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WO2005085393A1 - Procede de preparation en continu de deux ou de plusieurs types d'huile de base et distillats moyens - Google Patents

Procede de preparation en continu de deux ou de plusieurs types d'huile de base et distillats moyens Download PDF

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Publication number
WO2005085393A1
WO2005085393A1 PCT/EP2005/050857 EP2005050857W WO2005085393A1 WO 2005085393 A1 WO2005085393 A1 WO 2005085393A1 EP 2005050857 W EP2005050857 W EP 2005050857W WO 2005085393 A1 WO2005085393 A1 WO 2005085393A1
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WO
WIPO (PCT)
Prior art keywords
base oil
oil
fraction
precursor fraction
dewaxed
Prior art date
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PCT/EP2005/050857
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English (en)
Inventor
Jacob Willem Duininck
Kevin John Anthony Polder
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Shell Internationale Research Maatschappij B.V.
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Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP05708063A priority Critical patent/EP1733008A1/fr
Priority to JP2007501274A priority patent/JP2007526380A/ja
Priority to US10/591,115 priority patent/US20070175794A1/en
Publication of WO2005085393A1 publication Critical patent/WO2005085393A1/fr

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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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

Definitions

  • the invention relates to a process to continuously prepare two or more base oil grades and middle distillates.
  • Background of the invention WO-A-0250213 describes a process wherein different base oil grades are made in a so-called blocked out mode. In this process a bottoms fraction of a fuels hydrocracking process, which thus also yields middle distillates as products, is separated into various base oil precursor fractions. These fractions are subsequently catalytically dewaxed one after the other using a platinum-ZSM-5 based catalyst.
  • WO-A-9718278 discloses a process wherein up to 4 base oil grades, e.g. a 60N, 100N and 150N, are prepared starting from the bottoms fraction of a fuels hydrocracker.
  • the bottoms fraction is fractionated in a vacuum distillation into 5 fractions of which the heavier 4 fractions are further processed to different base oil grades by first performing a catalytic dewaxing followed by a hydrofinishing step.
  • O-A-02/50213 discloses a so-called blocked-out process to prepare different base oil grades from the bottoms fraction of a fuels hydrocracking process.
  • a disadvantage of the above processes is that the process is not continuous. In other words the base oil grades are not made at the same time but sequential. This requires tankage for the intermediate products as obtained when the hydrocracker bottoms are fractionated and are awaiting their turn to be catalytically dewaxed.
  • a further disadvantage are the mode switches which result in heating up of equipment and cooling of equipment causing erosion of equipment.
  • EP-A-649896 discloses a process to prepare a residue comprising a base oil by means of a process involving a hydrotreating step and a hydrocracking step on a heavy petroleum feedstock. The hydroprocessing steps yield a product from which middle distillates and a bottoms fraction (residue) are obtained. This bottoms fraction is subsequently solvent dewaxed to a single base oil grade.
  • EP-A-O 272 729 discloses a process for the manufacture of lubricating base oils, wherein a flashed distillate produced via a residue conversion process is fed to a hydrocracking unit. The effluent from the hydrocracking unit is fed to a catalytic dewaxing unit and thereafter optionally the whole dewaxed stream is subjected to a hydrotreatment .
  • O-A-9723584 discloses a process wherein the bottoms fraction of a fuels hydrocracker is subjected to a catalytic dewaxing step. The dewaxed oil is partly recycled to the hydrocracking step and partly obtained as the lubricating base oil.
  • a disadvantage of the above process as described in WO-A-9723584 is that if more than one base oil grade is isolated from the dewaxed oil a large pour point distribution occurs. In other words the resulting lower viscous base oil grades will have a too low pour point. This pour point give away, or difference with the desired value, is indicative for yield loss of said lower viscous base oil grade.
  • One object of the present invention is to provide a process, which is capable of preparing two or more base oil grades simultaneously and wherein their respective pour points are more close to the desired values. It is another object of the present invention to provide an alternative process . Summary of the invention The following process achieves one ore more of the above or other objects.
  • Process to prepare simultaneously two or more base oil grades and middle distillates from a de-asphalted oil or a vacuum distillate feed or their mixtures by performing the following steps: (a) hydrocracking the feed, thereby obtaining an effluent; (b) distillation of the effluent as obtained in step (a) into one or more middle distillates and a residue boiling substantially above 340 °C; (c) separating, by means of a further distillation step said residue into a light base oil precursor fraction and a heavy base oil precursor fraction; (d) reducing the pour point of each separate base oil precursor fraction in two simultaneously and parallel operated catalytic dewaxing reactors obtaining a first and second dewaxed oil; (e) hydrotreating the first dewaxed oil as obtained when dewaxing the heavy base oil precursor fraction in step (d) ; (f ) isolating from the second dewaxed oil from the light base oil precursor fraction from step (d) and the hydrotreated oil from step (e) two or more base oil grades
  • the feed to step (a) may be any typical mineral crude derived feed to a hydrocracker.
  • feedstocks may be the vacuum gas oil or heavier distillate fractions as obtained when distilling at near vacuum conditions the atmospheric residue of a crude mineral oil feedstock.
  • the deasphalted oil as obtained when deasphalting the residue as obtained in said vacuum distillation may also be used as feed.
  • Light and heavy cycle oils as obtained in a fluid catalytic cracking process (FCC), thermally flashed distillate and aromatic rich extracts as for example obtained in solvent extraction process steps in traditional base oil processing may also be used as feed.
  • FCC fluid catalytic cracking process
  • thermally flashed distillate and aromatic rich extracts as for example obtained in solvent extraction process steps in traditional base oil processing may also be used as feed.
  • Mixtures of the above described feeds and optionally other hydrocarbon sources are also suitable as feedstocks.
  • An optional alternative hydrocarbon source which may be present in addition to the above feedstocks, preferably in amounts of between 2 and 30 wt% of the feed to step (a) , are the paraffin wax as obtained in a Fischer-Tropsch process.
  • the feed to step (a) consists of a mineral crude derived feed.
  • Step (a) may be performed at a conversion level of between 15 and 90 wt%. The conversion is expressed in the weight percentage of the fraction in the feed which boils above 370 °C which are converted to products boiling below 370 °C.
  • the main products boiling below 370 °C are naphtha, kerosene and gas oil.
  • step (a) Examples of possible hydrocracker processes suitable for performing step (a) are described in EP-A-699225, EP-A-649896, WO-A-9718278, EP-A-705321, EP-A-994173 and US-A-4851109.
  • the operating conditions of a single step hydrocracking process include preferably a temperature in the range of from 350 to 450 °C, a hydrogen pressures in the range of from 9 to 200 MPa, more preferably above 11 MPa, a weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per liter of catalyst per hour (kg/l/hr), preferably from 0.2 to 5 kg/l/hr, more preferably from 0.5 to 3 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 liters of hydrogen per liter of oil.
  • WHSV weight hourly space velocities
  • the hydrocracker is operated in two steps, consisting of a preliminary hydrotreating step followed by a hydrocracking step.
  • the fuels-hydrocracker is more preferably operated by first (i) hydrotreating a hydrocarbon feed at a feed conversion, wherein the conversion, as defined above, of less than 30 wt% and preferably between 15 and 25 wt%, and (ii) hydrocracking the product of step (i) in the presence of a hydrocracking catalyst at such a conversion level that the overall conversion of step (i) and (ii) is between 15 and 90 wt% and preferably between 40 and 85 wt%.
  • the operating conditions of a hydrotreating step are preferably a temperature in the range of from 350 to 450 °C, a hydrogen pressures in the range of from 9 to 200 MPa, more preferably above 11 MPa, a weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per liter of catalyst per hour (kg/l/hr), preferably from 0.2 to 5 kg/l/hr, more preferably from 0.5 to 3 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 liters of hydrogen per liter of oil.
  • the operating conditions of a hydrocracking step performed in combination with a hydotreatings step are preferably a temperature in the range of from 300 to
  • a hydrogen pressures in the range of from 9 to 200 MPa, more preferably above 11 MPa, a weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per liter of catalyst per hour (kg/l/hr), preferably from 0.2 to 5 kg/l/hr, more preferably from
  • the residues as prepared by the processes as described above have a very low content of sulphur, typically below 250 or even below 150 ppmw, and a very low content of nitrogen, typically below 30 ppmw.
  • the residue is preferably a full range residue. It has been found that by performing the combined hydrotreating and hydrocracking step as described above a residue is obtained which yields a high quantity of the more viscous grade base oil, also referred to as medium machine oil grade, and of acceptable quality with respect to viscosity index. In addition a sufficient quantity of naphtha, kerosine and gas oils are obtained by this process.
  • a fuels hydrocracker process wherein simultaneously products ranging from naphtha to gas oil and a residue is obtained, which residue has the potential to yield a medium machine oil base oil grade.
  • the viscosity index of the resulting base oil grades is suitably between 95 and 120, which is acceptable to yield base oils having a viscosity index according to the API Group II specifications. It has been found that in the hydrotreating step (i) the viscosity index of the residue and the resulting base oil grades increases with the conversion in said hydrotreating step. By operating the hydrotreating step at high conversion levels of more than 30 wt% viscosity index values for the resulting base oils of well above 120 can be achieved.
  • step (i) A disadvantage of such a high conversion in step (i) is however that the yield of medium machine oil fraction will be undesirably low.
  • an API Group II medium machine oil grade base oil can be obtained in a desired quantity.
  • the minimum conversion in step (i) will be determined by the desired viscosity index, of between 95 and 120, of the resulting base oil grades and the maximum conversion in step (i) is determined by the minimum acceptable yield of medium machine oil grade.
  • the preliminary hydrotreating step is typically performed using catalyst and conditions as for example described in the above-mentioned publications related to hydrocracking.
  • Suitable hydrotreating catalysts generally comprise a metal hydrogenation component, suitably Group IVB or VIII metal, for example cobalt-molybdenum, nickel-molybdenum, on a porous support, for example silica-alumina or alumina.
  • the hydrotreating catalysts suitably contains no zeolite material or a very low content of less than 1 wt%.
  • hydrotreating catalysts examples include the commercial ICR 106, ICR 120 of Chevron Research and Technology Co.; 244, 411, DN-120, DN-180, DN-190 and DN-200 of Criterion Catalyst Co.; TK-555 and TK-565 of Haldor Topsoe A/S; HC-k, HC-P, HC-R and HC-T of UOP; KF-742, KF-752, KF-846, KF-848 STARS and KF-849 of AKZO Nobel/Nippon Ketjen; and HR-438/448 of Procatalyse SA.
  • the hydrocracking step is preferably a catalyst comprising an acidic large pore size zeolite within a porous support material with an added metal hydrogenation/dehydrogenation function.
  • the metal having the hydrogenation/dehydrogenation function is preferably a Group VIII/Group VIB metal combination, for example nickel-molybdenum and nickel-tungsten.
  • the support is preferably a porous support, for example silica-alumina and alumina. It has been found that a minimum amount of zeolite is advantageously present in the catalyst in order to obtain a high yield of medium machine oil fraction in the full range residue when performing the hydrocracker at the preferred conversion levels as explained above. Preferably more than 1 wt% of zeolite is present in the catalyst.
  • zeolites are zeolite X, Y, ZSM-3, ZSM-18, ZSM-20 and zeolite beta of which zeolite Y is most preferred.
  • suitable hydrocracking catalysts are the commercial ICR 220 and ICR 142 of Chevron Research and Technology Co; Z-763, Z-863, Z-753, Z-703, Z-803, Z-733, Z-723, Z-673, Z-603 and Z-623 of Zeolist International; TK-931 of Haldor Topsoe A/S; DHC-32, DHC-41, HC-24, HC-26, HC-34 and HC-43 of UOP; KC2600/1, KC2602, KC2610, KC2702 and KC2710 of AKZO Nobel/Nippon Ketjen; and HYC 642 and HYC 652 of Procatalyse SA.
  • the effluent of the hydrocracker is separated into one or more of the above referred to fuels fractions and a residue.
  • the residue wherein the residue boils predominately above 340 °C, is used as feed to step (c) .
  • boiling predominately above 340 °C is especially meant that more than 80 wt%, preferably more than 90 wt%, boils above 340 °C.
  • a substantial fraction of the residue may boil in the gas oil range a considerable amount of gas oil is recovered after dewaxing having excellent cold flow properties.
  • Preferably between 10 and 40 wt% of the dewaxed oil as obtained in this process boils in the heavy gas oil range being between from 350 to 400 °C.
  • step (c) lower boiling gas oil fractions are obtained in step (c) .
  • the final boiling point of the residue will be partly determined by the final boiling point of the feed to step (a) and may be far greater than 700 °C up to values of which cannot be determined by means of the standard test methods.
  • part of the residue as obtained in step (b) may be recycled to step (a) as for example described in EP-A-0994173, which publication is incorporated by reference.
  • the residue may be recycled to only the hydrocracking step of step (a) as for example described in EP-B-0699225, which publication is incorporated by reference.
  • Preferably less than 15 wt% of the residue is recycled to step (a) and more preferably no residue is recycled to step (a) .
  • API Group II base oils may be prepared having a good quality without having to perform such a recycle.
  • the feed is separated by means of distillation into a light base oil precursor fraction and a heavy base oil precursor fraction and optionally a vacuum gas oil fraction.
  • a vacuum gas oil is not separated from the light base oil precursor fraction but remains combined with said fraction in order to be dewaxed as well in step (d) .
  • the distillation is suitably performed at reduced pressures, more preferably the vacuum distillation is performed at a pressure of between 0.01 and 0.3 bara .
  • the 10 wt% recovery point of the heavy base oil precursor fraction as obtained in step (c) is preferably between 420 and 550 °C and more preferably between 440 and 520 °C.
  • the feed to step (d) will comprise of the base oil precursor fractions as obtained in step (c) .
  • some partly isomerised paraffin wax boiling in the heavy or light base oil precursor fractions boiling range may be present in a mixture with said light base oil precursor fraction.
  • This paraffin product is also referred to as waxy raffinate, as obtained in a Fischer- Tropsch or Gas-to-Liquids Process.
  • Such a waxy Raffinate may be prepared according the process as described in WO-02070630, which publication is incorporated herein by reference.
  • a noble metal guard bed may be positioned just upstream the dewaxing catalyst bed in the dewaxing reactor in step (d) in order to decrease the level of sulphur and especially nitrogen compounds.
  • a guard bed may be especially advantageous in the dewaxing reactor in which the heavy base oil precursor fraction is processed.
  • An example of such a process is described in WO-A-9802503, which reference is hereby incorporated by reference.
  • the catalytic dewaxing step in the parallel operated reactors in step (d) can be performed by any process wherein in the presence of a catalyst and hydrogen the pour point of the base oil fraction is reduced.
  • the pour point is reduced by at least 10 °C and more suitably by at least 20 °C.
  • Suitable dewaxing catalysts are heterogeneous catalysts comprising a molecular sieve and optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals.
  • Molecular sieves, and more suitably intermediate pore size zeolites have shown a good catalytic ability to reduce the pour point of a base oil fraction under catalytic dewaxing conditions.
  • the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 n .
  • Suitable intermediate pore size zeolites are ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48.
  • SAPO silica-alumirtaphosphate
  • SAPO-11 is most preferred as for example described in US-A-4859311.
  • 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. Suitable Group VIII metals are nickel, cobalt, platinum and palladium. Examples of possible combinations are
  • Ni/ZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11 Further details and examples of 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 process according the present invention makes it possible to continuously prepare base oils using dewaxing catalysts, which show a relatively large pour point distribution in case the full range residue is processed as for example described in WO-A-9723584. By making use of the present invention such a large pour point distribution can be avoided while using such relatively poor performing dewaxing catalysts .
  • the dewaxing catalyst suitably also comprises a binder.
  • the binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, silica 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: 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.
  • binder materials are silica, zirconia, titanium dioxide, germanium dioxide, boria and mixtures of two or more of these of which examples are listed above.
  • the most preferred binder is silica.
  • a preferred class of dewaxing catalysts comprise intermediate zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above, wherein the surface of the alu inosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment.
  • a preferred 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.
  • suitable dewaxing catalysts as described above a silica bound and dealuminated Pt/ZSM-5 and silica bound and dealuminated Pt/ZSM-23, silica bound and dealuminated Pt/ZSM-12 and 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, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/l/hr), suitably from 0.2 to 5 kg/l/hr, more suitably from 0.5 to 4 kg/l/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil.
  • WHSV weight hourly space velocities
  • the weight hourly space velocities (WHSV) in the catalytic dewaxing step in which the light base oil precursor fraction is processed is preferably higher than the WHSV in the dewaxing step of the heavy base oil precursor fraction. More preferably the WHSV in the dewaxing step of the light base oil precursor fraction is between 1 and 5 kg/l/hr. If the dewaxing step and the hydrofinishing step are performed in cascade the pressure level in both steps in suitably of the same order. Because higher pressures are preferred in the hydrofinishing step in order to obtain a base oil having the desired properties the dewaxing step is suitably also performed at these hig-her pressures, even though a more selective dewaxing could have been achieved at lower pressures.
  • a lower catalytic dewaxing pressure can advantageously be applied. Suitable pressures are from 15 to 100 bar and more suitably from 1.5 to 6.5 MPa.
  • the hydrotreating step (e) also referred to as a hydrofinishing step is to improve the quality of the dewaxed fraction. In this step lube range olefins are saturated, heteroatoms and colour bodies are removed and if the pressure is high enough residual aromatics are saturated.
  • the conditions are so chosen to obtain a base oil grade comprising more than 95 wt% saturates and more preferably such that a base oil is obtained comprising more than 98 wt% saturates.
  • the hydrofinishing step is suitably carried out in cascade with the dewaxing step of the heavy base oil precursor fraction.
  • the hydrofinishing step is suitable carried out at a temperature between 230 and 380 °C, a total pressure of between 1 to 25 MPa and preferably above 10 MPa and more preferably between 12 and 25 MPa.
  • the WHSV Weight hourly space velocity ranges from 0.3 to 10 kg of oil per litre of catalyst per hour (kg/l.h).
  • the hydrofinishing or hydrogenation catalyst is suitably a supported catalyst comprising a dispersed
  • Group VIII metal Possible Group VIII metals are cobalt, nickel, palladium and platinum. Cobalt and nickel containing catalysts may also comprise a Group VIB metal, suitably molybdenum and tungsten.
  • Suitable carrier or support materials are low acidity amorphous refractory oxides. Examples of suitable amorphous refractory oxides include inorganic oxides, such as alumina- silica, titania, zirconia, boria, silica-alumina, fluorided alumina, fluorided silica- alumina and mixtures of two or more of these.
  • Suitable hydrogenation catalysts include those catalysts comprising as one or more of nickel (Ni) and cobalt (Co) in an amount of from 1 to 25 percent by weight (wt%), preferably 2 to 15 wt%, calculated as element relative to total weight of catalyst and as the Group VIB metal component one or more of in an amount of from 5 to 30 wt%, preferably 10 to 25 wt%, calculated as element relative to total weight of catalyst .
  • nickel-molybdenum containing catalyst are KF-847 and KF-8010 (AKZO Nobel) M-8-24 and M-8-25 (BASF) , and C-424, DN-190, HDS-3 and HDS-4 (Criterion) .
  • nickel-tungsten containing catalysts are NI-4342 and NI-4352 (Engelhard) , C-454 (Criterion) .
  • suitable cobalt-molybdenum containing catalysts are KF-330 (AKZO-Nobel) , HDS-22 (Criterion) and HPC-601 (Engelhard) .
  • platinum containing and more preferably platinum and palladium containing catalysts are used.
  • the total amount of these noble Group VIII metal component (s) present on the catalyst is suitably from 0.1 to 10 wt%, preferably 0.2 to 5 wt%, which weight percentage indicates the amount of metal (calculated as element) relative to total weight of catalyst.
  • Preferred supports for these palladium and/or platinum containing catalysts are amorphous silica- alumina, whereby more preferably the silica-alumina comprises from 2 to 75 wt% of alumina. Examples of suitable silica-alumina carriers are disclosed in
  • a preferred catalyst comprises an alloy of palladium and platinum preferably supported on an amorphous silica-alumina carrier of which the commercially available catalysts C-624 and C—654 of Criterion Catalyst Company (Houston, TX) are examples.
  • the two or more base oil grades and optionally a gas oil comprising fraction are isolated from the light base oil precursor fraction from step (d) and the hydrotreated oil from step (e) .
  • the base oils and the optional gas oil comprising fraction are preferably isolated from a mixture of these streams.
  • any compounds present in the heavy base oil precursor fraction which are converted in step (d) to a boiling range of a lighter base oil grade will then contribute to the base oil yield of said lighter base oil grade.
  • the gas oil product as obtained as described above has been subjected to a catalytic dewaxing step a fuel product is obtained having a very low content of aromatics and sulphur in combination with excellent low temperature properties.
  • a gas oil may be obtained in step (d) having a very low sulphur content of below 10 pp , a low aromatics content of below 0.1 mmol/100 grams, excellent a cold flow properties like a pour point of below -30 °C and a cold filter plugging point of below -30 °C.
  • the gas oil also has excellent lubricity properties. This makes such a gas oil especially an excellent refinery blending component to blend low sulphur gas oil.
  • the gas oil may also be used as a drilling mud fluid component, an electrical oil, a cutting oil, an aluminium rolling oil or as a fruit spray oil.
  • Step (f) may be performed by withdrawing products along a distillation column operating at near vacuum conditions as well known to the skilled person.
  • Preferably so-called side-strippers are used to isolate the base oil products . Intermediate fractions may also be withdrawn in order to meet the volatility requirements of the desired base oil grades. Suitably before the above low pressure distillation step a higher pressure distillation step, at about atmospheric conditions, may be performed in order to separate any naphtha, kerosene and gas oil fractions, separately or as a mixture, from the dewaxed oil. These middle distillate fractions may be used as such or recycled to step (b) such that a mixture of dewaxed and hydrocracked middle distillate fuels are obtained.
  • step (f) gaseous tops, a liquid tops comprising the above middle distillates, and various base oil grades, as for example a spindle oil, a light machine oil and a medium machine oil are obtained in the final distillation of step (f) .
  • spindle oil, light machine oil and medium machine oil will refer to base oil grades having an increasing kinematic viscosity at 100 °C and wherein the spindle oil additionally has a maximum volatility specification. The advantages of the present process are achieved for any group of base oils having such different viscosity requirement and volatility specification.
  • a spindle oil is a light base oil product having a kinematic viscosity at 100 °C of below 5.5 cSt and preferably above 3.5.
  • the spindle oil can have either a Noack volatility, as determined by the CEC L-40-T87 method, of preferably below 20% and more preferably below 18% or a flash point, as measured according to ASTM D93, of above 180 °C.
  • the light machine oil has a kinematic viscosity at 100 °C of below 9 cSt and preferably above 6.5 cSt and more preferably between 8 and 9 cSt.
  • the medium machine oil has a kinematic viscosity at 100 °C of below 14 cSt and preferably above 10 cSt and more preferably between 11 and 13 cSt.
  • the corresponding base oil grade can have a viscosity index of between 95 and 120.
  • Gas oil as obtained in the process according the invention will boil typically from 150 and 370 °C and will have a T90wt% of between 340-400 °C.
  • Figure 1 shows a hydrocarbon feed line (1) to hydrocracker (2) .
  • the hydrocrakate (3) is separated into a naphtha (5), kerosene (6), a gas oil (7) a bottoms fraction (8) in distillation column (4) .
  • the bottoms fraction or full range residue (4) is split into a light base oil precursor fraction (10) and a heavy base oil precursor fraction (11) in distillation column (9) .
  • the light base oil precursor fraction (10) is dewaxed in dewaxing reactor (12) yielding a dewaxed oil (16; "second dewaxed oil”) .
  • the heavy base oil precursor fraction (11) is dewaxed in dewaxing reactor (13) .
  • the dewaxed oil (15; “first dewaxed oil”) is hydrotreated in hydrofinishing reactor (14) yielding a dewaxed and hydrotreated oil (17) . Oils (16) and (17) are combined.
  • Hydrogen (19) is separated in separator (18) and recycled to the dewaxing units (12) and (13) after adding fresh hydrogen (20) .
  • the oil (21) is subsequently separated into a low boiling fraction (26), a spindle oil grade (23), a light machine oil grade (24) and a medium machine oil grade (25) is distillation column (22) .
  • the fraction (26) is recycled to the work-up section of the hydrocracker (2) in order to isolate the valuable fuels fractions.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de préparation simultanée de deux ou de plusieurs types d'huiles de base et de distillats moyens à partir d'une huile désasphaltée ou une charge de distillat sous vide ou leurs mélanges, qui consiste: (a) à hydrocraquer ladite charge, ce qui permet d'obtenir un effluent; (b) à distiller l'effluent obtenu en (a) en un ou plusieurs distillats moyens et un résidu bouillant sensiblement au-dessus de 340 °C; (c) à séparer lors d'une autre étape de distillation ledit résidu en une fraction de précurseur d'huile de base légère et une fraction de précurseur d'huile de base lourde; (d) à réduire le point d'écoulement de chaque fraction de précurseur d'huile de base séparée en deux réacteurs de déparaffinage catalytique fonctionnant simultanément et en parallèle pour obtenir une première et une seconde huiles déparaffinées; (e) à hydrotraiter la première huile déparaffinée obtenue lors du déparaffinage de la fraction de précurseur d'huile de base lourde de l'étape (d); (f) à isoler de la seconde huile déparaffinée à partir de la fraction de précurseur d'huile de base légère obtenue en (e), deux plusieurs types d'huile de base.
PCT/EP2005/050857 2004-03-02 2005-03-01 Procede de preparation en continu de deux ou de plusieurs types d'huile de base et distillats moyens WO2005085393A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP05708063A EP1733008A1 (fr) 2004-03-02 2005-03-01 Procede de preparation continue de deux ou plusieures huiles de base et de distillats moyens
JP2007501274A JP2007526380A (ja) 2004-03-02 2005-03-01 ２種以上の基油グレード及び中間蒸留物の連続的製造方法
US10/591,115 US20070175794A1 (en) 2004-03-02 2005-03-01 Process to continuously prepare two or more base oil grades and middle distillates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04290569 2004-03-02
EP04290569.5 2004-03-02

Publications (1)

Publication Number Publication Date
WO2005085393A1 true WO2005085393A1 (fr) 2005-09-15

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/050857 WO2005085393A1 (fr) 2004-03-02 2005-03-01 Procede de preparation en continu de deux ou de plusieurs types d'huile de base et distillats moyens

Country Status (6)

Country Link
US (1) US20070175794A1 (fr)
EP (1) EP1733008A1 (fr)
JP (1) JP2007526380A (fr)
KR (1) KR20060130675A (fr)
CN (1) CN1926220A (fr)
WO (1) WO2005085393A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009001314A1 (fr) 2007-06-25 2008-12-31 Bruno Weber Produit de substitution du fuel

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102209772A (zh) * 2008-10-01 2011-10-05 雪佛龙美国公司 具有改进性能的170中性基础油
KR101779605B1 (ko) * 2010-06-04 2017-09-19 에스케이이노베이션 주식회사 감압증류된 탈아스팔트유를 이용한 윤활기유 제조방법
US8992764B2 (en) 2010-06-29 2015-03-31 Exxonmobil Research And Engineering Company Integrated hydrocracking and dewaxing of hydrocarbons
US9487723B2 (en) 2010-06-29 2016-11-08 Exxonmobil Research And Engineering Company High viscosity high quality group II lube base stocks
US9914887B2 (en) 2013-09-12 2018-03-13 Chevron U.S.A. Inc. Two-stage hydrocracking process for making heavy lubricating base oil from a heavy coker gas oil blended feedstock
US10479949B2 (en) 2014-09-17 2019-11-19 Ergon, Inc. Process for producing naphthenic bright stocks
KR102269994B1 (ko) * 2014-09-17 2021-06-25 에르곤,인크 나프텐계 베이스 오일의 제조 방법
ES2740837T3 (es) * 2015-04-15 2020-02-06 Neste Corp Un procedimiento para producir componentes a base de aceite
US9796936B2 (en) * 2015-09-09 2017-10-24 Chevron U.S.A. Inc. Production of heavy API group II base oil
CA3045781A1 (fr) * 2016-12-29 2018-07-05 Exxonmobil Research And Engineering Company Huiles de base et compositions lubrifiantes les contenant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876522A (en) * 1972-06-15 1975-04-08 Ian D Campbell Process for the preparation of lubricating oils
US4605488A (en) * 1984-05-03 1986-08-12 Mobil Oil Corporation Catalytic dewaxing of light and heavy oils in dual parallel reactors
EP0272729A1 (fr) * 1986-12-10 1988-06-29 Shell Internationale Researchmaatschappij B.V. Procédé de production d'huiles lubrifiantes de base
WO1997018278A1 (fr) * 1995-11-14 1997-05-22 Mobil Oil Corporation Procede integre d'amelioration de lubrifiant
WO2002050213A2 (fr) * 2000-12-19 2002-06-27 Shell Internationale Research Maatschappij B.V. Procede de preparation d'une huile a broche et d'une qualite d'huile de base d'huile pour machine legere et pour machine moyenne provenant de la fraction lourde d'un procede d'hydrocraquage de combustibles

Family Cites Families (8)

* 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
US4764266A (en) * 1987-02-26 1988-08-16 Mobil Oil Corporation Integrated hydroprocessing scheme for production of premium quality distillates and lubricants
US4851109A (en) * 1987-02-26 1989-07-25 Mobil Oil Corporation Integrated hydroprocessing scheme for production of premium quality distillates and lubricants
US5252527A (en) * 1988-03-23 1993-10-12 Chevron Research And Technology Company Zeolite SSZ-32
US5053373A (en) * 1988-03-23 1991-10-01 Chevron Research Company Zeolite SSZ-32
US6569313B1 (en) * 1995-12-22 2003-05-27 Exxonmobil Research And Engineering Company Integrated lubricant upgrading process
CA2350581C (fr) * 1998-11-16 2009-12-29 Shell Internationale Research Maatschappij B.V. Procede de deparaffinage catalytique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876522A (en) * 1972-06-15 1975-04-08 Ian D Campbell Process for the preparation of lubricating oils
US4605488A (en) * 1984-05-03 1986-08-12 Mobil Oil Corporation Catalytic dewaxing of light and heavy oils in dual parallel reactors
EP0272729A1 (fr) * 1986-12-10 1988-06-29 Shell Internationale Researchmaatschappij B.V. Procédé de production d'huiles lubrifiantes de base
WO1997018278A1 (fr) * 1995-11-14 1997-05-22 Mobil Oil Corporation Procede integre d'amelioration de lubrifiant
WO2002050213A2 (fr) * 2000-12-19 2002-06-27 Shell Internationale Research Maatschappij B.V. Procede de preparation d'une huile a broche et d'une qualite d'huile de base d'huile pour machine legere et pour machine moyenne provenant de la fraction lourde d'un procede d'hydrocraquage de combustibles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009001314A1 (fr) 2007-06-25 2008-12-31 Bruno Weber Produit de substitution du fuel

Also Published As

Publication number Publication date
CN1926220A (zh) 2007-03-07
EP1733008A1 (fr) 2006-12-20
KR20060130675A (ko) 2006-12-19
US20070175794A1 (en) 2007-08-02
JP2007526380A (ja) 2007-09-13

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