KR20080066843A - How to control byproducts or pollutants from fuel combustion - Google Patents

Abstract

The present invention provides a mixture of (a) at least two metal bases, each of which has a metal oxide of at least (+2) average oxidation number, (b) at least one surfactant; And (c) burning a fuel containing at least one organic medium, the fuel containing a dispersion wherein said metal base is uniformly dispersed in said organic medium. Way.

Description

METHOD OF CONTROLLING BY-PRODUCTS OR POLLUTANTS FROM FUEL COMBUSTION}

The present invention relates to a method comprising providing a dispersion in a fuel, the dispersion comprising: (a) at least two, each of the metals of the metal base having an average oxidation number of (+2) or more; It contains a mixture of metal bases. The method can control byproducts or pollutants from fuel combustion.

Recently, efforts have been made to reduce the amount of pollutants / emissions emitted from combustion of fuels. Examples of contaminants include sulfur oxides (eg, sulfur trioxide), nitrogen oxides, carbon monoxide, carbon dioxide and particulate matter. These pollutants are known to adversely affect greenhouse gas concentrations or to cause other problems such as smog. Even in the case of particulate matter, many studies indicate that it also adversely affects the well being of humans, animals and plants. Other byproducts of fuel combustion include vanadate deposits. Vanadate precipitates are believed to form low-melting caustic slags that form precipitates. It would be desirable to burn fuel while minimizing contaminants.

International publication WO 2005/097952 discloses the provision of a fuel composition containing a metal base with a solids content of at least about 35% relative to the dispersion. The disclosed compositions utilize one metal base per dispersion.

International publication WO 04/026996 discloses a fuel additive composition which can reduce vanadate deposits. The composition contains metal inorganic oxygen-containing compounds, oil soluble liquids and dispersants such as fatty acids or ester derivatives thereof.

However, none of the dispersions provided an improved method of reducing the various pollutants emitted during fuel combustion. It would therefore be advantageous to provide a method of controlling pollutants from fuel combustion. The present invention provides such a method by providing a dispersion that synergistically reduces various pollutants emitted during combustion of a fuel.

Summary of the Invention

The present invention provides a composition comprising: (a) a mixture of at least two metal bases, each of which has a metal oxide base having an average oxidation number of (+2) or more, (b) at least one surfactant; And (c) burning a fuel containing at least one organic medium, the fuel containing a dispersion wherein the metal base is uniformly dispersed in the organic medium. Provide a way to.

In one embodiment, the invention provides a mixture of (a) at least three metal bases, each of which has a mean oxidation number of at least (+2) metal, (b) at least one surfactant; And (c) burning a fuel containing at least one organic medium, the fuel containing a dispersion wherein the metal base is uniformly dispersed in the organic medium. Provide a way to.

In one embodiment, the invention provides a mixture of (a) at least three metal bases, each of which has a mean oxidation number of at least (+2) metal, (b) at least one surfactant; And (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium.

In one embodiment, the present invention provides a composition comprising (i) a fuel; And (ii) a mixture of (a) at least two metal bases, each of which has a metal oxide of at least (+2) average oxidation number, (b) at least one surfactant; And (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium.

In one embodiment, the present invention provides a composition comprising (i) a fuel; And (ii) a mixture of at least three metal bases, each of which (a) a metal of a metal base has an average oxidation number of at least (+2), (b) at least one surfactant; And (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium.

In one embodiment, the invention provides a dispersion (at least three metal bases in which the metals of (a) metal bases each have an average oxidation number of (+2) or more in the fuel to reduce by-products or contaminants formed in fuel combustion). (B) at least one surfactant; and (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium.

Detailed description of the invention

The present invention provides a method of controlling byproducts or pollutants from fuel combustion as disclosed above. The present invention further provides a composition as disclosed above.

In one embodiment, the present invention is other than a moisture-containing emulsion.

As used in this specification and claims, the term “free of” as used herein for all chemicals disclosed herein, except for metal bases, refers to amounts present as impurities, such as trace amounts. Or means that no substance is present except for an ineffective amount. Typically in such embodiments, the amount present will be less than about 0.05% to less than about 0.005% by weight of the dispersant.

As will be appreciated by those skilled in the art (hereinafter referred to as 'the person skilled in the art'), the impurities in the metal base are typically from about 1% to about 3% by weight of the metal base. It is believed that the reason why the impurities are typically present from about 1% to about 3% by weight of the metal base is due to the mining method. Typically the main impurities in the metal base include calcium carbonate, silica or silicate.

In other embodiments, the dispersion may be opaque or translucent or translucent or transparent, or a gradation between such transparency.

fuel

Fuels include liquid fuels, biofuels, solid fuels, or mixtures thereof. In one embodiment, the fuel is a solid fuel. In another embodiment, the fuel is a liquid fuel. Examples of suitable solid fuels include coal.

If the fuel comprises a liquid fuel, the liquid fuel may also be used as an organic medium suitable for preparing the dispersion. Therefore, in order to avoid duplication of explanation, the detailed description of the liquid fuel is disclosed in the following paragraph of organic medium.

Metal base

Dispersions of metal bases contain divalent, trivalent, tetravalent metals or mixtures thereof.

In embodiments, the metal base may further comprise a monovalent metal base. In one embodiment, the metal base is derived from a monovalent metal including lithium, potassium, sodium, copper, or mixtures thereof. In one embodiment, the metal oxidized water of the metal base is oxidized water other than (+1).

In other embodiments, the average oxidation number of the metal base is in the range of about (+2) to about (+4), or in the range of about (+2) to about (+3). Typically the metal of the metal base is a divalent or trivalent metal. In one embodiment, the metal base is derived from a divalent metal such as magnesium, calcium, barium or mixtures thereof. The metal may also be multiple valences such as monovalent or divalent or trivalent, examples being cerium, copper or iron. In one embodiment the metal base is derived from a tetravalent metal such as cerium.

In other embodiments, the base of the metal base includes oxides, carbonates, bicarbonates, hydroxides, sulfonates, carboxylates (such as C _1-30 or C _8-24 straight or branched chain alkyl carboxylates), nitrates, Phosphates, sulphates, sulphites, nitrites, phosphonates, or mixtures thereof.

In other embodiments, the base of the metal base includes oxides, carbonates, bicarbonates, hydroxides, sulfonates, carboxylates, or mixtures thereof. In some cases, the metal base additionally contains water of crystallization or absorbed water. In one embodiment, the metal base is crystalline.

In another embodiment, the first metal base includes iron oxide (Fe ₂ O ₃ , FeO or Fe ₃ O ₄ ), iron carbonate (eg, a salt of iron and octadecanoic acid), magnesium hydroxide, calcium hydroxide, calcium carbonate , Magnesium carbonate, calcium oxide, magnesium oxide or mixtures thereof.

In another embodiment, the second metal base includes cerium oxide (CeO or CeO ₂ ), cerium sulphonate, iron oxide (Fe ₂ O ₃ , FeO or Fe ₃ O ₄ ), iron carbonate (eg, octa with iron) Decanoic acid), copper oxide (CuO) or chromium oxide.

In one embodiment, the metal base is magnesium hydroxide, calcium hydroxide, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, cerium oxide (CeO or CeO ₂ ), iron oxide (Fe ₂ O ₃ , FeO or Fe ₃ O ₄ ), oxidation It is substantially free of metals other than two or three bases selected from the group consisting of copper (CuO) or chromium oxide, and mixtures thereof.

In one embodiment, the first metal base contains a metal selected from the group consisting of iron, magnesium, calcium and mixtures thereof; The second metal base contains a metal selected from the group consisting of magnesium, calcium, cerium, iron, copper, chromium, and mixtures thereof, provided that the first metal base is different from the second metal base.

In one embodiment where at least two metal bases are present in the mixture, each metal of the metal base has an oxidation number of about (+2) or higher oxidation number and the metal may be selected under the following conditions:

(i) the first metal base contains a metal selected from the group consisting of iron, magnesium, calcium and mixtures thereof;

(ii) the second metal base contains a metal selected from magnesium, calcium, cerium, iron, copper, chromium, and mixtures thereof, wherein the first metal base and the second metal base are different;

(iii) optionally, another metal base other than the metal base of (i) or (ii) is selected.

In one embodiment, the first metal base is present more than the weight of the second metal base. The weight of the first metal base may be at least about 50%, or at least about 75%, or at least about 95% by weight of the total amount of metal base present. The weight of the second metal base present may be less than about 50 weight percent, or less than about 25 weight percent, or less than about 5 weight percent of the total amount of metal base present.

In one embodiment, where at least three metal bases are present in the mixture, each metal of the metal base has an oxidation number of about (+2) or higher, and the metal is selected under the following conditions:

(i) the first metal base contains a metal selected from the group consisting of iron, magnesium, calcium and mixtures thereof;

(ii) the second metal base contains a metal selected from magnesium, calcium, cerium, iron, copper, chromium, and mixtures thereof, wherein the first metal base and the second metal base are different;

(iii) the metal of at least one other metal base is selected from the group consisting of calcium, magnesium, cerium, iron, copper, chromium, barium, platinum, lead, manganese, strontium, and mixtures thereof; Provided that the third metal base is different from the metal base already used in (i) and (ii).

In one embodiment, the metal of the metal base of (iii) is selected from the group consisting of calcium, magnesium, cerium, iron, copper, chromium and mixtures thereof, provided that the third metal base is in (i) and (ii) It is different from the metal base already used.

When at least three metal bases are used, in one embodiment the two metal bases are derived from calcium and magnesium bases. The third (or higher, ie fourth or fifth) metal base may be derived from a metal selected from the group consisting of cerium, iron, copper, chromium, and mixtures thereof.

The amount of metal base present in the dispersion, in other words, the solids content, is at least about 15% by weight of the dispersion and ranges from about 17% to about 90% by weight, or from about 25% to about 80% by weight, or about 35 weight percent to about 70 weight percent, or about 40 weight percent to about 65 weight percent. This amount is determined on the basis of the original dispersion and then does not include additional diluents that the dispersion is admixed, e.g. to form a fully formulated lubricating composition, and includes solids or non-volatile components from other sources. Nor is it.

Metal bases are typically present in the form of solids and insoluble in the organic medium. In other embodiments, the average particle size of the metal base in the dispersion is in the range of about 20 nanometers to less than about 1 micrometer, or in the range of about 30 nanometers to about 0.7 micrometers, in the range of about 50 nanometers to about 0.4 micrometers, or about 80 nanometers. To about 0.3 μm.

Metal bases generally comprise at least one of oxides, hydroxides or carbonates. Examples of suitable metal bases include magnesium hydroxide, calcium hydroxide, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, cerium oxide, iron oxide or mixtures thereof. In one embodiment of the invention, the metal base is present as a mixture, such as commercially available dolomitic lime.

If the present invention additionally contains a metal base having an oxidation number of (+1), examples of suitable metal bases include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, anhydrous lithium hydroxide, hydroxide Lithium monohydrate, lithium carbonate, lithium oxide or mixtures thereof.

In one embodiment, the dispersion additionally contains a coordination compound, such as ferrocene (cyclopentadienyl based), carboxylate or sulfonate.

Surfactants

Surfactants include ionic (cationic or anionic) or non-ionic compounds. In general, surfactants stabilize the dispersion of metal bases in an organic medium.

Suitable surfactant compounds include hydrophilic lipophilic (HLB) ranges from about 1 to about 40 ranges, or about 1 to about 20 ranges, or about 1 to about 18 ranges, or about 2 to about 16 ranges, or about 2.5 to about 15 Included are surfactant compounds. In other embodiments, the HLB is about 11-14, or less than about 10, such as about 1 to about 8, or about 2.5 to about 6. Combinations of surfactants having individual HLB values outside this range can also be used provided the composition of the mixture of final surfactants is within this range. If the surfactant has an acidic group available, the surfactant may be a metal salt of the acidic group, with the metal derived from the metal base.

Examples of surfactants suitable for the present invention are disclosed in McCuchen's Emulsifiers and Detergent , 1993, North American & International Edition. Comprehensive examples include alkanolamides, alkylarylsulphonates, amine oxides, poly (oxyalkylene) compounds, such as block copolymers comprising alkylene oxide repeat units (eg, Pluronic ^™ ), carboxylated Alcohol ethoxylates, ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated amines and amides, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters, glycerol esters, glycol esters, imidazoline derivatives, Phenates, lecithins and derivatives, lignin and derivatives, monoglycerides and derivatives, olefin sulphonates, phosphate esters and derivatives, propoxylated and ethoxylated fatty acids or alcohols or alkyls Phenols, sorbitan derivatives, sucrose esters and derivatives, sulfates or alcohols or ethoxylations Alcohol or fatty esters, polyisobutylene succinimide and derivatives.

In one embodiment, the surfactant comprises a polyester as defined in US Pat. No. 3,778,287, line 2, line 44 to line 3, line 39. Examples of suitable polyester surfactants are prepared as disclosed in Polyester Examples A to F of US Pat. No. 3,778,287, including salts thereof.

In one embodiment, the surfactant is a hydrocarbyl substituted aryl sulfonic acid (or sulfonate) of alkali metals, alkaline earth metals or mixtures thereof. The aryl group of aryl sulfonic acid may be phenyl or naphthyl. In one embodiment, hydrocarbyl substituted aryl sulfonic acids include alkyl substituted benzene sulfonic acids.

Hydrocarbyl (particularly alkyl) groups typically contain about 8 to about 30, or about 10 to about 26, or about 10 to about 15 carbon atoms. In one embodiment, the surfactant is a mixture of C ₁₀ to C ₁₅ alkylbenzene sulfonic acids. Examples of sulfonates include dodecyl and tridecyl benzene sulfonates or condensed naphthalene or petroleum sulfonate as well as sulfosuccinates and derivatives.

In one embodiment, the surfactant is typically present in the form of neutral or overbased surfactants that form salts with alkali or alkyllitometals. Alkali metals include lithium, potassium or sodium; Alkaline earth metals include calcium or magnesium. In one embodiment, the alkali metal is sodium. In one embodiment, the alkaline earth metal is calcium.

In one embodiment, the surfactant is a derivative of polyolefin. Typical examples of polyolefins include polyisobutene; Polypropylene; Polyethylene; Copolymers derived from isobutene and butadiene; Copolymers derived from isobutene and isoprene; Or mixtures thereof.

Typically derivatives of polyolefins include polyolefin-substituted acylating agents which are optionally reacted further to form esters and / or aminoesters. Acylating agents may be prepared in carboxyl reactants (which, when reacted with polyolefins, provide a substrate of a preferred acylating agent, ie surfactant). Carboxylic reactants include functional groups such as carboxylic acids or anhydrides thereof. Examples of carboxyl reactants include alpha, beta-unsaturated mono- or polycarboxylic acids, anhydrous esters or derivatives thereof. Thus, examples of carboxyl reactants include (meth) acrylic acid, methyl (meth) acrylate, maleic acid or anhydrides, fumaric acid, itaconic acid or anhydrides, or mixtures thereof, Each of these may typically be in the form of a saturated material (eg, succinic anhydride) after reaction with the polyolefin.

은 약 250미만이고, 보다 빈번하게는 유도체를 제조하기 위해 이용된 폴리이소부틸렌의

은 약 800 이상이다. 유도체를 제조하는데 이용되는 폴리이소부틸렌은 바람직하게는 약 30% 이상의 터미널 비닐리덴 그룹, 보다 빈번하게는 약 60% 이상 또는 약 75% 이상 또는 약 85% 이상의 터미널 비닐리덴 그룹을 함유한다. 유도체를 제조하는데 이용되는 폴리이소부틸렌의 다분산성(polydispersity),

은 약 5보다 클 수 있고, 보다 빈번하게는 약 6 내지 20일 수 있다.In one embodiment, the polyolefin is a derivative of polyisobutene having a number average molecular weight of at least 250, 300, 500, 600, 700, or 800 to 5000 or more, often up to 3000, up to 2500, up to 1600, up to 1300 or up to 1200 . Typically, less than about 5% by weight of the polyisobutylene used to prepare the derivative molecule

Is less than about 250 and, more frequently, of the polyisobutylene used to make the derivatives

Is about 800 or more. The polyisobutylenes used to prepare the derivatives preferably contain at least about 30% terminal vinylidene groups, more frequently at least about 60% or at least about 75% or at least about 85% terminal vinylidene groups. Polydispersity of polyisobutylene used to prepare derivatives,

May be greater than about 5, and more frequently between about 6 and 20.

In various embodiments, the polyisobutene is substituted with succinic anhydride, and the number average molecular weight of the polyisobutene substituent is about 1,500 to about 3,000, or about 1,800 to about 2,300, or about 700 to about 1,700, or about 800 to About 1000. The ratio of succinic acid groups per equivalent weight of polyisobutene is typically about 1.3 to about 2.5, or about 1.7 to about 2.1, or about 1.0 to about 1.3, or about 1.0 to about 1.2.

In one embodiment, the surfactant is a polyisobutenyl-dihydro-2,5-furandione ester with pentaerythritol or a mixture thereof. In one embodiment, the surfactant is a polyisobutylene succinic anhydride derivative such as polyisobutylene succinimide or derivatives thereof. In one embodiment, the surfactant contains substantially no to basic nitrogen.

Other typical derivatives of polyisobutylene succinic anhydride include hydrolyzed succinic anhydrides, esters or diacids. Polyisobutylene succan derivatives are preferred for preparing metal base dispersions. Many groups of polyisobutylene succinic anhydride derivatives are taught in US 4,708,753 and US 4,234,435.

In another embodiment, the surfactant comprises saixarene (or salalixarate in the form of a metal salt). Salixsaren is defined as the organic substrate of salixsarate. Salixarene may be represented by a substantially straight chain compound comprising at least one unit of formula (I) or (II):

or

Each terminal of the compound has a terminal group of formula (III) or (IV)

The groups are linked by divalent briding groups, which may be the same or different for each bond; F is about 1, 2 or 3, in one embodiment 1 or 2; R ² is a hydroxyl or hydrocarbyl group and j is about 0, 1, or 2; R ³ is hydrogen or a hydrocarbyl group; R ⁴ is a hydrocarbyl group or a substituted hydrocarbyl group; g is about 1, 2 or 3, provided that at least one R ⁴ group contains at least 8 carbon atoms and the compound, on average, comprises at least one of units (I) or (III) and unit (II) or (IV) The ratio of the total number of units (I) and (III) to the total number of units (II) and (IV) in the composition containing at least one of is from about 0.1: 1 to about 2: 1.

The U groups of formulas (I) and (III) are -OH or -NH ₂ or -NHR ¹ or -N (R ¹ ) ₂ groups located at one or more ortho, meta, or para positions relative to the -COOR ³ group. Can be. R ¹ is a hydrocarbyl group having 1 to 5 carbon atoms. When the U group comprises an -OH group, formulas (I) and (III) are derived from 2-hydroxybenzoic acid (often called salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid or mixtures thereof do. When U is a -NH ₂ group, formulas (I) and (III) are derived from 2-aminobenzoic acid (often called anthranilic acid), 3-aminobenzoic acid, 4-aminobenzoic acid or mixtures thereof .

Divalent bridging groups that may be the same or different in each case include alkylene or methylene bridges, such as —CH ₂ — or —CH (R) — and —CH ₂ OCH ₂ — or —CH (R) OCH ( Ether bridges such as R)-, wherein R is an alkyl group having 1 to 5 carbon atoms, and methylene and ether crosslinks are derived from formaldehyde or aldehyde having 2 to 6 carbon atoms.

Often, terminal groups of formula (III) or (IV) comprise one or two hydroxymethyl groups located at ortho relative to the hydroxy group. In one embodiment of the invention, hydroxymethyl groups are present. In one embodiment of the invention there is no hydroxymethyl group. A more detailed description of salixarene and salixarate chemistry is disclosed in EP 1 419 226 B1, and as defined in Examples 1 to 23 (pages 11, lines 42 to 13, page 47, line 47) of the patent. Together is disclosed.

In one embodiment, the surfactant is substantially free or free of fatty acids or derivatives thereof, such as esters. In one embodiment, the surfactant is other than a fatty acid or derivative thereof.

In one embodiment, the surfactant comprises at least hydrocarbyl substituted aryl sulfonic acid, derivatives of polyolefins, polyesters or salixsarene (or salixarates).

In other embodiments, the surfactant is substantially free or free of phospholipids (such as lecithin) and / or amino acids (such as sarcosine).

In one embodiment, the molecular weight of the surfactant is less than 1000, in other embodiments less than about 950, such as about 250, about 300, about 500, about 600, about 700, or about 800.

The amount of surfactant in the dispersion and the total amount of powder and constituents can vary as shown in Table 1, with the remaining amount being the organic medium and optionally water. In one embodiment, the amount of organic medium present in the dispersion varies from about 25% to about 55% by weight.

Organic medium

The organic medium may include oils of lubricating viscosity, liquid fuels, hydrocarbon solvents or mixtures thereof. Organic solvents typically include oils or liquid fuels of lubricating viscosity.

If desired, the organic medium may typically contain up to about 1 weight percent, or up to about 2 weight percent, or up to about 3 weight percent water of the dispersion. In other embodiments, the organic medium contains substantially no or no water.

Oil of lubricating viscosity

In one embodiment the organic medium comprises an oil of lubricating viscosity. Such oils include oils derived from natural and synthetic oils, hydrocracking, hydrogenation, and hydrofinishing, crude, refined and re-refined oils, and mixtures thereof.

Unrefined oils are generally those obtained directly from natural or synthetic sources with no (or little) further purification.

Refined oils are similar to unrefined oils except that they have been further processed in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis and similar methods.

Re-refined oils, also known as reclaimed or reprocessed oils, are obtained by methods similar to those used to obtain refined oils, and often used additives and oil breakdown products. It is further processed by techniques relating to the removal of

Natural oils useful for preparing the lubricants of the present invention include mineral oils such as animal oils, vegetable oils (eg castor oil, lard oil), liquefied petroleum oils and paraffinic, naphthenic or mixed paraffinic-naphthenic Solvent-treated or acid-treated mineral lubricants and oils derived from coal or shale or mixtures thereof.

Synthetic lubricants are useful and include hydrocarbon oils such as polymeric tetrahydrofuran, polymerized and interpolymerized olefins (eg polybutylene, polypropylene, propyleneisobutylene copolymers); Poly (1-hexene), poly (1-octene), poly (1-decene), and mixtures thereof; Alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene); Polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenyls); Alkylated diphenyl esters and alkylated diphenyl sulfides and their derivatives, analogs and homologs thereof or mixtures thereof.

Other synthetic lubricants are included. Synthetic oils can be produced by Fischer-Tropsch reactions and are typically hydroisomerised Fischer-Tropsch hydrocarbons or waxes.

Lubricant viscosity oils may also be defined as specified in the American Peroleum Institude (API) base oil compatibility guidelines. The five base oil groups are as follows: group I (sulfur content> 0.03 wt%, and / or <90 wt% saturates, viscosity index 80-120); Group II (sulfur content ≦ 0.03 wt%, and ≧ 90 wt% saturated bonds, viscosity index 80-120); Group III (sulfur content ≦ 0.03% by weight, and ≧ 90% saturated bonds, viscosity index ≧ 120); Group IV (all polyalphaolefins (PAOs)); And Group V (all other base oils not included in Groups I, II, III, or IV). Lubricating viscosity oils contain API Group I, Group II, Group III, Group IV, Group V oils and mixtures thereof. Often oils of lubricating viscosity are API group I, group II, group III, group IV oils and mixtures thereof. Optionally, oils of lubricating viscosity are often API Group I, Group II, Group III oils or mixtures thereof.

Liquid fuel

Liquid fuel is normally liquid at ambient conditions. Liquid fuels include hydrocarbon fuels, biofuels (eg biodiesel), non-hydrocarbon fuels, or mixtures thereof. The hydrocarbon fuel may be a petroleum distillate, such as gasoline as defined by the American Society for Testing and Materials D4814 or diesel fuel as defined by ASTM standard D975. In one embodiment, the liquid fuel is gasoline, and in other embodiments the liquid fuel is leaded gasoline, or unleaded gasoline. In another embodiment, the liquid fuel is diesel fuel. Hydrocarbon fuels contain hydrocarbons produced by a gas to liquid process, such as a Fischer-Tropsch method. Non-hydrocarbon fuels include oxygen-containing compositions (often called oxygenates), alcohols, ethers, ketones, esters of carboxylic acids, nitroalkanes, or mixtures thereof. Non-hydrocarbon fuels include cross-esterified oils and / or fats derived from plants and animals such as methanol, ethanol, methyl t-butyl ether, methyl ethyl ketone, rapeseed methyl esters and soybean methyl esters, and Nitromethane is included. Mixtures of hydrocarbon and non-hydrocarbon fuels include gasoline and methanol and / or ethanol, diesel fuel and ethanol, and cross-esterified vegetable oils such as diesel fuel and rapeseed methyl ester. In one embodiment, the liquid fuel is a non-hydrocarbon fuel or a mixture thereof.

The dispersion can be used as the only additive to the fuel composition. In one embodiment, the dispersion is used as one additive in combination with other functional additives to provide a fuel composition. In one embodiment, the present invention provides a composition comprising (i) (a) a metal base; (b) surfactants; And (c) a dispersion containing an organic medium in which metal bases are dispersed; (ii) oils of lubricating viscosity; And (iii) other functional additives.

Thus, the fuel composition may contain an oil of lubricating viscosity, as defined above, in addition to the amount that may be present as the organic medium of the dispersion.

Other functional additives

The fuel composition may optionally contain other functional additives. Other functional additives include metal deactivators, detergents, dispersants, friction modifiers, corrosion inhibitors, antioxidants, antifoams, anti-emulsifiers, pour point depressants, seal swelling agents, biocides, anti-adhesives (anti-) foulant), flow improvers (eg, polymethacrylates, maleic anhydride-styrene interpolymers, polyalphaolefins, and ethylene vinyl acetate), cooling flow improvers, or mixtures thereof. Typically, a fully blended fuel will contain one or more of the above functional additives.

Functional additives such as antiwear agents are typically contained in the fuel as diesel cylinder lubricants for two-stroke marine.

Demulsifier

Antiemulsifiers are known. In one embodiment, the dispersion may further contain antiemulsifiers, or mixtures thereof. Examples of anti-emulsifiers include trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers, alkoxylated alkyl phenol resins or mixtures thereof.

Dispersant

Dispersants are often known as ashless-type dispersants because, prior to mixing in the lubricating oil composition, they do not contain ash-forming metals and normally contribute to any ash forming metals when they are added to the lubricant. Because it does not. Dispersants also include polymeric dispersants. Ashless dispersants are characterized by polar groups bonded to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides having polyisobutylene substituents having a number average molecular weight in the range of 350 to 5000, or 500 to 3000. Succinimide dispersants and methods for their preparation are disclosed, for example, in US Pat. No. 4,234,435. Succinimide dispersants are typically imides formed from polyamines, typically poly (ethyleneamine).

In one embodiment, the present invention additionally contains at least one dispersant derived from polyisobutylene succinimide having a number average molecular weight of 350 to 5000, or 500 to 3000. Polyisobutylene succinimide may be used alone or in admixture with other dispersants.

In one embodiment, the present invention additionally contains at least one dispersant derived from polyisobutylene, amine and zinc oxide to form a polyisobutylene succinimide complex with zinc. Zinc and polyisobutylene succinimide complexes may be used alone or in combination.

Another class of ashless dispersants is Mannich bases. Mannich dispersants are reaction products of aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines) with alkyl phenols. Alkyl groups typically contain at least 30 carbon atoms.

In one embodiment, dispersants include polyisobutylene-amines disclosed in US Pat. Nos. 5,567,845 and 5,496,383 and commercially available from BASF.

Dispersants may also be worked up by conventional methods by reaction with any of a variety of agents. Some of these are boron sources such as boric acid or borate, urea, thiourea, dimercaptothiadiazole, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, Maleic anhydride, nitrile, epoxide, and phosphorus compounds.

Freshener

The fuel composition optionally contains additional neutral or overbased detergents. Suitable detergent materials include sulphonates, salixates, carboxylates, phosphates, phenates, including mono and / or di-thiophosphates, alkyl phenates and sulfur-bonded alkyl phenates, or salinine ( saligenin).

In other embodiments, the fuel composition additionally contains at least one of sulfonates and phenates. If present, detergents are typically overbased. The ratio of TBN carried by the dispersion to TBN carried by the detergent may range from 1:99 to 99: 1, or 15:85 to 85:15.

Antioxidant

Antioxidant compounds are known and include amine antioxidants (such as alkylated diphenylamines), hindered phenols, molybdenum dithiocarbamates, and mixtures thereof. Antioxidant compounds may be used alone or in combination.

Non-free phenolic antioxidants often contain secondary butyl and / or tertiary butyl groups as sterically hindered groups. Phenolic groups are often substituted with bridging groups that additionally link to hydrocarbyl groups and / or second aromatic groups. Examples of suitable non-free phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4 -Propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol 2,6-di-tert-butylphenol. In one embodiment, the minor free phenolic antioxidant is an ester, which may include, for example, Irganox ^™ L-135 from Ciba. A more detailed description of the chemistry of suitable ester-containing non-free phenolic antioxidants can be found in US Pat. No. 6,559,105.

Suitable examples of molybdenum dithiocarbamates that can be used as antioxidants include the brand names Vanlube 822 ^™ and Moyvan ^™ A. Asahi Denka Kogyo K under the commercial materials and trade names Adeka Sakura-Lube ^™ S-100, S-165 and S-600 sold by Vanderbilt Co., Ltd. Commercial materials sold in Asahi Denka Kogyo K. K and mixtures thereof.

Antiwear

The fuel composition optionally further contains at least one antiwear agent. Examples of suitable antiwear agents include sulfurized olefins, sulfur-containing ashless antiwear additives, metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates), thiocarbamate-containing compounds such as thiocarbamate esters, Thiocarbamate amides, thiocarbamic ethers, alkylene-bonded thiocarbamates and bis (S-alkyldithiocarbamyl) disulfides.

Dithiocarbamate-containing compounds can be prepared by reacting dithiocarbamic acid or a salt with an unsaturated compound. Dithiocarbamate containing compounds may also be prepared by simultaneously reacting amines, carbon disulfides and unsaturated compounds. In general, the reaction takes place at a temperature of 25 ° C to 125 ° C. U.S. Patent Nos. 4,758,362 and 4,997,969 disclose dithiocarbamate compounds and methods of making the same.

Examples of suitable olefins that can be sulfided to form sulfurised olefins include propylene, butylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene , Tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof and dimers, trimers and tetramers are particularly useful olefins. . Optionally, the olefin can be unsaturated esters such as Diels-Alder adducts such as 1,3-butadiene and butyl (meth) acrylates.

Other populations of sulfurized olefins include fatty acids and esters thereof. Fatty acids are often obtained from vegetable or animal oils and typically comprise 4 to 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Often, fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. In one embodiment the fatty acids and / or esters are mixed with olefins.

In alternative embodiments, the ashless antiwear agent may be a monoester and aliphatic carboxylic acid of a polyol, often an acid having 12 to 24 carbon atoms. Often monoesters and aliphatic carboxylic acids of polyols are present in the form of a mixture with sunflower seed oil or the like, sunflower seed oil or the like in an amount of 5 to 95% by weight in the friction modifier mixture, in other embodiments 10 To 90% by weight, or 20 to 85% by weight, or 20 to 80% by weight. Aliphatic carboxylic acids (particularly monocarboxylic acids) which form esters are aliphatic carboxylic acids having 12 to 24 or 14 to 20 carbon atoms. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, oleic acid.

Polyols include diols, triols, and alcohols with high levels of alcoholic OH groups. Polyhydric alcohols include ethylene glycols such as di-, tri- and tetraethylene glycol; Propylene glycols such as di-, tri- and tetrapropylene glycols; Glycerol; Butane diol; Hexane diol; Sorbitol; Arabitol; Mannitol; Sucrose; Fructose; Glucose; Cyclohexane diol; Erythritol; And pentaerythritols such as di- and tripentaerythritol. Often the polyol is diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or dipentaerythritol.

Commercially available monoesters known as “glycerol monooleates” contain 60 ± 5 wt% glycerol monooleate species and less than 5 wt% trioleate and oleic acid with 35 ± 5 wt% glycerol dioleate. It is considered to contain.

Corrosion inhibitors such as condensation products of fatty acids with polyamines such as octylamine octanoate, dodecyl succinic acid or anhydrides and oleic acid; Metal deactivators such as derivatives of benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; Antifoaming agents such as ethyl acrylate and 2-ethylhexyl acrylate and optionally copolymers of vinyl acetate; Pour point depressants such as esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides; And other functional additives such as friction modifiers such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines and amine salts of alkylphosphoric acids, may also be used in fuel compositions.

Manufacturing method of the dispersion

Dispersions can be prepared by physical methods, that is, by any one or more of various physical methods, ie physical processing steps. Examples of physical methods include stirring, milling, grinding, crushing or a mixture thereof. Typically, the method grinds the metal base so that the average particle size is at least 10 nanometers but less than 1 μm. Milling methods include rotor stator mixers, vertical bead mills, horizontal bead mills, basket mills, ball mills, pearl mills, or mixtures thereof. In one embodiment, the physical method for preparing the dispersion comprises using vertical or horizontal bead mills.

In one embodiment, the present invention further provides a method of preparing a dispersion comprising the following steps:

(1) (a) at least two metal bases having an oxidation number of at least about (+2) metal of each metal base; (b) mixing the surfactant and (c) the organic medium to form a slurry; And

(2) grinding the slurry of step (1) to form a dispersion.

In another embodiment, the dispersion can be prepared by a single metal dispersion, as taught in WO2005 / 097952, by mixing (by mixing them together) a variety of single metal base dispersions of each metal of the metal base. At least two metal bases having an oxidation number of about (+2) or more; It may also comprise the additional step of forming a dispersion containing (b) a surfactant and (c) an organic medium. When the dispersion is prepared by mixing various single metal base dispersions, it is common for all single metal base dispersions to contain the same or compatible with the surfactant compound and the organic medium. If the surfactant and the organic medium are not friendly, an unstable dispersion can be formed.

In other embodiments, the milling method can be performed in a vertical or horizontal bead mill. The bead mill method reduces particle size of the metal base by high energy impact of the metal base with at least one bead; Reduce the size of agglomerates, aggregates, solid particles or mixtures of other metal bases. The beads typically have an average particle size and mass that is larger than the desired average particle size of the metal base. In some cases, the beads may be a mixture of different average particle sizes. Beads used for grinding may be materials known to those skilled in the art, such as metal ceramics, glass, stone, or composite materials.

The mill typically comprises beads present in at least about 40%, or at least about 60%, by volume of the wheat. For example, the range from 60% to 95% by volume is included. A more detailed description of making the dispersion is disclosed in US Patent Application No. US05 / 010631.

Industrial use

In methods of controlling byproducts or pollutants from fuel combustion, dispersions are useful for a variety of open or closed flame combustion systems. Suitable combustion systems include power plants, internal combustion engines, industrial and marine compression engines and turbines (typically burning distillate, residue or heavy fuel oil).

In other embodiments, suitable dispersions are added to the fuel in the range of about 1 ppm to about 10,000 ppm, or about 20 ppm to about 7500 ppm, or about 100 ppm to about 5000 ppm, or about 200 ppm to about 3000 ppm, or about 500 ppm to about 2000 ppm. .

In one embodiment, the present invention provides a method of controlling by-products or contaminants from fuel combustion comprising supplying a fuel containing a dispersion as disclosed herein. The use of dispersions in fuels can give means to control byproducts or pollutants from fuel combustion. Typically, byproducts or contaminants from fuel combustion include two or more properties in controlled sulfur oxide emissions, controlled nitrogen oxide emissions, controlled particulate matter emissions, controlled vanadate production, or a mixture of these properties. In one embodiment, the fuel dispersion contains calcium bases and the bases can regulate the release of sulfur oxides and the production of particulate matter. In one embodiment, the fuel dispersion contains magnesium bases, which bases can regulate vanadate production, emissions of sulfur oxides, and production of particulate matter.

The following examples provide illustrations of the present invention. These examples are not intended to be exhaustive or to limit the scope of the invention.

Spare of Dispersion Example

A series of dispersions (preparative examples 1 to 3) containing metal bases, organic media and surfactants were prepared on a commercial scale commercially available from W.A.B.A., Basel. It was prepared using about 15 kg slurry and 0.3 mmφ zirconia / yttria beads using a Dyno-Mill ECM Multi-Lab horizontal bead mill and a residence time of about 10 minutes at a tip speed of about 8 ms ⁻¹ . At appropriate times, the average particle size of the dispersion particles was measured with a Coulter® LS230 particle size analyzer after cooling. The prepared dispersion could be poured.

Spare Example  1: magnesium oxide Dispersion

In the presence of about 40% by weight 100N base oil and about 10% by weight alkylbenzene sulfonic acid surfactant, about 50% by weight magnesium oxide, Magchem 40 ex Martin Marietta was milled to disperse the dispersion. Manufactured.

Spare Example  2: iron oxide Dispersion

A dispersion was prepared by milling about 70% by weight of iron oxide (Fe ₂ O ₃ ) commercially available from Bayer, about 18% by weight 100N base oil and about 12% by weight alkylbenzene sulfonic acid surfactant as Bayferrox®160. did.

Spare Example  3: cerium oxide Dispersion

Dispersions were prepared by milling about 50% by weight cerium oxide (CeO), about 40% by weight 100N base oil and about 10% by weight surfactant (polyolefin amino esters esterified with 2- (dimethylamino) ethanol).

Example 1 Dispersion of Three Metals

Dispersions of three metals were prepared by mixing the commercially available cerium sulfonate powder and octadecanoate of iron with the product of Preliminary Example 1. The metal weight ratio of magnesium: cerium: iron of the obtained product was about 150: 10: 5. The product formed a stable dispersion that showed no significant stratification after 12 weeks.

Example 2: Dispersion of Three Metals

Dispersions of the three metals were prepared by mixing the parts of the product formed in Preliminary Examples 1-3. The metal weight ratio of magnesium: cerium: iron of the obtained product was about 150: 10: 5. The product formed a stable dispersion that did not show significant layer separation after 12 weeks. The dispersion had at least about 85% of the dispersion particles having a particle size of less than 0.46 microns.

Example 3 of Three Metals Dispersion

Magnesium oxide, calcium hydroxide and iron oxide (Fe ₂ O ₃ ) were mixed in the form of a powder to prepare a dispersion of three metals. Thereafter, about 10% by weight of the succinimide surfactant, about 39.6% by weight of SN 100 base oil, and about 0.4% by weight of an emulsifier were added to the obtained powder of the three metals. The final dispersion contained 37.5 wt% magnesium oxide, about 10.5 wt% calcium hydroxide and about 2 wt% iron oxide. The resulting dispersion could be poured out and the average particle size was about 0.14 to about 0.2 microns.

Fuel composition 1-3

Examples 1-3 were each processed at about 1000 ppm to produce a liquid fuel. The fuel obtained was combusted and the dispersion was used to reduce by-products or contaminants from fuel combustion.

Fuel composition 4-6

Examples 4-6 were each processed at about 1300 ppm to produce liquid fuels. The fuel obtained was combusted and the dispersion was used to reduce by-products or contaminants from fuel combustion.

Fuel Composition 7-9

Examples 7-9 were each processed at about 1500 ppm to produce liquid fuels. The fuel obtained was combusted and the dispersion was used to reduce by-products or contaminants from fuel combustion.

Fuel composition 10-12

Examples 10-12 were each processed at about 700 ppm to prepare a liquid fuel. The fuel obtained was combusted and the dispersion was used to reduce by-products or contaminants from fuel combustion.

Fuel composition 13-15

Examples 13-15 were each processed at about 1750 ppm to produce a liquid fuel. The fuel obtained was combusted and the dispersion was used to reduce by-products or contaminants from fuel combustion.

While the invention has been described in connection with its preferred embodiments, it should be understood that various modifications of the invention will become apparent to those skilled in the art upon reading this specification. Accordingly, it is to be understood that the invention disclosed herein is intended to cover all such modifications as fall within the scope of the appended claims.

Claims (20)

(a) a mixture of at least two metal bases in which the metal of the metal base has an average oxidation number of at least (+2), (b) at least one surfactant; And (c) burning a fuel containing at least one organic medium, the fuel containing a dispersion wherein said metal base is uniformly dispersed in said organic medium. Way. The method of claim 1, wherein the average oxidation number of each metal base is in the range of about (+2) to about (+4), or in the range of about (+2) to about (+3). The method of claim 1 wherein the metal base comprises an oxide, carbonate, bicarbonate, hydroxide, sulfonate, carboxylate, or mixtures thereof. The method of claim 1, wherein the mixture of the at least two metal bases, (i) a first metal base containing a metal selected from the group consisting of iron, magnesium, calcium and mixtures thereof; (ii) a second metal base containing a metal selected from the group consisting of magnesium, calcium, cerium, iron, copper, chromium, and mixtures thereof, wherein the second metal base is different from the first metal base; And (iii) optionally containing another metal base other than the metal base of (i) or (ii). The method of claim 4, wherein the first metal base is present in at least about 50% by weight of the total amount of the metal base present; And wherein the second metal base is present in less than about 50% by weight of the total amount of metal base present. The method of claim 4, wherein the first metal base is present in at least about 75% by weight of the total amount of the metal base present; Wherein the second metal base is present at less than about 25% by weight of the total amount of metal base present. The method of claim 1, wherein the dispersion contains a metal base present in the range of about 25% to about 80%, or about 35% to about 70% by weight of the dispersion. The method of claim 1, wherein the average particle size of the metal base in the dispersion is in the range of about 20 nanometers to less than about 1 μm. The method of claim 1 wherein the hydrophilic lipophilic equilibrium (HLB) of the surfactant is in the range of about 1 to about 40. The method of claim 1, wherein the surfactant comprises at least hydrocarbyl substituted aryl sulfonic acid, a polyolefin-substituted acylating agent, or salixarene. The composition of claim 1, wherein the dispersion comprises: (a) 40-65 weight percent metal base; (b) 5-25% surfactant; And (c) an organic medium in which the metal base is dispersed. The method of claim 1, wherein the fuel comprises a liquid fuel, a solid fuel, or a mixture thereof. The method of claim 1, wherein the by-products or pollutants from fuel combustion are at least two characteristics in controlled sulfur oxide emissions, controlled nitrogen oxide emissions, controlled particulate matter generation, controlled vanadate production, or a mixture of these properties. Characterized in that it comprises a. (a) a mixture of at least three metal bases in which the metal of the metal base has an average oxidation number of at least (+2), (b) at least one surfactant; And (c) burning a fuel containing at least one organic medium, the fuel containing a dispersion wherein the metal base is uniformly dispersed in the organic medium. Way. The method of claim 14, wherein the mixture of the at least three metal bases, (i) a first metal base containing a metal selected from the group consisting of iron, magnesium, calcium and mixtures thereof; (ii) a second metal base containing a metal selected from the group consisting of magnesium, calcium, cerium, iron, copper, chromium, and mixtures thereof, wherein the second metal base is different from the first metal base; And (iii) the metal of the metal base is selected from the group consisting of calcium, magnesium, cerium, iron, copper, chromium, barium, platinum, lead, manganese, strontium, and mixtures thereof, wherein the third metal base is ( characterized by containing at least one other metal base which is different from the metal base already used in i) and (ii). (i) fuel; And (ii) a mixture of (a) at least two metal bases, each of which metal of the metal base has at least about (+2) oxidation number, (b) at least one surfactant; And (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium. 17. The composition of claim 16 wherein said dispersion contains at least three metal bases. 17. The method of claim 16, wherein the metal deactivator, detergent, dispersant, friction modifier, corrosion inhibitor, antioxidant, antifoam, anti emulsifier, pour point depressant, seal swelling agent, biocide, anti-adhesion agent ( anti-foulant), flow improving agent, cooling flow improving agent, and mixtures thereof. (a) a mixture of at least three metal bases, each of which the metal of the metal base has an average oxidation number of at least about (+2), (b) at least one surfactant; And (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium. (A) a mixture of at least two metal bases, each of which has an average oxidation number of at least about (+2) metals, in order to reduce by-products or contaminants formed in combustion of the fuel, (b) at least one Surfactants; And (c) at least one organic medium, wherein the metal base is uniformly dispersed in the organic medium.