Oligomeric butylbenzene sulfonates for lubricants and fuels

Abstract

The present invention relates to a process for preparing an oligomeric butylbenzene sulfonate, the process comprising the steps of oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butene having a molecular weight of 220 to 2000 g / mol, alkylating benzene with the olefin blend to produce oligomeric butylbenzene, the oligomeric butylbenzene is sulfonated to produce an oligomeric butylbenzene sulfonic acid, and the oligomeric butylbenzene sulfonic acid is neutralized to produce the oligomeric butylbenzene sulfonate. The invention also relates to an oligomeric butylbenzene sulfonate obtainable by this process; the oligomeric butylbenzenesulfonic acid can be obtained by the method; the oligomeric butylbenzene can be obtained by the method; a lubricant comprising the oligomeric butylbenzene sulfonate; a fuel comprising the oligomeric butylbenzene sulfonate; and the use of the oligomeric butylbenzene sulfonate as a lubricant additive or a fuel additive.

Description

[0001] The present invention relates to a method for preparing oligomeric butylbenzene sulfonate, which comprises the steps of oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol, alkylating benzene with the olefin blend to produce oligomeric butylbenzene, sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and neutralizing the oligomeric butylbenzene sulfonic acid to produce the oligomeric butylbenzene sulfonate.

[0002] The invention also relates to oligomeric butylbenzene sulfonates obtainable by the method; oligomeric butylbenzene sulfonic acid obtainable by the method; oligomeric butylbenzene obtainable by the method; lubricants containing the oligomeric butylbenzene sulfonates; fuels containing the oligomeric butylbenzene sulfonates; and the use of the oligomeric butylbenzene sulfonates as lubricant additives or fuel additives. Combinations of preferred embodiments with other preferred embodiments are within the scope of the invention.

[0003] Alkylbenzene sulfonate is a useful additive for lubricants and fuels. The purpose is to overcome shortcomings and find improved synthesis of alkylbenzene sulfonate and improved lubricants or fuels containing this alkylbenzene sulfonate. Another purpose is to improve lubricants, wherein the lubricant has good rheological behavior, high viscosity index, good low temperature performance (such as in low temperature crankcase simulation), low viscosity under operating conditions (such as in high temperature high shear HTHS viscosity test), high shear stability or low viscosity loss after many use cycles. Another purpose is to find fuel or lubricant additives with higher solubility. Another purpose is to find lubricant additives and fuel additives, which cause improved storage stability, prevent precipitation, corrosion protection, improve composability (such as miscibility with other components of mixture) or filterability.

[0004] These objects are solved by a process for preparing oligomeric butylbenzene sulfonates, which comprises the following steps

[0005] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0006] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0007] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0008] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce the oligomeric butylbenzene sulfonate.

[0009] The butene mixture useful for the oligomerization comprises 1-butene and 2-butene. The 2-butene may be cis-2-butene, trans-2-butene, or a mixture thereof.

[0010] The butene mixture may contain 20 to 99 wt%, preferably 50 to 99 wt%, and particularly 70 to 95 wt% of 1-butene and 2-butene, based on the total olefin content.

[0011] The ratio of 1-butene to 2-butene in the butene mixture is generally in the range of 20:1 to 1:2, preferably 10:1 to 1:1.

[0012] The butene mixture may comprise less than 5% by weight, in particular less than 3% by weight, of isobutene.

[0013] The butene mixture is preferably obtainable from the raffinate II. Industrially obtainable butene mixtures are usually produced by cracking hydrocarbons in petroleum processing, for example by catalytic cracking (such as fluid catalytic cracking (FCC), thermal cracking or hydrocracking) and subsequent dehydration. A suitable industrial butene mixture is the C4 cut, which is obtainable, for example, by fluid catalytic cracking or steam cracking of gas oil and / or by steam cracking of naphtha.

[0014] Depending on the composition of the C4 fraction, a distinction is made between the full C4 fraction (crude C4 fraction), the so-called raffinate I obtained after separation of 1,3-butadiene and the raffinate II obtained after separation of isobutene. Isobutene can be separated from the C4-olefin mixture (such as raffinate I) by one of the following methods: separation by molecular sieves, fractional distillation, reversible hydration to tert-butanol, acid-catalyzed addition of alcohols to tert-ethers (for example addition of methanol to methyl tert-butyl ether (MTBE)), irreversible catalytic oligomerization to diisobutene and triisobutene or irreversible polymerization to polyisobutene.

[0015] The butene mixture can be obtained as a crude C4 fraction which is obtainable by fluid catalytic cracking or steam cracking of gas oil and / or by steam cracking of naphtha.

[0016] Butene mixtures can be obtained from the crude C4 fraction.

[0017] The butene mixture may be obtained from the raffinate I, wherein the raffinate I is obtained from the crude C4 fraction after separation of 1,3-butadiene.

[0018] The butene mixture can be obtained from the raffinate II, wherein the raffinate II is obtained from the raffinate I after separation of isobutene.

[0019] For example, the butene mixture obtainable as raffinate II may comprise

[0020] - 0.5 to 5% by weight of isobutane,

[0021] - 5 to 20% by weight of n-butane,

[0022] - 20 to 40% by weight of trans-2-butene,

[0023] - 10 to 20% by weight of cis-2-butene,

[0024] - 25 to 55% by weight of 1-butene, and

[0025] - 0.5 to 5% by weight of isobutylene.

[0026] The butene mixture may contain traces of gases such as 1,3-butadiene, propene, propane, cyclopropane, propadiene, methylcyclopropane, vinylacetylene, pentene, pentane, in each case in the range of up to 1% by weight. If dienes or alkynes are present in the butene mixture, they can be removed from the butene mixture before the oligomerization to preferably less than 100 ppm. They are preferably removed by selective hydrogenation, particularly preferably by selective hydrogenation to a residual content of less than 50 ppm.

[0027] The raffinate II has the following typical composition: isobutane: 3% by weight, n-butane: 15% by weight, isobutene: 2% by weight, 1-butene: 30% by weight, trans-2-butene: 32% by weight, cis-2-butene: 18% by weight.

[0028] For the oligomerization of butene mixture, a reaction system including one or more identical or different reactors can be used. In the simplest case, a single reactor is used to carry out oligomerization. However, two or more reactors can also be used, each of which has identical or different mixing characteristics. These independent reactors can be optionally separated once or multiple times by internals. If two or more reactors form a reaction system, these reactors can be connected to each other in any desired manner (e.g., in parallel or in series). In a suitable configuration, for example, a reaction system consisting of two reactors connected in series is used.

[0029] Suitable pressure-resistant reaction equipment for oligomerization is a reactor for gas-solid and gas-liquid reaction, such as tubular reactor, stirred tank reactor, gas circulation reactor, bubble tower, etc., which can be separated by internals if appropriate. Preferably, a tube bundle reactor or a shaft furnace is used. If a heterogeneous catalyst is used for oligomerization, the heterogeneous catalyst can be arranged in one or more catalyst fixed beds. At this, different catalysts can be used in different reaction zones. However, it is preferred to use the same catalyst in all reaction zones.

[0030] The temperature during the oligomerization reaction is generally in the range of about 20° C. to 280° C., preferably 25° C. to 200° C., in particular 30° C. to 140° C. The pressure during the oligomerization reaction is generally in the range of about 1 to 300 bar, preferably 5 to 100 bar and in particular 20 to 70 bar. If the reaction system comprises more than one reactor, these reactors can have the same or different temperatures and the same or different pressures. Thus, for example, in the second reactor of the reactor cascade, a higher temperature and / or a higher pressure can be established than in the first reactor, for example in order to achieve a conversion that is as complete as possible.

[0031] In a particular embodiment, the temperature and pressure values ​​for the oligomerization are selected such that the olefin-containing feed is liquid or in a supercritical state.

[0032] The oligomerization reaction is preferably carried out adiabatically. The term should be understood in the following technical sense rather than in the physicochemical sense. Therefore, the oligomerization reaction is usually carried out exothermically so that the reaction mixture experiences a temperature rise when flowing through the reaction system (e.g., catalyst bed). An adiabatic reaction procedure is understood to mean a procedure in which the heat released in the exothermic reaction is absorbed by the reaction mixture in the reactor and is not cooled using a cooling device. Therefore, in addition to the residual portion released from the reactor to the surrounding environment by natural heat conduction and heat radiation, the reaction heat dissipates from the reactor with the reaction mixture.

[0033] For oligomerization, a transition metal-containing catalyst is used. These catalysts are preferably heterogeneous catalysts. Preferably, an oligomerization catalyst comprising nickel is used. In this regard, a heterogeneous catalyst comprising nickel oxide is preferably used. The heterogeneous nickel-containing catalyst used can have different structures. In principle, non-supported catalysts and supported catalysts are suitable. The latter is preferably used. The support material can be, for example, silicon dioxide, clay, aluminosilicate, aluminosilicate and zeolite with a layered structure (such as mordenite, faujasite, zeolite X, zeolite Y and ZSM-5), zirconium oxide treated with acid, or sulfated titanium dioxide. Particularly suitable is a precipitated catalyst, which is obtained by mixing and calcining an aqueous solution of a nickel salt and a silicate (such as sodium silicate) with nickel nitrate and, if appropriate, an aluminum salt (such as aluminum nitrate). In addition, a catalyst prepared by mixing Ni 2+ Catalysts obtained by incorporating ions into natural or synthetic sheet silicates (such as montmorillonite) by ion exchange. Suitable catalysts can also be obtained by impregnation of silica, clay or aluminosilicates with aqueous solutions of soluble nickel salts (such as nickel nitrate, nickel sulfate or nickel chloride) and subsequent calcination.

[0034] Catalysts containing nickel oxide are preferred. Particularly preferred are catalysts consisting essentially of NiO, SiO2, TiO2 and / or ZrO2 and, if appropriate, Al2O3. Most preferred are catalysts containing, as basic active ingredients, 10 to 70% by weight of nickel oxide, 5 to 30% by weight of titanium dioxide and / or zirconium dioxide, 0 to 20% by weight of aluminum oxide, and, as the remainder, silicon dioxide. Such catalysts are obtainable by precipitating the catalyst substance at a pH of 5 to 9 by adding an aqueous solution containing nickel nitrate to an alkali metal water glass solution containing titanium dioxide and / or zirconium dioxide, filtering, drying and heating at 350° C. to 650° C.

[0035] The catalyst is preferably in the form of tablets, for example in the form of tablets with a diameter of 2 to 6 mm and a height of 3 to 5 mm, rings with an outer diameter of 5 to 7 mm, a height of 2 to 5 mm and a pore diameter of 2 to 3 mm, or strips of different lengths with a diameter of 1.5 to 5 mm. Such forms are obtained in a manner known per se by tableting or extrusion, usually using tableting aids such as graphite or stearic acid.

[0036] The crude oligomerization product can be enriched by distillation. The distillation separation of the oligomerization product can be carried out continuously or intermittently (discontinuously).

[0037] Suitable distillation apparatuses are conventional equipment known to those skilled in the art. These include, for example, distillation columns, such as plate columns, which, if desired, can be equipped with internals, valves, side stream take-offs, etc.; evaporators, such as thin-film evaporators, falling-film evaporators, wiper-blade evaporators, Sambay evaporators, etc.; and combinations thereof. Preferably, C 16 The olefin fraction is separated by fractional distillation. The distillation can be carried out in one or more distillation columns connected together.

[0038] The distillation column used can comprise separation internals, such as separation trays, for example perforated trays, bubble-cap trays or valve trays; structured packings (for example metal sheets and fabric packings), or random packings. In the case of using a plate column with downcomers, the downcomer residence time is preferably at least 5 seconds, particularly preferably at least 7 seconds. Suitable evaporators and condensers are likewise types of equipment known per se. As evaporators, heatable containers customary for this purpose or evaporators with forced circulation, for example falling film evaporators, can be used. If two distillation columns are used for the distillation, these distillation columns can be provided with identical or different evaporators and condensers.

[0039] Preferably, the bottom temperatures established during the distillation are at most 300° C., particularly preferably at most 250° C. In order to maintain these maximum temperatures, the distillation can, if desired, be carried out under a suitable vacuum.

[0040] The butene mixture is oligomerized to produce an olefin blend comprising oligomerized butenes having a molecular weight of 220 to 2000 g / mol. The olefin blend is preferably obtainable by oligomerization in the presence of a nickel-containing heterogeneous catalyst.

[0041] Oligomeric butene can have the molecular weight of 220 to 1000g / mol, 220 to 700g / mol, 220 to 500g / mol or 220 to 350g / mol.Molecular weight can be determined by GPC using polystyrene standards, for example as described in DIN 55672-1.Molecular weight can be determined by gas chromatography-mass spectrometry (GC-MS).Molecular weight can be determined by HPLC-mass spectrometry (HPLC-MS).

[0042] Olefin blends can include at least 40wt%, 50wt%, 60wt% or 80wt% of the molecular weight being 220 to 2000g / mol of oligomeric butenes. In another form, olefin blends can include at least 40wt%, 50wt%, 60wt% or 80wt% of the molecular weight being 220 to 1000g / mol of oligomeric butenes. In another form, olefin blends can include at least 40wt%, 50wt%, 60wt% or 80wt% of the molecular weight being 220 to 500g / mol of oligomeric butenes. In another form, olefin blends can include at least 40wt%, 50wt%, 60wt% or 80wt% of the molecular weight being 220 to 350g / mol of oligomeric butenes.

[0043] Olefin blends typically contain C 16 Olefins, C 20 Olefins, and C 24 The olefin blend typically comprises a total of at least 20, 30, 40, 50, 60, 70, 80 or 90 wt% C 16 Olefins, C 20 Olefins, and C 24 Olefins. The olefin blend preferably comprises a total amount of at least 45 wt% C 16 Olefins, C 20 Olefins, and C 24 In another form, the olefin blend preferably comprises a total of at least 55 wt% C 16 Olefins, C 20 Olefins, and C 24 Olefins.

[0044] The olefin blend may include terminally unsaturated oligomeric butenes, such as terminally unsaturated C 16 Olefins, terminal unsaturated C 20Olefins, and terminal unsaturated C 24 Olefins. The term "terminally unsaturated olefin" generally refers to 1-olefins (eg, 1-hexadecene). The olefin blend may contain at least 5 wt%, 15 wt%, 25 wt%, or 35 wt% of terminally unsaturated oligomeric butenes.

[0045] The olefin blend may include β-unsaturated oligomeric butenes, such as β-unsaturated C 16 Olefins, β-unsaturated C 20 Olefins, and β-unsaturated C 24 Olefins. The term "beta-unsaturated olefins" generally refers to 2-olefins, such as 2-hexadecene. The olefin blend may contain at least 5 wt%, 15 wt%, 25 wt% or 35 wt% of beta-unsaturated oligomeric butenes.

[0046] The olefin blend may contain terminally and beta-unsaturated oligomeric butenes, such as terminally and beta-unsaturated C 16 Olefins, terminal and β-unsaturated C 20 Olefins, as well as terminal and β-unsaturated C 24 Olefins. The olefin blend may comprise at least 10 wt%, 30 wt%, 50 wt% or 70 wt% in total of terminally and beta-unsaturated oligomeric butenes.

[0047] The olefin blend may include a mixture of linear and branched oligomeric butenes, such as linear and branched C 16 Mixtures of olefins, linear and branched C 20 A mixture of olefins, as well as straight-chain and branched C 24 The branching of oligomeric butenes generally depends on the oligomeric butene mixture. The butene mixture may contain less than 20wt%, 15wt%, 10wt%, or 5wt% isobutylene. The olefin blend may contain less than 5wt%, 3wt%, 1wt%, 0.5wt%, or 0.1wt% oligomeric isobutylene. In another form, the olefin blend may contain less than 5wt%, 3wt%, 1wt%, 0.5wt%, or 0.1wt% oligomeric isobutylene with a molecular weight higher than 220g / mol. In another form, the olefin blend is substantially free of oligomeric isobutylene. In another form, the olefin blend is substantially free of oligomeric isobutylene with a molecular weight higher than 220g / mol.

[0048] The olefin blend may include a mixture of terminally unsaturated linear and branched oligomeric butenes, such as terminally unsaturated linear and branched C 16 A mixture of olefins, terminally unsaturated straight-chain and branched C 20 A mixture of olefins, as well as terminally unsaturated straight-chain and branched C 24 A mixture of olefins.

[0049] The olefin blend may contain lower oligomeric butenes, which are oligomeric butenes having a molecular weight below 220 g / mol, such as C 12 Olefins or C8 olefins. The olefin blend preferably comprises a C 12 The olefin blend may contain up to 60, 50, 45, or 40 wt% of a lower oligomeric butene such as C 12 Olefins. The olefin blend may contain 0.1 to 60, 1 to 50, 10 to 45 wt%, or 20 to 45 wt% of lower oligomeric butenes, such as C 12 Olefins. Low oligomeric butenes are usually terminal unsaturated olefins, such as terminal unsaturated C8 olefins or terminal unsaturated C 12 Olefins.

[0050] Olefin blends typically contain

[0051] -20-85wt% C 16 Olefins,

[0052] -5-30wt% C 20 Olefins, and

[0053] -2-20wt% C 24 Olefins.

[0054] In another form, the olefin blend comprises

[0055] -20-85wt% C 16 Olefins,

[0056] -5-30wt% C 20 Olefins,

[0057] -2-20wt% C 24 Olefins, and

[0058] Optionally further oligomeric butenes having a molecular weight of 220 to 2000 g / mol.

[0059] In another form, the olefin blend comprises

[0060] -20-85wt% C 16 Olefins,

[0061] -5-30wt% C 20 Olefins,

[0062] -2-20wt% C 24 Olefins, and

[0063] Optionally, lower oligomeric butenes such as C 12 Olefins.

[0064] In another form, the olefin blend comprises

[0065] -20-85wt% C 16 Olefins,

[0066] -5-30wt% C 20 Olefins,

[0067] -2-20wt% C 24 Olefins, and

[0068] optionally further oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0069] and optionally lower oligomeric butenes such as C 12 Olefins.

[0070] In another form, the olefin blend comprises

[0071] -20-85wt% C 16 Olefins,

[0072] -5-30wt% C 20 Olefins,

[0073] -2-20wt% C 24 Olefins,

[0074] -20-60wt% C 12 Olefins, and

[0075] Optionally further oligomeric butenes having a molecular weight of 220 to 2000 g / mol.

[0076] Oligobutylbenzenes are generally produced by alkylating benzene with a blend of olefins.Alkylation is generally a Friedel Crafts type reaction in which an alkylation catalyst is typically used to catalyze the electrophilic aromatic substitution of an aromatic ring by an alkylating agent (e.g., an alkyl halide or an olefin).

[0077] Suitable alkylation catalysts for alkylation are heterogeneous acids, hydrofluoric acid, aluminum chloride, or boron fluoride, wherein heterogeneous acids are preferred. Suitable alkylation catalysts for alkylation are heterogeneous acids selected from the group consisting of

[0078] - clays, in particular montmorillonite or montmorillonite-containing materials, such as, for example, K10 and K20 from Südchemie,

[0079] - Strongly acidic ion exchangers such as those from Rohm & Haas 36 or 15 or from DuPont or / Silicon dioxide,

[0080] - acidic metal oxides, such as, for example, M(I)O3-M(II)O2-M(I)=W, Mo and M(II)=Zr, Ti, Mn and / or Sn, Al2O3-SiO2, TiO2-ZrO2, TiO2, Nb2O5, Ta2O5,

[0081] - Sulfated metal oxides, such as ZrO2-SO3, TiO2-SO3, Al2O3-SO3, WO3-SO3, Nb2O5-SO3,

[0082] -Supported heteropolyacids, such as PW 12 -HPA / SiO2, PMo 12 -HPA / coal, P2W 18 -HPA / TiO2, and

[0083] -Zeolite.

[0084] Preferred alkylation catalysts for alkylation are zeolites.

[0085] Preference is given to zeolites of the following structural types: BIK, BRE, ERI, CHA, DAC, EAB, EDI, EPI, FER, pentasils with MFI or MEL structure, faujasites such as, for example, Y, LTL, MOR, BEA, GME, HEU, KFI, MAZ, OFF, PAU, RHO, STI. Particular preference is given to L, Y (including USY types), BEA and MOR. These zeolites are preferably used in the H and / or La form, although traces of Na, K, Mg or Ca may be present depending on the preparation process. The lattice aluminum may be partially or completely exchanged with B, Ga or Fe.

[0086] The catalyst can be used directly as a fine powder in suspension, in the case of zeolites these are, for example, particle sizes between 100 nm and a few μm. In most cases, however, these catalysts are shaped together with a binder material to give shaped bodies with a diameter of 0.1 to 5 mm. For use in a fixed bed, 1 to 3 mm is preferred, 0.001 to 1 mm in suspension and 0.1 to 3 mm in a moving bed. Suitable binders are in particular clays, aluminum oxides such as, for example, Purals, Sirals and Versals and silica gels. In addition, inert fillers such as SiO2 (e.g., Siloxane from Degussa) can be added. ). Examples of suitable shaped bodies are tablets, strips, rings, ribs, stars or wheel-shaped extrudates.

[0087] The catalyst may have a mass of 30 to 2000 m 2 / g, preferably 100 to 700m 2 The volume of pores with a diameter of 2-20 nm is typically 0.05-0.5 ml / g, preferably 0.1-0.3 ml / g, the volume of pores with a diameter of 20-200 nm is typically 0.005 to 0.2 ml / g, preferably 0.01 to 0.1 ml / g, and the volume of pores with a diameter of 200-2000 nm is typically 0.05-0.5 ml / g, preferably 0.05 to 0.3 ml / g.

[0088] In most cases, the deactivated catalyst can be regenerated by burning it off in air or depleted air at 250° C. to 550° C. Alternatively, it can be treated with compounds that have an oxidizing effect at lower temperatures (optionally also in the liquid phase), in this context particular mention being made of NOx, H2O2 and halogens. The regeneration can be carried out directly in the alkylation reactor or externally.

[0089] The alkylation can be carried out in the liquid phase (i.e. in the absence of a gas phase), which can be achieved by means of a corresponding system pressure. The pressure is generally the autogenous pressure (vapor pressure of the system) or greater. The alkylation temperature can be 100° C. to 250° C., preferably 120° C. to 220° C., in particular 130° C. to 200° C. Suitable pressures are in the range of 1 to 35 bar.

[0090] Alkylation can be carried out in batch or continuous mode. In batch mode, a typical method is to use a stirred autoclave or glass flask that can be heated to the desired reaction temperature. The continuous process is most effective in a fixed bed process. The space velocity range in the fixed bed process can be 0.01 to 10 or greater weight hourly space velocity. In a fixed bed process, the alkylation catalyst is loaded into a reactor and activated or dried at a temperature of at least 150° C. under vacuum or flowing inert dry gas. After activation, the alkylation catalyst is cooled to ambient temperature and an aromatic hydrocarbon compound (optionally toluene) stream is introduced. The pressure is increased by a back pressure valve so that the pressure is higher than the bubble point pressure of the aromatic hydrocarbon feed composition at the desired reaction temperature. After the system is pressurized to the desired pressure, the temperature is increased to the desired reaction temperature. The olefin stream is then mixed with the aromatic hydrocarbon and allowed to flow through the catalyst. The reactor effluent containing alkylated aromatic hydrocarbons, unreacted olefins and excess aromatic hydrocarbon compounds is collected. Excess aromatic hydrocarbon compounds are then removed by distillation, stripping, evaporation under vacuum, or any other means known to those skilled in the art.

[0091] Oligobutylbenzenesulfonic acid is usually produced by sulfonating oligobutylbenzene.

[0092] The sulfonation of oligobutylbenzene can be carried out by reacting oligobutylbenzene with a sulfonating agent, such as concentrated sulfuric acid, oleum, sulfur trioxide diluted in nitrogen or air, or sulfur trioxide dissolved in sulfur dioxide. Preferably, the sulfonation is carried out with sulfur trioxide. The sulfonation reaction can be carried out in a stirred vessel or in a falling film reactor.

[0093] After sulfonation, the crude product can optionally be purified by conventional methods, such as washing with water or by heat treatment under stirring with nitrogen bubbling.

[0094] The sulfonic acid group in the oligobutylbenzenesulfonic acid may be in the ortho-position, meta-position, or para-position of the oligobutyl group, with the para-position being preferred.

[0095] The sulfonate group in the oligobutylbenzene sulfonate may be in the ortho-, meta-, or para-position of the oligobutyl group, with the para-position being preferred.

[0096] Oligomeric butylbenzene sulfonates are generally produced by neutralizing oligomeric butylbenzene sulfonic acid.

[0097] Bases can be used to neutralize the oligomeric butylbenzene sulfonic acid. Examples of suitable bases include alkali metals (e.g., sodium, potassium), alkaline earth metals (e.g., calcium, magnesium), ammonium hydroxide or amine (e.g., isopropylamine, methylamine, triethanolamine) salts, carbonates or oxides. For example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, calcium hydroxide and calcium carbonate and mixtures thereof can be used for neutralization.

[0098] After neutralization, the sulfonate salt may be purified, for example, by filtration, centrifugation, washing, drying, and / or other methods for removing solid sulfonate salt product from aqueous solution.

[0099] The oligomeric butylbenzene sulfonates may be in the form of neutral or overbased alkali metal salts, alkaline earth metal salts or ammonium salts.

[0100] The oligomeric butylbenzene sulfonate may exist in the form of a salt having a cationic counterion. The oligomeric butylbenzene sulfonate may have the form of an alkali metal salt (such as lithium, sodium, potassium), an alkaline earth metal salt (such as magnesium, calcium, strontium and barium), or an ammonium salt.

[0101] In another form, the oligomeric butylbenzene sulfonate is a calcium salt of oligomeric butylbenzene sulfonate, a magnesium salt of oligomeric butylbenzene sulfonate, or a barium salt of oligomeric butylbenzene sulfonate.

[0102] The oligomeric butylbenzene sulfonate may be present as an overbased sulfonate, for example a low overbased sulfonate or a high overbased sulfonate.

[0103] Overbased sulfonates can be characterized by their base number (also referred to as BN). BN refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher BN values ​​reflect a more basic product and therefore greater basicity retention. The BN of a sample can be determined by ASTM test number D2896. Low overbased alkyl aryl sulfonates generally refer to overbased sulfonates having a BN of about 2 to about 60. High overbased alkyl aryl sulfonates generally refer to overbased sulfonates having a BN of at least 250.

[0104] Overbased sulfonates can be prepared by adding a stoichiometric excess of base (eg, hydroxide, oxide, carbonate) based on the amount required to react with the acidic portion of the sulfonate. A diluent (eg, mineral oil) is typically incorporated into the overbased sulfonate.

[0105] In a preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps:

[0106] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0107] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0108] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0109] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0110] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0111] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0112] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0113] In a preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps:

[0114] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0115] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0116] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0117] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0118] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0119] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0120] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0121] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0122] In a preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps:

[0123] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0124] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0125] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0126] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0127] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0128] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins,

[0129] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0130] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0131] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0132] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps: i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 700 g / mol,

[0133] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0134] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0135] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0136] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0137] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0138] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0139] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps: i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 700 g / mol,

[0140] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0141] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0142] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0143] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0144] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0145] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0146] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0147] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps: i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 700 g / mol,

[0148] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0149] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0150] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0151] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0152] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins,

[0153] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0154] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0155] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0156] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps: i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0157] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0158] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0159] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0160] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0161] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0162] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0163] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the following steps: v) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0164] vi) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0165] vii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0166] viii) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0167] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0168] wherein the oligomerization is carried out in the presence of a heterogeneous catalyst containing nickel,

[0169] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0170] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0171] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the steps of i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0172] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0173] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0174] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0175] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0176] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0177] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0178] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0179] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the steps of i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0180] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0181] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0182] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0183] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0184] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins,

[0185] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0186] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0187] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0188] In another preferred form, the process for preparing oligomeric butylbenzene sulfonate comprises the steps of i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0189] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0190] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0191] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0192] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0193] wherein the oligomerization is carried out in the presence of a heterogeneous catalyst containing nickel,

[0194] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins,

[0195] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0196] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0197] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0198] The present invention also relates to oligomeric butylbenzene obtainable by a process for preparing oligomeric butylbenzene sulfonate. Oligomeric butylbenzene is generally obtainable by a process for preparing oligomeric butylbenzene sulfonate as an intermediate.

[0199] Oligomeric butylbenzene is generally obtainable by a process comprising the following steps:

[0200] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0201] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzenes.

[0202] Oligomeric butylbenzene is preferably obtainable by a process comprising the following steps:

[0203] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0204] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0205] The oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol.

[0206] Oligomeric butylbenzene is preferably obtainable by a process comprising the following steps:

[0207] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0208] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0209] wherein the oligomerization is in the presence of a nickel-containing heterogeneous catalyst, and wherein the oligomerized butenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol.

[0210] Oligobutylbenzene is also preferably obtainable by a process comprising the steps of

[0211] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0212] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0213] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0214] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content, and

[0215] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0216] Oligobutylbenzene is also preferably obtainable by a process comprising the steps of

[0217] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0218] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0219] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0220] wherein the oligomerization is in the presence of a nickel-containing heterogeneous catalyst, wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene, based on the total olefin content, and

[0221] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0222] Oligobutylbenzene is also preferably obtainable by a process comprising the steps of

[0223] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0224] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0225] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0226] wherein the oligomerization is in the presence of a nickel-containing heterogeneous catalyst, wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene, based on the total olefin content, and

[0227] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0228] The present invention also relates to an oligomeric butylbenzene sulfonic acid obtainable by a process for preparing oligomeric butylbenzene sulfonates. Oligomeric butylbenzenes are generally obtainable by a process for preparing oligomeric butylbenzene sulfonates as an intermediate.

[0229] Oligomeric butylbenzenesulfonic acid is generally obtainable by a process comprising the following steps:

[0230] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0231] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene, and

[0232] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid.

[0233] The oligomeric butylbenzene sulfonic acid is preferably obtainable by a process comprising the following steps:

[0234] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0235] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene, and

[0236] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0237] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide,

[0238] The oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol.

[0239] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0240] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0241] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0242] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0243] wherein the oligomerization is in the presence of a heterogeneous catalyst containing nickel,

[0244] wherein the sulfonation is performed by reacting the oligomeric butylbenzene with sulfur trioxide, and wherein the oligomeric butenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol.

[0245] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0246] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0247] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0248] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0249] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0250] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide,

[0251] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content, and

[0252] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0253] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0254] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0255] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0256] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0257] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0258] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide,

[0259] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0260] wherein the sulfonic acid group in the oligobutylbenzenesulfonic acid is located at the para position of the oligobutyl group, and

[0261] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0262] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0263] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0264] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0265] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0266] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0267] wherein the oligomerization is carried out in the presence of a heterogeneous catalyst containing nickel,

[0268] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, wherein the butene mixture contains 50 to 99 wt % of 1-butene and 2-butene, based on the total olefin content, and

[0269] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0270] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0271] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0272] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0273] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0274] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0275] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide,

[0276] wherein the oligomerization is in the presence of a nickel-containing heterogeneous catalyst, wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene, based on the total olefin content, and

[0277] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0278] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0279] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0280] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0281] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0282] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0283] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide,

[0284] wherein the oligomerization is in the presence of a nickel-containing heterogeneous catalyst, wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene, based on the total olefin content,

[0285] wherein the sulfonic acid group in the oligobutylbenzenesulfonic acid is located at the para position of the oligobutyl group, and

[0286] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0287] Oligobutylbenzenesulfonic acid is also preferably obtainable by a process comprising the following steps:

[0288] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0289] ii) alkylating benzene with the olefin blend to produce the oligomeric butylbenzene,

[0290] iii) sulfonating the oligomeric butylbenzene to produce the oligomeric butylbenzene sulfonic acid,

[0291] wherein the oligobutenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol,

[0292] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide,

[0293] wherein the oligomerization is in the presence of a nickel-containing heterogeneous catalyst, wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene, based on the total olefin content,

[0294] wherein the sulfonic acid group in the oligobutylbenzenesulfonic acid is located at the para position of the oligobutyl group, and

[0295] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins.

[0296] The present invention further relates to a lubricant comprising oligomeric butylbenzene sulfonate. In another form, the lubricant comprises oligomeric butylbenzene sulfonate obtainable by a process for preparing oligomeric butylbenzene sulfonate, the process comprising the steps of

[0297] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0298] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0299] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0300] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate.

[0301] In another form, the lubricant comprises oligomeric butylbenzene sulfonate obtainable by a process for preparing oligomeric butylbenzene sulfonate comprising the steps of i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0302] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0303] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0304] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0305] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0306] wherein the oligomerization is in the presence of a heterogeneous catalyst containing nickel,

[0307] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins,

[0308] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0309] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0310] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0311] Typically, lubricants contain

[0312] - base oil,

[0313] - oligomeric butylbenzene sulfonates, and

[0314] - Additional lubricant additives.

[0315] The lubricant may contain at least 0.1 wt%, preferably at least 0.5 wt% and especially at least 1 wt% of oligomeric butylbenzene sulfonate.In another form, the lubricant may contain 0.1-20 wt%, preferably 0.1-150 wt% and especially at least 0.1-10 wt% of oligomeric butylbenzene sulfonate.

[0316] The lubricant may comprise at least 30 wt%, preferably at least 50 wt% and in particular at least 70 wt% of base oil.The lubricant may comprise 30-99.9 wt%, preferably 50-99 wt% and in particular 70-95 wt% of base oil.

[0317] The lubricant may contain up to 20 wt %, preferably up to 15 wt % and in particular up to

[0318] 10 wt% of additional lubricant additives.

[0319] Lubricants generally refer to compositions capable of reducing friction between surfaces (preferably metal surfaces), such as surfaces of mechanical devices. Mechanical devices can be parts consisting of devices that work under mechanical principles. Suitable mechanical devices are bearings, gears, joints and guidance. Mechanical devices can operate at temperatures in the range of -30°C to 80°C.

[0320] Lubricants are typically fluids, oils or greases.

[0321] Lubricants are usually formulated specifically for almost all types of machines and manufacturing processes. The type and concentration of base oils and / or lubricant additives used for these lubricants can be selected based on the requirements of the lubricated machinery or process, the quality required by the builder and user of the machinery, and government regulations. Typically, each lubricant has a set of unique performance requirements. In addition to the proper lubrication of the machine or process, these requirements can also include the maintenance of the quality of the lubricant itself and the use and treatment of the lubricant to the impact on energy use, environmental quality and user health.

[0322] Typical lubricants are automotive lubricants (e.g. gasoline engine oils, diesel engine oils, gas engine oils, gas turbine oils, automatic transmission oils, gear oils) and industrial lubricants (e.g. industrial gear oils, pneumatic tool lubricants, high temperature oils, gas compressor oils, hydraulic oils, metalworking fluids).

[0323] Examples of lubricants are shaft lubrication, medium and heavy duty engine oils, industrial engine oils, marine engine oils, automotive engine oils, crankshaft oils, compressor oils, refrigeration oils, hydrocarbon compressor oils, very low temperature lubricating oils and fats, high temperature lubricating oils and fats, wire rope lubricants, textile machine oils, refrigeration oils, aviation and aerospace lubricants, aviation turbine oils, transmission oils, gas turbine oils, spindle oils, spindle oils, traction fluids, fluid), transmission oil, plastic transmission oil, passenger car transmission oil, truck transmission oil, industrial transmission oil, industrial gear oil, insulating oil, instrument oil, brake fluid, transmission fluid, shock absorber oil, heat distribution medium oil, transformer oil, fat, chain oil, medium quality lubricant for metalworking operations, oil for warm working and cold working, oil for water-based metalworking fluid, oil for neat metalworking fluid, oil for semi-synthetic metalworking fluid, oil for synthetic metalworking fluid, drilling cleaner for soil survey, hydraulic oil, biodegradable lubricant or grease or lubricating wax, chain saw oil, mold release agent, molding fluid, gun lubricant, pistol lubricant and rifle lubricant or watch lubricant and food grade approved lubricant.

[0324] The lubricant may generally have a thickness of at least 10, 50, 100, 150, 200, 300, 400, 500, 600, 900, 1400, or 2000 mm at 40°C. 2 In another form, the lubricant may generally have a kinematic viscosity of 200 to 30,000 mm at 40°C. 2 / s (cSt), preferably 500 to 10 000 mm 2 / s, and particularly 1000 to 5000 mm 2 / s kinematic viscosity.

[0325] The lubricant may generally have a thermal conductivity of at least 2, 3, 5, 10, 20, 30, 40, or 50 mm at 100°C. 2 In another form, the lubricant may have a kinematic viscosity of 10 to 5000 mm at 100°C. 2 / s (cSt), preferably 30 to 3000 mm 2 / s, and particularly 50 to 2000 mm 2 / s kinematic viscosity.

[0326] The lubricant may have a viscosity index (VI) of at least 150, 160, 170, 180, 190, or 200.

[0327] The base oil may be selected from the group consisting of mineral oils (Group I, II or III oils), polyalphaolefins (Group IV oils), polymerized olefins and interpolymerized olefins, alkyl naphthalenes, alkylene oxide polymers, silicone oils, phosphate esters and carboxylates (Group V oils). Preferably, the base oil is selected from Group I, Group II, Group III base oils according to the definition of API or a mixture thereof. The definition of base oil is the same as that found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, 14th Edition, December 1996, Appendix 1, December 1998. The publication classifies base oils as follows:

[0328] a) Group I base oils contain less than 90% saturates (ASTM D 2007) and / or greater than 0.03% sulfur (ASTM D 2622) and have a viscosity index greater than or equal to 80 and less than 120 (ASTM D 2270).

[0329] b) Group II base oils contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120.

[0330] c) Group III base oils contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120.

[0331] d) Group IV base oils contain polyalphaolefins. Polyalphaolefins (PAOs) include known PAO materials, which typically contain relatively low molecular weight hydrogenated polymers or oligomers of alpha olefins (including but not limited to C2 to about C32 alpha olefins, wherein C8 to about C16 alpha olefins, such as 1-octene, 1-decene, 1-dodecene, etc. are preferred). Preferred polyalphaolefins are poly-1-octene, poly-1-decene, and poly-1-dodecene.

[0332] e) Group V base oils contain any base oil not described by Group I to Group IV. Examples of Group V base oils include alkyl naphthalene, alkylene oxide polymers, silicone oils, and phosphate esters.

[0333] Synthetic base oils include hydrocarbon oils and halogen-substituted hydrocarbon oils, such as polymerized olefins and interpolymerized olefins (e.g., polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene)); alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenylenes (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof.

[0334] Alkylene oxide polymers and interpolymers and derivatives thereof in which the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic base oils. These are exemplified by polyoxyalkylene polymers prepared by the polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl polyisopropylene glycol ether having a molecular weight of 1000 or diphenyl ether of polyethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic acid esters thereof, for example, acetates of tetraethylene glycol, mixed C3-C8 fatty acid esters and C13 oxo acid diesters.

[0335] Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy silicone oils and silicate oils constitute another class of useful synthetic base oils; such base oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl) disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other synthetic base oils include liquid esters of phosphorus acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofuran.

[0336] The lubricant may further comprise a lubricant additive. Suitable lubricant additives may be selected from viscosity index improvers, polymer thickeners, corrosion inhibitors, detergents, dispersants, defoamers, dyes, wear protection additives, extreme pressure additives (EP additives), antiwear additives (AW additives), friction modifiers, metal passivators, pour point depressants.

[0337] The combined total amount of lubricant additives in the lubricant may be included in the range of 0-25 wt%, or 0.01-20 wt%, or 0.1-15 wt%, or 0.5-10 wt%, or 1-5 wt% of the lubricant.

[0338] Viscosity index improvers include high molecular weight polymers whose relative viscosity at high temperatures is higher than their relative viscosity at low temperatures. Viscosity index improvers include polyacrylates, polymethacrylates, alkyl methacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidone, polybutene, olefin copolymers such as ethylene-propylene copolymers or styrene-butadiene copolymers or polyolefins such as PIB, styrene / acrylate copolymers and polyethers, and combinations thereof. The most common V1 improvers are methacrylate polymers and copolymers, acrylate polymers, olefin polymers and copolymers, and styrene-butadiene copolymers. Other examples of viscosity index improvers include polymethacrylates, polyisobutylene, alpha-olefin polymers, alpha-olefin copolymers (e.g., ethylene-propylene copolymers), polyalkyl styrenes, phenol condensates, naphthalene condensates, styrene-butadiene copolymers, etc. Among these, polymethacrylates having a number average molecular weight of 10000 to 300000 and α-olefin polymers or α-olefin copolymers having a number average molecular weight of 1000 to 30000, particularly ethylene-α-olefin copolymers having a number average molecular weight of 1000 to 10000 are preferred. The viscosity index improver may be conveniently added and used alone or in a mixture in an amount ranging from ≥0.05% to ≤20.0% by weight relative to the weight of the base stock.

[0339] Suitable (polymer) thickeners include, but are not limited to, polyisobutylene (PIB), oligomeric copolymers (OCP), polymethacrylates (PMA), copolymers of styrene and butadiene, or high viscosity esters (complex esters).

[0340] Corrosion inhibitors may include various oxygen-containing, nitrogen-containing, sulfur-containing and phosphorus-containing materials, and may include metal-containing compounds (salts, organometallic compounds, etc.) and non-metal-containing or ashless materials. Corrosion inhibitors may include, but are not limited to, additive types such as the following hydrocarbyl-, aryl-, alkyl-, arylalkyl- and alkylaryl forms: detergents (neutral, overbased), sulfonates, phenates, salicylates, alkoxides, carboxylates, salixarates, phosphites, phosphates, thiophosphates, amines, amine salts, amine phosphates, amine sulfonates, alkoxylated amines, etheramines, polyetheramines, amides, imides, azoles, diazoles, Triazole, benzotriazole, benzothiazole, mercaptobenzothiazole, tolyltriazole (TTZ-type), heterocyclic amine, heterocyclic thioether, thiazole, thiadiazole, mercaptothiadiazole, dimercaptothiadiazole (DMTD-type), imidazole, benzimidazole, dithiobenzimidazole, imidazoline, oxazoline, Mannich reaction products, glycidyl ether, anhydride, carbamate, thiocarbamate, dithiocarbamate, polyglycol, etc., or mixtures thereof.

[0341] Detergents include detergents that adhere to dirt particles to prevent dirt particles from attaching to critical surfaces. Detergents can also adhere to the metal surface itself to keep the metal surface clean and prevent corrosion from occurring. Detergents include calcium alkyl salicylates, calcium alkyl phenates, and calcium alkyl aryl sulfonates, in which selected metal ions such as magnesium, barium, or sodium are used. Examples of detergents and dispersants that can be used include metal-based detergents, such as neutral and basic alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates, alkenyl succinimides and alkenyl succinimides esters and their borohydrides, phenates, salienius composite detergents, and ashless dispersants that have been modified with sulfur compounds. These agents can be conveniently added and used individually or in a mixture in an amount ranging from ≥0.01% to ≤1.0% by weight relative to the weight of the base stock; these can also be high total base number (TBN), low TBN, or high / low TBN mixed forms.

[0342] Dispersants are lubricant additives that help prevent sludge, varnish and other deposits from forming on key surfaces. Dispersants can be succinimide dispersants (e.g., N-substituted long-chain alkenyl succinimides), Mannich dispersants, ester-containing dispersants, condensation products of aliphatic monocarboxylic acid acylating agents with amines or ammonia, alkylaminophenol dispersants, alkyl-amine dispersants, polyether dispersants or polyetheramine dispersants. In one embodiment, succinimide dispersants include polyisobutylene-substituted succinimides, wherein the polyisobutylene derived from the dispersant can have a number average molecular weight of about 400 to about 5000, or about 950 to about 1600. In one embodiment, dispersants include borated dispersants. Typically, borated dispersants include succinimide dispersants (including polyisobutylene succinimides), wherein the polyisobutylene derived from the dispersant can have a number average molecular weight of about 400 to about 5000. Borated dispersants are described in more detail above in the description of extreme pressure agents.

[0343] The defoamer may be selected from silicones, polyacrylates, etc. The amount of the defoamer in the lubricant composition described herein may be in the range of ≥ 0.001 wt.-% to ≤ 0.1 wt.-%, based on the total weight of the formulation. As a further example, the defoamer may be present in an amount of about 0.004 wt.-% to about 0.008 wt.-%.

[0344] Suitable extreme pressure agents are sulfur-containing compounds. In one embodiment, the sulfur-containing compound can be a sulfurized olefin, a polysulfide, or a mixture thereof. Examples of sulfurized olefins include sulfurized olefins derived from propylene, isobutylene, pentene; organic sulfides and / or polysulfides (including benzyl disulfide); bis-(chlorobenzyl) disulfide; dibutyl tetrasulfide; di-tert-butyl polysulfide; and sulfurized methyl oleate, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, sulfurized Diels-Alder adduct, N'N dialkyl dithiocarbamic acid alkyl sulfonic acid phenyl ester; or a mixture thereof. In one embodiment, the sulfurized olefin includes a sulfurized olefin derived from propylene, isobutylene, pentene or a mixture thereof. In one embodiment, the extreme pressure additive sulfur-containing compound includes dithiothiadiazole or a derivative, or a mixture thereof. Examples of dimercaptothiadiazoles include compounds such as 2,5-dimercapto-1,3,4-thiadiazoles or alkyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles, or oligomers thereof. Hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole oligomers are typically formed in the following manner: sulfur-sulfur bonds are formed between 2,5-dimercapto-1,3,4-thiadiazole units to form two or more derivatives or oligomers of the thiadiazole units. Suitable 2,5-dimercapto-1,3,4-thiadiazole derived compounds include, for example, 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazoles or 2-tert-nonyldithio-5-mercapto-1,3,4-thiadiazoles. The number of carbon atoms on the hydrocarbyl substituent of the hydrocarbyl substituted 2,5-dimercapto-1,3,4-thiadiazole typically includes 1 to 30, or 2 to 20, or 3 to 16. Extreme pressure additives include compounds containing boron and / or sulfur and / or phosphorus. The extreme pressure agent can be present in the lubricant composition at 0 wt.-% to about 20 wt.-%, or about 0.05 wt.-% to about 10.0 wt.-%, or about 0.1 wt.-% to about 8 wt.-%.

[0345] Examples of antiwear additives include organic borates, organic phosphites such as didodecylphosphite, organic sulfur-containing compounds such as sulfurized whale oil or sulfurized terpenes, zinc dialkyl dithiophosphates, zinc diaryl dithiophosphates, phosphosulfurized hydrocarbons, and any combination thereof.

[0346] Friction modifiers can include metal-containing compounds or materials and ash-free compounds or materials, or mixtures thereof. Metal-containing friction modifiers include metal salts or metal ligand complexes, wherein the metal may include alkali metals, alkaline earth metals, or transition metals. Such metal-containing friction modifiers can also have low ash characteristics. Transition metals can include Mo, Sb, Sn, Fe, Cu, Zn, and others. Ligands can include the following hydrocarbon derivatives: alcohols, polyols, glycerol, partial ester glycerol, thiol, carboxylic acid esters, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles, and other polar molecular functional groups containing effective amounts of O, N, S or P, either individually or in combination. In particular, Mo-containing compounds may be particularly effective, such as, for example, Mo-dithiocarbamate (Mo(DTC)), Mo-dithiophosphate (Mo(DTP)), Mo-amine (Mo(Am)), Mo-alkoxide, Mo alcohol-amine, and the like.

[0347] Ashless friction modifiers may also include lubricant materials containing effective amounts of polar groups, such as hydrocarbon base oils containing hydroxyl groups, glycerides, partial glycerides, glyceride derivatives, and the like. The polar groups in the friction modifier may include hydrocarbon groups containing effective amounts of O, N, S, or P, either alone or in combination. Other friction modifiers that may be particularly effective include, for example, salts (both ash-containing and ashless derivatives) of fatty acids, fatty alcohols, fatty amides, fatty esters, carboxylates containing hydroxyl groups, and similar synthetic long-chain hydrocarbon acids, alcohols, amides, esters, hydroxycarboxylates, and the like. In some cases, fatty organic acids, fatty amines, and sulfurized fatty acids may be used as suitable friction modifiers. Examples of friction modifiers include fatty acid esters and amides, organic molybdenum compounds, dialkylthiocarbamates, and dialkyl dithiophosphates.

[0348] Suitable metal deactivators include benzotriazole and its derivatives, such as 4- or 5-alkylbenzotriazole (e.g., triazole) and its derivatives, 4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole or triazole, such as 1-[bis(2-ethyl-hexyl)aminomethyl)triazole and 1-[bis(2-ethylhexyl)aminomethyl)benzotriazole; and alkoxyalkylbenzotriazoles, such as 1-(nonyloxymethyl)benzotriazole, 1-(1-butoxyethyl)benzotriazole and 1-(1-cyclohexyloxybutyl)triazole, and combinations thereof. Additional non-limiting examples of one or more metal deactivators include 1,2,4-triazole and its derivatives, such as 3-alkyl (or aryl)-1,2,4-triazole, and Mannich bases of 1,2,4-triazole, such as 1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazole such as 1-(1-butoxyethyl)-1,2,4-triazole; and acylated 3-amino-1,2,4-triazole, imidazole derivatives, such as 4,4'-methylenebis(2-undecyl-5-methylimidazole) and bis[(N-methyl)imidazol-2-yl]methanol octyl ether, and combinations thereof. Additional non-limiting examples of one or more metal deactivators include sulfur-containing heterocyclic compounds, such as 2-mercapto-benzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and derivatives thereof; and 3,5-bis[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazoline-2-one, and combinations thereof. Even additional non-limiting examples of one or more metal deactivators include amino compounds, such as salicylidene propylenediamine, salicylaminoguanidine and salts thereof, and combinations thereof. The amount of one or more metal deactivators in the composition is not particularly limited, but is typically present in an amount of about 0.01 to about 0.1, about 0.05 to about 0.01, or about 0.07 to about 0.1 wt.-%, based on the weight of the composition. Alternatively, one or more metal deactivators may be present in an amount of less than about 0.1, less than about 0.7, or less than about 0.5 wt.-%, based on the weight of the composition.

[0349] Pour point depressants (PPDs) include polymethacrylates, alkylated naphthalene derivatives, and combinations thereof. Commonly used additives such as alkyl aromatic polymers and polymethacrylates may also be used for this purpose. Typically, the treat rate is in the range of ≥ 0.001 wt.-% to ≤ 1.0 wt.-% relative to the weight of the base stock.

[0350] Demulsifiers include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures thereof.

[0351] The present invention also relates to a fuel comprising oligomeric butylbenzene sulfonate. In another form, the fuel comprises oligomeric butylbenzene sulfonate, which is obtainable by a method for preparing oligomeric butylbenzene sulfonate, the method comprising the steps of

[0352] i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol,

[0353] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0354] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0355] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate.

[0356] In another form, the fuel comprises oligomeric butylbenzene sulfonate obtainable by a process for preparing oligomeric butylbenzene sulfonate comprising the steps of i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 500 g / mol,

[0357] ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes,

[0358] iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and

[0359] iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce oligomeric butylbenzene sulfonate,

[0360] wherein the butene mixture contains 50 to 99 wt% of 1-butene and 2-butene based on the total olefin content,

[0361] wherein the oligomerization is carried out in the presence of a heterogeneous catalyst containing nickel,

[0362] The olefin blend comprises 20-85 wt% of C 16 Olefins, 5-30wt% C 20 Olefins, and 2-20wt% C 24 Olefins,

[0363] wherein the alkylation catalyst used in the alkylation is a zeolite,

[0364] wherein the sulfonation is carried out by reacting the oligomeric butylbenzene with sulfur trioxide, and

[0365] The base used for neutralization is selected from alkali metals, alkaline earth metals, ammonium hydroxide or amine salts, carbonates or oxides.

[0366] The fuel may contain at least 1 mg / kg, preferably at least 10 mg / kg and in particular at least 50 mg / kg of oligomeric butylbenzene sulfonate.

[0367] In another form, a fuel, such as a motor vehicle fuel for a car or truck, may contain 1 mg / kg to 1000 mg / kg, preferably 10 mg / kg to 500 mg / kg and especially at least 50 to 200 mg / kg of oligomeric butylbenzene sulfonate.

[0368] In another form (such as for bunker fuel or aviation fuel), the fuel may contain 0.001-10 wt%, preferably 0.001-5 wt% and especially at least 0.01-2.5 wt% of oligomeric butylbenzene sulfonate.

[0369] Fuels are understood to mean middle distillate fuels of fossil, vegetable or animal origin, biofuels (“biodiesel”) and mixtures of such middle distillate fuels and biofuels.

[0370] Middle distillate fuels (hereinafter also referred to as "middle distillates") are to be understood in particular as meaning fuels which are obtained by distillation of crude oil as a first process step and which boil in the range of 120° C. to 450° C. Such middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, diesel fuel and heating oil being particularly preferred. Preference is given to using low-sulfur middle distillates, i.e. those which contain less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur, in particular less than 50 ppm of sulfur. In exceptional cases, they contain less than 10 ppm of sulfur; these middle distillates are also referred to as "sulfur-free". They are generally crude oil fractions which have been refined under hydrogenation conditions and therefore contain only a small proportion of polyaromatic compounds and polar compounds. They are preferably those middle distillates which have a 90% distillation point below 370° C., in particular below 360° C. and in exceptional cases below 330° C.

[0371] Low sulfur and sulfur-free middle distillates can also be obtained from relatively heavy mineral oil fractions that cannot be distilled at atmospheric pressure. Typical conversion methods for preparing middle distillates from heavy crude oil fractions include: hydrocracking, thermal cracking, catalytic cracking, coking and / or visbreaking. According to the method, these middle distillates are obtained in a low sulfur or sulfur-free form, or are refined under hydrogenation conditions. Middle distillates preferably have an aromatics content of less than 28% by weight, especially less than 20% by weight. The content of normal paraffin is between 5% by weight and 50% by weight, preferably between 10% and 35% by weight.

[0372] In the context of the present invention, middle distillate fuels are also understood to mean those fuels that can be indirectly derived from fossil sources such as mineral oil or natural gas, or produced by biomass through gasification and subsequent hydrogenation. A typical example of a middle distillate fuel indirectly derived from a fossil source is a GTL ("gas to liquids") diesel fuel obtained by Fischer-Tropsch synthesis. Middle distillates are prepared from biomass, for example by BTL ("biomass to liquids") process, and can be used as fuel alone or in admixture with other middle distillates. Middle distillates also include hydrocarbons obtained by hydrogenation of fats and fatty oils. They mainly contain normal paraffins.

[0373] In a preferred embodiment, the fuel is a diesel fuel (without any additives) having a CP value according to ASTM D2500 / ASTM D97 of 0°C to -15°C, preferably 0°C to -10°C, and more preferably -5°C to -10°C, and / or preferably having a normal paraffin content of from 10% to 27% by weight, more preferably from 15% to 25% by weight, and most preferably from 17% to 23% by weight.

[0374] In addition to its use in the middle distillate fuels of fossil, plant or animal origin (essentially hydrocarbon mixtures), the copolymers of the invention can also be used in biofuel oils and mixtures of the middle distillates and biofuel oils to improve the low temperature flow characteristics. Such mixtures are commercially available and usually contain a small amount of biofuel oil, based on the total amount of the middle distillate of fossil, plant or animal origin and the biofuel oil, the amount is typically 1% to 30% by weight, in particular 3% to 10% by weight.

[0375] Biofuels are usually based on fatty acid esters, preferably substantially based on alkyl esters of fatty acids derived from plant and / or animal oils and / or fats. Alkyl esters are preferably understood to mean lower alkyl esters, especially C1- to C4-alkyl esters, which can be obtained by transesterification of glycerides, especially triglycerides present in plant and / or animal oils and / or fats with lower alcohols such as ethanol or, in particular, methanol ("FAME"). Typical lower alkyl esters based on plant and / or animal oils and / or fats and that can be used as biofuel oils or components thereof are, for example, HVO (hydrogenated vegetable oils), sunflower methyl esters, palm oil methyl esters ("PME"), soybean oil methyl esters ("SME"), and especially rapeseed oil methyl esters ("RME").

[0376] The fuel may be a marine fuel such as MGO (marine gas oil), MDO (marine diesel oil), IFO (intermediate fuel oil), MFO (marine fuel oil), or HFO (heavy fuel oil). Further examples of marine fuels are IFO 380 (intermediate fuel oil with a maximum viscosity of 380 centistokes (<3.5% sulfur)), IFO 180 (intermediate fuel oil with a maximum viscosity of 180 centistokes (<3.5% sulfur)), LS380 (low sulfur (<1.0%) intermediate fuel oil with a maximum viscosity of 380 centistokes), LS180 (low sulfur (<1.0%) intermediate fuel oil with a maximum viscosity of 180 centistokes), LSMGO (low sulfur (<0.1%) marine gas oil, which is generally used in European ports and anchorages according to the EU sulfur directive 2005 / 33 / EC), or ULSMGO (ultra-low sulfur marine gas oil, also known as ultra-low sulfur diesel (maximum sulfur 0.0015%)). Further suitable marine fuels are the categories ISO-F-DMX, DMA, DFA, DMZ, DFZ, or DFB, or ISO-F RMA, RMB, RMD, RME, RMG or RMK according to DIN ISO 8217. Further suitable marine fuels are distillate marine diesel or residual marine diesel.

[0377] The fuel may contain additional additives such as carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators and / or dyes.

[0378] The invention also relates to the use of oligomeric butylbenzene sulfonates as lubricant additives or fuel additives. Oligomeric butylbenzene sulfonates can be added to lubricants or fuels, for example, to improve their properties.

[0379] The lubricant additive may comprise 1-80 wt%, preferably 5-50 wt% and in particular at least 20-70 wt% of oligomeric butylbenzene sulfonate.The lubricant additive may comprise further lubricant additives or a base oil, such as a mineral oil.

[0380] The fuel additive may comprise 1-80 wt%, preferably 5-50 wt% and in particular at least 20-70 wt% of oligomeric butylbenzene sulfonate.The fuel additive may comprise further lubricant additives or a base oil, such as a mineral oil.

[0381] Examples

[0382] Example 1 - Oligomerization of Butene Mixtures

[0383] The olefin blend was prepared starting from a butene mixture obtained from the raffinate II stream. The butene mixture contained about

[0384]

[0385] The butene mixture was oligomerized in the presence of a nickel-containing heterogeneous catalyst at 20 bar and 80° C. in an isothermally operated reactor having a length of about 1.5 m and a diameter of 30 mm.

[0386] The heterogeneous catalyst containing nickel is a material produced in the form of pellets (5 mm×5 mm) as described in WO 1995 / 14647. The composition of the active components in % by weight is typically: 50% by weight NiO, 12.5% ​​by weight TiO2, 33.5% by weight SiO2, 4% by weight Al2O3.

[0387] The throughput was 0.75 kg of raffinate II / (l(cat)×h). The reaction was carried out without recycling of C4 hydrocarbons. The C4 conversion was about 52.0% by weight, based on the butenes contained in the raffinate II. The selectivity in % by weight in the olefin blend was as follows: C8 olefins: 76.9; C 12 Olefins: 18.4; and C 16 and higher olefins: 4.7.

[0388] 2.0 kg of this olefin blend was fractionally distilled on an 80 cm packed column (wire mesh coil) at a reflux ratio of 1:5 to produce in the distillation column bottom:

[0389] - 1.45 kg of fraction A (mainly containing C8 olefins) having a boiling range of 100°C to 130°C at 950 mbar

[0390] -0.35kg fraction B (mainly containing C 12 Olefins) having a boiling range of 100°C to 130°C at 950 mbar

[0391] -0.18kg fraction C (mainly containing C 16 and higher olefins).

[0392] According to GC analysis, fraction C consisted of 7% C 12 Olefins, 70% C 16 Olefins, 17% C 20 Olefins, and 6% C 24 and higher olefins.

[0393] Example 2 - Alkylation of Benzene with a Fractional C Olefin Blend

[0394] Oligobutylbenzenes were prepared starting from benzene and fraction C from Example 1, which contained the following oligomeric butenes:

[0395] -7% C 12Olefins

[0396] -70% C 16 Olefins

[0397] -17% C 20 Olefins, and

[0398] -6% C 24 and higher olefins.

[0399] The alkylation catalyst was a zeolite, and Friedel-Crafts alkylation was successfully carried out to produce the corresponding oligomeric butylbenzenes.

[0400] Example 3 - Alkylation of Benzene with an Olefin Blend of Fractions B and C

[0401] Oligobutylbenzenes were prepared starting from benzene and a mixture of fractions B and C from Example 1, which contained the following oligomeric butenes:

[0402] -38% C 12 Olefins

[0403] -43% C 16 Olefins

[0404] -13% C 20 Olefins, and

[0405] -6% C 24 and higher olefins.

[0406] The alkylation catalyst was a zeolite, and Friedel-Crafts alkylation was successfully carried out to produce the corresponding oligomeric butylbenzenes.

[0407] Example 4 - Sulfonation of Oligobutylbenzene of Example 2

[0408] Oligobutylbenzenesulfonic acid was prepared by sulfonating the oligobutylbenzene from Example 2. The sulfonation was carried out by reacting the oligobutylbenzene with sulfur trioxide. The sulfonic acid groups were mainly located in the para position of the oligobutyl group, which could be determined by H-NMR.

[0409] Example 5 - Sulfonation of Oligobutylbenzene of Example 3

[0410] Oligobutylbenzenesulfonic acid was prepared by sulfonating the oligobutylbenzene from Example 2. The sulfonation was carried out by reacting the oligobutylbenzene with sulfur trioxide. The sulfonic acid groups were mainly located in the para position of the oligobutyl group, which could be determined by H-NMR.

[0411] Example 6 - Sulfonate produced by neutralization

[0412] The oligomeric butylbenzenesulfonic acid from Example 4 was neutralized with equimolar amounts of:

[0413] - Calcium hydroxide to produce oligobutylbenzenesulfonic acid calcium salt.

[0414] - magnesium carbonate, to produce magnesium oligobutylbenzenesulfonate.

[0415] To prepare the overbased sulfonate, the oligomeric butylbenzenesulfonic acid from Example 4 was added.

[0416] Neutralize with a molar excess of

[0417] - Calcium hydroxide to produce overbased oligomeric butylbenzenesulfonic acid calcium salt.

[0418] -magnesium carbonate to produce overbased magnesium oligomeric butylbenzenesulfonate.

[0419] Example 7 - Sulfonate produced by neutralization

[0420] The oligomeric butylbenzenesulfonic acid from Example 5 was neutralized with equimolar amounts of:

[0421] - Calcium hydroxide to produce oligobutylbenzenesulfonic acid calcium salt.

[0422] - magnesium carbonate, to produce magnesium oligobutylbenzenesulfonate.

[0423] To prepare the overbased sulfonate, the oligomeric butylbenzenesulfonic acid from Example 5 was added.

[0424] Neutralize with a molar excess of

[0425] - Calcium hydroxide to produce overbased oligomeric butylbenzenesulfonic acid calcium salt.

[0426] -magnesium carbonate to produce overbased magnesium oligomeric butylbenzenesulfonate.

Claims

1. A method for preparing oligomeric butylbenzene sulfonate, the method comprising the following steps i) oligomerizing a butene mixture comprising 1-butene and 2-butene to produce an olefin blend comprising oligomeric butenes having a molecular weight of 220 to 2000 g / mol, ii) alkylating benzene with the olefin blend to produce oligomeric butylbenzenes, iii) sulfonating the oligomeric butylbenzene to produce oligomeric butylbenzene sulfonic acid, and iv) neutralizing the oligomeric butylbenzene sulfonic acid to produce the oligomeric butylbenzene sulfonate.

2. The method according to claim 1, wherein: These oligomeric butenes have a molecular weight of 220 to 1000 g / mol, 220 to 700 g / mol, 220 to 500 g / mol, or 220 to 350 g / mol.

3. The method according to claim 1 or 2, wherein: The butene mixture contains 20 to 99 wt%, preferably 50 to 99 wt%, of 1-butene and 2-butene, based on the total olefin content.

4. A method according to any one of the preceding claims, wherein: The butene mixture comprises 0.5 to 5% by weight of isobutane, 5 to 20% by weight of n-butane, 20 to 40% by weight of trans-2-butene, 10 to 20% by weight of cis-2-butene, 25 to 55% by weight of 1-butene, and 0.5 to 5% by weight of isobutylene.

5. A method according to any one of the preceding claims, wherein: The butene mixture is obtainable from the raffinate II.

6. A method according to any one of the preceding claims, wherein: The olefin blend comprises C 16 Olefins, C 20 Olefins, and C 24 Olefins.

7. A method according to any one of the preceding claims, wherein: The olefin blend comprises 20-85wt% of the C 16 Olefins, 5-30wt% of the C 20 Olefins, and 2-20wt% of the C 24 Olefins.

8. A method according to any one of the preceding claims, wherein: The olefin blend contains terminally unsaturated C 16 Olefins, terminal unsaturated C 20 Olefins, and terminal unsaturated C 24 Olefins.

9. A method according to any one of the preceding claims, wherein: The olefin blend is obtainable by oligomerization in the presence of a nickel-containing heterogeneous catalyst.

10. A method according to any one of the preceding claims, wherein: The sulfonic acid group in the oligobutylbenzenesulfonic acid is located at the para position of the oligobutyl group.

11. An oligomeric butylbenzene sulfonate obtainable by the process according to any one of claims 1 to 10.

12. Oligobutylbenzenesulfonate according to claim 11 in the form of a neutral or overbased alkali metal salt, alkaline earth metal salt or ammonium salt.

13. Oligomeric butylbenzenesulfonic acid obtainable by the process according to any one of claims 1 to 10.

14. Oligomeric butylbenzene obtainable by the process according to any one of claims 1 to 10.

15. A lubricant, preferably a lubricating fluid, lubricating oil or lubricating grease, comprising the oligomeric butylbenzene sulfonate according to any one of claims 11 or 12 or the oligomeric butylbenzene sulfonate obtainable by the process according to any one of claims 1 to 10.

16. A fuel comprising the oligomeric butylbenzene sulfonate according to claim 11 or 12 or obtainable by the process according to any one of claims 1 to 10.

17. Use of an oligomeric butylbenzene sulfonate according to claim 11 or 12 or obtainable by a process according to any one of claims 1 to 10 as a lubricant additive or fuel additive.

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