EP2992070A2 - Procédé de préparation d'une huile de base lourde - Google Patents

Procédé de préparation d'une huile de base lourde

Info

Publication number
EP2992070A2
EP2992070A2 EP14720073.7A EP14720073A EP2992070A2 EP 2992070 A2 EP2992070 A2 EP 2992070A2 EP 14720073 A EP14720073 A EP 14720073A EP 2992070 A2 EP2992070 A2 EP 2992070A2
Authority
EP
European Patent Office
Prior art keywords
range
catalyst
process according
hydrofinishing
dewaxing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14720073.7A
Other languages
German (de)
English (en)
Inventor
Laurent Georges Huve
John Joseph Baric
Nariman Boumendjel
Jakob Willem Duininck
Godfried Johannes Aarts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP14720073.7A priority Critical patent/EP2992070A2/fr
Publication of EP2992070A2 publication Critical patent/EP2992070A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G65/02—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
    • C10G65/08—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 hydrogenation of the aromatic hydrocarbons
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • the present invention relates to a process for preparing a heavy base oil.
  • base oils such as motor oils to protect the internal combustion engines in motor vehicles.
  • the lubricants are generally composed of a majority of base oil and a variety of additives to obtain the desired properties.
  • Light lubricating base oils are mainly used in automotive applications and heavy lubricating base oils are used in heavy duty applications such as ship engines and industrial processes.
  • Base oils for use in lubricants are on a large scale prepared by firstly hydrotreating a vacuum gas oil distillate and/or a deasphalted oil and by subsequently catalytically dewaxing and hydrofinishing of the
  • a noble metal dewaxing catalyst is applied in the catalytic dewaxing step.
  • Noble metal dewaxing catalysts are well known to be poisoned by organic nitrogen and organic sulphur compounds and therefore a severe hydrotreating step has to be applied in order to sufficiently reduce the levels of organic nitrogen and organic sulphur compounds in the 370 °C plus product of the hydrotreater .
  • hydrotreater improves the quality of the 370 °C plus hydrotreated product which serves as feedstock for a base oil plant.
  • a higher hydrotreating severity means that the yield of the 370 °C plus hydrotreated product becomes lower and the overall hydrotreated product lighter (boiling point shift due to severe
  • a reduction of the yield of heavy lubricating base oils is undesirable in periods that there is a high demand for heavy base oils.
  • Object of the present invention is therefore to provide an upgrading process for hydrocarbonaceous feedstocks in which a high yield of heavy lubricating base oils is obtained.
  • This object is achieved when a hydrocarbonaceous feedstock is subjected to an upgrading process which comprises a particular sequence of processing steps.
  • the present invention relates to a process for preparing a heavy base oil comprising the steps of:
  • step (c) removing at least 50% of the N3 ⁇ 4 and 3 ⁇ 4S which is present in the hydrotreated product as obtained in step (b) ;
  • step (c) hydrotreated product as obtained in step (c) with a dewaxing catalyst in the presence of a hydrogen- containing gas under catalytic dewaxing conditions to obtain a dewaxed product, which dewaxing catalyst
  • alumina comprises a Group VIII metal hydrogenation component, dealuminated aluminosilicate zeolite crystallites and a low acidity refractory oxide binder material which is essentially free of alumina;
  • step (e) hydrofinishing at least part of the dewaxed product as obtained in step (d) with a hydrofinishing catalyst in the presence of a hydrogen-containing gas under
  • the heavy lubricating base oils obtained include Group II and Group II
  • the hydrocarbonaceous feedstock as provided in step (a) preferably contains more than 65%, but at least 50% by weight of hydrocarbons boiling above 460°C.
  • the hydrocarbonaceous feedstock as provided in step (a) has a 370 °C plus fraction that has a viscosity at 100 °C of above 12 cSt, preferably at least 14 cSt.
  • the hydrocarbonaceous feedstock contains nitrogen in an amount in the range of from 800-2500 ppmw, preferably in the range of from 1000-1500 ppmw, and sulphur in an amount in the range of from 1.2 to 4.0 %wt, preferably in the range of from 1.5 - 3.0 %wt
  • the ratio of the fraction of hydrocarbons boiling in the range of from 370-460 °C and the fraction of hydrocarbons boiling in the range of from 460 to 800°C is preferably less than 10.
  • hydrocarbonaceous feedstock examples include straight-run gasoil, hydrocracked gasoil, thermal cracked gasoil, coker gasoil, vacuum gasoil, light or heavy cycle oil, deasphalted oil (DAO) or a combination of two or more thereof.
  • the hydrocarbon feedstock may also be a solvent extracted waxy raffinate. At least part of the
  • hydrocarbonaceous feedstock as provided in step (a) can suitably be a blend obtained by blending at least one distillate fraction, preferably a vacuum distillate fraction, and a deasphalted oil (DAO) .
  • the DAO that can be used is suitably obtained by deasphalting a residual hydrocarbon oil, preferably a vacuum residue.
  • a well known and suitable deasphalting method is solvent deasphalting, which involves the counter-current treatment of the residual hydrocarbon oil feed with an extracting solvent.
  • This extracting solvent usually is a light hydrocarbon solvent containing paraffinic compounds having 3 to 8 carbon atoms, such as propane, butane, isobutane, pentane, isopentane, hexane and mixtures of two or more of these.
  • Preferred paraffinic hydrocarbons are those having 3 to 5 carbon atoms with propane, butane, pentane and mixtures thereof being most
  • the solvent deasphalting treatment is conveniently carried out in a rotating disc contactor or a plate column with the residual hydrocarbon oil feed entering in the top section and the extracting solvent entering in the bottom section.
  • the lighter hydrocarbons present in the residual hydrocarbon oil dissolve in the extracting solvent and are withdrawn at the top of the apparatus. From this top-fraction, the DAO is obtained after recovery of the extracting solvent.
  • asphaltenes which are insoluble in the extracting solvent, are withdrawn at the bottom of the apparatus.
  • deasphalting is carried out at a total extracting solvent to residual hydrocarbon oil ratio of 1.5-8 wt/wt, a pressure of 1-50 bar and a temperature of 50-230 °C.
  • the deasphalted oil may be obtained by deasphalting a residue fraction, preferably a vacuum residue fraction, containing hydrocarbons that have a boiling point of at least460 °C.
  • step (b) the hydrocarbonanceous feedstock is hydrotreated with a suitable hydrotreating catalyst or hydrotreating catalyst package in the presence of a hydrogen-containing gas under hydrotreating conditions to obtain a hydrotreated product which contains nitrogen in an amount in the range of from 30-80 ppmw and sulphur in an amount in the range of from 200-450 ppmw.
  • the hydrotreating catalyst or catalyst package to be used in the first reaction zone in step (a) can suitably be a desulphurisation catalyst or a combination of desulphurisation catalysts (including a possible
  • the desulphurisation catalyst may be any hydrodesulphurisation catalyst known in the art or combination of hydrotreating catalysts that will deliver hydrotreated effluent with the prescribed levels of nitrogen and sulphur.
  • these catalysts comprise a Group VIII metal of the Periodic Table and a compound of a Group VIB metal of the Periodic Table as
  • hydrogenation components on a porous catalyst support usually alumina or amorphous silica-alumina.
  • alumina usually alumina or amorphous silica-alumina.
  • suitable combinations of hydrogenation compounds are cobalt-molybdenum, nickel-molybdenum, nickel-tungsten, and nickel-cobalt-molybdenum.
  • hydrodesulphurisation catalyst comprising compounds of nickel and/or cobalt and molybdenum as hydrogenation compounds is preferred.
  • the hydrotreated product as obtained in step (b) contains nitrogen in an amount in the range of from 30-80 ppmw and sulphur in an amount in the range of from 200-450 ppmw, which means that the hydrotreating in step (b) is not a severe hydrotreating process.
  • use is made of hydrotreating catalysts or hydrotreating catalyst combinations that are not too active. Therefore, preferably use is made of an alumina-based hydrotreating catalyst.
  • the catalyst is substantially free of a cracking component.
  • a catalyst or combination of catalysts comprising nickel and/or cobalt and molybdenum supported on alumina without a zeolitic cracking compound is particularly preferred.
  • step (b) also use can be made of stacked-bed configurations in which two or more hydrotreating
  • the temperature in the hydrotreating step is suitably in the range of from 250-480 °C, preferably in the range of from 280-450 °C, and more preferably in the range of from 350-420 °C.
  • Suitable hydrotreating pressures are in the range of from 30-250 bara.
  • the hydrotreating pressure is in the range of from 110 to 180 bara, more preferably in the range of from 120 to 170 bara.
  • the weight hourly space velocity is suitably in the range of from 0.2-10 hr -1 , preferably in the range of from 0.2-2.0 hr -1 , and more preferably in the range of from 0.2-1.0 hr "1 .
  • step (a) will inter alia depend on the catalyst used, and the sulphur content and nitrogen content of the hydrocarbon feedstock.
  • the ratio of the amount of nitrogen and the amount of sulphur (N/S) in the hydrotreated product as obtained in step (b) is suitably in the range of from 0.1-0.3, preferably in the range of from 0.12-0.28
  • step (c) at least 50% of the N3 ⁇ 4 and 3 ⁇ 4S which is present in the hydrotreated product as obtained in step (b) is removed.
  • at least part of the N3 ⁇ 4 and 3 ⁇ 4S which is present in the hydrotreated product as obtained in step (b) is removed by means of stripping, preferably steam stripping.
  • the stripping is carried out at a temperature ranging from 100 to 350C, preferably from 130 to 240C and a pressure ranging from 1 to 50 bar, preferably from 1.5 to 10 bar.
  • the stripping is carried out at a temperature ranging from 100 to 350C, preferably from 130 to 240C and a pressure ranging from 1 to 50 bar, preferably from 1.5 to 10 bar.
  • step (c) preferably at least 95% of the N3 ⁇ 4 and 3 ⁇ 4S which is present in the hydrotreated product as obtained in step (b) is removed from the hydrotreated product in step (c) .
  • step (c) also hydrocarbons boiling below
  • step (b) the entire hydrotreated product as obtained in step (b) is subjected to step (c) .
  • step (d) at least part of the hydrotreated product as obtained in step (c) is catalytically dewaxed with a dewaxing catalyst in the presence of a hydrogen- containing gas under catalytic dewaxing conditions to obtain a dewaxed product, which dewaxing catalyst comprises a Group VIII metal hydrogenation component, dealuminated aluminosilicate zeolite crystallites and a low acidity refractory oxide binder.
  • step (c) the entire hydrotreated product as obtained in step (c) is subjected to step (d) .
  • catalytic dewaxing is here meant a process for decreasing the pour point of lubricating base oil products by selectively converting the components of the oil feed which impart a high pour point to products which do not impart a high pour point.
  • Products which impart a high pour point are compounds having a high melting point. These compounds are referred to as waxes. Wax compounds include for example high temperature melting normal paraffins, iso-paraffins and mono-ringed
  • the pour point is preferably reduced by at least 40 °C and more preferably by at least 60 °C.
  • the hydrocarbonacous feedstock in the process according to the present invention will thus contain waxy molecules which impart an undesirable high pour point. Small amounts of these compounds can strongly influence the pour point.
  • the feedstock will suitably contain between less than 2% and up to 80% of these waxy compounds.
  • the hydrotreated feedstock is contacted under catalytic dewaxing conditions with a catalyst composition comprising a Group VIII metal hydrogenation component, dealuminated aluminosilicate zeolite crystallites and a low acidity refractory oxide binder.
  • the aluminosilicate zeolite crystallites preferably have pores with a diameter in the range of from 0.35 to 0.80 nm. This diameter refers to the maximum pore
  • the pores in a molecular sieve are polygonal shaped channels having a minimum and a maximum pore diameter.
  • the maximum pore diameter is the critical parameter, because it determines the size of the waxy molecules which can enter the pores.
  • aluminosilicate zeolites which are suitable to be used in the present invention are
  • the zeolitic component is ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM- 35, ZSM-38, ZSM-48, ZSM-57, SSZ-23, SSZ-24, SSZ-25, SSZ- 26, SSZ-32, SSZ-33 and MCM-22 and mixtures of two or more of these.
  • the zeolitic component is ZSM-5,
  • the zeolitic component in the dewaxing catalyst is present in an amount in the range of from 10- 50 wt%, based on the total weight of the dewaxing
  • Preferred aluminosilicate zeolites are of the MFI- topology for example ZSM-5.
  • the dewaxing catalyst also comprises a low acidity refractory oxide binder material which is essentially free of alumina. Examples are low acidity refractory oxides such as silica, zirconia, titanium dioxide, germanium dioxide, boria and mixtures of two or more of these.
  • the most preferred binder is silica.
  • the weight ratio of modified molecular sieve to binder is suitably within the range of from 05/95 to 95/05.
  • alumina moiety refers to an
  • a ⁇ C ⁇ -unit which is part of the framework of the alumino- silicate zeolite, i.e. which has been incorporated via covalent bindings with other oxide moieties, such as silica (S1O2), in the framework of the aluminosilicate zeolite.
  • the mole percentage of alumina present in the aluminosilicate zeolite is defined as the percentage of moles AI2O3 relative to the total number of moles of oxides constituting the aluminosilicate zeolite (prior to dealumination) or modified molecular sieve (after
  • the surface of the zeolite crystallites is selectively dealuminated .
  • dealumination results in a reduction of the number of surface acid sites of the zeolite crystallites, whilst not affecting the internal structure of the zeolite crystallites .
  • Dealumination can be attained by methods known in the art. Particularly useful methods are those, wherein the dealumination selectively occurs, or anyhow is claimed to occur selectively, at the surface of the crystallites of - li the molecular sieve. Examples of dealumination processes are described in the afore mentioned WO-A-9641849.
  • dealumination is performed by a process in which the zeolite is contacted with an aqueous
  • fluorosilicate salt is represented by the formula:
  • ⁇ ⁇ ' is a metallic or non-metallic cation other than H+ having the valence x b' .
  • This treatment will be also referred to as the AHS treatment.
  • cations x b' are alkylammonium, NH4 + , Mg ++ , Li + , Na + , K + , Ba ++ , Cd ++ , Cu+, Ca ++ , Cs+, Fe ++ , Co ++ , Pb ++ , Mn ++ , Rb+, Ag + , Sr ++ , Tl + , and Zn ++ .
  • ⁇ ⁇ ' is the ammonium cation.
  • the zeolite material may be contacted with the fluorosilicate salt at a pH of suitably between 3 and 7.
  • Such a dealumination process is for example described in US-A-5157191.
  • the dealumination treatment is referred to as the AHS-treatment .
  • the dewaxing catalyst to be used in accordance with the present invention is preferably prepared by first extruding the aluminosilicate zeolite with the binder and subsequently subjecting the extrudate to a dealumination treatment, preferably the AHS treatment as described above. It has been found that an increased mechanical strenght of the catalyst extrudate is obtained when prepared according to this sequence of steps.
  • the Group VIII metal of the Periodic Table is
  • the catalyst extrudate comprising the dealuminated aluminosilicate zeolite crystallites by known techniques, such as ion-exchange techniques.
  • Typical ion-exchange techniques call for contacting the selected zeolite with a salt of the desired replacing cation.
  • a salt of the desired replacing cation a wide variety of salts can be employed, particular preference is given to chloride, nitrates and sulphates.
  • Representative ion-exchange techniques are disclosed in a wide variety of patents including
  • step (d) use is made of dewaxing catalyst which comprises a Group VIII metal hydrogenation component.
  • Group VIII metal components include those components based on both noble and non-noble metals.
  • Particularly suitable Group VIII metal components are palladium, platinum, nickel and/or cobalt in sulphidic, oxidic and/or elemental form.
  • the total amount Group VIII metal of the Periodic Table will suitably not exceed 10% by weight calculated as element and based on total weight of support, and preferably is in the range of from 0.1 to 5.0% by weight, more preferably from 0.2 to 3.0% by weight. If both platinum and palladium are present, the weight ratio of platinum to palladium may vary within wide limits, but suitably is in the range of from 0.05 to 10, more suitably 0.1 to 5. Catalysts comprising
  • hydrogenation component is preferably platinum or
  • the catalytic dewaxing conditions in step (d) of the process according to the invention are typical catalytic dewaxing conditions. Therefore, the temperature is suitably in the range of from 300-400 °C, preferably in the range of from 320-390 °C, and more preferably in the range of from 330-380 °C. Suitable dewaxing pressures are in the range of from 80-240 bara. Preferably, the
  • dewaxing pressure is in the range of from 100-180 bara, more preferably in the range of from 120-170 bara.
  • the weight hourly space velocity in step (d) is suitably in the range of from 0.4 to 7 hr -1 , preferably in the range of from 0.5 to 2.5 hr -1 , and more preferably in the range of from 0.65 to 2.25 hr -1 .
  • Step (d) is carried out in the presence of hydrogen.
  • Hydrogen is suitably supplied to the second reaction zone at a rate of 350 to 1500 Nl/kg feed.
  • the dewaxed product as obtained in step (d) has a viscosity index (VI) which enables the production of high VI lubricating base oils.
  • the dewaxed product as obtained in step (d) suitably contains sulphur in an amount of less than 350 ppmw, preferably less than 300 ppmw, and it contains nitrogen in an amount of less than 80 ppmw, preferably less than 60 ppmw.
  • the dewaxed product has suitably a viscosity at 100 °C in the range of 10 to 17 cSt, preferably in the range of from 10 to 15 cSt.
  • step (e) at least part of the dewaxed product as obtained in step (d) is hydrofinished with a
  • hydrofinishing catalyst in the presence of a hydrogen- containing gas under hydrofinishing conditions to obtain a heavy base oil.
  • step (d) the entire dewaxed product as obtained in step (d) is subjected to step (e) .
  • Hydrofinishing is known in the art and examples of suitable hydrofinishing steps are disclosed in, for instance, US-A-5139647, WO-A-9201657 and WO-A-9201769.
  • hydrofinishing comprises contacting a
  • hydrocarbon feed in this case a feed comprising the dewaxed lubricating base oil, with a hydrogenation catalyst under relatively mild conditions in order to saturate at least part of the aromatics still present in the dewaxed base oil.
  • Suitable catalysts are those normally applied for this purpose with noble metal-based catalysts, such as those comprising Pt and/or Pd supported on an amorphous silica-alumina carrier.
  • a non- noble metal hydrofinishing catalyst a so-called base metal hydrofinishing catalyst such as nickel-molybdenum on an alumina support.
  • Hydrofinishing conditions as per invention involve operating temperatures up to 390 °C and preferably in the range of from 300 to 380 °C, more preferably 330 to
  • 200 bara preferably in the range of from 100 to 170 bara, and weight hourly space velocities in the range of from 0.3-2.5 hr -1 , preferably in the range of from 0.5 - 1.5 hr "1 .
  • the yield of the heavy base oil in step (e) is high when compared to known processes for preparing base oils wherein use is made of hydrocracking and catalytically dewaxing steps.
  • This high yield of heavy base oils can be expressed as the ratio of heavy base oil over light base oil as obtained in step (e) .
  • the high yield of heavy base oil can for instance be expressed as the ratio of 500N base oil over 150N base oil as obtained in step (e) .
  • the 500 N base oil is a heavy Group II base oil having typically a viscosity at 100 °C in the range of from 10.0-12.9 cSt, whereas the 150N base oil is a light Group
  • the ratio of 500N base oil over 150N base oil as obtained in step (e) is at least 1.0, preferably at least 1.5, more preferably at least 2.5, and most preferably at least 3.0.
  • step (f) the heavy base oil is recovered.
  • the heavy base oil as obtained in step (e) can for instance be separated from the other components of the effluent from the hydrofinishing process, including light base oils, by means of conventional methods, such as by distillation under atmospheric or reduced pressure. Of these, distillation under reduced pressure, including vacuum flashing and vacuum distillation, is most suitably applied.
  • the cut point (s) of the distillate fraction (s) is/are selected such that each product distillate
  • the heavy base oil as recovered in step (f) suitably contains sulphur in an amount of less than 300 ppmw, preferably less than 200 ppmw, and it contains nitrogen in an amount of less than 80 ppmw, preferably less than 50 ppmw.
  • the heavy base oil has suitably a viscosity at
  • a Basrah Light waxy distillate feedstock is provided in a step (a) .
  • Table 1 Main characteristics of the feedstock
  • a step (b) the feedstock is hydrotreated.
  • the feedstock as described in Table 1 is hydrotreated over a conventional NiMo on alumina hydrotreating catalyst (for this example C-424 from Criterion catalyst portfolio) aiming at producing a hydrotreated effluent (370 °C+ fraction) containing ca. 50 ppm nitrogen and ca. 300 ppm sulphur.
  • a conventional NiMo on alumina hydrotreating catalyst for this example C-424 from Criterion catalyst portfolio
  • iMo/Al20 3 -type-II hydrotreating catalyst like for example DN-3100 from Criterion catalyst portfolio.
  • the operating conditions and main outcome of the hydroprocessing step are indicated in Table 3.
  • step (c) products obtained in step (c) are subjected to a dewaxing step in accordance with the present invention and a conventional dewaxing step.
  • Example 1 The 370 °C+ fraction of Example 1 is catalytically dewaxed on Shell commercial dewaxing catalyst SLD-800, a base metal (Ni) catalyst specifically developed for the dewaxing of severely contaminated feedstocks.
  • Example 2 The 370 °C+ fraction of Example 2 is catalytically dewaxed on Shell commercial dewaxing catalyst SLD-821, a noble metal (Pt) catalyst specifically developed for the dewaxing of deeply hydrotreated feedstocks for base oil
  • step (e) the dewaxed product as obtained in step (d) according to the present invention is
  • Example 3 The 370 °C+ fraction of Example 3, stripped from any gases, is submitted to a hydrofinishing step using either a base metal hydrofinishing catalyst (high active
  • Example 5a or a noble metal hydrofinishing catalyst (like Criterion LN-5) ;
  • Example 5b known for its high hydrogenation power and resistance to sulphur and nitrogen poisoning.

Landscapes

  • 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)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation d'une huile de base lourde comprenant les étapes suivantes : (a) la préparation d'une matière première hydrocarbonée qui contient au moins 50 % en poids d'hydrocarbures ayant un point d'ébullition supérieur à 460 °C, de l'azote en une quantité dans la plage allant de 800 à 2 500 ppm en poids, et du soufre en une quantité dans la plage allant de 1,5 à 4,0 ppm en poids ; (b) l'hydrotraitement de la matière première hydrocarbonée avec un catalyseur d'hydrotraitement en présence d'un gaz contenant de l'hydrogène dans des conditions d'hydrotraitement pour obtenir un produit hydrotraité qui contient de l'azote en une quantité dans la plage allant de 30 à 80 ppm en poids et du soufre en une quantité dans la plage allant de 200 à 450 ppm en poids ; (c) l'élimination d'au moins 50 % du N¾ et du ¾S présents dans le produit hydrotraité tel qu'obtenu à l'étape (b) ; (d) le déparaffinage catalytique d'au moins une partie du produit hydrotraité tel qu'obtenu à l'étape (c) avec un catalyseur de déparaffinage en présence d'un gaz contenant de l'hydrogène dans des conditions de déparaffinage catalytique pour obtenir un produit déparaffiné, ledit catalyseur de déparaffinage comprenant un composant d'hydrogénation métallique du groupe VIII, des cristallites de zéolithe aluminosilicate désaluminée et un matériau liant oxydique réfractaire de faible acidité qui est essentiellement exempt d'alumine ; (e) l'hydrofinition d'au moins une partie du produit déparaffiné tel qu'obtenu à l'étape (d) avec un catalyseur d'hydrofinition en présence d'un gaz contenant de l'hydrogène dans des conditions d'hydrofinition pour obtenir une huile de base lourde ; et (f) la récupération de l'huile de base lourde.
EP14720073.7A 2013-05-02 2014-04-22 Procédé de préparation d'une huile de base lourde Withdrawn EP2992070A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14720073.7A EP2992070A2 (fr) 2013-05-02 2014-04-22 Procédé de préparation d'une huile de base lourde

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13166276 2013-05-02
EP14720073.7A EP2992070A2 (fr) 2013-05-02 2014-04-22 Procédé de préparation d'une huile de base lourde
PCT/EP2014/058144 WO2014177424A2 (fr) 2013-05-02 2014-04-22 Procédé de préparation d'une huile de base lourde

Publications (1)

Publication Number Publication Date
EP2992070A2 true EP2992070A2 (fr) 2016-03-09

Family

ID=48190394

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14720073.7A Withdrawn EP2992070A2 (fr) 2013-05-02 2014-04-22 Procédé de préparation d'une huile de base lourde

Country Status (5)

Country Link
EP (1) EP2992070A2 (fr)
KR (1) KR20160003203A (fr)
CN (1) CN105209580B (fr)
RU (1) RU2671862C2 (fr)
WO (1) WO2014177424A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10533141B2 (en) 2017-02-12 2020-01-14 Mag{tilde over (e)}mã Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10550341B2 (en) * 2015-12-28 2020-02-04 Exxonmobil Research And Engineering Company Sequential deasphalting for base stock production
US10472579B2 (en) 2016-11-21 2019-11-12 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrocracking and steam cracking
US10472574B2 (en) 2016-11-21 2019-11-12 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating delayed coking of vacuum residue
US10472580B2 (en) 2016-11-21 2019-11-12 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating steam cracking and conversion of naphtha into chemical rich reformate
US10407630B2 (en) 2016-11-21 2019-09-10 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating solvent deasphalting of vacuum residue
US10619112B2 (en) 2016-11-21 2020-04-14 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrotreating and steam cracking
US10870807B2 (en) 2016-11-21 2020-12-22 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate
US10487276B2 (en) 2016-11-21 2019-11-26 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum residue hydroprocessing
US10487275B2 (en) * 2016-11-21 2019-11-26 Saudi Arabian Oil Company Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum residue conditioning and base oil production
US20180142167A1 (en) 2016-11-21 2018-05-24 Saudi Arabian Oil Company Process and system for conversion of crude oil to chemicals and fuel products integrating steam cracking and fluid catalytic cracking
WO2018226416A1 (fr) * 2017-06-07 2018-12-13 Exxonmobil Research And Engineering Company Production de diesel et d'huiles de base à partir de pétrole brut
US10696906B2 (en) 2017-09-29 2020-06-30 Marathon Petroleum Company Lp Tower bottoms coke catching device
US11975316B2 (en) 2019-05-09 2024-05-07 Marathon Petroleum Company Lp Methods and reforming systems for re-dispersing platinum on reforming catalyst
US11352578B2 (en) 2020-02-19 2022-06-07 Marathon Petroleum Company Lp Low sulfur fuel oil blends for stabtility enhancement and associated methods
US11898109B2 (en) 2021-02-25 2024-02-13 Marathon Petroleum Company Lp Assemblies and methods for enhancing control of hydrotreating and fluid catalytic cracking (FCC) processes using spectroscopic analyzers
US20220268694A1 (en) 2021-02-25 2022-08-25 Marathon Petroleum Company Lp Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US11905468B2 (en) 2021-02-25 2024-02-20 Marathon Petroleum Company Lp Assemblies and methods for enhancing control of fluid catalytic cracking (FCC) processes using spectroscopic analyzers
US11692141B2 (en) 2021-10-10 2023-07-04 Marathon Petroleum Company Lp Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using a renewable additive
CA3188122A1 (fr) 2022-01-31 2023-07-31 Marathon Petroleum Company Lp Systemes et methodes de reduction des points d'ecoulement de gras fondus

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY125670A (en) * 1995-06-13 2006-08-30 Shell Int Research Catalytic dewaxing process and catalyst composition
BR9710321A (pt) * 1996-07-16 1999-08-17 Chevron Usa Inc Processo para produzir uma mat-ria prima de Äleo lubrificante e mat-ria prima de Äleo lubrificante
TWI277649B (en) * 2001-06-07 2007-04-01 Shell Int Research Process to prepare a base oil from slack-wax
US7282137B2 (en) * 2002-10-08 2007-10-16 Exxonmobil Research And Engineering Company Process for preparing basestocks having high VI
CN1317368C (zh) * 2004-03-31 2007-05-23 中国石油化工股份有限公司 一种润滑油基础油的制备方法
EP1997868A1 (fr) * 2007-05-30 2008-12-03 Shell Internationale Researchmaatschappij B.V. Procédé pour la production d'huile à base naphténique
US8182672B2 (en) * 2007-12-28 2012-05-22 Exxonmobil Research And Engineering Company Process for preparing lube basestocks having superior low temperature properties at high VI

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014177424A3 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10533141B2 (en) 2017-02-12 2020-01-14 Mag{tilde over (e)}mã Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US10563133B2 (en) 2017-02-12 2020-02-18 Magëmä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US10563132B2 (en) 2017-02-12 2020-02-18 Magēmā Technology, LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization
US10584287B2 (en) 2017-02-12 2020-03-10 Magēmā Technology LLC Heavy marine fuel oil composition
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US10655074B2 (en) 2017-02-12 2020-05-19 Mag{hacek over (e)}m{hacek over (a)} Technology LLC Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil
US10836966B2 (en) 2017-02-12 2020-11-17 Magēmā Technology LLC Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil
US11136513B2 (en) 2017-02-12 2021-10-05 Magëmä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11203722B2 (en) 2017-02-12 2021-12-21 Magëmä Technology LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization
US11345863B2 (en) 2017-02-12 2022-05-31 Magema Technology, Llc Heavy marine fuel oil composition
US11441084B2 (en) 2017-02-12 2022-09-13 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US11447706B2 (en) 2017-02-12 2022-09-20 Magēmā Technology LLC Heavy marine fuel compositions
US11492559B2 (en) 2017-02-12 2022-11-08 Magema Technology, Llc Process and device for reducing environmental contaminates in heavy marine fuel oil
US11530360B2 (en) 2017-02-12 2022-12-20 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
US11795406B2 (en) 2017-02-12 2023-10-24 Magemä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11884883B2 (en) 2017-02-12 2024-01-30 MagêmãTechnology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US11912945B2 (en) 2017-02-12 2024-02-27 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit

Also Published As

Publication number Publication date
RU2015151620A3 (fr) 2018-03-19
RU2015151620A (ru) 2017-06-07
KR20160003203A (ko) 2016-01-08
WO2014177424A2 (fr) 2014-11-06
CN105209580B (zh) 2018-06-08
CN105209580A (zh) 2015-12-30
WO2014177424A3 (fr) 2015-01-08
RU2671862C2 (ru) 2018-11-07

Similar Documents

Publication Publication Date Title
WO2014177424A2 (fr) Procédé de préparation d'une huile de base lourde
CA2351676C (fr) Procede de deparaffinage catalytique
EP2566938B1 (fr) Méthode de fabrication simultanée d'huile de base lourde et d'huile de base naphténique de haute qualité
EP0629230B1 (fr) Procede de production de lubrifiant
AU724363B2 (en) Layered catalyst system for lube oil hydroconversion
EP2578668B1 (fr) Procédé de préparation d'huiles de base lubrifiantes faisant appel à une huile désasphaltée distillée sous vide
JP7137585B2 (ja) 原油からのディーゼルおよびベースストックの製造
US20150152343A1 (en) Hydrocracking of gas oils with increased distillate yield
EP1720959B1 (fr) Procede de preparation d'huile de base lubrifiante
WO2014025598A1 (fr) Coproduction d'huiles de base lourde et légère
CN110114443B (zh) 用于调整重质中性基础油料的颜色和芳烃分布的溶剂提取
EP0140468A1 (fr) Procédé combiné pour la production d'huiles lubrifiantes à partir de pétroles bruts marginaux
EP3397723B1 (fr) Production d'huile de base lubrifiante à partir de charges désavantagées
US10655075B2 (en) Hydrotreating and dewaxing process
CN116745391A (zh) 提高基础油产率的工艺
CN102686709A (zh) 催化脱蜡法
CN116867880A (zh) 用于制造光亮油料基础油产品的工艺
CN116888244A (zh) 用于制造重质等级基础油产品的工艺

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20151117

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20170411

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20171002