • the fraction boiling above 380 °C, or even boiling above 750 °C may be provided in step (a).
  • the Fischer-Tropsch product provided in step (a) preferably is the full high boiling fraction, i.e. no heavy compounds, e.g. C 21 + compounds, are removed from the high boiling fraction.
  • the Fischer-Tropsch product provided in step (a) preferably is relatively heavy.
  • the relatively heavy Fischer-Tropsch product provided in step (a) preferably has at least 30 wt%, more preferably at least 50 wt%, and even more preferably at least 55 wt% of compounds having at least 30 carbon atoms.
  • the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms of the Fischer-Tropsch product preferably is at least 0.2, more preferably at least 0.4 and even more preferably at least 0.55.
  • the Fischer-Tropsch product comprises a C 20 + fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor derived from the C 20 compounds and the C 40 compounds of the Fischer-Tropsch product stream) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.
  • ASF-alpha value Anderson-Schulz-Flory chain growth factor derived from the C 20 compounds and the C 40 compounds of the Fischer-Tropsch product stream
  • any compounds having 4 or less carbon atoms and any compounds having a boiling point in that range are separated from a Fischer-Tropsch synthesis product before the Fischer-Tropsch synthesis product is used in step (b) or (c).
  • step (a) A part of the Fischer-Tropsch product provided in step (a) is used in step (b) and another part is used in step (c).
  • the Fischer-Tropsch product provided in step (a) may be simply split into two equal parts and the two parts are used as feed in steps (b) and (c).
  • Fischer-Tropsch product from one or more parallel operated Fischer-Tropsch synthesis reactor types for example slurry bubble or multi-tubular reactors
  • one or more other parallel operated Fischer-Tropsch reactor types provide the feed for step (c).
  • step (a) in addition to steps (b) and (c), more parallel operated hydroconversion/hydrocracking reactors are present. It is understood that the Fischer-Tropsch product provided in step (a) will then be split over more than two feeds provided that at least two reactors operate at a different conversion according to the present invention.
  • each feed stream comprises at least 20 wt% of the feed stream of compounds boiling above 360 °C, more preferably at least 40 wt%, more preferably at least 60 wt%, still more preferably at least 85 wt%.
  • the feed for steps (b) and (c) may next to the Fischer-Tropsch product also comprise of mineral crude derived fractions and/or gas field condensates.
  • These additional sulphur containing co-feeds are advantageous when a sulphided catalyst is used in steps (b) and (c).
  • the sulphur in the feed will keep the catalyst in its sulphided form.
  • the sulphur may be removed in a down stream treating unit or, in case the quantities are very low, become part of the product of the present invention.
  • step (b) a part of the Fischer-Tropsch product of step (a) is subjected to hydroconversion/hydroisomerisa tion
  • step (c) a part of the Fischer-Tropsch product of step (a) is subjected to hydroconversion/hydroisomerisa tion
  • the catalyst used in step (b) comprises platinum and/or palladium, amorphous silica-alumina (ASA), and less than 0.1 wt% zeolite, preferably less than 0.01 wt% zeolite, more preferably no zeolite.
  • ASA amorphous silica-alumina
  • the catalyst used in step (c) comprises platinum and/or palladium, amorphous silica-alumina (ASA), and 0.1-15 wt% wt% zeolite, preferably 0.1-15 wt% zeolite beta.
  • ASA amorphous silica-alumina
  • the platinum and/or palladium is preferably present in an amount of from 0.1 to 5.0% by weight, more suitably from 0.2 to 2.0% by weight, calculated as element and based on total weight of ASA. If both platinum and palladium are present in the catalyst, the weight ratio of platinum to palladium in the catalyst may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5.
  • the catalyst support is amorphous silica-alumina with preferably between 5 and 96 wt% alumina, more preferably between 20 and 85 wt% alumina, calculated on the total weight of silica-alumina.
  • the silica content as SiO 2 preferably is between 15 and 80 wt%, calculated on the total weight of silica-alumina.
  • a catalyst suitable for step (b) has, for example, been described in EP0532117A and in WO02/070628 .
  • a catalyst suitable for step (c) has, for example, been described in WO2011064236 .
  • the catalyst used in step (b) and the catalyst used in step (c) are preferably reduced before being used.
  • the metallic catalyst may be obtained as an oxidic or a prereduced catalyst.
  • the above catalysts which are used in a sulphided form may be obtained in an oxidic, a pre-sulphided or a presulphurised form.
  • Preferably the start-up procedure of the catalyst manufacturer is followed.
  • Pre-reducing the catalyst for use in a metallic form may also be achieved in situ by reducing the catalyst by contacting with hydrogen.
  • the contacting is achieved by contacting the catalyst at an elevated temperature with hydrogen in e.g. nitrogen mixture stream. More preferably the hydrogen content is increased over time and/or the temperature is gradually increased.
  • a skilled person will be able to achieve a successful reduction of the catalyst by applying generally applied skills.
  • step (b) and (c) the feed is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure.
  • step (b) the hydrogen partial pressure is in the range of between 45 and 75 bara, preferably between 50 and 70 bara, and the temperature is in the range of between 280 and 425 °C, preferably between 325 and 400 °C.
  • step (c) the hydrogen partial pressure is in the range of between 20 and 55 bara, preferably between 30 and 50 bara, whereby the hydrogen partial pressure in step (c) is at least 5 bara, preferably at least 10 bara lower than the pressure in step (b).
  • step (c) the temperature is in the range of between 175 and 375 °C, preferably between 250 and 375 °C, whereby the temperature in step (c) is at least 10 °C lower, preferably at least 20 °C lower than the temperature in step (b).
  • the hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/1/hr (mass feed/volume catalyst bed/time), preferably higher than 0.5 kg/1/hr and more preferably lower than 2 kg/1/hr.
  • hydrogen may be supplied at a ratio of hydrogen to hydrocarbon feed from 100 to 5000 Nl/kg and preferably from 250 to 2500 Nl/kg.
  • Steps (b) and (c) are preferably performed in reactors provided with beds of the heterogeneous catalysts as described above.
  • the reactors may have the same size or a different size.
  • steps (b) and (c) is defined as the weight percentage of the feed boiling above 370 °C which reacts per pass to a fraction boiling below 370 °C.
  • the feed as used in this definition is the total hydrocarbon feed fed to steps (b) and (c), thus including any optional recycle feeds.
  • step (b) the hydroconversion/hydroisomerisation is performed at a conversion in the range of between 50 and 90 wt%, preferably between 50 and 80 wt%, more preferably between 50 and 70 wt%.
  • step (c) the hydroconversion/hydroisomerisation is performed at a conversion in the range of between 30 and 60 wt%, preferably between 30 and 45 wt%, whereby the conversion in step (c) is at least 5 wt% lower as compared to the conversion in step (b).
  • the conversion in step (c) is at least 5 wt% lower as compared to the conversion in step (b), preferably at least 10 wt% lower, more preferably at least 15 wt% lower.
  • the conversion in step (c) preferably is at most 35 wt% lower as compared to the conversion in step (b), more preferably at most 30 wt% lower, even more preferably at most 25 wt% lower.
  • the feed Prior to the hydroconversion/hydroisomerisation steps (b) and (c) the feed may optionally be subjected to a mild hydrotreatment step, in order to remove any oxygenates and saturate any olefinic compounds present in the reaction product of the Fischer-Tropsch reaction.
  • a mild hydrotreatment step in order to remove any oxygenates and saturate any olefinic compounds present in the reaction product of the Fischer-Tropsch reaction.
  • the hydrogenation step reduces the level of oxygenates to below 150 ppm as measured by infrared absorption spectrometry and reduces the level of unsaturated compounds to below the detection limit of the infrared absorption spectrometry.
  • Such a hydrotreatment is for example described in EP668342B .
  • the mildness of the hydrotreating step is preferably expressed in that the degree of conversion in this step is less than 20 wt% and more preferably less than 10 wt%, even more preferably less than 5 wt%.
  • the conversion is here defined as the weight percentage of the feed boiling above 370 °C, which reacts to a fraction boiling below 370 °C.
  • lower boiling compounds having four or less carbon atoms and other compounds boiling in that range, will preferably be removed from the effluent before it is used in step (a).
  • suitable catalysts are noble metal catalyst as for example platinum based hydrogenation catalysts or non-noble catalysts such as high content nickel catalysts.
  • step (d) a combination of at least a part of the reaction product obtained in step (b) and at least a part of the reaction product obtained in step (c) is subjected to distillation.
  • a fraction boiling in the gas oil range a fraction boiling in the distillate base oil range, and a fraction heavier than the fraction boiling in the distillate base oil range are isolated.
  • a fraction boiling in the gas oil range is defined as a fraction boiling in the range between 180 and 400 °C, preferably in the range between 190 and 380 °C.
  • a fraction boiling in the distillate base oil range is defined as a fraction having a T10wt% boiling point of between 200 and 520 °C, preferably between 300 and 500 °C, and having a T90wt% boiling point between 400 and 650°C, preferably between 450 and 600°C.
  • a fraction heavier than a fraction boiling in the distillate base oil range is defined as a fraction having a T5wt% boiling point of between 400 and 650 °C, preferably between 450 and 600 °C.
  • This fraction preferably comprises at least 50 wt% of material boiling above 540 °C.
  • This fraction preferably has a pour point of below 150 °C, more preferably below 130 °C, even more preferably below 110 °C.
  • boiling points in this context are the xxth percentiles of the true boiling point distribution as measured by a gas chromatographic simulation as in IP 480-02.
  • step (e) at least a part of the fraction heavier than the fraction boiling in the distillate base oil range is recycled to step (c).
  • fraction heavier than the fraction boiling in the distillate base oil range may be subjected to a pour point reducing step.
  • the fraction heavier than the fraction boiling in the distillate base oil range may also be referred to as extra heavy waxy raffinate.
  • extra heavy waxy raffinate is subjected to a pour point reducing step, for example to catalytic dewaxing, extra heavy base oil can be obtained.
  • step (f) a pour point reducing step is performed on at least a part of the fraction boiling in the distillate base oil range.
  • base oils can be obtained.
  • the pour point reducing step of step (f) may, for example, be a solvent dewaxing treatment or a catalytic pour point reducing treatment step.
  • pour point reducing treatment is understood every process wherein the pour point, as measured by ASTM D 97, of the base oil is reduced by more than 10 °C, preferably more than 20 °C, more preferably more than 25 °C.
  • the pour point reducing step of step (f) is a catalytic pour point reducing treatment step such as catalytic dewaxing.
  • the catalytic pour point reducing process can be performed by any process wherein, in the presence of a catalyst and hydrogen the pour point of the fraction after processing is improved, as specified above.
  • Suitable dewaxing catalysts are heterogeneous catalysts comprising a molecular sieve optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals.
  • Preferred molecular sieves are intermediate pore size zeolites.
  • the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm.
  • Suitable intermediate pore size zeolites and other aluminosilicate materials are zeolite beta mordenite, ZSM-5, ZSM-12, ZSM-22, ZSM-23, MCM-68, SSZ-32, ZSM-35 and ZSM-48.
  • Another preferred group of molecular sieves are the silica-aluminophosphate (SAPO) materials of which SAPO-11 is most preferred as for example described in US-A-4859311 .
  • SAPO silica-aluminophosphate
  • ZSM-5 may optionally be used in its HZSM-5 form in the absence of any Group VIII metal.
  • the other molecular sieves are preferably used in combination with an added Group VIII metal, or mixtures of said metals.
  • Suitable Group VIII metals are nickel, cobalt, platinum and palladium.
  • Pt/Zeolite beta PtPd/Zeolite beta
  • Ni/ZSM-5 Pt/ZSM-23
  • Pd/ZSM-23 Pt/ZSM-48
  • Pt/ZSM-12 Pt/SAPO-11.
  • suitable molecular sieves and dewaxing conditions are for example described in WO-A-9718278 , US-A-5053373 , US-A-5252527 and US-A-4574043 .
  • the crystallite size of the aluminosilicate zeolite may be as high as 100 micron. Preferably small crystallites are used in order to achieve an optimum catalytic activity. Preferably crystallites smaller than 10 micron and more preferably smaller than 1 micron are used. The practical lower limit is suitably 0.1 micron as measured by XRD line broadening. The critical size to measure is the length of the crystallite in the direction of the pores.
  • the dewaxing catalyst suitably also comprises a binder.
  • the binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, and/or metal oxides. Natural occurring clays are for example of the montmorillonite and kaolin families.
  • the binder is preferably a porous binder material, for example a refractory oxide of which examples are: silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions for example silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. More preferably a low acidity refractory oxide binder material which is essentially free of alumina is used. Examples of these binder materials are silica, zirconia, titanium dioxide, germanium dioxide, and mixtures of two or more of these of which examples are listed above. The most preferred binder is silica.
  • a refractory oxide of which examples are: silica, alumina, silica-alumina, silica
  • a preferred class of dewaxing catalysts comprise intermediate pore size zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above.
  • the zeolite has been subjected to a dealumination treatment such as steaming. More preferably the surface of the aluminosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment.
  • a preferred surface dealumination treatment is by contacting an extrudate of the binder and the zeolite with an aqueous solution of a fluorosilicate salt as described in for example US-A-5157191 or WO-A-2000029511 .
  • suitable dewaxing catalysts as described above are silica bound and dealuminated Pt/ZSM-5, silica bound and dealuminated Pt/ZSM-23, silica bound and dealuminated Pt/ZSM-12, silica bound and dealuminated Pt/ZSM-22 as for example described in WO-A-200029511 and EP-B-832171 .
  • Catalytic dewaxing conditions typically involve operating temperatures in the range of from 200 to 500 °C, suitably from 250 to 400 °C, hydrogen pressures in the range of from 10 to 200 bar, preferably from 15 to 100 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/1/hr), suitably from 0.2 to 5 kg/1/hr, more suitably from 0.5 to 3 kg/1/hr and hydrogen to oil ratios in the range of from 100 to 2,000 normal litres of hydrogen per litre of oil.
  • WHSV weight hourly space velocities
  • One or more base oils grades may be obtained by distillation of the dewaxed product. Preferably such a distillation is performed in one distillation step performed under low pressure.
  • the base oil products may be blended with other types of base oils, for example with base oils obtained from a mineral petroleum crude source or base oils as prepared by means of oligomerisation of lower olefins, for example C 3 -C 12 olefins and/or from C 4 -C 12 di-olefins.
  • base oils obtained from a mineral petroleum crude source or base oils as prepared by means of oligomerisation of lower olefins, for example C 3 -C 12 olefins and/or from C 4 -C 12 di-olefins.
  • these other base oils are co-fed to the pour point reducing step with the fractions obtained in step (c). In this manner a base oil having just the targeted pour point, viscosity and Noack volatility is advantageously obtained.
  • the base oil products preferably comprise of at least a medium grade base oil having a kinematic viscosity at 100 °C of between 3.0 and 5.6 cSt and a heavy base oil grade having a kinematic viscosity at 100 °C of greater than 6 cSt.
  • the upper viscosity limit will depend on the fractions of heavy Fischer-Tropsch compounds that are still present in the feed to the catalytic dewaxing unit and may range to 30 cSt at 100 °C.
  • the Noack volatility of the medium grade base oil is preferably between 9 and 40% more preferably between 9 and 25%. Typical distillation operations will be suited to obtain base oils having the current volatility specifications of base oils in general.
  • the viscosity index may range from 110 for the lower viscosity grades to up to 170 for the more viscous grades.
  • the viscosity index (VI) will also depend on the severity of the dewaxing step wherein lower VI values are found for base oils having a lower pour point.
  • Figure 1 shows a process scheme in which the process according to the present invention may be suitably be carried out.
  • a Fischer-Tropsch product is provided, for example by a Fischer-Tropsch reactor (1).
  • a part of the Fischer-Tropsch product is subjected to hydroconversion/hydroiso merisation in reactor (2) at a conversion in the range of between 50 and 90 wt%, a hydrogen partial pressure in the range of between 45 and 75 bar a, and a temperature in the range of between 280 and 425 °C, using a Pt comprising catalyst with a non-zeolitic ASA support.
  • Another part of the Fischer-Tropsch product is subjected to hydroconversion/hydroisomerisation in reactor (3) at a conversion in the range of between 30 and 60 wt%, a hydrogen partial pressure in the range of between 20 and 55 bar a, and a temperature in the range of between 175 and 375 °C, using a Pt comprising catalyst with an ASA support comprising zeolite beta.
  • the products of reactors 2 and 3 are combined and distilled in distillation column (4).
  • the products obtained by the distillation in distillation column (4) are naphtha, kerosene, gas oil, waxy raffinate and extra heavy waxy raffinate. A part of the extra heavy waxy raffinate is recycled to reactor (3).
  • Waxy raffinate which is a fraction boiling in the distillate base oil range, is subjected to catalytic dewaxing in reactor (6) and base oil is obtained.
  • Extra heavy waxy raffinate which is a fraction heavier than a fraction boiling in the distillate base oil range, is subjected to catalytic dewaxing in reactor (7) and extra heavy base oil is obtained.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP12197722.7A 2012-12-18 2012-12-18 Procédé pour préparer une huile de base et du gazole Withdrawn EP2746367A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016138165A1 (fr) * 2015-02-25 2016-09-01 Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) Systèmes, procédés et appareils pour réacteurs de fischer-tropsch montés en cascade

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4574043A (en) 1984-11-19 1986-03-04 Mobil Oil Corporation Catalytic process for manufacture of low pour lubricating oils
US4859311A (en) 1985-06-28 1989-08-22 Chevron Research Company Catalytic dewaxing process using a silicoaluminophosphate molecular sieve
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US5053373A (en) 1988-03-23 1991-10-01 Chevron Research Company Zeolite SSZ-32
US5059299A (en) 1987-12-18 1991-10-22 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils
US5157191A (en) 1986-01-03 1992-10-20 Mobil Oil Corp. Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index
EP0532117A1 (fr) 1991-09-12 1993-03-17 Shell Internationale Researchmaatschappij B.V. Catalyseur d'hydroconvertion
US5252527A (en) 1988-03-23 1993-10-12 Chevron Research And Technology Company Zeolite SSZ-32
EP0668342A1 (fr) 1994-02-08 1995-08-23 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'une huile lubrifiante de base
WO1997018278A1 (fr) 1995-11-14 1997-05-22 Mobil Oil Corporation Procede integre d'amelioration de lubrifiant
EP0776959A2 (fr) 1995-11-28 1997-06-04 Shell Internationale Researchmaatschappij B.V. Procédé pour la production d'huiles lubrifiantes
WO1999020720A1 (fr) 1997-10-20 1999-04-29 Mobil Oil Corporation Compositions d'huiles de base de lubrifiant isoparaffiniques
WO1999034917A1 (fr) 1997-12-30 1999-07-15 Shell Internationale Research Maatschappij B.V. Catalyseur fischer-tropsh a base de cobalt
EP0832171B1 (fr) 1995-06-13 2000-01-05 Shell Internationale Researchmaatschappij B.V. Procede catalytique de deparaffinage
WO2000029511A1 (fr) 1998-11-16 2000-05-25 Shell Internationale Research Maatschappij B.V. Procede de deparaffinage catalytique
WO2002070629A1 (fr) 2001-03-05 2002-09-12 Shell Internationale Reserach Maatschappij B.V. Procede de preparation d'une huile de base lubrifiante et de gazole
WO2002070628A2 (fr) 2001-03-05 2002-09-12 Shell Internationale Research Maatschappij B.V. Elaboration de distillats moyens
WO2006067174A1 (fr) 2004-12-23 2006-06-29 Shell Internationale Research Maatschappij B.V. Procede de preparation de deux produits iso-paraffiniques a partir d'une alimentation derivee de fischer-tropsch
US20080314800A1 (en) 2004-11-18 2008-12-25 Shell International Research Maatschappij B.V. Process to Prepare a Base Oil
US20100300933A1 (en) * 2007-09-28 2010-12-02 Yuichi Tanaka Method of manufacturing diesel fuel
WO2011064236A1 (fr) 2009-11-27 2011-06-03 Shell Internationale Research Maatschappij B.V. Procédé de conversion d'une charge paraffinique

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4574043A (en) 1984-11-19 1986-03-04 Mobil Oil Corporation Catalytic process for manufacture of low pour lubricating oils
US4859311A (en) 1985-06-28 1989-08-22 Chevron Research Company Catalytic dewaxing process using a silicoaluminophosphate molecular sieve
US5157191A (en) 1986-01-03 1992-10-20 Mobil Oil Corp. Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US5059299A (en) 1987-12-18 1991-10-22 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils
US5053373A (en) 1988-03-23 1991-10-01 Chevron Research Company Zeolite SSZ-32
US5252527A (en) 1988-03-23 1993-10-12 Chevron Research And Technology Company Zeolite SSZ-32
EP0532117A1 (fr) 1991-09-12 1993-03-17 Shell Internationale Researchmaatschappij B.V. Catalyseur d'hydroconvertion
EP0668342B1 (fr) 1994-02-08 1999-08-04 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'une huile lubrifiante de base
EP0668342A1 (fr) 1994-02-08 1995-08-23 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'une huile lubrifiante de base
EP0832171B1 (fr) 1995-06-13 2000-01-05 Shell Internationale Researchmaatschappij B.V. Procede catalytique de deparaffinage
WO1997018278A1 (fr) 1995-11-14 1997-05-22 Mobil Oil Corporation Procede integre d'amelioration de lubrifiant
EP0776959A2 (fr) 1995-11-28 1997-06-04 Shell Internationale Researchmaatschappij B.V. Procédé pour la production d'huiles lubrifiantes
WO1999020720A1 (fr) 1997-10-20 1999-04-29 Mobil Oil Corporation Compositions d'huiles de base de lubrifiant isoparaffiniques
WO1999034917A1 (fr) 1997-12-30 1999-07-15 Shell Internationale Research Maatschappij B.V. Catalyseur fischer-tropsh a base de cobalt
WO2000029511A1 (fr) 1998-11-16 2000-05-25 Shell Internationale Research Maatschappij B.V. Procede de deparaffinage catalytique
WO2002070629A1 (fr) 2001-03-05 2002-09-12 Shell Internationale Reserach Maatschappij B.V. Procede de preparation d'une huile de base lubrifiante et de gazole
WO2002070628A2 (fr) 2001-03-05 2002-09-12 Shell Internationale Research Maatschappij B.V. Elaboration de distillats moyens
US20080314800A1 (en) 2004-11-18 2008-12-25 Shell International Research Maatschappij B.V. Process to Prepare a Base Oil
WO2006067174A1 (fr) 2004-12-23 2006-06-29 Shell Internationale Research Maatschappij B.V. Procede de preparation de deux produits iso-paraffiniques a partir d'une alimentation derivee de fischer-tropsch
US20080194901A1 (en) * 2004-12-23 2008-08-14 Michiel Cramwinckel Process To Prepare Two Iso Paraffinic Products From A Fischer-Tropsch Derived Feed
US20100300933A1 (en) * 2007-09-28 2010-12-02 Yuichi Tanaka Method of manufacturing diesel fuel
WO2011064236A1 (fr) 2009-11-27 2011-06-03 Shell Internationale Research Maatschappij B.V. Procédé de conversion d'une charge paraffinique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RYLAND; LLOYD B.; TAMELE, M.W.; WILSON, J.N.: "Cracking Catalysts, Catalysis: volume VII", 1960, PUBLISHING CORPORATION, pages: 5 - 9

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016138165A1 (fr) * 2015-02-25 2016-09-01 Sgc Energia S.A. (Formerly-Gi-Gasification International S.A.) Systèmes, procédés et appareils pour réacteurs de fischer-tropsch montés en cascade

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