EP1558711A1 - Composition d'hydrocarbures lourds utilisee comme huile de base pour lubrifiants lourds - Google Patents

Composition d'hydrocarbures lourds utilisee comme huile de base pour lubrifiants lourds

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Publication number
EP1558711A1
EP1558711A1 EP03770718A EP03770718A EP1558711A1 EP 1558711 A1 EP1558711 A1 EP 1558711A1 EP 03770718 A EP03770718 A EP 03770718A EP 03770718 A EP03770718 A EP 03770718A EP 1558711 A1 EP1558711 A1 EP 1558711A1
Authority
EP
European Patent Office
Prior art keywords
composition according
heavy
carbon atoms
composition
measured
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Withdrawn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
EP03770718A
Other languages
German (de)
English (en)
Inventor
Jack Wayne Johnson
Adeana Richelle Bishop
William Berlin Genetti
Loren Leon Ansell
Rocco Anthony Fiato
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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
Priority claimed from US10/266,344 external-priority patent/US6846778B2/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1558711A1 publication Critical patent/EP1558711A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
    • 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
    • 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
    • C10G45/62—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 platinum group metals or compounds thereof
    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/02—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon well-defined aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material

Definitions

  • the invention relates to a heavy hydrocarbon composition useful as a heavy lubricant base stock, produced by isomerizing Fischer-Tropsch wax, to a heavy lubricant base stock and to a heavy lubricant formed from the base stock.
  • Heavy lubricants are used for high viscosity applications in which a lubricant based on a lighter oil will not provide sufficient lubrication between moving parts, such as heavy machine oils, gear boxes, deep drawing oils, and manual transmissions.
  • a heavy lubricant is formed by combining a heavy lubricant base stock, which is a heavy oil possessing lubricating oil qualities, with one or more lubricant additives.
  • Most heavy lubricant base stocks are derived from naturally occurring petroleum oil and contain aromatic unsaturates, including polynuclear aromatics, along with sulfur and nitrogen containing compounds. These compounds tend to reduce the viscosity and stability of the oil and the heavy lubricant. Refining the oil to remove these components results in a low yield of the product oil.
  • Heavy paraffins can be refined to low levels of unsaturates and heteroatom compounds, but have unacceptably high pour and cloud points.
  • U.S. Patent 6,090,989 discloses a liquid hydrocarbon composition of paraffinic hydrocarbon components in which the extent of branching, as measured by the percentage of methyl hydrogens (BI), and the proximity of branching, as measured by the percentage of recurring methylene carbons which are four or more carbons removed from an end group or branch (CH 2 >4), are such that:
  • the base stocks of U.S. patent 6,090,989 are characterized by very low pour points (PP) of less than or equal to -18°C, and the kinematic viscosities range from preferably about 4 cSt to about 8 cSt at 100°C. While the compositions according to U.S. patent 6,090,989 have excellent utility as lubricant base stocks, certain applications require the use of heavy lubricants, especially with a kinematic viscosity at 100°C greater than 8 cSt. This will generally require the presence of relatively long chain hydrocarbon molecules in the base stock.
  • hydrocarbon compositions which are useful, for example as a heavy white oil, a pharmaceutical oil, a carrier or base for medicinal formulations, in chemical and the pharmaceutical manufacturing and the like. Such applications generally require a pure and chemically inert material, which will for instance not cause allergies in medicinal applications. In other words, there is a need for a hydrocarbon composition which is very low in aromatics and heteroatom containing components.
  • the present invention provides for a heavy hydrocarbon composition which has both high viscosity and low pour and cloud points.
  • the invention relates to a relatively pure, premium quality, heavy hydrocarbon composition useful as or in a heavy lubricant base stock, to a heavy lubricant base stock, and to a heavy lubricant formed from the heavy lubricant base stock.
  • the heavy hydrocarbon composition comprises mostly (e.g. > 98 wt%) saturated, paraffinic hydrocarbon molecules, is an oily liquid having a kinematic viscosity at 100°C greater than 8 cSt (centistokes), with an initial (5%) boiling point of at least 850°F (454°C) and an end (95%) boiling point of at least 1,000°F (538°C).
  • the heavy hydrocarbon composition comprises at least 95 wt% paraffin molecules, of which at least 90 wt% are isoparaffins. Isoparaffins make up for at least 90 wt.% of the paraffin molecules of the heavy hydrocarbon composition according to the invention.
  • the heavy hydrocarbon composition contains hydrocarbon molecules having consecutive numbers of carbon atoms.
  • branching index BI
  • branching proximity a percentage of recurring methylene carbons which are four or more carbon atoms removed from an end group or branch
  • the heavy hydrocarbon composition has utility in or as a heavy lubricant base stock.
  • the branching proximity (CH 2 >4) describes the n-paraffinic character of a paraffin molecule in the hydrocarbon.
  • compositions are desired that contain paraffin molecules having a relatively high n-paraffinic character, i.e. a small number of branches and/or short branches.
  • paraffins having a relatively high n-paraffinic character are expected to give undesired pour and cloud points, because n-paraffins tend to crystallize out from paraffin mixtures at a rather high temperature.
  • the branching index as measured by the percentage of methyl hydrogens, is a measure of the number of branches attached to the backbone. If there is an abundance of branches and the branches are primarily methyl groups, the branching index will be large.
  • a paraffin molecule with a large number of branches and long branches on a relatively short backbone i.e. a rather small n-paraffinic character
  • a branching proximity CH 2 >4 which is relatively small.
  • a paraffin molecule having the same total number of carbon atoms, but with a small number of branches and/or branches which have a larger distance to each other or to an end group, and with a relatively long backbone, i.e. a paraffin molecule with a more n-paraffinic character, will have a branching proximity (CH 2 >4) which is relatively large.
  • U.S. Patent 6,090,989 relates to a liquid hydrocarbon composition in which BI - 0.5(CH 2 >4) > 15. It has now surprisingly been found that heavy hydrocarbon compositions with a relatively high viscosity, but low pour and cloud points may be obtained if (a) BI - 0.5(CH 2 >4) ⁇ 15. In other words, according to the invention, the branching proximity (CH 2 >4) is rather large, as compared to the compositions exemplified in U.S. Patent 6,090,989. This finding was unexpected because the heavy hydrocarbon compositions according to the invention contain paraffin molecules with a more n-paraffinic character, as expressed by a relatively large branching proximity, and still have very low pour and cloud points. In fact, the finding is contrary to the common belief that low pour and cloud points require a small n-paraffinic and a relatively large isoparaffinic character.
  • the BI is preferably less than 24 and the branching proximity, (CH 2 >4), is preferably greater than 17.
  • the invention relates to a heavy lubricant formed by combining the heavy lubricant base stock of the invention with one or more lubricant additives.
  • the heavy hydrocarbon composition of the invention is useful as a heavy lubricant base stock, it will have other uses such as, for example, a heavy white oil, a pharmaceutical oil, as a carrier or base for medicinal formulations, in chemical and pharmaceutical manufacturing, and the like.
  • the invention comprises one or more of the following, of or in which at least a portion uses or is based on the heavy hydrocarbon composition of the invention; a heavy white oil, a pharmaceutical oil, a carrier or base for medicinal formulations, chemical and pharmaceutical manufacturing processes.
  • the invention relates to a base stock comprising the heavy hydrocarbon composition according to the invention.
  • this embodiment relates to the use of the heavy hydrocarbon composition in or as a base stock.
  • the base stock according to the invention consists of the heavy hydrocarbon composition.
  • the Figure is a graph plotting the BI and % CH2>4 values derived from NMR spectra of the heavy hydrocarbon compositions of the invention, the comparative examples of this application, and the data of U.S. Patent 6,090,989 which includes other hydrocarbon compositions, as has been described above.
  • the disclosure of U.S. Patent 6,090,989 is incorporated herein in its entirety by reference.
  • the shaded area on the plot defines the NMR parameter space of the heavy hydrocarbon compositions of the invention. Only the heavy hydrocarbon composition of this invention which are preferably derived from Fischer- Tropsch synthesized waxy hydrocarbons and PAO base stocks fall in this area of parameter space.
  • the molecular composition of the PAO stocks are different from the heavy hydrocarbon compositions of the invention in that (i) they do not contain, hydrocarbon molecules having consecutive numbers of carbon atoms, (ii) the percentage of hydrogen atoms from CH 3 groups on the molecules is below 15, whereas those for the heavy hydrocarbon composition of the invention is preferably above 20, (iii) the percentage of hydrogen atoms from CH groups for the PAO stocks is preferably above 3, whereas for the heavy hydrocarbon compositions of the invention it is preferably less than 2.
  • the invention provides for a heavy hydrocarbon composition
  • a heavy hydrocarbon composition comprising at least 95 wt% paraffin molecules, of which at least 90 wt% are isoparaffin, containing hydrocarbon molecules having consecutive numbers of carbon atoms, is a liquid at 100°C, at which temperature its kinematic viscosity is above 8 cSt (ASTM D-445), has respective initial and end boiling points of at least 850 and 1000°F (454 and 538°C), wherein the branching index (BI), as measured by the percentage of methyl hydrogens, and the branching proximity (CH 2 >4), as measured by the percentage of recurring methylene carbons which are four or more carbon atoms removed from an end group or branch, of said isoparaffinic hydrocarbon molecules, are such that:
  • the heavy hydrocarbon composition of the invention is produced from Fischer-Tropsch wax and comprises mostly (> 98 wt%) saturated, paraffinic hydrocarbons, of which at least 90 wt% are non-cyclic hydrocarbons and no more than 10 wt% cyclic hydrocarbons. At least 90 and preferably at least 95 wt%, more preferably at least 98 wt%, most preferably at least 99 wt% of the paraffinic hydrocarbon molecules are isoparaffins. While paraffinic cyclic hydrocarbons may be present in an amount of up to 5 wt%, more typically they will not exceed 1 wt%, if present.
  • the kinematic viscosity of the heavy hydrocarbon compositions of the invention at 100°C, as measured according to ASTM D-445, is greater than 8 cSt.
  • the heavy hydrocarbon composition of the invention contains molecules having consecutive numbers of carbon atoms and preferably at least 95 wt% C 30+ hydrocarbon molecules.
  • the initial boiling point is at least 850°F (454°C), preferably 900°F (482°C) and the end boiling point is at least 1,000°F (538°C).
  • the heavy hydrocarbon composition is typically a liquid at the temperature and pressure conditions of use and typically, but not always, at ambient conditions of 75 °F (24°C) and one atmosphere (101 kPa) pressure.
  • the initial and end boiling points values referred to herein are nominal and refer to the T5 and T95 cut points (boiling temperatures) obtained by gas chromatograph simulated distillation (GCD), using the method set forth below.
  • the extent of branching of the isoparaffinic hydrocarbon components as measured by the percentage of methyl (CH 3 ) hydrogens or branching index (BI), and the proximity of the branches (or branching proximity), as measured by the percentage of recurring methylene carbons which are four or more carbon atoms removed from an end group or branch (CH 2 >4), are such that:
  • the heavy hydrocarbon composition also preferably contains at least 75 wt% of C 35+ hydrocarbon molecules.
  • the heavy hydrocarbon composition of the invention is different from one derived from petroleum oil, slack wax, a PAO oil and the lubricant base stock disclosed in U.S. Patent 6,090,989, which was obtained by isomerizing Fischer-Tropsch wax.
  • Sulfur, nitrogen and metals in the form of hydrocarbon compounds containing them are present in amounts of less than 50 wppm.
  • Heavy hydrocarbon compositions of the invention that have been made from Fischer- Tropsch wax usually contain less than 1 wppm sulfur, nitrogen and metals. These were not detectable by X-ray or Antek Nitrogen tests.
  • the heavy hydrocarbon composition of the invention is a mixture of various molecular weight paraffinic hydrocarbons
  • the residual normal paraffin content remaining after hydrodewaxing is less than 5 wt% and more typically less than 1 wt%, with at least 95% of the oil molecules containing at least one branch, at least half of which are methyl branches. At least half, and more preferably at least 75% of the remaining branches are ethyl, with less than 25% and preferably less than 15% of the total number of branches having three or more carbon atoms.
  • the total number of branch carbon atoms is typically less than 25%, preferably less than 20% and more preferably no more than 15% (e.g., 10-15%) of the total number of carbon atoms comprising the hydrocarbon molecules.
  • PAO oils are an oligomerization product of even carbon numbered linear alpha olefins, typically 1-decene.
  • the PAO oil molecules therefore comprise a mixture of even carbon numbered hydrocarbon molecules, differing from each other in the number of carbon atoms by multiples of the number of carbon atoms in the linear alpha olefin starting monomer. Even if a mixture of linear alpha olefin monomers having even numbers of carbon atoms (e.g., decene and dodecene) were oligomerized to form a heavy lubricant base stock oil, the number of carbon atoms in the resulting hydrocarbon molecules would still have even numbers of carbon atoms.
  • That hydrocarbon molecules of the heavy hydrocarbon composition of the invention differ from each other by consecutive numbers of carbon atoms is a consequence of the Fischer-Tropsch hydrocarbon synthesis reaction from which the wax feed, which was isomerized to form the heavy hydrocarbon composition of the invention may be produced.
  • a preferred heavy hydrocarbon composition is prepared from synthetic sources rather than sources on a mineral oil basis, and may thus be termed a synthetic heavy hydrocarbon composition
  • the heavy hydrocarbon composition of the invention is not limited to be based on synthetic sources. In a preferred embodiment, however, the heavy hydrocarbon composition is based on a synthetic source, and is more preferably based on a Fischer-Tropsch product.
  • hydrocarbon molecules of the heavy hydrocarbon composition of the invention have a more linear structure, comprising a relatively long backbone with short and few branches.
  • the classic textbook description of a PAO is a star-shaped molecule, and in particular tridecane, which is illustrated as three decane molecules attached at a central point. While an ideal star-shaped molecule is theoretical, nevertheless PAO molecules have fewer and longer branches than the hydrocarbon molecules that make up the base stock of the invention.
  • the molecular make up of a heavy hydrocarbon composition of the invention preferably comprises at least 95 wt% isoparaffins (with no more than 5 wt% saturated cyclics) having a relatively linear molecular structure, with less than half the branches having two or more carbon atoms and less than 25% of the total number of carbon atoms present in the branches.
  • more than half the branches contain two or more carbon atoms and more than 25% of the total number of carbon atoms are in the branches.
  • a lubricant base stock sometimes also referred to as a lubricating or lube oil base stock, including a heavy lubricant base stock, is an oil boiling in the lubricating oil range, having a lubricating quality and is useful for preparing various lubricants such as lubricating oils and greases.
  • the heavy hydrocarbon composition boils in the heavy lubricant oil range.
  • Fully formulated heavy lubricants or heavy lubricating oils are prepared by adding to the heavy lubricant base stock an effective amount of at least one additive or, more typically, an additive package containing more than one additive.
  • Illustrative, but non- limiting examples of such additives include one or more of a detergent, a dispersant, an antioxidant, an antiwear additive, an extreme pressure additive, a pour point depressant, a VI improver, a friction modifier, a demulsifier, an antioxidant, an antifoamant, a corrosion inhibitor, and a seal swell control additive.
  • a heavy hydrocarbon composition of the invention preferably comprises a dewaxed oil, and has low temperature properties able to meet target specifications or requirements and will be a clear and bright, oily liquid at the temperature and pressure conditions under which it is used. Typically, but not always, it will be an oily liquid at room temperature and pressure conditions of 75°F (24°C) and one atmosphere (101 kPa) pressure and is an oily liquid at this pressure and a temperature of 100°C. In some cases the cloud point may be higher than 75°F (24°C).
  • a heavy hydrocarbon composition of the invention, having an end boiling point above 1,250°F (677°C), with respective cloud and pour points of 1°C and -31°C, has been made according to the invention.
  • a heavy lubricant composition is prepared by forming a mixture of a heavy lubricant base stock of the invention and an effective amount of at least one additive or, more typically, an additive package containing more than one additive, as mentioned above.
  • the heavy lubricant base stock of the invention used in forming the mixture will typically have been mildly hydrofinished and/or dehazed after hydrodewaxing to improve its color, appearance and stability.
  • haze is cloudiness or a lack of clarity, and is an appearance factor. Dehazing is typically achieved by either catalytic or absorptive methods to remove those constituents that result in haziness. Hydrofinishing is a very mild, relatively cold hydrogenating process, which employs a catalyst, hydrogen and mild reaction conditions to remove trace amounts of heteroatom compounds, aromatics and olefins, to improve oxidation stability and color.
  • Hydrofinishing reaction conditions include a temperature of from 302 to 662°F (150 to 350°C) and preferably from 302 to 482°F (150 to 250°C), a total pressure of from 400 to 3000 psig (2859 to 20786 kPa), a liquid hourly space velocity ranging from 0.1 to 5 LHS V (hr " ) and preferably 0.5 to 3 hr " .
  • the hydrogen treat gas rate will range from 2550 to 10000 scf B (44.5 to 1780 m 3 /m 3 ).
  • the catalyst will comprise a support component and one or catalytic metal components of metal from Groups VIB (Mo, W, Cr) and/or iron group (Ni, Co) and noble metals (Pt, Pd) of Group VIII.
  • the metal or metals may be present from as little as 0.1 wt% for noble metals, to as high as 30 wt% of the catalyst composition for . non-noble metals.
  • Preferred support materials are low in acid and include, for example, amorphous or crystalline metal oxides such as alumina, silica, silica alumina and ultra large pore crystalline materials known as mesoporous - crystalline materials, of which MCM-41 is a preferred support component.
  • amorphous or crystalline metal oxides such as alumina, silica, silica alumina and ultra large pore crystalline materials known as mesoporous - crystalline materials, of which MCM-41 is a preferred support component.
  • MCM-41 is a preferred support component.
  • the preparation and use of MCM-41 is disclosed, for example, in U.S. patents 5,098,684, 5,227,353 and 5,573,657.
  • the waxy feed or Fischer-Tropsch wax comprises the waxy hydrocarbon fraction produced in a Fischer-Tropsch hydrocarbon synthesis reactor, which is liquid at the reaction conditions. It is referred to as wax, because it is solid at 75°F (24°C) and one atmosphere (101 kPa) pressure. It must contain sufficient waxy material boiling above 1000°F (538°C) to produce the heavy hydrocarbon composition of the invention.
  • the waxy feed is typically dewaxed in one or more catalytic dewaxing steps in which the feed is contacted with hydrogen and a dewaxing catalyst under dewaxing conditions.
  • the iso- to normal paraffin ratio is measured by performing GC-FID for a composition containing molecules with up to 20 carbon atoms and a combination of GC-FID with lj C-NMR for a composition containing molecules with > 20 carbon atoms.
  • Aromatics are determined by X-Ray Fluorescence (XRF), as described in ASTM Standard D-2622. Sulfur is measured by XRF as per ASTM standard D-2622 and nitrogen by syringe/inlet oxidative combustion with chemiluminescence detection per ASTM standard D-4629.
  • the catalyst useful in the hydrodewaxing step comprises a solid acid component, a hydrogenation component and a binder.
  • suitable catalyst components useful for hydrodewaxing include, for example, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ZSM-22 also known as theta one or TON, and the silica " aluminophosphates known as SAPO's (e.g., SAPO-11, 31 and 41), SSZ-32, zeolite beta, mordenite and rare earth ion exchanged ferrierite.
  • SAPO's e.g., SAPO-11, 31 and 41
  • SSZ-32 zeolite beta
  • mordenite and rare earth ion exchanged ferrierite also useful are alumina and amorphous silica aluminas.
  • a matrix material also known as a binder, which is resistant to the temperatures and other conditions employed in the dewaxing process herein.
  • matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides, e.g., alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides.
  • Use of a material in conjunction with the solid acid component, i.e., combined therewith, which is active, may enhance the conversion and/or selectivity of the catalyst herein.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate or reaction.
  • crystalline silicate materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin. These materials, i.e., clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength since in a petroleum refinery the catalyst is often subject to rough handling which tends to break the catalyst down into powderlike materials which cause problems in processing.
  • Naturally occurring clays which can be composited with the solid acid component include the montmorillonite and kaolin families which include the sub-bentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • the solid acid component can be composited with a porous matrix material such as silica-alumina, silica- magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the matrix can be in the form of a cogel. Mixtures of these components can also be used.
  • the relative proportions of finely divided solid acid component and inorganic oxide gel matrix vary widely with the crystalline silicate content ranging from about 1 to about 90 percent by weight, and more usually in the range of about 2 to about 80 percent by weight, of the composite.
  • ZSM-48 is preferably used.
  • the hydrogenation component will comprise at least one Group VIII metal component and preferably at least one noble Group VIII metal component, as in Pt and Pd.
  • Noble metal concentrations will range from about 0.1-5 wt% of the metal, and more typically from about 0.2-1 wt%, based on the total catalyst weight, including the ZSM-48 zeolite component and any binder used in the catalyst composite.
  • the Group VIII referred to herein refers to Group VIII as found in the Sargent- Welch Periodic Table of the Elements copyrighted in 1968 by the Sargent- Welch Scientific Company.
  • ZSM-48 ZSM-48 zeolites include EU-2, EU- 11 and ZBM-30 which are structurally equivalent
  • ZSM-48 zeolites include EU-2, EU- 11 and ZBM-30 which are structurally equivalent
  • Other hydrodewaxing catalysts useful in the practice of the invention include any of the well known catalysts that dewax mostly by isomerization and not by cracking or hydrocracking.
  • Zeolites comprising ten and twelve membered ring structures are useful as dewaxing catalysts, particularly when combined with a catalytic metal hydrogenating component.
  • Hydrodewaxing reaction conditions employed to produce a hydrocarbon or heavy lubricant composition of the invention include a respective temperature, hydrogen partial pressure and space velocity broadly ranging from 450-750°F (232-399°C), 10-2,000 psig (69-13790 kPa), and 0.1-5.0 LHSV. These conditions will more generally range from 500-700°F (260-371°C), 100-1000 psig (690-6895 kPa) and 0.5-3.0 LHSV, with a pressure of from 200-700 psig (1379-4827 kPa) more typical.
  • the wax feed comprised the entire 430°F+ (221 °C) waxy hydrocarbon fraction produced in a slurry Fischer-Tropsch hydrocarbon synthesis reactor, that contained a titania supported, rhenium-promoted, non- shifting cobalt hydrocarbon synthesis catalyst.
  • the wax comprised at least 90 wt% normal paraffinic hydrocarbons and 26.2 wt% of a 1000°F+ (538 °C) fraction. It was hydrodewaxed with hydrogen in the presence of a ZSM-48 hydrodewaxing catalyst with a Pt noble metal component to form an isomerate.
  • the isomerate was fractionated to remove the 700°F- (371°C-) hydrocarbons and the remaining 700°F+ (371°C+) fraction then fractionated to remove and recover a 950°F+ (510°C+) heavy lubricant isomerate fraction.
  • This heavy isomerate fraction was then further hydrodewaxed with hydrogen, over the same ZSM-48 hydrodewaxing catalyst in a separate reactor, to form heavy hydrocarbon compositions or heavy lubricant base stocks of the invention.
  • the hydrodewaxing conditions in the first and second reactors included respective temperatures of 586°F (308°C) and 616°F (324°C) and a low hydrogen pressure of 250 psi (1724 kPa). These compositions, the properties of which are shown in the Table, had kinematic viscosities of 13 and 15 cSt at 100°C.
  • the ZSM-48 hydrodewaxing catalyst in both reactors comprised 0.6 wt% Pt as the hydrogenating component, on a composite of the hydrogen form of a ZSM-48 zeolite and an alumina binder.
  • the hydrogen form of the ZSM-48 zeolite was prepared according to the procedure in U.S. patent 5,075,269, the disclosure of which is incorporated herein by reference.
  • the Pt compo ⁇ ent was added by impregnation, followed by calcining and reduction, using known procedures.
  • the wax feed was Paraflint C-80, a commercally available, hydrotreated Fischer-Tropsch wax produced by Sasol in a fixed bed Fischer-Tropsch reactor from a shifting iron catalyst.
  • the untreated raw wax contains relatively high levels of aromatic and aliphatic unsaturates, and heteroatom compounds, which is hydrotreated to produce the Paraflint C-80 wax.
  • This solid wax is a distillate fraction having a viscosity ranging from 6-10 cSt at 100°C and a nominal T5 boiling point of about 850°F (454°C).
  • Example 2 This run was similar to that of Example 1 , except that the nominally 700-950°F (371-510°C) isomerate was then further hydrodewaxed with hydrogen, over the same ZSM-48 hydrodewaxing catalyst in a separate reactor, to form a composition not of the invention, which had a viscosity of 4 cSt at 100°C.
  • Proton NMR analysis of the samples was performed in a 5 mm switchable probe, with approximately 80 mg samples dissolved in 1 gm chloroform-d. Sample preparation and data acquisition were performed at 50°C on a Varian Unity 1 Plus 500. Free induction decays of 64 coaveraged transients were acquired, employing a 90° excitation pulse, a relaxation decay of 8.4 seconds, and an acquisition time of 3.2 seconds. No relaxation agent was used in the proton NMR.
  • the Figure is a graph plotting the BI and % CH 2 >4 values derived from NMR spectra of the heavy hydrocarbon compositions of the invention, the comparative examples of this application, and the data of U.S. Patent 6,090,989 which includes other hydrocarbon compositions.
  • the disclosure of U.S. patent 6,090,989 is incorporated herein in its entirety by reference.
  • the shaded area on the plot defines the NMR parameter space of the heavy hydrocarbon compositions of the invention.
  • the molecular composition of the PAO stocks are different from the heavy hydrocarbon compositions of the invention in that (i) they do not contain hydrocarbon molecules having consecutive numbers of carbon atoms, (ii) the percentage of hydrogen atoms from CH 3 groups on the molecules is below 15, whereas those for the composition of the invention are typically above 20, (ii) the percentage of hydrogens from CH groups for the PAO stocks is above 3, whereas for the compositions of the invention it is typically less than 2.

Abstract

L'invention concerne un composition d'hydrocarbures lourds utilisée comme huile de base pour lubrifiants lourds, comprenant au moins 95 % en poids de molécules de paraffine, dont au moins 90 % en poids sont des molécules d'hydrocarbures isoparaffiniques, présentant des nombres d'atomes de carbone consécutifs. Ladite composition est liquide à 100 °C, température à laquelle sa viscosité cinématique, mesurée selon ASTM D-445, est supérieure à 8 cSt. Ladite composition présente un point initial d'ébullition d'au moins 850 °F (454 °C) et un point final d'ébullition d'au moins 1000 °F (538 °C). L'indice de ramification (BI), mesuré au moyen du pourcentage de méthylhydrogènes, et la proximité de ramifications (CH2>4) desdites molécules d'hydrocarbures isoparaffiniques, mesurée au moyen du pourcentage de carbones de méthylène récurrents qui constituent au moins quatre atomes de carbone retirés d'une ramification ou d'un groupe terminal, sont tels que: (a) BI-0,5(CH2>4)<15; et (b) BI + 0,85(CH2>4)<45; mesuré par rapport à la totalité de la composition d'hydrocarbures lourds.
EP03770718A 2002-10-08 2003-10-07 Composition d'hydrocarbures lourds utilisee comme huile de base pour lubrifiants lourds Withdrawn EP1558711A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US10/266,344 US6846778B2 (en) 2002-10-08 2002-10-08 Synthetic isoparaffinic premium heavy lubricant base stock
US266344 2002-10-08
US10/652,389 US7241375B2 (en) 2002-10-08 2003-08-29 Heavy hydrocarbon composition with utility as a heavy lubricant base stock
US652389 2003-08-29
PCT/US2003/032097 WO2004033607A1 (fr) 2002-10-08 2003-10-07 Composition d'hydrocarbures lourds utilisee comme huile de base pour lubrifiants lourds

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EP1881758B1 (fr) * 2005-05-20 2014-08-13 Shell Internationale Research Maatschappij B.V. Composition d'huile blanche obtenue par le procede fischer-tropsch et d'engrais
EP2038383A1 (fr) * 2006-07-12 2009-03-25 Shell Internationale Research Maatschappij B.V. Ensemble combiné lubrifiant et carburant utilisé dans un moteur à combustion interne
US20110290702A1 (en) * 2007-08-13 2011-12-01 Gilbert Robert Bernard Germaine Lubricating base oil blend
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CN101998986B (zh) 2007-12-20 2014-12-10 国际壳牌研究有限公司 燃料组合物
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EP2864456B1 (fr) 2012-06-21 2018-10-31 Shell International Research Maatschappij B.V. Compositions lubrifiantes à base d'huiles de fischer-tropsch lourdes et d'huiles aromatiques alkylées
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US6080301A (en) * 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
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BR0315011A (pt) 2005-08-09
NO20051775D0 (no) 2005-04-11
NO20051775L (no) 2005-04-11
CA2499405A1 (fr) 2004-04-22
KR20050070045A (ko) 2005-07-05

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