EP0604474A1 - Detergents surbasiques contenant des metaux. - Google Patents

Detergents surbasiques contenant des metaux.

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Publication number
EP0604474A1
EP0604474A1 EP92918587A EP92918587A EP0604474A1 EP 0604474 A1 EP0604474 A1 EP 0604474A1 EP 92918587 A EP92918587 A EP 92918587A EP 92918587 A EP92918587 A EP 92918587A EP 0604474 A1 EP0604474 A1 EP 0604474A1
Authority
EP
European Patent Office
Prior art keywords
metal
ultrasound
oil
overbased
containing detergent
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.)
Granted
Application number
EP92918587A
Other languages
German (de)
English (en)
Other versions
EP0604474B1 (fr
Inventor
John Frederick Marsh
Neal Allan Hawkins
John Arthur Cleverley
William David Read
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 Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
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Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0604474A1 publication Critical patent/EP0604474A1/fr
Application granted granted Critical
Publication of EP0604474B1 publication Critical patent/EP0604474B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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
    • 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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol 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
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising

Definitions

  • the invention relates to a process for preparing overbased metal-containing detergents, to overbased detergents produced by the process, and to oil-based compositions containing the detergents.
  • compositions for example, lubricants, greases and fuels.
  • the overbased detergents function both as detergents and acid neutralizers, thereby reducing wear and corrosion and, when used in engines, extending engine life.
  • overbased metal-containing detergents include overbased oil-soluble sulphonates, phenates, sulphurized phenates, thiophosphonates, salicylates, naphthenates and other carboxylates of the alkali and alkaline earth metals and magnesium, particularly
  • preferred metals being calcium and magnesium.
  • preferred processes involve a neutralization step followed by an overbasing step.
  • the last-mentioned step is often referred to as a carbonation step, since in practice carbon dioxide is almost invariably used as the acidic gas.
  • overbased metal- containing detergents to be used as additives for oil- based compositions have a relatively high basicity since this results in the most economic use of the metal.
  • the basicity is usually expressed in terms of the Total Base Number (TBN) of the product, the TBN being the number of milligrams of potassium hydroxide equivalent to 1 gram of the product when titrating with a strong acid.
  • TBN Total Base Number
  • the invention is particularly concerned with detergents having a TBN of 50 mg KOH/g or more and, for some
  • the TBN be at least 300, preferably at least 400, mg KOH/g, as measured by ASTM D2896.
  • mixture as used herein includes both a mixture of starting materials and the mixture when in reaction.
  • the invention accordingly provides a process for the preparation of an overbased metal-containing detergent, in which process a starting material, a reaction mixture, or a reaction product is treated with ultrasound.
  • the invention also provides overbased metal-containing detergents produced by the process, and oil-based
  • compositions containing such detergents are provided.
  • the invention further provides a process for the preparation of an overbased metal-containing detergent which comprises treating with an acidic gas a mixture comprising a metal-containing detergent and a metal- containing basic compound, in which process a starting material, reaction mixture or reaction product is
  • an overbased metal-containing detergent which comprises reacting an oil-soluble acid with a metal-containing basic compound to give a metal- containing detergent, and treating with an acidic gas a mixture of the metal-containing detergent and a metal- containing basic compound, in which process a starting material, reaction mixture or reaction product is treated with ultrasound.
  • the metal-containing detergent may if desired contain more than one metal, so in principle a mixture of basic compounds could be used in the neutralizing step and/or the overbasing step, and/or different basic compounds could be used in these two steps.
  • the invention has particular relevance to processes for the preparation of overbased metal-containing detergents in which purification of the product involves a filtration step, although in some cases an improvement is obtained when purification is effected by an
  • the waste to be disposed of at the end of a process in which purification is effected by filtration includes not only the sediment itself, but also filter- aid added before filtration.
  • the amount of filter-aid used is normally in direct proportion to the amount of sediment, so that a reduction in the amount of sediment will normally also make possible a reduction in the amount of filter-aid used.
  • a reduction in the amount of waste to be disposed of at the end of a process is an important advantage from the ecological viewpoint when working on a large scale.
  • the invention also provides the use of ultrasound in the preparation of an overbased metal-containing detergent.
  • the invention further provides the use of ultrasound to reduce sediment levels in the preparation of an overbased metal-containing detergent.
  • the invention also provides the use of ultrasound to reduce the proportion of waste material obtained in the preparation of an overbased metal-containing
  • the invention further provides the use of ultrasound to increase filtration rates in the preparation of an overbased metal-containing detergent.
  • ultrasound is usually used to denote sound having a frequency above that normally audible to the human ear.
  • the term “ultrasound” advantageously denotes sound having a frequency of about 16 to 100 kHz, preferably 16 to 80 kHz.
  • the intensity of sound becomes attenuated with distance from the source, sound of higher frequencies becoming attenuated more rapidly than sound of lower frequencies, and in many cases, therefore, it may be desirable to use low frequency ultrasound, for example, ultrasound having a frequency in the range of 20 to 50 kHz.
  • Commercially available power ultrasound equipment is in many cases tuned to operate at 20 kHz.
  • the sound intensity to be used in accordance with the invention will depend on the system to be treated and the optimum value for any particular system can be determined by routine experiment.
  • ultrasonic sources to be used in accordance with the invention will produce sound with intensities in the region of from 0.5 to 500 watts/cm 2 , especially 1 to 300 watts/cm 2 . As indicated above, intensities become attenuated with distance from the source, and the intensity of the sound produced by the source must be chosen with this in mind.
  • the treatment with ultrasound can be carried out by any suitable means.
  • a general discussion of some of the principles behind the generation of power ultrasound, and examples of a number of different sonicators, are given, for example, in T. J. Mason, Ed., "Sonochemistry: The Uses of Ultrasound in Chemistry", Royal Society of
  • One means for carrying out the treatment with ultrasound comprises an ultrasonic bath, which typically has the form of a liquid-filled tank with a plurality of transducers positioned around the base and walls.
  • An ultrasonic bath is a low intensity system, the intensity of the ultrasound at the transducer face typically being of the order of 1 to 2 watts/cm 2 .
  • ultrasonic bath could be used in a continuous process in which, for example, a fluid to be treated is caused to flow in a controlled manner through an ultrasonic tank and out over a weir.
  • a number of tanks could, if desired, be connected in series.
  • Another means for carrying out the treatment with ultrasound comprises an ultrasonic probe.
  • Such probes are typically capable of supplying much higher sound intensities.
  • the intensity at the face of the probe may be of the order of 100 to 500 watts/cm 2 .
  • one or more probes could, for example, be positioned in a flow pipe.
  • a further means for carrying out the treatment with ultrasound comprises apparatus in which the fluid to be treated is pumped at high velocity past a blade, causing the blade to vibrate ultrasonically.
  • ultrasound may be used in the preparation of any overbased metal-containing detergent suitable for use as an additive in an oil-based composition, for example, the overbased oil-soluble sulphonates, phenates, sulphurized phenates,
  • thiophosphonates for example, sodium, lithium, calcium, barium and magnesium.
  • metals are calcium and magnesium, mixtures of calcium and magnesium, and mixtures of calcium and/or magnesium with sodium.
  • the process of the invention finds particular use in the preparation of overbased calcium and magnesium alkaryl sulphonates and alkyl phenates, but is not limited thereto.
  • the invention is particularly concerned with the preparation of metal- containing detergents having a TBN of at least 50 mg KOH/g.
  • the preferred detergents comprise dispersed carbonate complexes, that is, the acidic gas used in their preparation is carbon dioxide.
  • Sulphonic acids suitable for use in preparing oil- soluble sulphonates are typically obtained by
  • alkyl-substituted aromatic hydrocarbons for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons, for example,
  • Alkylation of aromatic hydrocarbons may be carried out, in the presence of a catalyst, with alkylating agents having from about 3 to more than 50 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, and
  • polyolefins for example, polymers of ethylene
  • alkaryl sulphonates usually contain from about 9 to about 70 or more carbon atoms, preferably from about 16 to about 50 carbon atoms, per alkyl-substituted aromatic moiety.
  • neutralizing these alkaryl sulphonic acids to provide the sulphonates include the oxides, hydroxides and alkoxides, for example, calcium hydroxide or magnesium oxide.
  • Hydrocarbon solvents and/or diluent oils may also be included, as well as promoters and viscosity control agents, for example, formates and halides.
  • the highly basic metal sulphonates are usually produced by neutralizing an alkaryl sulphonic acid with a large excess of metal base over that required for
  • Neutral or slightly basic metal sulphonates may be used in place of the alkaryl sulphonic acid.
  • the reaction mixture may include organic solvents, for example, toluene, xylene, hexane, ohlorobenzene;
  • Highly basic metal sulphonates may have a TBN from about 50 to about 500, preferably 250 to 450, and contain about 10 to about 35 wt. % alkaryl sulphonate.
  • the following patents provide illustrative examples of overbased. sulphonates and/or processes for preparing them: EP 0 000 264, EP 0 000 318, EP 0 025 328,
  • sulphurized alkyl phenols which may be used for preparing sulphurized phenate detergents are phenols of the general structure:
  • R is an alkyl radical
  • n is an integer from 0 to 4
  • x is an integer from 1 to 4. All the R groups will normally be the same, but this is not essential.
  • the average number of carbon atoms in all of the R groups is preferably at least about 9 in order to ensure adequate solubility in oil.
  • the individual R groups may contain from 5 to 40, preferably 8 to 20 carbon atoms.
  • Alkylation of phenol may be carried out with, for example, alkylating agents of the types used to alkylate aromatic hydrocarbons in the manufacture of alkaryl sulphonates.
  • Dihydroxybenzenes may be used in place of phenol.
  • Sulphurization may be effected, for example, by reaction of the alkyl phenol with sulphur chloride or by reaction with sulphur. In the latter case, the alkyl phenol is usually present as the metal salt, although other sulphurization promoters may be used, for example, amines.
  • Highly basic metal phenates may be made by methods similar to those used to prepare highly basic metal sulphonates. Highly basic metal phenates may have a TBN from, for example, 100 to 400, preferably about 200 to 350.
  • the following patents provide illustrative examples of overbased phenates and/or processes for preparing them:
  • Highly basic metal thiophosphonates, salicylates, naphthenates and other mono- and dicarboxylates may also be used in oil-based compositions and may be prepared by methods similar to those used to prepare highly basic sulphonates and phenates.
  • a starting material or reaction mixture used in a process for the preparation of an overbased metal-containing detergent is subjected to treatment with ultrasound.
  • ultrasound is advantageously used to treat a metal- containing basic compound, preferably an oxide or
  • ultrasound may be used to treat a reaction mixture comprising a metal- containing basic compound and an oil-soluble acid capable of reacting with the basic compound to form a metal- containing detergent, and/or to treat a reaction mixture comprising an oil-soluble metal-containing detergent and a metal-containing basic compound, the last-mentioned reaction mixture preferably being treated with ultrasound while an acidic gas, preferably carbon dioxide, is passed into it to give an overbased product.
  • an acidic gas preferably carbon dioxide
  • treatment with ultrasound may be effected using an ultrasonic bath.
  • an ultrasonic bath may act as a heat sink, resulting in cooling of, for example, a reaction mixture and
  • the bath preferably comprises heating means so that the
  • bath can be maintained at a level at which the reaction is not inhibited, or at any other desired temperature.
  • ultrasound is used to treat a reaction mixture
  • the ultrasound treatment is preferably continued throughout the entire reaction period.
  • a reaction product is treated with ultrasound.
  • the applicants have surprisingly found that it is particularly advantageous to treat with ultrasound the product of the overbasing reaction employed in the preparation of overbased metal- containing detergents.
  • the applicants have found that filtration rates may be increased by treating an overbased product with ultrasound before filtration.
  • less product may be lost on the filter cake during filtration and, in some cases,
  • sediment levels may be reduced, leading, for example, to a reduction in the amount of waste material to be
  • treatment of the reaction product with ultrasound may eliminate, or reduce, the amount of gelatinous material in the product.
  • the product Before filtration of the product of an overbasing reaction, the product is normally stripped to remove volatile materials required in the production of the overbased product but not required in the final product, and a solvent may be added, normally to the stripped product, before filtration.
  • the ultrasound treatment may be carried out at any stage, for example, on the unstripped, partially stripped or fully stripped product, and before or after the addition of a solvent.
  • reaction product to be treated can be determined by routine experiment. Examples of treatment times and methods are given in the Examples herein.
  • Overbased detergents obtained by the process of the invention are useful as additives for oil-based
  • compositions for example, lubricants, greases and fuels, and the invention thus also provides such
  • compositions containing the overbased detergents When used in engine lubricants, the overbased detergents neutralize acids formed by the operation of the engine and help to disperse solids in the oil to reduce the formation of harmful deposits. They also enhance the antirust properties of the lubricants.
  • the amount of overbased detergents that should be included in the oil- based composition depends on the type of composition and its proposed application. Automotive crankcase
  • lubricating oils typically contain 0.01% to 3 mass % of the overbased detergent, on an active ingredient basis, based on the mass of the oil, while marine lubricating oils typically contain up to 13 mass % of the detergent, on the same basis.
  • overbased detergents prepared in accordance with the invention are oil-soluble or (in common with certain of the other additives referred to below) are
  • Oil-soluble dissolvable in oil with the aid of a suitable solvent, or are stably dispersible materials.
  • dissolvable, or stably dispersible as that terminology is used herein does not necessarily indicate that the materials are soluble, dissolvable, miscible, or capable of being suspended in oil in all proportions. It does mean, however, that the materials are, for instance, soluble or stably dispersible in oil to an extent
  • Additives including the overbased detergents prepared in accordance with the present invention, can be incorporated into a base oil in any convenient way.
  • Additives produced in accordance with the present invention may be useful in fuel oils or lubricating oils.
  • the normally liquid fuel oils are generally derived from petroleum sources, for example, normally liquid petroleum distillate fuels, although they may include those
  • Such fuel compositions have varying boiling ranges, viscosities, cloud and pour points, according to their end use, as is well known to those skilled in the art.
  • fuels are those commonly known as diesel fuels, distillate fuels, for example, gasoline, heating oils, residual fuels and bunker fuels, which are collectively referred to herein as fuel oils.
  • the properties of such fuels are well known to those skilled in the art as illustrated, for example, by ASTM Specification D 396-73, available from the American Society for Testing Materials, 1916 Race street, Philadelphia, Pennsylvania 19103.
  • Middle distillate fuel oils include distillates boiling from about 120 to 725°F (about 49 to 385oC)
  • Overbased detergents prepared in accordance with the invention are particularly useful in lubricating oil compositions which employ a base oil in which the
  • Base oils with which the overbased detergents may be used include those suitable for use as crankcase lubricating oils for spark- ignited and compression-ignited internal combustion engines, for example, automobile and truck engines, marine and railroad diesel engines. They may also be used, for example, in base oils suitable for use as aviation lubricants or as lubricants for two cycle engines.
  • Synthetic base oils include alkyl esters of
  • dicarboxylic acids polyglycols and alcohols
  • poly- ⁇ - olefins including polybutenes
  • alkyl benzenes alkyl benzenes
  • organic esters of phosphoric acids organic esters of phosphoric acids
  • polysilicone oils polysilicone oils
  • Natural base oils include mineral lubricating oils which may vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, mixed, or paraffinic-naphthenic, as well as to features used in their production, for example, as to the
  • natural lubricating oil base stocks which can be used may be straight mineral
  • lubricating oil or distillates derived from paraffinic, naphthenic, asphaltic, or mixed base crude oils derived from paraffinic, naphthenic, asphaltic, or mixed base crude oils.
  • oils may be employed as well as residual oils, particularly those from which asphaltic constituents have been removed.
  • the oils may be refined by any suitable method, for example, using acid, alkali, and/or clay or other agents such, for example, as aluminium chloride, or they may be extracted oils produced, for example, by solvent extraction with solvents, for example, phenol, sulphur dioxide, furfural, dichlorodiethyl ether, nitrobenzene, or crotonaldehyde.
  • the lubricating oil base stock conveniently has a viscosity of about 2.5 to about 12 cSt (about 2.5 x 10 -6 to about 12 x 10 -6 m 2 /s) and preferably about 2.5 to about 9 cSt. (about 2.5 x 10 -6 to about 9 x 10 -6 m 2 /s) at 100oC. Mixtures of synthetic and natural base oils may be used if desired.
  • An overbased detergent prepared in accordance with the present invention may be employed in a lubricating oil composition which comprises lubricating oil,
  • additives may be incorporated in the composition to enable it to meet particular requirements.
  • additives which may be included in lubricating oil compositions are other detergents and metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, dispersants, anti-foaming agents, anti-wear agents, pour point depressants, and rust inhibitors.
  • Additional detergents and metal rust inhibitors include other metal salts, preferably overbased metal salts, particularly calcium, magnesium and sodium salts, for example, oil-soluble overbased sulphonates, phenates, sulphurised phenates, thiophosphonates, salicylates, naphthenates, and other carboxylates, particularly carboxylates derived from mono- and di-carboxylic acids.
  • overbased metal salts particularly calcium, magnesium and sodium salts
  • carboxylates particularly carboxylates derived from mono- and di-carboxylic acids.
  • Viscosity index improvers impart high and low temperature operability to a
  • Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters, and viscosity index improver dispersants, which function as dispersants as well as viscosity index improvers.
  • Oil soluble viscosity modifying polymers generally have weight average molecular weights of from about 10,000 to 1,000,000, preferably 20,000 to 500,000, as determined by gel permeation chromatography or light scattering methods.
  • suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/ isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene.
  • Corrosion inhibitors also known as anti-corrosive agents, reduce the degradation of metallic parts
  • Oxidation inhibitors, or antioxidants reduce the tendency of mineral oils to deteriorate in service, evidence of such deterioration being, for example, the production of varnish-like deposits on the metal
  • Suitable oxidation inhibitors include ZDDPs, aromatic amines, for example alkylated phenylamines and phenyl
  • alphanapthylamine hindered phenols, alkaline earth metal salts of sulphurized alkyl-phenols having preferably C 5 to C 12 alkyl side chains, e.g., calcium nonylphenyl sulphide; barium octylphenyl.sulphide; and
  • ZDDPs which also act as antiwear agents, are zinc dihydrocarbyl dithiophosphates.
  • Especially preferred ZDDPs for use in oil-based compositions are those of the formula Zn[SP(S)(OR)(OR 1 )] 2 wherein R and R 1 may be the same or different hydrocarbyl radicals containing from 1 to 18, and preferably 2 to 12, carbon atoms, for example, alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals.
  • Particularly preferred as R and R 1 radicals are alkyl radicals having 2 to 8 carbon atoms.
  • radicals which R and R 1 may represent are ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl and butenyl radicals.
  • the total number of carbon atoms in R and R 1 will generally be about 5 or greater.
  • oil- soluble copper compounds comprise oil- soluble copper compounds.
  • the copper may be blended into the oil as any suitable oil-soluble copper compound.
  • oil-soluble it is meant that the compound is oil-soluble under normal blending conditions in the oil or additive package.
  • the copper compound may be in the cuprous or cupric form.
  • the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid.
  • suitable acids include C 8 to C 18 fatty acids, such, for example, as stearic or palmitic acid, but unsaturated acids such, for example, as oleic acid or branched carboxylic acids such, for example, as naphthenic acids of molecular weights of from about 200 to 500 , or
  • radicals such, for example, as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals.
  • R c and R d groups are alkyl groups of from 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, or butenyl radicals.
  • the total number of carbon atoms (i.e. the carbon atoms in R c and R d ) will generally be about five or greater. Copper sulphonates, phenates, and acetylacetonates may also be used.
  • Examples of useful copper compounds are copper Cu I and/or Cu II salts derived from an alkenyl succinic acid or anhydride.
  • the salts themselves may be basic, neutral or acidic. They may be formed by reacting (a) polyalkylene succinimides (typically having polymer groups of number average molecular weight of 700 to 5,000) derived from polyalkylene-polyamines, which have at least one free carboxylic acid group, with (b) a reactive metal compound.
  • Suitable reactive metal compounds include those such, for example, as cupric or cuprous hydroxides, oxides, acetates, borates, and carbonates or basic copper carbonate.
  • these metal salts are Cu salts derived from polyisobutenyl succinic anhydride, and Cu salts derived from polyisobutenyl succinic acid.
  • the copper is in its divalent form, Cu II .
  • the preferred substrates are polyalkenyl succinic acids in which the alkenyl group has a molecular weight greater than about 700.
  • the alkenyl group desirably has a from about 900 to 1,400, and up to 2,500, with a of about 950 being most preferred.
  • polyisobutylene succinic anhydride or acid are especially preferred.
  • a solvent for example, a mineral oil
  • a water solution (or slurry) of the metal-bearing material desirably be dissolved in a solvent, for example, a mineral oil, and heated in the presence of a water solution (or slurry) of the metal-bearing material to a temperature of about 70oC to about 200oC. Temperatures of 100oC to 140oC are normally adequate. It may be necessary, depending upon the salt produced, not to allow the reaction mixture to remain at a temperature above about 140oC for an extended period of time, e.g., longer than 5 hours, or decomposition of the salt may occur.
  • the copper antioxidants e.g., Cu-polyisobutenyl succinate, Cu-oleate, or mixtures thereof
  • Friction modifiers and fuel economy agents which are compatible with the other ingredients of the final oil may also be included.
  • examples of such materials are glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate, esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid, and oxazoline
  • Dispersants maintain oil-insoluble substances, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge formation and
  • ashless dispersants are organic materials which form substantially no ash on combustion, in contrast to the metal-containing (and thus ash-forming) detergents described above.
  • Suitable dispersants include, for example, derivatives of long chain hydrocarbon - substituted carboxylic acids in which the hydrocarbon groups contain 50 to 400 carbon atoms, examples of such derivatives being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • Such hydrocarbon- substituted carboxylic acids may be reacted with, for example, a nitrogen-containing compound, advantageously a polyalkylene polyamine, or with an ester.
  • nitrogen- containing and ester dispersants are well known in the art.
  • Particularly preferred dispersants are the reaction products of polyalkylene amines with alkenyl succinic anhydrides.
  • suitable dispersants include oil soluble salts, amides, imides, oxazolines and esters, or mixtures thereof, of long chain hydrocarbon-substituted mono and dicarboxylic acids or their anhydrides; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing about 1 molar proportion of a long chain substituted phenol with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of a polyalkylene polyamine.
  • long chain hydrocarbon groups are suitably derived from polymers of a C 2 to C 5 monoolefin, the polymers typically having a number average molecular weight of from 700 to 5000.
  • a viscosity index improver dispersant functions both as a viscosity index improver and as a dispersant. Examples of viscosity index
  • improver dispersants suitable for use in accordance with the invention include reaction products of amines, for example polyamines, with a hydrocarbyl-substituted mono - or dicarboxylic acid in which the hydrocarbyl
  • the viscosity index improver dispersant may be, for example, a polymer of a C 4 to C 24 unsaturated ester of vinyl alcohol or a C 3 to C 10
  • unsaturated mono-carboxylic acid or a C 4 to C 10 dicarboxylic acid with an unsaturated nitrogen-containing monomer having 4 to 20 carbon atoms a polymer of a C 2 to C 20 olefin with an unsaturated C 3 to C 10 mono- or dicarboxylic acid neutralized with an amine, hydroxyamine or an alcohol; or a polymer of ethylene with a C 3 to C 20 olefin further reacted either by grafting a C 4 to C 20 unsaturated nitrogen - containing monomer thereon or by grafting an unsaturated acid onto the polymer backbone and then reacting carboxylic acid groups of the grafted acid with an amine, hydroxy amine or alcohol.
  • dispersants and viscosity index improver dispersants which may be used in accordance with the invention may be found in European Patent Specification No. 24146 B, the disclosure of which is incorporated herein by reference.
  • Antiwear agents include zinc dihydrocarbyl
  • ZDDPs dithiophosphates
  • Pour point depressants otherwise known as lube oil flow improvers, lower the temperature at which the fluid will flow or can be poured.
  • Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polymethacrylates, and wax naphthalene.
  • Foam control can be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor.
  • each additive is typically blended into the base oil in an amount which enables the additive to provide its desired function.
  • crankcase lubricants are as follows:
  • marine diesel cylinder lubricants may contain 10 mass % or more, preferably 12.5 to 30 mass %, of detergent so that the lubricant has an overall TBN of at least 20, preferably at least 70.
  • additive concentrates comprising the additives
  • additive package concentrate being referred to herein as an additive package
  • Dissolution of the additive concentrate(s) into the lubricating oil may be
  • the concentrate(s) or additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
  • one or more overbased detergents prepared in accordance with the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from about 2.5 to about 90 mass %, and preferably from about 5 to about 75 mass %, and most preferably from about 8 to about 50 mass % by weight, additives in the appropriate proportions with the
  • the final formulations may employ typically about 10 mass % of an additive package as described above with the remainder being base oil.
  • the following Examples illustrate the invention.
  • sediment level of the product obtained at the end of carbonation is quoted in the Examples and Comparative Examples, this is the volume % of dense sediment determined by centrifuging a given volume of the actual reaction mixture, including reaction solvents, and observing, using a calibrated vessel, the volume of sediment obtained. Sediment levels at the end of
  • stripping to remove solvents and volatile materials were determined by diluting a sample of the stripping product with an equal volume of toluene, centrifuging the diluted sample, and observing the volume % of dense sediment.
  • TBN where quoted, was measured by the technique described in ASTM D2896.
  • a two litre reaction vessel provided with a stirrer was positioned in an ultrasonic bath capable of supplying ultrasound having a frequency of 38 kHz and an intensity of 1 to 2 watts/cm 2 (at the transducer face).
  • a mixture of 720g toluene, 365g of a 70 mass % solution of an alkyl benzene sulphonic acid (molecular weight 480) in diluent oil and 13g of methanol was slowly stirred in the reaction vessel (at a stirring rate lower than that normally required for conventional mixing). The bath was then energized, and 154g of magnesium oxide were added. There was an exotherm to about 35oC.
  • ethylene diamine carbamate solution comprised 16.5 mass % ethylene diamine, 12.2 mass % carbon dioxide, 35.65 mass % water and 35.65 mass % methanol.
  • the temperature of the reaction mixture was stabilized at 40oC, and carbon dioxide was then introduced into the mixture at a rate of 39g/hour.
  • the temperature of the ultrasonic bath was controlled by means of a heater situated in the bath so that the reaction temperature rose to about 68oC over a period of about 180 minutes and then fell back to 65oC, at which it was maintained. The ultrasound treatment was continued until carbonation was terminated.
  • Example 1 was repeated except that ultrasound was not applied and the stirrer speed was increased to give conventional mixing. Neutralization and carbonation were carried out with the reaction vessel positioned in the (unactivated) ultrasonic bath, and the same temperatures as in Example 1 were used, the temperature being
  • the mixture obtained at the end of carbonation contained 1.4 vol. % sediment.
  • the filtration rate was 115.
  • Example 1 was repeated except that during
  • the temperature of the ultrasonic bath was maintained at a level of about 2°C below the reaction temperature: the reaction temperature rose to about 75°C over a period of about 88 minutes, and then gradually declined to 65°C, at which it was maintained by heating.
  • the mixture obtained at the end of carbonation contained 0.4 vol. % sediment.
  • the filtration rate was 299 l/m 2 /hr, and the product had a TBN of 430 mg KOH/g. Comparative Example 2
  • Example 2 was repeated except that ultrasound was not applied and the stirrer speed was increased to give conventional mixing. Neutralization and carbonation were carried out with the reaction vessel positioned in the (unactivated) ultrasonic bath, and the same
  • Example 2 temperatures as in Example 2 were used, the temperature being controlled by means of the heater in the bath.
  • the mixture obtained at the end of carbonation contained 0.7 vol. % sediment.
  • the filtration rate was 131 l/m 2 /hr, and the product had a TBN of 426 mg KOH/g.
  • a mixture of 154g magnesium oxide and 500g of toluene was subjected for 6 minutes to treatment with an ultrasonic probe supplying ultrasound having a frequency of 20 kHz and an intensity of 140 watts/cm 2 (at the face of the probe) to form a magnesium oxide dispersion.
  • Example 3 was repeated, except that the magnesium oxide was not treated with ultrasound before use.
  • the sediment level at the end of carbonation was 0.5 vol. %, and that after stripping to remove water and solvents was 1.0 vol. %.
  • the treated mixture was returned to the reaction vessel and maintained at 33oC while 66.5g of carbon dioxide were introduced over a period of 1 hour 30
  • reaction mixture was then heated over a period of an hour to 60oC and then cooled to 33°C. 135g of calcium hydroxide were then added, following which 66.5g of carbon dioxide were introduced over a period of 1 hour 30 minutes.
  • the product contained 2.7 vol. % of sediment.
  • the reaction mixture was then heated over a period of an hour to 60oC, in a "heat soaking" step. After this heating step, the product contained 1.6 vol. % of
  • Example 4A was repeated, with the minor variations indicated below in the amounts of components, except that the treatment with ultrasound was carried out on an initial slurry of calcium hydroxide.
  • Example 4A The treated mixture was then introduced into a stirred reaction vessel and 584.2g of the mixture of alkyl benzene sulphonic acid and toluene used in Example 4A were added. 400.lg of methanol and 27.9g of water were then added, following which carbon dioxide was introduced as in Example 4A. Subsequent stages of the process were as described in Example 4A.
  • the product contained 3.0 vol. % sediment, while after a final heating step (to 65oC) the sediment level was 1.4 vol. %.
  • Example 4A was repeated except that the treatment with ultrasound was omitted. At the end of the second treatment with carbon dioxide, the product contained 3.2 vol. % of sediment, and after the final heating step the sediment level was 2.0 vol. %.
  • overbased calcium sulphonate having a TBN of about 400 mg KOH/g was prepared as follows:
  • a 400g sample of the stripped product contained 5 vol. % dense sediment and 9 vol. % black gel. This product would be expected to cause immediate blocking of a filter, so that the filtration rate would be zero.
  • the 400g sample was subjected for 10 minutes to treatment with an ultrasonic probe supplying ultrasound having a frequency of 20 kHz and an intensity (at the face of the probe) of 47 watts/cm 2 .
  • the sulphonate contained only 4.4 vol. % dense sediment, and there was no visible gel.
  • the level of dense sediment was reduced to 3.8 vol. % and, again, there was no visible gel.
  • the filtration rate was 288kg/m 2 /hr.
  • the filtered product had a TBN in excess of 388mg KOH/g.
  • the stripped product After stripping, by distillation, to remove solvents and volatile materials, the stripped product contained 2.4 vol. % dense sediment and 1.6 vol. % black gel.
  • the filtration rate was only 37kg/m 2 /hr, in contrast to the much higher rate of 288kg/m 2 /hr
  • Example 5 obtained in Example 5 when a product which initially contained a higher sediment level was subjected to
  • An overbased calcium sulphonate having a TBN of about 400mg KOH/g was prepared following the procedure described in Example 5 with the following differences: 33 g of water was used; the temperature was maintained at 28oC during the introduction of carbon dioxide; at the end of the first introduction of carbon dioxide, the reaction mixture was heated to 60°C over a period of 1 hour, and then held at 60°C for 15 minutes before
  • reaction mixture was heated to 62oC over a period of 1 hour and maintained at 62oC for 15 minutes.
  • the apparatus comprises two glass vessels and a fluid to be treated can be pumped from one vessel to the other through the ultrasonic head.
  • the fluid passes at high velocity through a special orifice and emerges as a thin flat stream which is bisected by a blade which is caused by the fluid to vibrate at 20 kHz.
  • the power to the pump can be set on a scale of from "low” to "high”.
  • the fluid can be passed once from the first vessel to the second through the head (single pass) or can then be pumped back to the first vessel (via the head), with, optionally, further passes in the same manner (multiple passes).
  • the apparatus can also be used in a "recycle" mode, wherein, after passing through the head, the feed is pumped directly back into the first vessel without passing through the head or into the second vessel.
  • a recycle mode wherein, after passing through the head, the feed is pumped directly back into the first vessel without passing through the head or into the second vessel.
  • sonication was continuous, using the recycle mode, and was carried out for 10 minutes with the pump control on the high setting.
  • the treated sample was filtered, through a filter cake, in admixture with a quantity of filter-aid, and the filtration rate, mass of separated sediment, and mass of product lost on the filter cake were noted (Example 6).
  • a further treated sample was filtered using approximately half the quantity of the admixed filter-aid (Example 7).
  • Example 6 and Comparative Example 6 shows that the ultrasound treatment increased the filtration rate .
  • Comparative Examples 6 and 7 show that , in the absence of ultrasound treatment , halving the amount of filter-aid mixed with the sample to be filtered also halved the filtration rate . As shown in Example 7 , however , there was a lower reduction in filtration rate , and less product was lost on the filter cake (while the filtration rate remained at an acceptable level), when the sample was treated with ultrasound before filtration. It will be noted that the mass of separated sediment was
  • Example 8 Five samples of an overbased calcium sulphonate were prepared, the procedure described in Examples 6 and 7 being used in each case. For Example 8, the samples were not mixed to form a masterbatch. Before filtration as described below, each sample was filtered rapidly through a 150 ⁇ m mesh as described in Examples 6 and 7. One sample (Sample 1) was filtered without treatment with ultrasound (Comparative Example 8), while each of the other samples was treated in the Minisonic apparatus described in Examples 6 and 7, with the power control half way between the low and high settings, and then filtered. All variables except the number of sonication passes were held constant. The results are summarized in Table II.
  • the sediment levels before ultrasound treatment show the variation to be expected at the levels of sediment in question.
  • the TBN was measured after filtration. A relatively low TBN will usually be obtained if a product filters very slowly (in this case at a rate of the order of 20 kg/m 2 /hr).
  • Example 1 One sample (Sample 1) was filtered without treatment with ultrasound (Comparative Example 9), while each of the other samples was treated in the Minisonic apparatus described in Examples 6 and 7, with the power control halfway between the low and high settings, and then filtered. All variables except the type and time of the treatment with ultrasound were kept constant. The results are summarized in Table III.
  • the sediment levels before ultrasound treatment show the variation to be expected at the level of sediment in question.
  • the TBN was measured after filtration.
  • Table III shows that, in all cases, sonication reduced the sediment level and increased the filtration rate. Once a high filtration rate was achieved, further sonication had no further effect.
  • Samples of approximately 700g were taken from the product prepared as described above.
  • One sample (Sample 1: Comparative Example 10) was filtered in a pressure filter through a bed of diatomaceous earth without further treatment.
  • Each of three other samples (Samples 2 to 4) was subjected to treatment with ultrasound for 10 minutes using an ultrasonic probe having a frequency of 20 kHz and a power output as indicated in Table IV below.
  • the treated samples were then filtered in the same manner as the untreated sample. The results obtained are summarized in Table IV.
  • the material used was a commercial overbased calcium phenate, having a TBN of 250mg KOH/g, from which the solids had been removed by centrifugation rather than filtration.
  • Example 11 820.6g of the commercial calcium phenate described in Example 11 were filtered as described in Example 11 , but without treatment with ultrasound.
  • the filtration rate was 977 kg/m 2 /hr, significantly lower than that obtained in Example 11.

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  • Engineering & Computer Science (AREA)
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Abstract

On utilise des ultrasons pour préparer des détergents surbasiques contenant des métaux, par exemple des sulfonates ou phénates surbasiques de calcium ou de magnésium, adaptés pour servir d'additifs pour les compositions à base d'huile, par exemple les huiles lubrifiantes et les combustibles. L'utilisation des ultrasons peut, par exemple, réduire les dépôts, réduire la quantité de déchets à évacuer, diminuer les pertes de produit pendant le filtrage, et/ou augmenter la vitesse de filtrage.
EP92918587A 1991-09-19 1992-09-05 Detergents surbasiques contenant des metaux Expired - Lifetime EP0604474B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB919120038A GB9120038D0 (en) 1991-09-19 1991-09-19 Overbased metal-containing detergents
GB9120038 1991-09-19
PCT/EP1992/002069 WO1993006195A1 (fr) 1991-09-19 1992-09-05 Detergents surbasiques contenant des metaux

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EP0604474A1 true EP0604474A1 (fr) 1994-07-06
EP0604474B1 EP0604474B1 (fr) 1996-07-17

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JP (1) JPH06511022A (fr)
CA (1) CA2119245A1 (fr)
DE (1) DE69212322T2 (fr)
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WO (1) WO1993006195A1 (fr)

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GB9416838D0 (en) 1994-08-19 1994-10-12 Bp Chemicals Additives Overbased metal salts, their preparation and use
GB9504034D0 (en) * 1995-02-28 1995-04-19 Exxon Chemical Patents Inc Low base number sulphonates
GB2321906A (en) * 1997-02-07 1998-08-12 Ethyl Petroleum Additives Ltd Fuel additive for reducing engine emissions
US6001786A (en) * 1997-02-19 1999-12-14 Ethyl Corporation Sulfurized phenolic antioxidant composition method of preparing same and petroleum products containing same
US6239309B1 (en) * 1999-12-21 2001-05-29 Chevron Oronite S.A. Synthesis of an overbased detergent from sludge coming from the production high BN overbased alkylaryl sulfonate or overbased sulfurized alkylphenate
US20050040072A1 (en) * 2003-07-21 2005-02-24 Marco Respini Stability of hydrocarbons containing asphal tenes
US7425259B2 (en) 2004-03-09 2008-09-16 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7935246B2 (en) 2004-03-09 2011-05-03 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US7935247B2 (en) 2004-03-09 2011-05-03 Baker Hughes Incorporated Method for improving liquid yield during thermal cracking of hydrocarbons
US8084404B2 (en) * 2005-07-20 2011-12-27 Chevron Oronite Company Llc Crankcase lubricating oil composition for protection of silver bearings in locomotive diesel engines
US7951758B2 (en) 2007-06-22 2011-05-31 Baker Hughes Incorporated Method of increasing hydrolytic stability of magnesium overbased products

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GB2058118A (en) * 1979-08-31 1981-04-08 Exxon Research Engineering Co Overbased calcium sulphonate production
DE3370356D1 (en) * 1982-12-08 1987-04-23 Exxon Research Engineering Co Preparation of overbased calcium sulphonates
GB2194239B (en) * 1986-08-01 1990-05-23 Shell Int Research Process for the thiophosphorylation of alcohols or phenols
EP0323088A1 (fr) * 1987-12-29 1989-07-05 Exxon Chemical Patents Inc. Préparation de sulfonate de magnésium superbasique
US5011618A (en) * 1989-09-05 1991-04-30 Texaco Inc. Process for producing an overbased sulfonate

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Title
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CA2119245A1 (fr) 1993-04-01
GB9120038D0 (en) 1991-11-06
DE69212322D1 (de) 1996-08-22
EP0604474B1 (fr) 1996-07-17
JPH06511022A (ja) 1994-12-08
DE69212322T2 (de) 1996-11-21

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