JPH0756036B2 - Fuel additive composition - Google Patents

Description

The present invention relates to a hydrocarbon soluble composition containing a transition metal salt of an organic acid and a hydrocarbon soluble ashless dispersant.

Typically, the organic acid is a carboxylic acid, a sulfonic acid or a phosphorus-containing acid and the ashless dispersant is a nitrogen-containing or nitrogen-free ester dispersant. The invention also relates to a hydrocarbon system, such as a hydrocarbon fuel, containing the above composition.

It is well known to treat hydrocarbon systems such as hydrocarbon fuels (solid or normally liquid, respectively) with transition metals and inorganic or organic transition metal containing compounds. This treatment is used to increase the resistance to oxidative degradation of the system, to promote conversion to agglomerated films in paints and lacquers, and to improve, for example, flammability as fuel.

Among the organic transition metal compounds used for the above purposes are carboxylates, sulfonates and mixtures thereof. For example, U.S. Pat. No. 4,162,986 discloses a transition metal salt of a mixture of an organic carboxylic acid and a sulfonic acid or a second carboxylic acid as a catalyst, an anti-knock agent, a flammability improver, a smoke suppressant, a hardener, a micronutrient It is described to be used as a source, an additive for a lubricant, and the like.

U.S. Pat.No. 3,762,890 describes a hydrolyzable manganese soap stabilized by the inclusion of propionic acid as a dryer for paints, varnishes and inks, as a stabilizer for various plastics, as an additive for greases and lubricants. It is described as an agent and also as a smoke suppressant for fuels and fuel oils and as an anticorrosion agent.

U.S. Pat. No. 3,723,152 describes the use of basic cobalt salts of carboxylic acids as a dryer composition for oil vehicles.

Also, for example, US Pat. No. 4202671 describes the use of organomagnesium compounds as fuel conditioners to reduce fuel demand and emissions.

With increasing concern over pollution and rising prices for hydrocarbon fuels, the use of transition metal compounds in such systems has become of interest. However, the use of transition metal compounds has a beneficial but adverse effect. Adverse effects may include acceleration of sediment and sludge, especially in fuel oils. Such deposits promote corrosion and interfere with oil storage and transfer by disrupting pumps, gauges and equipment.

Accordingly, it is an object of this invention to provide a hydrocarbon soluble (hydrocarbon soluble) composition containing an organic transition metal salt with an ashless dispersant that provides an optimal balance between beneficial and detrimental effects. To provide what you do.

The composition of the present invention comprises (A) at least one transition metal salt of at least one organic acid, and (B) at least one hydrocarbon-soluble ashless dispersant.

Hydrocarbon systems such as fuel compositions (eg, distillate fuel compositions comprising high amounts of hydrocarbon fuel and low amounts of the above salt / dispersant composition) are also within the scope of this invention.

Hereinafter, the composition of the present invention will be described for each component.

(A) Transition metal salt The transition metal in the organic salt used in the present invention is selected from copper, scandium, titanium, vanadium chromium, manganese, iron, cobalt, nickel and a combination of two or more thereof. Most commonly used are manganese salts, as well as salts containing manganese with other metals. Often, salts containing only manganese are used. Lead salts are also used.

The organic acids that make up the transition metal salts are those containing carbon atoms, such as carboxylic acids, especially those having 1 to 30 carbon atoms, sulfonic acids, especially alkyl groups having 4 to about 22 carbon atoms. Some include those containing one or more substituted aromatic rings (eg, benzene rings), and those containing phosphorus, especially those containing one or more organic groups having from 1 to about 30 or more carbon atoms.

The carboxylic acids, sulfonic acids and phosphorus-containing acids mentioned above are well known. The carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid (typically a dicarboxylic acid and a tricarboxylic acid). C ₁ -C _{7 for} monocarboxylic acids
Lower carboxylic acids (acetic acid, propionic acid, etc.) and higher carboxylic acids with C ₈ or higher (octanoic acid, decanoic acid, etc.) and approx.
Included are the well-known fatty acids having 12 to 30 carbon atoms, which often contain, for example, 5 to about 30 mole% straight chain acids and about 70 to about 95 mole% branched chain acids. It is a mixture of a straight chain acid and a branched chain acid. Other commercial fatty acid mixtures containing high proportions of linear acids are likewise useful. Acid mixtures obtained by dimerization of unsaturated fatty acids are also used.

The higher fatty acids include the well-known dicarboxylic acids prepared by alkylating maleic anhydride or its derivatives. This alkylation reaction product is a hydrocarbon-substituted succinic acid, its anhydride, or the like. Low molecular weight dicarboxylic acids such as polymethylene cross-linking acids (glutaric acid, adipic acid, etc.), as well as tetrapropenyl succinic acid and C ₃₀
Also used are low molecular weight substituted succinic acids, such as their analogs substituted with groups up to.

The high molecular weight substituted succinic acids, anhydrides and analogs useful in making the salts used in this invention are described in many patent references relating to acylated compounds useful as dispersants. A typical high molecular weight substituted succinic acid is 30 to 40
It is obtained by reacting a poly (isobutene) fraction having 0 (usually 50 to 250) carbon atoms with maleic anhydride. This acid is described in U.S. Pat.
No. 3219666 and No. 3272746. Monocarboxylic acids of similar molecular weight can be prepared by alkylating acrylic acid and its analogs. Mixtures of these acids are also used.

Salts useful in this invention include carbocyclic carboxylic acids,
It can also be prepared from acidic hydroxy compounds such as alkylated phenols. Such materials are described in U.S. Pat.
No. 085, particularly in columns 15 to 17.

The above-mentioned U.S. Pat. No. 4100082 also describes many of the sulfonic acids useful in the preparation of the salts used in this invention, especially those of
It is listed in column 14.

Transition metal salts prepared from phosphorus-containing acids are also useful. Phosphorus-containing acids are described in many documents including patent documents. For example, U.S. Pat. (Where M is the transition metal, R ¹ and R ² are hydrocarbon machines, X ¹ , X ² , X ³ and X ⁴ are oxygen or sulfur, and a and b are 0 or 1). Salts of phosphorus-containing acids are described.

Typically, the organic acid used to make the salt used in this invention is a carboxylic acid, a sulfonic acid, or a mixture thereof. Particularly useful salts are described in U.S. Pat. No. 4,162,986, which shows transition metal salts of organic acids for use in the compositions of this invention.

By the way, the transition metal salt used in the present invention is often overbased. That is, the transition metal is contained in an amount exceeding the amount that neutralizes the acid. In other words, the overbased salt contains more than 1 equivalent of transition metal per equivalent of acid-derived groups. Such salts are well known. For example, in addition to the above U.S. Pat.No. 4,162,986, U.S. Pat.Nos. 3,827,979, 3312618, 3616904, 3616905.
No. 2595790 and No. 3725441 (8) Ashless Dispersants Ashless dispersants useful in this invention are well known and are commonly used in hydrocarbon fuels such as liquid hydrocarbon fuels. Is a dispersant. Ashless dispersants are those that burn (metallic) leaving little or no residue or ash. This means that, in general, the ashless dispersants may contain elements such as phosphorus, sulfur, boron, etc. in addition to carbon, oxygen, hydrogen and often nitrogen, but are substantially metal-free.

Generally, the ashless dispersants used in this invention are C, H, O
And N only. In some cases, the ester dispersant (see below) may contain only C, H and O. More complex ashless dispersants may contain other elements such as sulfur, boron, phosphorus and the like. However, typically, the ashless dispersants used in this invention are nitrogen-containing or nitrogen-free ester dispersants.

Many types of ashless dispersants are known. For example, M.
See W. Lanny's Lubricant Additivesooly St. Development (1978) and Lubricant Additives (1973) (both published by Noyes Data, USA) and U.S. Pat. No. 4,136,403.

Listed below are examples of more commonly available and therefore useful hydrocarbon soluble ashless dispersants.

(1) An acylated nitrogen-containing dispersant as described in US Pat. No. 4100082, particularly columns 18 to 20.

This dispersant is obtained by reacting an acylating agent (for example a carboxylic acid or its anhydride) with an amino compound (for example an amine, a polyamine or another compound having a -NH- group). Typical acylating agents include the substituted succinic acids mentioned above and also described in US Pat. No. 4100082. Other useful acylating agents are also described in many patent documents, such as US Pat. No. 4,234,435. This U.S. patent discloses acylating agents and amino-containing and amino-free compounds used in the preparation of ashless dispersants.

The acylated ashless dispersants useful in this invention can be of high or low molecular weight. The ashless dispersants may include moieties derived from mono- and polyalcohols (including aminohydroxy compounds such as the well-known amino alcohols) in addition to moieties derived from amino compounds. Typical ashless dispersants are 2 to 7
Some are prepared from alkylene polyamines containing 1 amino group and 1 to 6 alkylene groups each having 2 to 4 carbon atoms. Commercially available ethylene polyamines are useful as the alkylene polyamines.

Low molecular weight acylated nitrogen-containing compounds are also useful as the dispersants used in this invention. This compound is prepared from the amino compound and a mono- or dicarboxylic acylating agent having from about 12 to about 20 carbon atoms. Dispersants of this type often contain imidazoline groups and are well known. For example, U.S. Pat.
See No. 3240575.

High molecular weight acylated nitrogen-containing ashless dispersants in which both amino and alcohol compounds (or amino alcohols) are acylated are also known and are useful in this invention. This dispersant is described in US Pat. No. 4136043.

(2) High molecular weight nitrogen-free ester.

As mentioned above, these esters are well known because they are produced by reacting the acylating agent (for example, poly (isobutene) -substituted succinic anhydride) with a polyol or a monoalcohol. For example,
See U.S. Pat. No. 3,522,179.

(3) Hydrocarbyl substituted amine.

Hydrocarbyl substituted amines useful as ashless dispersants are well known. For example, U.S. Pat.
See 8757, 3454555 and 3565804. Further, the description is given in the above-mentioned US Pat. No. 4100082. These patents disclose hydrocarbyl amines suitable as ashless dispersants in this invention.

(4) Nitrogen-containing condensates of phenols, aldehydes and amino compounds.

Phenol, aldehyde (eg formaldehyde)
And condensation products made from amino compounds such as those mentioned above are useful as ashless dispersants for use in this invention. This condensation product is known as the Mannich condensation product. Generally, the condensate is reacted with a hydrocarbon-substituted phenol (eg, an (alkylated) phenol having an alkyl group of about 34 to 400 carbon atoms), formaldehyde and an amino or polyamino compound having at least one -NH- group. Obtained by This condensate is well known. For example, US Pat.
See No. 00082 and references cited therein.

The hydrocarbon soluble composition of this invention is made by combining (A) at least one of the transition metal salts and (B) the hydrocarbon soluble ashless dispersant. The term "hydrocarbon soluble" means that the material has a solubility in the intended hydrocarbon system at 25 ° C of at least 0.001 part by weight. Any method may be used for combining the components (A) and (B). Generally, it is advantageous to avoid directly combining the salt and the dispersant directly. This is because the problem of precipitation does not occur. It is therefore common to mix either the dispersant, the salt with the inert solvent / diluent and then mix it with the other and / or the auxiliary substances. The solvent / diluent used is usually hydrocarbyl, may contain small amounts of other heteroatoms, and is often highly aromatic in order to increase solubility. Auxiliary substances used are dyes, antioxidants, metal deactivators and especially demulsifiers which prevent emulsification of the dispersants and / or salts in the fuel oil vehicle. Such demulsifiers are well known. See, for example, "Encyclopedia of Chemical Technology", Vol. 8, pages 151 and below, and Vol. 19, pages 507 and below (1965), by Kirku Osmer. A typical demulsifier is a surfactant containing a hydrophilic part and a hydrophobic part in the molecule. It can be obtained by reacting phenols or alcohols with ethylene oxide, propylene oxide or mixtures thereof.

As already mentioned, the composition according to the invention is used for treating hydrocarbon fuels.

The fuel may be solid or liquid. Coal as solid fuel,
There are shale charcoal, peat, wood, organic waste, and charcoal. Liquid fuels include light petroleum fractions such as gasoline, kerosene, and other fractions such as middle distillate fuels. Typical middle distillate fuel oils include No. 1, 2 and 4 fuel oils specified in ANSI / ASTM Standard D-396-67. Combinations of this oil with straight runs, vacuum runs or other specially treated bottoms can also be treated with the compositions of this invention.

The treated fuel composition has a salt of about 1 to 500 ppm by weight, preferably about 5 to 350 ppm by weight of the composition of the present invention as a transition metal, and about 5 to 1000 ppm by weight, preferably 10 to 800 ppm.
Contains ppm ashless dispersant. In fuel oils, in particular, about 10 to 200 ppm by weight of salts corresponding to transition metals and about
The compositions of this invention are used in proportions to provide from 15 to 450 ppm by weight dispersant.

Example 1 Poly (isobutene) -substituted succinic anhydride (substituent Mn =
A known ashless acylated nitrogen-containing dispersant was prepared by reacting about 1000) with a commercial ethylene polyamine mixture whose average composition corresponds to triethylene tetraamine. The reaction was carried out in an aromatic solvent / diluent and the acid anhydride to polyamine weight ratio was about 100: 9. The desired ashless dispersant which removes water and other low boiling products and impurities by heating and has a nitrogen content of about 2% by weight.

Example 2 10.82 parts of overbased manganese carboxylate containing 40% by weight of manganese (Moonie 910 manufactured by Mooney Chemical Co.), 14.43 parts of the ashless dispersant of Example 1, the first demulsifier (Trad of Petrolite). ) 285, ethoxylated / propylated hydroxy compound) 0.18 parts, second demulsifier (Nalco 5RD-648 manufactured by Nalco Chemical Co., ethoxylated propoxylated pentaerythritol) 0.14 parts and kauri gum-butanol 95 aromatic A hydrocarbon-soluble composition was prepared by mixing 74.43 parts of the solvent (HI-SOL). At this time, the aromatic solvent was used so that the carboxylic acid salt and the ashless dispersant would not come into direct contact with each other. The specific gravity of the obtained composition was 0.94 at 15.6 ° C,
The pour point was -57 ° C and the manganese content was 4.3-4.6% by weight.

Example 3 The composition of Example 2 was used to treat a typical commercial No2 middle distillate fuel oil. 1 part by weight of the composition of Example 2 was used per 4600 parts by weight of fuel oil. This was equivalent to 10.7 ppm of manganese per 1 part by weight of fuel. A commercial boiler was operated with the fuel thus treated and compared with the untreated fuel. It was found that the fuel oil treated with the composition of this invention had a 1.7% improvement in efficiency due to reduced fuel consumption.

Example 4 124 parts of naphthenic acid, 200 parts of methyl cellosolve, 10 parts of propylene glycol and 7 parts of acetic acid were heated to 60 ° C. Next, 42 parts of metallic manganese was added over about 30 minutes, and the mixture was heated under reflux for 4 hours. Then 100 parts of mineral oil and 10 parts of water were added to the mixture and then refluxed for 1 hour. Then 1.5ft ³ / h
The mixture was heated to 185 ° C. while blowing with nitrogen at a flow rate of r. Finally, the residue was used to obtain carboxylic acid manganic acid using 20 g of diatomaceous earth.

Example 5 184 parts neodecanoic acid, 63 parts propionic acid, 1 stearic acid
6 parts, 414 parts of textile benzine and 193 parts of tap water were placed in a suitable container. After heating the mixture to 40 ° C., 473 parts of metallic manganese was added over 1 hour. Furthermore, the temperature is 100 ℃
The benzine for the textile was removed by raising the temperature. Then naphthenic acid
After adding 414 parts to the mixture, the mixture is heated to 100-12 for 5 hours.
Heated to 0 ° C. The mixture was then heated to 150 ° C. while blowing with nitrogen at a flow rate of 15 ft ³ / hr. The mixture was then blown with air at a flow rate of 1 ft ³ / hr for 6 hours at 150-155 ° C. Then the mixture was cooled to room temperature and then toluene
100 parts were added. Finally heat the liquid to 170 ℃, 2ft ³ / h
When nitrogen was blown at a flow rate of r, manganese carboxylate was obtained as a residue.

Example 6 33 parts of n-heptanoic acid, 41 parts of 2-methoxyethanol, 82 parts of high flush naphtha, 1.7 parts of glacial acetic acid, 0.8 parts of ammonium chloride, 1.6 parts of calcium chloride and 39.5 of manganese oxide.
Parts were placed in a stainless steel autoclave.

The autoclave was sealed and purged twice with carbon dioxide. The reaction mixture was then stirred and heated to 101-104 ° C while maintaining the CO ₂ pressure at 2 atm. After 100 minutes, the temperature of the reaction mixture had risen to 114 ° C. and the vigorous reaction had occurred with the pressure decreasing. After cooling the reaction mixture to 104 ° C., carbon dioxide was added so that the pressure inside the autoclave was maintained at 2 atm. The temperature changed from 101 to 107 ° C. The addition of carbon dioxide was stopped when the pressure inside the autoclave increased. A total of 14 parts of carbon dioxide has been added.

The reaction mixture was held at 101-107 ° C for an additional 90 minutes, then 38
Cooled to ° C. Then passed the product. As a result, an overbased manganese heptanoate solution containing 14.3% by weight of manganese 20
7 copies were obtained.

When this solution was distilled under reduced pressure, a fluid substance containing 22% by weight of manganese was obtained.

Example 7 To a solution of stearic acid (3.3 parts) and a solution of dodecylbenzenesulfonic acid (14.7 parts) in xylene (150 ml), 54 parts of chromium oxide hydrate (K & K Laboratory) was added and stirred for 20 minutes. After stirring at room temperature for 1.5 hours, the mixture was heated to reflux. After removing water and xylene (60 ml), the product was centrifuged at 2200 rpm to remove 2.2 parts of insoluble matter.
After further concentrating the solution, acetic acid was added to reduce the viscosity and 144.5 parts of a liquid without impurities was obtained. Cr content is 16.
It was 9%.

Claims (15)

[Claims] 1. (A) At least one transition metal salt of at least one carboxylic acid having 1 to 30 carbon atoms selected from a manganese salt and a copper salt, and (B) poly (isobutene).
A fuel additive composition comprising a hydrocarbon-soluble ashless dispersant which is a reaction product of a substituted succinic anhydride and triethylene tetraamine. 2. The composition according to claim 1, wherein the carboxylic acid is a mixture of two or more kinds. 3. A composition according to claim 1 or 2 in which the carboxylic acid contains at least about 7 carbon atoms. 4. The composition according to any one of claims 1 to 3, wherein the transition metal salt is a manganese salt. 5. The composition according to any one of claims 1 to 4, wherein the transition metal salt is an overbased salt. 6. A method according to any one of claims 1 to 4 in the form of a concentrate present in a concentration of about 10 to 99% by weight in a substantially inert, normally liquid organic diluent. The composition according to item 1. 7. A fuel composition comprising a large amount of fuel and a small amount of the composition of claim 1. 8. The fuel composition according to claim 7, wherein the fuel is usually liquid. 9. The fuel according to claim 8, wherein the fuel is a fraction fuel oil, and the composition according to claim 1 is contained in a proportion of about 1 to 500 ppm of transition metal. Fuel composition. 10. (A) At least one carboxylic acid having 1 to 30 carbon atoms, at least one transition metal salt selected from manganese salts and copper salts, and (B) poly (isobutene) -substituted succinic anhydride. Hydrocarbon-soluble ashless dispersant which is a reaction product of a substance with triethylenetetramine, (C) at least one demulsifier, and (D) a substantially inert solvent /
A fuel additive composition consisting essentially of a diluent. 11. The composition according to claim 10, wherein the transition metal salt is an overbased manganese salt. 12. A composition according to claim 10 or 11 in the form of a concentrate present in a concentration of about 10-99% by weight in a substantially inert, normally liquid organic diluent. object. 13. A large amount of fuel and claim 10
A fuel composition comprising a minor amount of the composition of claim. 14. The fuel composition according to claim 13, wherein the fuel is usually liquid. 15. The fuel is a distillate fuel oil, and the composition of claim 10 contains about 10 to 200 ppm of transition metal.
15. The fuel composition according to claim 14, wherein the fuel composition is contained in the following ratio.