WO2006047091A2 - Detergents de carburant et d'huile - Google Patents

Detergents de carburant et d'huile Download PDF

Info

Publication number
WO2006047091A2
WO2006047091A2 PCT/US2005/036684 US2005036684W WO2006047091A2 WO 2006047091 A2 WO2006047091 A2 WO 2006047091A2 US 2005036684 W US2005036684 W US 2005036684W WO 2006047091 A2 WO2006047091 A2 WO 2006047091A2
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
group
alkylbenzene
alkylbenzenes
weight
Prior art date
Application number
PCT/US2005/036684
Other languages
English (en)
Other versions
WO2006047091A3 (fr
Inventor
Daniel R. Weaver
Daniel Szura
Christopher J. Whewell
Original Assignee
Huntsman Petrochemical Corporation
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 Huntsman Petrochemical Corporation filed Critical Huntsman Petrochemical Corporation
Priority to CA002584152A priority Critical patent/CA2584152A1/fr
Priority to US11/666,258 priority patent/US20080064616A1/en
Priority to EP05813032A priority patent/EP1805282A4/fr
Publication of WO2006047091A2 publication Critical patent/WO2006047091A2/fr
Publication of WO2006047091A3 publication Critical patent/WO2006047091A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10M127/06—Alkylated aromatic hydrocarbons
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M2203/06—Well-defined aromatic compounds
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to a oil-soluble compositions of matter useful as detergent components in hydrocarbon oils useful for a wide range of purposes, including without limitation general lubricants, lubricating oils for internal combustion engines, cutting fluids, emulsions, and dispersions. More particularly, the invention relates to oil-soluble alkylbenzenes comprising alkyl chains having between about 16 and 30 carbon atoms in which the alkylbenzenes have a low dialkylate content and unique isomer distribution, including their sulfonate and other water-soluble and solubilizable derivatives.
  • linear alkylbenzenes are produced by an alkylation reaction (according to one of any well known processes for producing such materials) in which the net result is the appendage of a hydrocarbyl radical to a benzene ring.
  • the source of the hydrocarbyl radical may be a branched or a linear olefin, either an internal olefin or an alpha olefin, and in practice a mixture of substantially linear olefins is typically used, which mixture comprises various olefins having different numbers of carbon atoms per molecule.
  • the range of carbon numbers (the number of carbon atoms per molecule of an olefin used) of an olefin mixture used in the alkylation reaction is typically in the range of between about 8 and 15 (inclusive) carbon atoms per molecule, which molecules are sometimes collectively referred to by those in the art as the "detergent range”.
  • this increased exposure provides increased availability for interaction with hydrophobic materials which are sought to be solubilized in an aqueous medium, when the alkylbenzene also includes a hydrophilic moiety, such as a sulfonate group bonded to the benzene ring.
  • Detergents useful as components in hydrocarbon oils are often possessive in general of the same properties as detergents useful in aqueous media, that is, their molecules contain both a hydrophilic and a hydrophobic portion.
  • alkylbenzenes having longer hydrocarbon chains on the benzene ring than those found in conventional detergents, for example to enhance solubility in hydrocarbon oils, or to provide increased compatibility and chemical inertness with respect to other components of the formulation, depending upon the intended use.
  • LAB linear alkylbenzene
  • the present invention employs hydrogen fluoride as a catalyst in the production of long-tail linear alkylbenzenes.
  • the processing conditions used in preparing the materials of this invention may in one form of the invention provide essentially any desired percentage content of 2-phenyl isomer in the range of about 8 to about 27 % (on a weight basis) in the finished product by adjusting the processing parameters, hi this way, LAB may be produced having any desired 2-phenyl isomer content in the range of about 10 % to 13% by weight based on the total weight of the alkylbenzene.
  • This invention in one broad respect, is a process for the production of linear
  • alkylbenzenes which comprises contacting benzene and an olefin having about 8 to about 30 carbons in the presence of an effective catalytic amount of hydrogen fluoride to form linear alkylbenzenes, wherein the isomerization of the olefins is conducted in the same process step as the alkylation of benzene
  • this invention is a process for the production of oil-soluble alkylbenzene sulfonates suitable for use in fluids used in the transportation industry, including without limitation, additives for passenger car engine oils, additives for diesel engine oils, driveline lubricants, transmission fluids, or any other application in which an oil-soluble sulfonate salt or an overbased sulfonate confers a beneficial property to the performance of the lubricant.
  • the alkylbenzenes within the prior art which are sold as a raw material from which overbased sulfonates may be prepared all contain benzene at a level of between about 3 and 10 parts per million. Benzene is notorious for causing leukemia.
  • the present invention provides alkylbenzenes from which overbased alkaline earth metal sulfonates may be prepared in which benzene is present at a level of less than 100 parts per billion.
  • the materials of the prior art all contain significant levels of 1 -phenyl (1-aryl) isomer. According to this invention, the 1 -phenyl (1-aryl) content is negligible, being less than 0.3 % by weight based on the total weight of all alkylaryl isomers present in a mixture of the invention.
  • the present invention provides a process for production of alkylaromatic compounds which comprises the steps of: a) co-mingling linear alpha olefins, having 16 to 40 carbon atoms per molecule, with a non-reactive diluent, such as normal or branched paraffin to form a mixture of alpha olefins and paraffins; b) feeding the mixture of alpha olefins and paraffins into a reaction zone along with a feed aromatic hydrocarbon and liquid hydrogen fluoride, under alkylation- promoting conditions, to produce an effluent stream containing the feed aromatic hydrocarbon, hydrogen fluoride, paraffin, and alkylaromatic hydrocarbon product; c) separating substantially all of the hydrocarbon mixture in the reaction zone effluent stream from the liquid phase hydrogen fluoride present in the effluent stream; and d) and recovering the product alkylaromatic hydrocarbon.
  • the product alkylaromatic hydrocarbon is conveniently recovered by a series of steps involving passage of the hydrocarbon mixture through a plurality of stripping columns to remove the feed aromatic hydrocarbon and paraffin diluent components.
  • the alkylaromatic product is recovered as a net bottom stream.
  • a process for producing an alkylaromatic hydrocarbon which comprises the steps of: a) dehydrogenating a paraffin to form an olefin; b) sending a feed stream of benzene and the olefin through a conduit to a linear alkylbenzenes alkylation reactor containing hydrogen fluoride under conditions which enable isomerization of the olefin to occur simultaneously with alkylation of benzene by the olefin, to form a crude linear alkylbenzenes stream; c) distilling the crude linear alkylbenzenes stream in a first distillation column to separate benzene that did not react and to form a benzene-free linear alkylbenzenes
  • Conv and “Conversion” mean the mole percentage of a given reactant converted to product. Generally, olefin conversion is about 95 percent or more in the practice of this ⁇
  • “SeI.” and “Selectivity” mean the mole percentage of a particular component in the product. Generally, selectivity to the 2-phenyl isomer is about 70 % or more in the practice of this invention.
  • "LAB” means a mixture linear alkylbenzenes which comprises a benzene ring appended to any carbon atom of a substantially linear alkyl chain having any number of carbon atoms in the range of 16 to 30, inclusive.
  • Hydrogen fluoride is useful as a catalyst useful in the production of LAB's in accordance with the process of manufacturing LAB's of this invention.
  • LAB is useful as starting material to produce sulfonated LAB, which is useful as a surfactant.
  • LAB sulfonates means LAB which has been sulfonated to include an acidic sulfonate group appended to the benzene ring (thus forming a "parent acid”), and subsequently rendered to a form more soluble to aqueous solution than the parent acid by neutralization using any of alkali metal hydroxides, alkaline earth hydroxides, ammonium hydroxides, allcylammonium hydroxides, or any chemical agent known by those skilled in the art to react with linear alkylbenzene sulfonic acids to form water-soluble LAB sulfonates.
  • Detergent range means an olefin, alkyl group, or molecular species (including without limitation LAB, LAB sulfonates, and overbased LAB sulfonates) that comprises any number of carbon atoms selected from: 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, as warranted by the context, including mixtures of two or more such species having different numbers of carbon atoms appended to the aromatic ring.
  • Substantially linear when referring to a hydrocarbon or alkyl chain that is part of an alkylbenzene, whether the alkylbenzene is sulfonated or not, means a hydrocarbon comprising between 16 and 30 carbon atoms linked to one another to form a straight chain, wherein the carbon atoms of said straight chain may have only hydrogen atoms or a methyl group bonded to them as appendages.
  • Branched alkyl when referring to a hydrocarbon or alkyl chain that is part of an alkylbenzene, whether the alkylbenzene is sulfonated or not, means a hydrocarbon comprising between 16 and 30 carbon atoms linked to one another to form a straight chain, wherein one or more of the carbon atoms of said straight chain may have a hydrogen atom and any alkyl group other than a methyl group (including without limitation ethyl groups), bonded to them as appendages.
  • Branched alkylbenzene means a molecular species which comprises a branched alkyl chain appended to a benzene ring.
  • Branched alkylbenzene sulfonate means a water-soluble salt of a branched alkylbenzene that has been sulfonated.
  • 2-phenyl alkylbenzenes means a benzene ring having at least one alkyl group attached to it, wherein the alkyl group comprises any number of carbon atoms between 16
  • the 2-phenyl isomer of substantially linear LAB produced in accordance with this invention is of the formula:
  • n is any integer between about 12 and about 30;
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of: hydrogen, a methyl group, an ethyl group, a propyl group, and a butyl group;
  • B is selected from the group consisting of: hydrogen, methyl, or ethyl;
  • B is attached to any single carbon atom along the -(CEb) n - portion of the alkyl chain;
  • the total 2-aryl isomer content of said mixture of alkylbenzenes is between about 8 % and about 30 % by weight based on the total weight of all alkylbenzenes present in said mixture and in which the 1-aryl isomer content is less than about 3 % by weight based on the weight of all isomers of alkylbenzene derivatives present.
  • Alkylbenzenes means all species containing an alkyl group, whether linear or branched, appended to a benzene ring. Within this definition are also embraced monoalkyltoluenes, monoalkylxylenes, alkylethylbenzenes, etc.
  • Sulfonated 2-phenyl alkylbenzenes means 2-phenyl alkylbenzenes as defined above which further comprise a sulfonate group attached to the benzene ring of a 2-aryl alkylbenzene, regardless of the position of the sulfonate group on the ring with respect to the location of the alkyl group.
  • the sulfonate group it is typical, though not always the case ( as in ortho isomers invariably present) for the sulfonate group to appear in the position R 3 above with respect to a single alkyl group attached to the benzene ring, as shown in the following structure:
  • R 1 , R 2 , R 4 , and R 5 are each independently selected from the group consisting of: hydrogen, a methyl group, an ethyl group, a propyl group, and a butyl group; B is selected from the group consisting of:
  • the total 2-aryl isomer content of said mixture of alkylbenzenes is between about 8 % and about 30 % by weight based on the total weight of all alkylbenzenes present in said mixture and in which the 1-aryl isomer content is less than about 3 % by weight based on the weight of all isomers of alkylbenzene derivatives present.
  • “Motor fuel” means those compositions generally recognized by those in the art as liquid hydrocarbon fuels in the gasoline boiling range, including hydrocarbon base fuels. Within the meaning of this term is included those fuels often termed as “petroleum distillate fuels" by those in the art and which have the above characteristic boiling points.
  • the term is, however, not intended to be restricted to straight-run distillate fractions.
  • the distillate fuel can be straight-run distillate fuel, catalytically or thermally cracked (including hydrocracked) distillate fuel, or a mixture of straight-run distillate fuel, naphthas and the like with cracked distillate stocks.
  • the base fuels used in the formulations of the fuel compositions of the present invention can be treated in accordance with well-known commercial methods such as acid or caustic treatments, hydrogen solvent refining, clay treatment, etc. Gasolines are supplied in a number of different grades depending upon the type of service for which they are intended.
  • the gasolines useful in the present invention include those designed as motor and aviation gasolines.
  • Motor gasolines include those defined by ASTM specification D-439-73 and are composed of a mixture of various types of hydrocarbons including aromatics, olefins, paraffins, isoparaffins, naphthalenes, and occasionally diolefins. Motor gasolines normally have a boiling range within the limits of about 20 degrees C to about 230 degrees C, while aviation gasolines have narrower boiling ranges, usually within the limits of about 37 degrees C. to 165 degrees C. Also within this definition are the kerosene range fuels, which include diesel fuels and jet fuel.
  • Base Number or "BN” refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher BN numbers reflect more alkaline products, and therefore a greater alkalinity reserve.
  • the BN of a sample can be determined by ASTM Test No. D2896 or any other equivalent procedure.
  • FIG. 1 shows a representation of a first continuous reactive distillation column employed in the practice of this invention.
  • FIG. 2 shows a representation of a second continuous reactive distillation column employed in the practice of this invention.
  • FIG. 3 shows a representative process scheme for one embodiment of this invention where a fluorine-containing mordenite is employed with a second, solid catalyst to achieve variable 2-phenyl isomer content depending on the relative proportions of the two catalysts.
  • benzene or a substituted benzene such as toluene, ethylbenzene, propylbenzene, butylbenzene, or one or more xylenes is alkylated with an olefinic material to form LAB.
  • Olefins and benzene can be handled and purified using standard techniques recognized by those of ordinary skill in the art. In this regard, it is preferred that the reactants are substantially free from hydric compounds such as water and alcohols, etc.
  • the olefins employed in the practice of this invention have from about 16 to about 30 carbons per molecule, and in one form of the invention preferably from about 20 to about 24 carbon atoms.
  • the olefinic material be a mono-olefin. It is most preferred that the mono-olefin be an alpha-olefin, in which the double bond is located in a terminal ethylenic unit; however, internal olefins are suitable as well, since they are isomerized in the same step as the alkylation, in one preferred form of the invention.
  • olefins would be available from a paraff ⁇ nic media of the same carbon range.
  • One route by which olefins in the 16 to 30 carbon number range are available is from dehydrogenating a mixture of paraffins in the same carbon number range, namely C -16 to C- 30 paraffins. Such dehydrogenation may be carried out even if such a paraffin mixture has any appreciable olefin content, for example, an olefin content in the range of about 5 to 20%. It is especially preferred to carry out such a process using our catalyst and processes as described in US Patents 6,417,135 and 6,700,028 , both of which are fully incorporated herein by reference thereto.
  • FIG. 1 a feed mixture of benzene and olefin, generally at a benzene-to-olefin molar ratio range of about 1:1 to 100:1 flows from feed pump 10 to feed inlet 14 via line 12.
  • the feed mixture falls to a region containing hydrogen fluoride gas 32 where alkylation and isomerization occurs.
  • FIG. 1 Alternatively, while not depicted in FIG.
  • the benzene and olefin can be introduced separately into the zone with mixing occurring in the HF zone, or the reactants can be mixed via an in-line mixer prior to introducing the reactants into the catalyst zone, or the reactants can be injected separately above the HF zone with mixing affected by use of standard packing above the zone, or the reactants can be sparged into the chamber above the zone.
  • the falling feed mixture also contacts rising vapors of unreacted benzene which has been heated to reflux in reboiler 42 by heater 40. Such rising vapors pass over thermocouple 38 which monitors temperature to provide feedback to heater 40.
  • the rising vapors of benzene and/or olefin also pass through standard packing 36 (e.g., 7.5 inches of goodloe packing).
  • the rising vapors heat thermocouple 30 which connects to bottoms temperature controller 28 which activates heater 40 when temperature drops below a set level.
  • the system may be flushed with nitrogen which enters via line 54 and which flows through line 58. After startup, a nitrogen blanket is maintained over the system. Also prior to startup and during nitrogen flush, it may be desirable to heat catalyst zone 32 so as to drive off water.
  • HF gas may be admitted to line 54.
  • Residual water from the feed mixture or which otherwise enters the system is collected in water trap 24 upon being liquefied at condenser 21 (along with benzene vapor). If the feed is very dry (free of water) the water trap 24 may not be needed. Removing water leads to better product quality. Hence, the water trap 24 is optional. The same applies to
  • Condenser 21 is cooled via coolant such as water entering condenser 21 via port 22 and exiting via port 20. As needed, water in water trap 24 may be drained by opening drain valve 26.
  • the bottoms LAB product may be removed from the system via line 47, using either gravity or bottoms pump 48 to withdraw the product.
  • valve 44 is opened.
  • dip tube 46 which is optional, is employed to slightly increase the pressure in reboiler 42 to thereby raise the boiling point of benzene a degree or two.
  • a pressure generator 56 may be optionally employed to raise the pressure of the system.
  • Other standard pressure increasing devices can be employed. Pressure can thus be increased in the
  • control mechanisms for heat shutoff 50 and pump shutoff 52 are depicted which serve to shut off heat and pump if the liquids level in the system rises to such levels. These control mechanisms are optional and may be included so that the catalyst zone does not come into contact with the bottoms of the reboiler.
  • the temperature in the catalyst zone may vary depending on reactants, rate of introduction into the catalyst zone, size of the catalyst zone, and so forth. Generally, the zone is maintained at the reflux temperature of benzene
  • the temperature of the catalyst zone is above about 70 ° C,
  • the temperature is in the range from about 80 ° C to about
  • the process may be operated at a variety of pressures during the contact of HF with the reactants, with pressures of about atmospheric most typically being employed.
  • the reboiler temperature is maintained such that benzene and olefin vaporize, the temperature varying depending on
  • olefin and generally being from about 80 ° C to about 250 0 C for olefins having 16 to 24 carbons.
  • the composition of the reboiler will vary over time, but is generally set initially to have a benzene olefin ratio of about 10:1, with this ratio being maintained during the practice
  • the rate of introduction of feed into the catalyst zone may vary, and is generally at a liquid hourly space velocity ("LHSV") of about 0.05 lir "1 to about 10 hr "1 , more typically from about 0.05 hr "1 to about 1 hr "1 .
  • LHSV liquid hourly space velocity
  • the mole ratio of benzene to olefin introduced into the catalyst zone is generally from about 1 : 1 to about 100: 1. In commercial benzene alkylation operations, it is common to run at mole ratios of from about 2:1 to about 20:1, which can suitably be employed in the practice of this invention, and to charge said olefins as an olefin-paraffin mixture comprising 5% to 20% olefin content.
  • FIG.2 Another continuous reactive distillation apparatus is depicted in FIG.2. m FIG.2, the feed mixture enters the reactor via feed inlet 114. The feed mixture falls through the column into catalyst zone 132, wherein alkylation to form LAB occurs. A thermowell 133 monitors the temperature of said catalyst zone 132. The catalyst zone 132 may be optionally heated externally and is contained within 1-1/4 inch stainless steel tubing. Goodloe packing is positioned at packing 136 and 137. LAB product, as well as unreacted benzene and olefin, fall through packing 136 into reboiler 142.
  • reboiler 142 electric heater 140 heats the contents of reboiler 142 such that heated vapors of benzene and olefin rise from the reboiler 142 to at least reach catalyst zone 132.
  • the bottoms LAB product may be removed from reboiler 142 by opening bottoms valve 144 after passing through line 147 and filter 145.
  • Residual water from the feed mixture, or which otherwise enters the system may be condensed at condenser 121 which is cooled with coolant via inlet line 122 and exit line 120. The condensed water falls to water trap 124, which can be drained as needed by opening drain valve 126.
  • Temperature in the system is monitored via thermocouples 138, 130, and 165.
  • the system includes pressure release valve 166.
  • a nitrogen blanket over the system is maintained by introduction of nitrogen gas via inlet line 154.
  • Level control activator 150 activates bottoms level control valve 151 to open when the liquids level in the reboiler rises to the level control activator 150.
  • FIG. 1 and FIG.2 show single catalyst zone systems, it must be appreciated that multi-catalyst zone reactors are within the scope of this invention, as well as multiple ports for inlet feeds, water traps, product removal lines, and so forth. Moreover, the process may be run in batch mode, or in other continuous processes using plugflow designs, trickle zone designs, and fluidized zone designs.
  • the selectivity to the 2-isomer is less than for lower molecular weight olefins. It is thus preferred, although not absolutely necessary, that the product of the alkylation using HF is sent to a second, finishing catalyst zone to improve yield.
  • a second catalyst is HF-treated clay such as montmorillonite clay treated in accordance with the invention to have about 0.5% fluoride and calcined as stated in Huntsman's earlier US Patent 6,630,430 which is fully incorporated herein by reference.
  • FIG.3 The scheme of FIG.3 is shown in the context of LAB alkylation based on a feed from a paraffin dehydrogenation facility.
  • fresh paraffin is fed to a conventional dehydrogenation apparatus 210 via line 211, with recycled paraffin being introduced from the paraffin column 250 via line 252.
  • Dehydrogenated paraffin from the dehydrogenation apparatus 210 is then pumped into an alkylation reactor (or reactors) 230 that contains hydrogen fluoride.
  • the dehydrogenated paraffin feed may of course be supplied from any provider.
  • the source of dehydrogenated paraffin (olefin) is not critical to the practice of this invention.
  • LAB product from alkylation unit 230 may thereafter be purified by a series of distillation towers.
  • alkylation effluent may be delivered to a benzene column 240 by way of line 231.
  • the alkylation product may be sent offsite for purification.
  • the particular purification scheme used is not critical to the practice of this invention.
  • the scheme depicted in FIG.3 is instead representative of a typical commercial operation.
  • unreacted benzene is distilled off from the crude LAB product.
  • Benzene is then recycled to the alkylation reactor 230.
  • the benzene-free LAB crude product from the benzene column 240 is pumped through line 241 to paraffin column 250 where any paraffin present is distilled off, with the distilled paraffin being recycled to paraffin dehydrogenation unit 210 via line 252.
  • Paraffin-free crude LAB from the paraffin column 250 is transported to a refining column 260 where purified LAB is distilled and removed via line 262. Heavies (e.g., dialkylates and olefin derivatives) are withdrawn from refining column 260 via conduit 261.
  • Heavies e.g., dialkylates and olefin derivatives
  • columns 240, 250, and 260 may be maintained at conditions (e.g., pressure and temperature) well known to those of skill in the art and may be packed with conventional materials, if desired.
  • Hydrocarbon and other base oils such as the vegetable oils are known to be rarely used in their pure forms in any application, but rather contain various chemical additives designed to increase the performance of such oils, or to extend the useful lives of either the oils themselves or the equipment in which they are designed to function.
  • the prior art teaches the use of various oil additives which include without limitation: detergents, dispersants, anti-wear agents, extreme pressure additives, antioxidants, corrosion inhibitors, viscosity modifiers, pour point depressants, antifoam agents, Motion modifiers, metal deactivators, water scavengers, free radical scavengers, and compatibilizers.
  • various oil additives include without limitation: detergents, dispersants, anti-wear agents, extreme pressure additives, antioxidants, corrosion inhibitors, viscosity modifiers, pour point depressants, antifoam agents, Motion modifiers, metal deactivators, water scavengers, free radical scavengers, and compatibilizers.
  • substituted benzenes are also useful as starting materials within the context of the present invention, provided that the chemical groups appended to the benzene ring are not prohibitively de-activating of the benzene ring structure, hi this regard, toluene is a functionally equivalent starting material which may be used in place of all or part of the benzene employed.
  • substituted benzenes such as xylenes are also useful in this regard, as well as ethylbenzene, propylbenzene, and butylbenzene.
  • reaction product consists predominantly of para-substituted reaction products, with some ortho substitution. Subsequent sulfonation of such a mixture to provide sulfonate derivatives results in a mixture of sulfonates or their salts or esters as well.
  • n is any integer between about 12 and about 30;
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of: hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a sulfonic acid group, an sulfonate group, and salts and esters thereof;
  • B is selected from the group consisting of: hydrogen, methyl, or ethyl; B is attached to any single carbon atom along the -(CH 2 ) n - portion of the alkyl chain; and the total 2-aryl isomer content of said mixture of alkylbenzenes is between about 8 % and about 30 % by weight based on the total weight of all alkylbenzenes present in said mixture and in which the 1-aryl isomer content is less than about 3 % by weight based on the weight of all isomers of alkylbenzene derivatives present.
  • One popular class of detergents used in lubricating oils, cutting fluids, and the like are the oil soluble sulfonates. Within this broad class are the aromatic sulfonates of the type described in this specification, particularly the LAB sulfonates. These materials are preferred because of their effectiveness and compatibility with other components found in finished oil products, their widespread availability, and relatively low cost. Additionally, many of these detergent materials are anionic in nature, which means that any one of a wide range of selected cationic species may accompany the anionic detergent, which is of particular benefit when it is desired to incorporate other metals into the composition. The most commonly used salts of these acids in hydrocarbon oils are the sodium, potassium, lithium, calcium, magnesium, strontium and barium salts.
  • the “basic salts” are those metal salts known to the art wherein the metal is present in a stoichiometrically larger amount than that necessary to neutralize the acid.
  • the calcium- and barium-overbased petrosulfonic acids are typical examples of such basic salts.
  • the terms "overbased,” “superbased,” and “hyperbased,” are terms of art which are generic to well known classes of the metallic sulfonates and other materials. These overbased materials have also been referred to as “complexes,” “metal complexes,” “high- metal containing salts,” and the like.
  • Overbased materials are characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular organic compound reacted with the metal, e.g., a sulfonic acid.
  • a monosulfonic acid such as an LAB sulfonate
  • a basic metal compound e.g., calcium hydroxide
  • the "normal" metal salt produced will contain one equivalent of calcium for each equivalent of acid.
  • various processes are available which result in an inert organic liquid solution of a product containing more than the stoichiometric amount of metal. The solutions of these products are referred to herein as overbased materials.
  • the sulfonic acid or an alkali or alkaline earth metal salt thereof can be reacted with a metal base and the product will contain an amount of metal in excess of that necessary to neutralize the acid, for example, 4.5 times as much metal as present in the normal salt or a metal excess of 3.5 equivalents.
  • the actual stoichiometric excess of metal can vary considerably, for example, from about 0.1 equivalent to about 30 or more equivalents depending on the
  • overbased materials useful in preparing the disperse systems will contain from about 3.5 to about 30 or more equivalents of metal for each equivalent of material which is overbased.
  • overbased is used to designate materials containing a stoichiometric excess of metal and is, therefore, inclusive of those materials which have been referred to in the art as overbased, superbased, hyperbased, etc., as discussed supra.
  • the present invention thus provides LAB from which LAB sulfonates may be prepared via conventional sulfonation techniques, and from which may further be prepared overbased sulfonates, using techniques known to those skilled in the art.
  • the overbased materials are prepared by treating a reaction mixture comprising the organic material to be overbased, a reaction medium consisting essentially of at least one inert, organic solvent for said organic material, a stoichiometric excess of a metal base, and a promoter with an acidic material.
  • a reaction mixture comprising the organic material to be overbased, a reaction medium consisting essentially of at least one inert, organic solvent for said organic material, a stoichiometric excess of a metal base, and a promoter with an acidic material.
  • U.S. Pat. No. 4,086,170 (De Clippeleir et al, Apr. 25, 1978) relates to calcium sulfonates and concentrated oily solutions thereof that are prepared by reacting a solution of alkylbenzene sulfonic acids with an excess of a calcium oxide having a medium or low activity towards water and with carbon dioxide. Oily solutions of overbased calcium sulfonate obtained from such a calcium oxide are limpid and filterable.
  • U.S. Pat. No. 4,604,219 (Whittle, Aug.
  • alkaline earth calcium sulfonates that are derived from natural or synthetic feedstocks or a mixture of both which can be overbased by introducing into a mixture comprising a neutral alkaline earth calcium sulfonate, a lower alcohol, a light hydrocarbon diluent carbon dioxide and water.
  • the water is introduced continuously and at a uniform rate over 1-4 hours, preferably 1-3 hours into the heated mixture with carbon dioxide.
  • Water is added in a molar ratio water/calcium oxide of 0.1 to 1.2 preferably 0.4 to 0.8. It has been found that both the water rate and amount are critical.
  • 4,954,272 (Jao, et al., Sep. 4, 1990) is directed to a process for producing an overbased oil soluble calcium sulfonate having a TBN of 325, said process comprising: (a) diluting a neutral calcium sulfonate with a hydrocarbon solvent and a lower alkanol; (b) adding to the diluted calcium sulfonate solution, CaO, Ca(OH). sub.2 and H 2 O in molar ratios of CaO : Ca(OH) 2 of about 90:10 to about 20:80 and of H 2 O:CaO of about 0.15:1 to about 0.30: 1; (c) heating the sulfonate mixture to a temperature ranging from about 100. degree. F.
  • a dispersant used in a hydrocarbon oil may be a multifunctional material that can confer other beneficial properties to a base oil
  • dispersants are primarily used in hydrocarbon oils for their ability to maintain small particles of dirt, combustion products, metal fines, etc. in the liquid phase, to prevent deposition and accumulation of sludges in places where eddy currents exist in various equipment and wares.
  • acylated nitrogen compounds as dispersants in lubricants is disclosed in
  • Ashless detergents and dispersants are so called despite the fact that, depending on
  • the dispersant may upon combustion yield a non- volatile material such as
  • boric oxide or phosphorus pentoxide does not ordinarily contain metal
  • Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)- substituted acrylates.
  • polar substituents e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)- substituted acrylates.
  • a composition according to this invention may also include a sulfur-, phosphorus-, or sulfur- and phosphorus-containing antiwear agent.
  • antiwear agent is used to refer to compounds which provide wear protection properties to lubricating compositions and functional fluids. Antiwear agents are useful in controlling wear and may sometimes also act as extreme pressure agents and as antioxidants. These antiwear agents include sulfurized organic compounds, hydrocarbyl phosphates, phosphorus-containing amides, phosphorus-containing carboxylic esters, phosphorus-containing ethers, and dithiocarbamate-containing compounds. Examples of hydrocarbyl phosphates include hydrocarbyl thiophosphates. Thiophosphates may contain from one to about three sulfur atoms, preferably one or two sulfur atoms.
  • Thiophosphates are prepared by reacting one or more phosphites with a sulfurizing agent including sulfur, sulfur halides, and sulfur containing compounds. Salts of thiophosphates include zinc dithiophosphates. Other antiwear agents known to those skilled in the art are useful as a component of a composition according to the invention. Other dispersants known to those skilled in the art are useful as a component of a composition according to the invention.
  • Anti-Oxidants A particularly valuable class of additives known as antioxidants are widely used in lubricating oil formulations, cutting oils, and functional fluids. Antioxidants are materials which inhibit oxidative decomposition of the oil under consideration. Although several examples are given below, these examples should be considered exemplary only of the wide variety of antioxidants which may be usefully combined with the detergent
  • Holtschmitt shows his compounds as containing free hydroxyl groups. Holtschmitt further discloses the use of aromatic amines containing a short aliphatic group on the aromatic ring, e.g. toluidine.
  • the alkyl phenothiazines of Cyphers are alkylated on the phenylene rings of the phenothiazine structure. Cyphers does not show or suggest the alkylation of the amine nitrogen in phenothiazine.
  • the Cyphers patent is directed to the utility of phenothiazine as an antioxidant and corrosion inhibiting additive for ester, polyester, polyether and other synthetic lubricants.
  • Cook et al also suggest that organic materials which are susceptible to oxidative degradation may benefit through the use of the compounds of their invention. Such uses include antioxidants for aliphatic hydrocarbons such as gasoline, lubricating oils, lubricating greases, mineral oils, waxes, natural and synthetic polymers such as rubber, vinyl, vinylidene, ethers, esters, amides and urethanes.
  • the compounds of Cook et al are also suggested for stabilizing aldehydes and unsaturated fatty acids or esters thereof. Still further utilities suggested by Cook et al include the stabilization of organo-metalloid substances such as silicone polymers.
  • Another class of uses of the compounds of Cook et al include the stabilization of vitamins, essential oils, ketones and ethers.
  • Waight et al describes antioxidants for ester-based lubricants.
  • Waight et al's compounds have an N-hydrocarbyl substituted phenothiazine structure.
  • the N- substituted phenothiazine compounds of Waight et al are also substituted in at least one position on the fused aromatic nuclei.
  • a second required component in the compositions of Waight et al is a secondary aromatic amine having two aromatic groups attached to the nitrogen atom.
  • alkylthioalkanols which are useful as intermediates for preparing the compounds of the present invention are described in U.S. Pat. No. 4,031,023 to Musser et al.
  • U.S. Pat. No. 2,194,527 to Winthrop et al which issued Nov. 24, 1959, describes pharmaceutical compounds such as omega-(10-phenothiazinyl)alkyl di-alkyl sulfonium salts which are useful as spasmolytics and in particular antihistaminics.
  • U.S. Pat. No. 4,915,858 describes a composition of matter, which is the amine terminated reaction product obtained from two equivalents of a secondary aromatic monoamine with at least two equivalents of a betathiodialkanol.
  • Other antioxidants known to those skilled in the art are useful as a component of a composition according to the invention.
  • Corrosion-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenyl phosphite, tridecyl pho
  • Viscosity modifiers generally are polymeric materials characterized as being hydrocarbon-based polymers generally having number average molecular weights between about 25,000 and 500,000 more often between about 50,000 and 200,000. Such materials are typically added to a hydrocarbon based oil and the oil is heated, with agitation, until the polymeric material is dissolved.
  • Polyisobutylene has been used as a viscosity modifier in lubricating oils.
  • Polymethacrylates are prepared from mixtures of methacrylate monomers having different alkyl groups. Most PMA's are viscosity-modifiers as well as pour point depressants.
  • the alkyl groups may be either straight chain or branched chain groups containing from 1 to about 18 carbon atoms.
  • Ethylene-propylene copolymers can be prepared by copolymerizing ethylene and propylene, generally in a solvent, using known catalysts such as a Ziegler-Natta initiator.
  • the ratio of ethylene to propylene in the polymer influences the oil-solubility, oil-thickening ability, low temperature viscosity, pour point depressant capability and engine performance of the product.
  • the common range of ethylene content is 45-60% by weight and typically is from 50% to about 55% by weight.
  • Some commercial OCP's are terpolymers of ethylene, propylene and a small amount of , nonconjugated diene such as 1,4-hexadiene.
  • EPDM ethylene propylene diene monomer
  • Esters obtained by copolymerizing styrene and maleic anhydride in the presence of a free radical initiator and thereafter esterifying the copolymer with a mixture of C 4-18 alcohols also are useful as viscosity modifying additives in motor oils.
  • the styrene esters generally are considered to be multifunctional premium viscosity modifiers.
  • the styrene esters in addition to their viscosity modifying properties also are pour point depressants and exhibit dispersancy properties when the esterification is terminated before its completion leaving some unreacted anhydride or carboxylic acid groups. These acid groups can then be converted to imides by reaction with a primary amine.
  • Hydrogenated styrene-conjugated diene copolymers are another class of commercially available viscosity modifiers for motor oils.
  • styrenes include styrene, alpha-methyl styrene, ortho-methyl styrene, meta-methyl styrene, para-methyl styrene, para-tertiary butyl styrene, etc.
  • the conjugated diene contains from four to six carbon atoms.
  • conjugated dienes examples include piperylene, 2,3- dimethyl- 1,3 -butadiene, chloroprene, isoprene and 1,3 -butadiene, with isoprene and butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.
  • the styrene content of these copolymers is in the range of about 20% to about 70% by weight, preferably about 40% to about 60% by weight.
  • the aliphatic conjugated diene content of these copolymers is in the range of about 30% to about 80% by weight, preferably about 40% to about 60% by weight.
  • copolymers typically have number average molecular weights in the range of about 30,000 to about 500,000, preferably about 50,000 to about 200,000.
  • the weight average molecular weight for these copolymers is generally in the range of about 50,000 to about 500,000, preferably about 50,000 to about 300,000.
  • Hydrogenated styrene-butadiene copolymers useful as viscosity modifiers in the lubricating oil compositions of the present invention are available commercially from, for example, BASF under the general trade designation "Glissoviscal".
  • Glissoviscal A particular example is a hydrogenated styrene-butadiene copolymer available under the designation Glissoviscal 5260 which has a molecular weight!, determined by gel permeation chromatography, of about 120,000.
  • Hydrogenated styrene- isoprene copolymers useful as viscosity modifiers are available from, for example, The Shell Chemical Company under the general trade designation "Shellvis”.
  • Shellvis 40 from Shell Chemical Company is identified as a diblock copolymer of styrene and isoprene having a number average molecular weight of about 155,000, a styrene content of about 19 mole percent and an isoprene content of about 81 mole percent.
  • Shellvis 50 is available from Shell Chemical Company and is identified as a diblock copolymer of styrene and isoprene having a number average molecular weight of about 100,000, a styrene content of about 28 mole percent and an isoprene content of about 72 mole percent.
  • Other viscosity modifiers known to those skilled in the art are useful as a component of a composition according to the invention.
  • Pour Point Depressants may also be included in a formulation according to the invention. They are a particularly useful type of additive often included in the lubricating oils and functional fluids such as cutting oils or other lubricants, and often comprise oil- soluble polymers. Examples of pour point depressants include those on page 8 of Lubricant Additives" by C. V. Smalheer and R. Kennedy Smith (Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967, which book is incorporated in its entirety herein by reference thereto). Other pour point depressants known to those skilled in the art are useful as a component of a composition according to the invention.
  • Anti-foam agents may be used to reduce or prevent the formation of stable foam and include silicones or organic polymers. Examples of these and additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162, which book is incorporated in its entirety herein by reference thereto. Other antifoam agents known to those skilled in the art are useful as a component of a composition according to the invention.
  • the oil compositions of the present invention also may contain at least one friction modifier to provide the lubricating oil with the proper frictional characteristics for a given application.
  • Various amines, particularly tertiary amines are effective friction modifiers.
  • tertiary amine friction modifiers include N-fatty alkyl-N,N-diethanol amines, N-fatty alkyl-N,N-diethoxy ethanol amines, etc.
  • Such tertiary amines can be prepared by reacting a fatty alkyl amine with an appropriate number of moles of ethylene oxide.
  • Tertiary amines derived from naturally occurring substances such as coconut oil and oleoamine are available from Armour Chemical Company under the trade designation "Ethomeen".
  • Sulfur- containing compounds such as sulfurized C 12-24 fats, alkyl sulfides and polysulfides wherein the alkyl groups contain from 1 to 8 carbon atoms, and sulfurized polyolefms also may function as friction modifiers in the lubricating oil compositions of the invention.
  • Other friction modifiers known to those skilled in the art are useful as a component of a
  • Base Oils The present invention is broad with respect to the selection of base oil component used in its blending.
  • compositions according to the invention comprise a base oil as a major component of the composition.
  • base oil is intended to include those materials which are recognized as possessing lubricity characteristics by those of ordinary skill in the art.
  • Such materials include, without limitation, materials falling within the following classes: 1) lubricity agents such as synthetic polymers (e.g., polyisobutene having a number average molecular weight in the range of about 750 to about 15,000, as measured by vapor phase osmometry or gel permeation chromatography); 2) the polyol ethers (e.g., poly(oxyethylene-oxypropylene)ethers); 3) ester oils including natural and synthetic triglycerides; 4) natural oil fractions such as mineral oils and those referred to as bright stocks (including all relatively viscous products formed during conventional lubricating oil manufacture from petroleum).
  • any oil or other material recognized by those skilled in the art as possessing lubricity characteristics may be used as a base oil for purposes of this invention.
  • Ashless Dispersants Within the prior art in the realm of motor fuel are a wide range of materials regarded as ashless dispersants by those of ordinary skill in such art. There are a great many materials capable of functioning in this regard, including various Mannich bases, ethyleneamines, polylakylene polyamines, and other primary, secondary and tertiary amines known in the art. The following is provided to be exemplary and not delimitive of the scope of ashless dispersants which may be employed in the context of the present invention.
  • ashless dispersants are derivatives of high molecular weight carboxylic acid acylating agents.
  • the acylating agents are prepared by reacting an olefin (e.g., a polyalkene such as polybutene) or a derivative thereof, containing for example at least about 10 aliphatic carbon atoms or generally at least 30 to 50 aliphatic carbon atoms, with an unsaturated carboxylic acid or derivative thereof such as acrylic acid, methylacrylate, maleic acid, fumaric acid and maleic anhydride.
  • an olefin e.g., a polyalkene such as polybutene
  • unsaturated carboxylic acid or derivative thereof such as acrylic acid, methylacrylate, maleic acid, fumaric acid and maleic anhydride.
  • Dispersants are prepared from the high molecular weight carboxylic acid acylating agents by reaction with, for example, amines characterized by the presence within their structure of at least one N-H group, alcohols, reactive metal or reactive metal compounds, and combinations of the above.
  • amines characterized by the presence within their structure of at least one N-H group, alcohols, reactive metal or reactive metal compounds, and combinations of the above.
  • the prior art relative to the preparation of such carboxylic acid derivatives is summarized in U.S. Pat. No. 4,234,435.
  • carboxylic acid derivative compositions such as those described above can be post-treated with various reagents to modify and improve the properties of the compositions.
  • Acylated nitrogen compositions prepared by reacting the acylating reagents described above with an amine can be post-treated, for example, by contacting the acylated nitrogen compositions thus formed with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acid, carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, phosphoric acid, epoxides, etc.
  • 1,367,939 describe deter gent-covcosxon inhibitors for lubricating oils prepared by combining a polyamine with a high molecular weight succinic anhydride and thereafter contacting the resulting product with an aromatic dicarboxylic acid of from 8 to 14 carbon atoms wherein the carboxyl groups are bonded to annular carbon atoms separated by at least one annular carbon atom.
  • aromatic dicarboxylic acids are isophthalic acid,
  • Lubricating compositions containing amine salts of a phthalic acid are described in U.S. Pat. No. 2,900,339.
  • the amine salts are thermally unstable salts of the phthalic acid and a basic tertiary amine.
  • U.S. Pat. No. 3,692,681 describes dispersions of phthalic acid in hydrocarbon media containing highly hindered acylated alkylene polyamines.
  • the polyamines are prepared by reaction of an alkenyl succinic anhydride with an alkylene polyamine such as ethylene polyamine or propylene polyamine.
  • terephthalic acid or its derivative is dissolved in an auxiliary solvent such as a tertiary alcohol or DMSO, and a terephthalic acid solution is combined with a hydrocarbon solution containing the hindered acylated amine address detergent.
  • auxiliary solvent such as a tertiary alcohol or DMSO
  • lubricant additives which are compositions derived from the acylation of alkylene polyamines. More specifically, the compositions are obtained by reaction of an alkylene amine with an acidic mixture consisting of a hydrocarbon-substituted succinic acid having at least about 50 aliphatic carbon atoms in the hydrocarbon group and an aliphatic monocarboxylic acid, and thereafter removing the water formed by the reaction.
  • the ratio of equivalents of said succinic acid to the mono ⁇ carboxylic acid in the acidic mixture is from about 1:0.1 to about 1:1.
  • the aliphatic mono- carboxylic acids contemplated for use include saturated and unsaturated acids such as acetic acid, dodecanoic acid, oleic acid, naphthenic acid, formic acid, etc. Acids having 12 or more aliphatic carbon atoms, particularly stearic acid and oleic acid, are especially useful.
  • the products described in the '936 patent also are useful in oil-fuel mixtures for two-cycle internal combustion engines.
  • British Pat. No. 1,162,436 describes ashless dispersants useful in lubricating compositions and fuels.
  • the compositions are prepared by reacting certain specified alkenyl substituted succinimides or succinic amides with a hydrocarbon-substituted
  • hydrocarbon substituents is greater than 50 carbon atoms.
  • Formamides of monoalkenyl succinimides are described in U.S. Pat. No. 3,185,704. The formamides are reported to be useful as additives in lubricating oils and fuels.
  • compositions prepared by post- treating mono- and polycarboxylic acid esters with mono- or polycarboxylic acid acylating agents are reported to be useful as dispersants in lubricants and fuels.
  • compositions according to the invention is to begin with a major amount of a base oil material and add the other selected ingredients to the base oil, with sufficient agitation to provide a homogeneous mixture within a reasonable time.
  • a base oil material When the viscosity of the additive is much greater than that of the base oil, it is beneficial to provide heating to the base oil to facilitate dissolution and homogeneity. This is especially true in the cases where polymeric materials are added to base oils.
  • the dissolution of all of the additives used in the invention in a base oil is well known in the art and is thus within the skill level of an ordinary artisan in the oil additives field.
  • compositions of the present invention may vary widely in composition depending upon the intended use of the final composition.
  • those of ordinary skill in formulating lubricating oils, functional fluids, cutting oils, emulsions, etc., in which LAB based detergent materials are used as a component readily recognize that the detergents prepared from LAB materials provided by the invention may be used as direct, drop-in substitutes for many detergent components in current formulations, including those which are based on linear alkylbenzenes and those which are not.
  • compositions which include detergents based upon the linear alkylbenzenes of the invention offer superior detergency over formulations which contain linear alkylbenzene based detergent materials of the prior art, on a molar basis, owing to the unique isomer distribution provided by the present invention.
  • LAB surfactants of this invention may be anionic in nature, such as in the cases when the detergent molecule is a sulfonate, it is possible to provide charge balance using a cation which is known to impart beneficial properties to motor fuels. Such cations may include the alkali and alkaline earth metals as the use of such are well known for the properties they impart to fuel compositions.
  • ashless dispersants useful as additives in fuels and lubricant compositions Many of these are cationic in nature and are thus capable of providing charge balance to chemical compounds in which the anionic portion is derived from the LAB according to this invention, to provide a neutral, oil or fuel soluble material which possesses both detergent and dispersant characteristics.
  • One particular and surprising advantage of using the catalysts of this invention to produce alkylbenzenes is that a low content of dialkylbenzene components are found in the alkylbenzene product mixture. This is important since dialkylbenzenes are generally regarded as undesirable, and the presence of such species tends to raise the viscosity of the alkylbenzene reaction product mixture.
  • dialkylbenzenes are generally regarded as undesirable, and the presence of such species tends to raise the viscosity of the alkylbenzene reaction product mixture.
  • alkylbenzenes made by alkylation of benzene with olefins in the C 16 - C 30 range using catalysts an procedures taught herein
  • Alkylate 300 is available from Huntsman in commercial quantities. Huntsman's
  • Alkylate 300 is has a 2-phenyl isomer content in the range of between about 10 and 13%
  • Huntsman's Alkylate 300 is suitable for sulfonation from which alkylbenzene
  • sulfonates may be produced using means known to those skilled in the art which may
  • a sulfur trioxide to alkyl aromatic product molar ratio a sulfur trioxide to alkyl aromatic product molar ratio
  • the sulfonated Alkylate 300 emerges from the sulfonation reactor as the acid form of the sulfonate, which is sometimes referred to as an alkylbenzenesulfonic acid.
  • acid may be neutralized using conventional alkalis such as hydroxides, oxides, carbonates,
  • Alkylate 300 for using Alkylate 300 is to sulfonate the Alkylate 300 to form the alkylbenzenesulfonic
  • a composition of one form of the present invention is a mixture of two or more alkylbenzenes which have a 2-aryl isomer content in the range of between about 8 and 30% by weight based on the total weight of all of the linear monoalkylbenzenes (including 2-aryl and non-2-aryl) present in the mixture.
  • alkylbenzenes and detergent-dispersant products derived therefrom according to this invention are substantially free from benzene, having a benzene content less than 2 ppm in one form of the invention, less than 1 ppm in another form of the invention, less than 0.5 ppm in another form of the invention and less than 100 parts per billion in another form of the invention.
  • an alkylbenzene and detergent-dispersant products derived therefrom according to the invention contain less than about 28 % branching.
  • alkylbenzenes according to the invention are substantially free from 1-aryl isomers of alkylbenzenes, which are isomers where the benzene ring is attached to the 1 -position of a linear alkyl chain having more than about 14 carbon atoms.
  • the present invention includes any overbased sulfonate described herein with any one or more conventional additives useful in motor oils and the like specified herein.
  • the 2-aryl isomer content has been described in quantities relative to the total weight of a mixture in which such isomers are present.
  • the present invention also includes embodiments in which the percentages specified herein relate to the 2-isomer content when calculated by taking the weight of the 2-isomer content in a given sample, and dividing it by the weight in the same sample of linear alkylbenzenes, and multiplying this quotient by 100 to arrive at a percentage 2-isomers, with all remaining claim limitations held constant.
  • a specification sheet for Alkylate 300 is available from Huntsman LLC of Houston, Texas.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions lubrifiantes contenant des composants détergents-dispersants dérivés d'alkylbenzènes sensiblement linéaires renfermant des sulfonates, des sulfonates surbasiques, ainsi que des sels et des esters de ceux-ci. Les détergents selon l'invention présentent une faible teneur en isomères 1-aryl par rapport aux matières des techniques actuelles. De plus, ils sont préparés à l'aide de mélanges qui ont une teneur en benzène sensiblement réduite par rapport aux matières des techniques actuelles. L'invention concerne enfin des compositions utilisées pour formuler des lubrifiants, des huiles de moteurs, et analogues.
PCT/US2005/036684 2004-10-25 2005-10-14 Detergents de carburant et d'huile WO2006047091A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002584152A CA2584152A1 (fr) 2004-10-25 2005-10-14 Detergents de carburant et d'huile
US11/666,258 US20080064616A1 (en) 2004-10-25 2005-10-14 Fuel And Oil Detergents
EP05813032A EP1805282A4 (fr) 2004-10-25 2005-10-14 Detergents de carburant et d'huile

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62189204P 2004-10-25 2004-10-25
US60/621,892 2004-10-25

Publications (2)

Publication Number Publication Date
WO2006047091A2 true WO2006047091A2 (fr) 2006-05-04
WO2006047091A3 WO2006047091A3 (fr) 2006-06-01

Family

ID=36228218

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/036684 WO2006047091A2 (fr) 2004-10-25 2005-10-14 Detergents de carburant et d'huile

Country Status (4)

Country Link
US (1) US20080064616A1 (fr)
EP (1) EP1805282A4 (fr)
CA (1) CA2584152A1 (fr)
WO (1) WO2006047091A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2490790A (en) * 2011-05-11 2012-11-14 Johnson Matthey Plc Tracers and method of marking hydrocarbon liquids

Family Cites Families (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2239974A (en) * 1941-04-29 Detergent composition
US3172855A (en) * 1965-03-09 Barium-calcium sulfonate complexes and lubricating compositions con- taining same
US2194527A (en) * 1929-07-05 1940-03-26 Automatic Appliance Company Apparatus for determining the lubricating values of oils
US2197800A (en) * 1938-06-30 1940-04-23 Du Pont Reaction of aliphatic hydrocarbons with sulphur dioxide and chlorine and products thereof
US2228598A (en) * 1938-06-30 1941-01-14 Charles L Horn Purification of hydrocarbon-sulphur dioxide-chlorine reaction products
US2193824A (en) * 1938-06-30 1940-03-19 Du Pont Countercurrent reaction of hydrocarbons with sulphur dioxide and chlorine
US2315514A (en) * 1938-11-22 1943-04-06 Du Pont Preparation of organic sulphinic acids
NL55470C (fr) * 1938-12-30
US2276090A (en) * 1939-02-17 1942-03-10 Charles L Horn Hydrolysis of products obtained by reacting saturated hydrocarbons with sulphur dioxide and chlorine
BE466717A (fr) * 1939-05-01
US2282710A (en) * 1939-06-14 1942-05-12 Du Pont Stabilization of petroleum hydrocarbons
US2276097A (en) * 1939-07-25 1942-03-10 Du Pont Aliphatic sulphonyl fluorides and their preparation
US2383319A (en) * 1939-08-23 1945-08-21 Du Pont Production of sulphonyl chlorides
US2321022A (en) * 1940-10-10 1943-06-08 Du Pont Chemical compound and process
US2273236A (en) * 1940-10-17 1942-02-17 Teletype Corp Printing telegraph system
US2319121A (en) * 1940-11-12 1943-05-11 Du Pont Reaction of hydrocarbon sulphonyl halides with alcohols
US2374193A (en) * 1942-06-30 1945-04-24 Standard Oil Co Preparation of organic sulphonates
US2781318A (en) * 1952-03-28 1957-02-12 Exxon Research Engineering Co Mineral lubricating oil additive
US2777874A (en) * 1952-11-03 1957-01-15 Lubrizol Corp Metal complexes and methods of making same
US2798852A (en) * 1954-02-15 1957-07-09 Lubrizol Corp Oil-soluble metal-containing materials and methods for preparing same
US3027325A (en) * 1955-11-07 1962-03-27 Lubrizol Corp Oil-soluble calcium carbonate dispersions and method of preparation
US2883340A (en) * 1956-02-20 1959-04-21 Union Oil Co High viscosity index detergent lubricating oils
US2968642A (en) * 1957-01-17 1961-01-17 Lubrizol Corp Stabilizers for polymeric compositions
BE533324A (fr) * 1957-02-06
US2989463A (en) * 1958-09-26 1961-06-20 Lubrizol Corp Lubricants containing basic metal additives
US2971014A (en) * 1958-09-26 1961-02-07 Lubrizol Corp Oil soluble metal containing compositions and process for making same
US3170880A (en) * 1959-02-20 1965-02-23 Bray Oil Co Dispersions of calcium compounds in oils
DE1248643B (de) * 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Verfahren zur Herstellung von öllöslichen aeylierten Aminen
US3444170A (en) * 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3488284A (en) * 1959-12-10 1970-01-06 Lubrizol Corp Organic metal compositions and methods of preparing same
US3133019A (en) * 1960-01-14 1964-05-12 Socony Mobil Oil Co Inc Method for preparing high metal-con-tent salts of sulfonic acids
US3232883A (en) * 1961-12-28 1966-02-01 Lubrizol Corp Basic mixtures of metal salts and lubricants containing them
US3492231A (en) * 1966-03-17 1970-01-27 Lubrizol Corp Non-newtonian colloidal disperse system
US3242079A (en) * 1962-04-06 1966-03-22 Lubrizol Corp Basic metal-containing thickened oil compositions
US3449250A (en) * 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3329658A (en) * 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3170881A (en) * 1962-07-20 1965-02-23 Bray Oil Co Superbased barium containing lubricants
US3240608A (en) * 1962-08-30 1966-03-15 Lever Brothers Ltd Margarine oil and method of making
US3185704A (en) * 1962-09-04 1965-05-25 Exxon Research Engineering Co Formamide of mono-alkenyl succinimide
US3282835A (en) * 1963-02-12 1966-11-01 Lubrizol Corp Carbonated bright stock sulfonates and lubricants containing them
US3194823A (en) * 1963-03-18 1965-07-13 Lubrizol Corp Organic complexes
US3242080A (en) * 1963-03-20 1966-03-22 Texaco Inc Hyperbasic metal complex
NL129113C (fr) * 1963-05-24
US3250710A (en) * 1963-06-03 1966-05-10 Continental Oil Co Preparation of over-based sulfonate composition
US3455832A (en) * 1963-09-09 1969-07-15 Monsanto Co Schiff bases
US3455831A (en) * 1963-09-27 1969-07-15 Monsanto Co Imines containing a polyalkenylsuccinic anhydride substituent
US3658836A (en) * 1964-04-16 1972-04-25 Monsanto Co Hydroxyboroxin-amine salts
US3310492A (en) * 1964-09-08 1967-03-21 Chevron Res Oils for two-cycle engines containing basic amino-containing detergents and aryl halides
NL145565B (nl) * 1965-01-28 1975-04-15 Shell Int Research Werkwijze ter bereiding van een smeermiddelcompositie.
NL130771C (fr) * 1965-03-12
US3574576A (en) * 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3413347A (en) * 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
FR1142932A (fr) * 1966-07-15 1957-09-24 Lubrizol Corp Compositions métalliques organiques et leur procédé de fabrication
US3519565A (en) * 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3554911A (en) * 1967-11-30 1971-01-12 Phillips Petroleum Co Viscosity index improvers
US3725480A (en) * 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) * 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3576743A (en) * 1969-04-11 1971-04-27 Lubrizol Corp Lubricant and fuel additives and process for making the additives
US3595790A (en) * 1969-10-22 1971-07-27 Lubrizol Corp Oil soluble highly basic metal salts of organic acids
US3632511A (en) * 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3649229A (en) * 1969-12-17 1972-03-14 Mobil Oil Corp Liquid hydrocarbon fuels containing high molecular weight mannich bases
US3708522A (en) * 1969-12-29 1973-01-02 Lubrizol Corp Reaction products of high molecular weight carboxylic acid esters and certain carboxylic acid acylating reactants
US3639242A (en) * 1969-12-29 1972-02-01 Lubrizol Corp Lubricating oil or fuel containing sludge-dispersing additive
US3649659A (en) * 1970-03-24 1972-03-14 Mobil Oil Corp Coordinated complexes of mannich bases
US3708422A (en) * 1971-01-29 1973-01-02 Cities Service Oil Co Electric discharge machining fluid
US3803140A (en) * 1971-03-12 1974-04-09 Ciba Geigy Corp Substituted phenothiazines
US3798012A (en) * 1971-06-09 1974-03-19 Lubrizol Corp Combustion process and fuel compositions
US3804763A (en) * 1971-07-01 1974-04-16 Lubrizol Corp Dispersant compositions
US4181618A (en) * 1974-12-03 1980-01-01 Institut Francais Du Petrole Grafted copolymers and their use as additives for lubricating oils
US4203855A (en) * 1975-08-27 1980-05-20 The Lubrizol Corporation Phenoxide-halo carboxylic acid condensate additives for lubricants
US4100082A (en) * 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4031023A (en) * 1976-02-19 1977-06-21 The Lubrizol Corporation Lubricating compositions and methods utilizing hydroxy thioethers
GB1572496A (en) * 1976-02-20 1980-07-30 Exxon Research Engineering Co Stabilisation of alkylaryl sulphonic acids and sulphonates
US4094801A (en) * 1976-04-29 1978-06-13 The Lubrizol Corporation Magnesium-containing complexes, method for their preparation, and compositions containing the same
US4086170A (en) * 1976-10-08 1978-04-25 Labofina S. A. Process for preparing overbased calcium sulfonates
US4211665A (en) * 1978-10-26 1980-07-08 Gulf Research And Development Company Electrical apparatus insulated with a high fire point synthetic alkylaromatic fluid
US4260500A (en) * 1979-02-21 1981-04-07 The Lubrizol Corporation Magnesium-containing complexes, method for their preparation, and compositions containing the same
US4252659A (en) * 1979-10-12 1981-02-24 Tenneco Chemicals, Inc. Process for the production of overbased manganese salts of organic acids
US4372862A (en) * 1980-10-10 1983-02-08 Exxon Research & Engineering Co. Oil-soluble metal containing sulfonated polymers useful as oil additives
US4505718A (en) * 1981-01-22 1985-03-19 The Lubrizol Corporation Organo transition metal salt/ashless detergent-dispersant combinations
NZ206213A (en) * 1982-11-16 1985-12-13 Unilever Plc Foaming liquid detergent compositions containing alkylbenzenesulphonates and alkyl ether sulphates
US4915858A (en) * 1987-06-09 1990-04-10 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
US4938881A (en) * 1988-08-01 1990-07-03 The Lubrizol Corporation Lubricating oil compositions and concentrates
GB9111257D0 (en) * 1991-05-24 1991-07-17 Exxon Chemical Patents Inc Preparation of overbased magnesium sulphonates
FR2731427B1 (fr) * 1995-03-08 1997-05-30 Chevron Chem Sa Alkylaryl-sulfonates lineaires isomerises, utiles comme additifs pour huiles lubrifiantes et hydocarbures alkylaryliques correspondants
US6849588B2 (en) * 1996-02-08 2005-02-01 Huntsman Petrochemical Corporation Structured liquids made using LAB sulfonates of varied 2-isomer content
US6887839B2 (en) * 1996-02-08 2005-05-03 Huntsman Petrochemical Corporation Solid alkylbenzene sulfonates and cleaning compositions having enhanced water hardness tolerance
US6562776B1 (en) * 1996-02-08 2003-05-13 Huntsman Petrochemical Corporation Solid alkylbenzene sulfonates and cleaning compositions having enhanced water hardness tolerance
US6995127B1 (en) * 1996-02-08 2006-02-07 Huntsman Petrochemical Corporation Alkyl toluene sulfonate detergent
US7008914B2 (en) * 1996-02-08 2006-03-07 Huntsman Petrochemical Corporation Alkylbenzene detergents with high 2-isomer content
GB2321906A (en) * 1997-02-07 1998-08-12 Ethyl Petroleum Additives Ltd Fuel additive for reducing engine emissions
US6015778A (en) * 1998-03-27 2000-01-18 The Lubrizol Corporation Process for making overbased calcium sulfonate detergents using calcium oxide and a less than stoichiometric amount of water
US6197075B1 (en) * 1998-04-02 2001-03-06 Crompton Corporation Overbased magnesium deposit control additive for residual fuel oils
EP1739975A3 (fr) * 1998-06-29 2007-01-17 Matsushita Electric Industrial Co., Ltd. Circuit discriminateur de système d'émission en couleurs intérieur à une télévision
US6071864A (en) * 1998-07-17 2000-06-06 Mobil Oil Corporation Methods for preparation of arylated poly∝olefins
EP0976810A1 (fr) * 1998-07-31 2000-02-02 Chevron Chemical S.A. Mélange d'alkyl-phenyl-sulfonates de métaux alcalino-terreux, son application comme additif pour huile lubrifiante et procédés de préparation
FR2783824B1 (fr) * 1998-09-25 2001-01-05 Chevron Chem Sa Sulfonates d'alkylaryle faibles surbases et huile de lubrification les contenant
EP1059301B1 (fr) * 1999-06-10 2003-05-21 Chevron Chemical S.A. Des sulfonates de métaux alcalino-terreux, leur application comme additifs pour huile lubrifiante et procédé de préparation
US6417135B1 (en) * 1999-08-27 2002-07-09 Huntsman Petrochemical Corporation Advances in dehydrogenation catalysis
US6337310B1 (en) * 2000-06-02 2002-01-08 Chevron Oronite Company Llc Alkylbenzene from preisomerized NAO usable in LOB and HOB sulfonate
MXPA03002349A (es) * 2000-09-19 2003-10-15 Huntsman Spec Chem Corp Detergentes de sulfonato de alquilo tolueno.
MXPA04009472A (es) * 2002-03-29 2005-02-03 Exxonmobil Chem Patents Inc Preparacion de hidrocarburos alquilaromaticos y alquilaril sulfonatos.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of EP1805282A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2490790A (en) * 2011-05-11 2012-11-14 Johnson Matthey Plc Tracers and method of marking hydrocarbon liquids
GB2490790B (en) * 2011-05-11 2014-01-01 Johnson Matthey Plc Tracers and method of marking hydrocarbon liquids
US9678054B2 (en) 2011-05-11 2017-06-13 Johnson Matthey Public Limited Company Method of marking hydrocarbon liquids
US10106754B2 (en) 2011-05-11 2018-10-23 Johnson Matthey Public Limited Company Method of marking hydrocarbon liquids
US10816533B2 (en) 2011-05-11 2020-10-27 Johnson Matthey Public Limited Company Method of marking hydrocarbon liquids

Also Published As

Publication number Publication date
EP1805282A4 (fr) 2010-08-04
WO2006047091A3 (fr) 2006-06-01
US20080064616A1 (en) 2008-03-13
EP1805282A2 (fr) 2007-07-11
CA2584152A1 (fr) 2006-05-04

Similar Documents

Publication Publication Date Title
JP5001479B2 (ja) アルカリ土類金属アルキルトルエンスルホネートの製造方法
CN105814180B (zh) 船用柴油机汽缸润滑剂油组合物
CN105829513B (zh) 船用柴油机汽缸润滑剂油组合物
US6630430B1 (en) Fuel and oil detergents
EP0217591B1 (fr) Catéchols monoalcoylés en C18 à C24 normalement liquides
EP0614962B1 (fr) Compositions de faible viscosité à base de sel surbasique de métal du groupe II d'alkylphenol sulfuré, le groupe alkyl contenant 12 à 22 carbones
JPH04345690A (ja) スクシンイミド組成物
JP2010031054A (ja) 硫化フェノール添加剤、中間体および組成物の製造方法
CZ282081B6 (cs) Způsob výroby sulfonátu hořečnatého s vysokým číslem bazicity
JPS62502473A (ja) ホウ素−硫黄含有組成物，および該ホウ素−硫黄含有組成物を含有する添加濃縮物および潤滑オイル
US4282106A (en) Low viscosity oils
US3470097A (en) Overbased dialkylbenzene sulfonates
US3125521A (en) Calcium mixed-salt lubricant stabilized
US20080064616A1 (en) Fuel And Oil Detergents
US3755170A (en) Preparation of highly basic alkylphenates and sulfurized alkyphenates
JP3461351B2 (ja) オレフィン又はアルコールとフェノールとを酸性アルキル化触媒の存在下で反応させることにより製造されたアルキルフェノールから誘導された中性及び低過塩基性アルキルフェノキシスルホネート添加剤組成物
CN101245278A (zh) 用于改进抗磨损性的添加剂和润滑制剂
CA2254614A1 (fr) Azote contenant des ameliorants de dispersion de la viscosite
WO1994005747A1 (fr) Compositions additives de sulfonates d'alkylphenoxy neutres et a faible quantite excedentaire de base
EP0206748A2 (fr) Additif pour huile lubrifiante et composition lubrifiante contenant ceux-ci
CA2583901C (fr) Composition de super-sulfonates polyalkenyls et de super- sulfonates alkylaryls surbases, et processus de fabrication
US2644792A (en) Compounded lubricating oil
CA2545952C (fr) Detergent de sulfonate de calcium a indice de base eleve
US3053766A (en) High detergency automotive engine lubricant
CN101418251A (zh) 使用乙醇基燃料工作的发动机中的发动机磨损防护

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BW BY BZ CA CH CN CO CR CU CZ DK DM DZ EC EE EG ES FI GB GD GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV LY MD MG MK MN MW MX MZ NA NG NO NZ OM PG PH PL PT RO RU SC SD SG SK SL SM SY TJ TM TN TR TT TZ UG US UZ VC VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): BW GH GM KE LS MW MZ NA SD SZ TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IS IT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2584152

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2005813032

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 2005813032

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 11666258

Country of ref document: US