JPH03502819A - fuel stabilizer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to stabilizing fuels, particularly diesel fuels, against discoloration.

This discoloration is sometimes associated with the formation of insoluble material.

Oimudate star five In general, fuels, particularly middle distillate fuels, are prone to the formation of insoluble materials. This insoluble The substance can block fuel systems, fuel filters, and even storage tanks. causing blockage.

Insoluble substances in the fuel can cause blockages in the tips of the fuel injectors in diesel engines. Even if it appears. No matter where gelation occurs, the fuel will not flow and therefore the fuel's intent The intended use cannot be obtained. The formation of insoluble materials in middle distillate fuels is usually associated with discoloration of the fuel.

However, all of the discolorations in middle distillate fuels indicate impending formation of insoluble material. It does not indicate that. Therefore, if discoloration of middle distillate fuel is observed, In such cases, the user does not know whether the fuel is safe to use. insoluble substances Since it is impractical to test small amounts of fuel for the tendency to form Customers must consume fuel quickly. There is no guarantee that there will be no formation of insoluble materials before the material is consumed. a or the fuel is returned to the seller or processed to avoid the formation of insolubles. can be done. Either way, it will be a considerable expense.

Therefore, the present invention provides a method for discoloration, whether or not the discoloration is related to the formation of insoluble matter. , relating to preventing coloration in fuel. The composition here is a middle distillate fuel. It is also useful for processing to avoid the formation of insolubles.

With formaldehyde or acetaldehyde and hydroxybenzaldehyde Using an organic polyamine having at least one reacted primary amino group This allows normal liquid petroleum fractions to be treated for color and sludge. is a rice paper published by Chaot on November 7, 1967. It is known from National Patent No. 3.351.662. Chamot, 1965 A similar disclosure is made in U.S. Patent No. 3.1J14.294, issued May 18, states. Connie Kirk (Nevkirk) Published April 4, 1972 No. 3,654,158, bis-1,3-alkylamino- 2- Discloses that hydrocarbon corrosion can be prevented by using propa tools. Ru.

U.S. Pat. No. 4.6 issued by Reid on March 3, 1987. No. 47.290 is tho(2-aminoethyl)piperazine and N,N-diethyl - Describes a color stabilized distillate fuel containing hydroxylamine. Lee No. 4,648, issued March 1, 1987. H5 issue gave a similar disclosure, and his color stabilizing system further included triethylenetetra. Contains lamin. Recently, the Reed has been published on March 3, 1987. National Patent No. 4.647.289 also describes similar chemicals.

U.S. Patent No. 3 issued February 3, 1976 by Alink ．． No. 936.279 discloses that hexahydropyrimidine is used to prevent deterioration of distillate fuels. Describes the use of gin. Thompson et al., 1982 In U.S. Patent No. 4,311.841, issued on January 19, describes the further use of hexahydropyrimidine as an anti-tarnish agent for There is. Qat tuso is an American brand issued on January 18, 1977. National Patent No. 4,003.718 discloses that The use of substituted tetrahydropyrimidines is described.

Vong et al., U.S. Patent No. 4, issued August 18, 1981, No. 284,415, Reaction of alkoxyalkylamines with epihalohydrins Preventing sedimentation and suppressing deterioration of hydrocarbon fuels by using products is described. Kelp No. 4 issued on December 16, 1980 ．． No. 239.497, in order to prevent sedimentation and suppress deterioration of hydrocarbon fuels, Related to the reaction products of shrimp halohydrin and poly(oxyalkylene) amines Discloses similar chemicals. Hanlan (Hanson) December 1980 2.4- or 2 ．． 6-di-tertiary alkyl “hindered” phenol, polyamine, formalde a hydride-generating reagent and at least one active or acidic hydrogen-containing reagent; Both describe Mannich additives formed from one hydrocarbon compound. 1 U.S. Pat. No. 3, issued by Worrel on April 6, 1976. No. 948.619 is a phenol (preferably a high molecular weight alkylphenol) , an aldehyde, and an amine having a free -N()I)- group. It describes cleaning internal combustion engines using gasoline containing a certain amount of detergent.

US Patent issued by Braxton on April 9, 1985 No. 4.509.932 requires a small amount of alkyl to stabilize against degradation. The addition of diethylamine to distillate fuels is disclosed.

No. 3,649,229, issued March 14, 1972, ) - (Qtto) is used as a detergency improver for liquid hydrocarbon fuels. Hydroxyaromatic compounds substituted with molecular weight alkyl groups, amines, and aldehyde describes the reaction product with

Hanlon is a U.S. patent issued on November 19, 1985. No. 4.553.979, fuel injection with a distillate fuel composition containing the following components: Described to reduce coking around gun nozzles: this composition , organic nitrate ignition promoters, and phenols (preferably high molecular weight alkyl condensation product of phenol), aldehyde, and amine having -N(H)- group Contains. Sung et al. No. 4.501.595, diesel oil with improved storage stability is The two diesel oils disclosed are tetraethylenepentamine and paraform. Aldehyde, 2゜6-di-t-butylphenol, and polyimbutenyl anhydride Contains a condensate with uccinic acid. September 4, 1979 by Harle U.S. Pat. No. 4,166,726, issued in and describes a fuel composition: where this additive is a polyalkylene amine , and a reaction product of an alkylphenol, an aldehyde, and an amine. . Jackisch was published on September 26, 1978. In U.S. Pat. No. 4,116,644, phenol and alkylphenol A gas containing a condensation product of alcohol, an aldehyde, and an amine having a -N(H)- group. The use of phosphorus to clean the fuel induction system is described. Chibu Chibnik, U.S. Patent No. 4, issued April 11, 1978, , No. 083.699, by adding the following compounds: The compound is described to improve the cleaning properties of a high-molecular-weight alkyl A hydroxy aromatic compound substituted with a group and a polyoxyethylene polyamine is a Mannich base product prepared by reacting with an aldehyde. Ru.

Published by Cardiner et al. on March 16, 1976. U.S. Pat. No. 3,944,397 describes gasoline compositions and benzyl polyamide Preparation of compound (where the benzyl group is substituted with a hydroxy group) is described. Gardiner also describes hydrocarbon solvent concentrates of active ingredients. ing.

Japanese Patent Application Laid-Open No. 63-386, filed on June 19, 1986, is about the safety of fuel oil. describes a stabilized composition. Special Publication No. 63-30.594 discloses that phenol Derived from desulfurized heavy oil, hue stabilized with compounds containing structural and polyamine structures. It describes the new light cycle oil.

Many compositions are available in the art for the stabilization and color protection of middle distillate fuels. however, any composition may be as useful as the composition of the present invention. has not been proven. Therefore, the present invention provides for coloring in intermediate distillate fuel compositions. The present invention relates to a method for preventing the formation of insoluble substances.

To the extent that references set forth herein apply to the present invention, their contents are hereby incorporated by reference. has been done. Throughout this specification and claims, unless otherwise indicated, Cents and ratios are by weight and temperatures are in degrees Celsius. The range shown is an example are shown and may be combined. Pressures are shown in KPa gauge unless otherwise indicated. be done.

λ bean Δ Hikyu The present invention relates to a composition containing the following (A) and (B) = (A) intermediate distillate minute fuel; and (B) an aromatic compound substituted with a hydrocarbyl group and a hydroxy group; reaction product of a dehyde or ketone with at least 19 alkylene polyamines .

The invention further describes compositions containing (A) and (B): (A) middle distillate fuel; and (B) monohydrocarbyl-substituted phenol; formaldehyde; Reaction product with diamine.

Yet another feature of the invention resides in a composition containing: (A) a middle distillate fuel; ;and (B) Compound of the following formula: RPh　(OH)CH2NHC2H4NHCH2Ph　(OH)R; Here, R is a hydrocarbyl 1m group of at least li, and Ph (OH) is an aromatic It is a part containing a functional hydroxyl group.

A further feature of the invention is a composition containing: (A) a middle distillate fuel; Approximately d (B) Compound of [R], Ph (OH) [C(R+) (R2)X] n reaction product between and alkylene polyamine, Here, Ph (0■) is a phenol residue, R is at least one hydrocarbyl Substituent; R1 is hydrogen or hydrocarbyl group; R2 is hydrogen or hydrocarbyl group; Building group; X is (R3)2N-1OH or 0R3 (where sRs is a hydrocarbon n is 1 to 3; m is O to 2, where n+m is greater than 5. No.

The present invention provides (A) middle distillate fuel with (B) hydrocarbyl groups and hydroxy groups. with aromatic compounds substituted with; with aldehydes or ketones; with alkylene polyamides; This coloration in the fuel can be prevented by adding sufficient amounts of reaction products with the fuel. Also describe the method.

The present invention also describes a method for preventing coloration in middle distillate fuels, which method contacting the middle distillate fuel (A) with a sufficient amount of a compound of the formula: RPh (OH) CH2NHCaHJHCH2Ph (OH) R where, R is a hydrocarbyl substituent, and Ph (OH) is an aromatic hydroxy moiety. It is.

Still another feature of the present invention is a method for preventing coloration in middle distillate fuel. The method involves mixing middle distillate fuel (A) with (B) a compound of the following formula and an alkylene polyamine. contacting with the reaction product of: [R1mPh(OH)[C(R+)(R2)X]11 Here, Ph(OH) is The phenol residue ζR is at least one hydrocarbyl substituent: R1 is hydrogen or is a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2 N-1OH or OR3 (where R3 is a hydrocarbyl group) Hn is 1 to 3; and m is O~2, where n+m does not exceed 5; where (B ) is an amount sufficient to prevent coloring of (A).

& Iodan 1 Madness Kasari The present invention, as previously described, provides solutions for preventing or maximizing coloration in middle distillate fuels. It's about keeping things to a minimum. Typically, middle distillate fuels are used in power plants and for domestic use. heating source, jet fuel, in liquid oil or as diesel fuel It is a fuel of hydrocarbon raw materials such as. In particular, the present invention relates to diesel fuel.

Diesel fuel is typically manufactured according to specifications set forth by the American Society for Testing and Materials. , defined. This specification, known as ASTM D 975-81, , describes key aspects of the invention, including the definition of diesel fuel.

As mentioned above, for treating diesel fuel with the composition of the present invention, this fuel The materials must be completely free from any inappropriateness. i.e. some kind of diesel Some fuels discolor and form insolubles, whereas other fuels may discolor The exact reason why insoluble materials do not form is not known.

One theory is that diesel fuel with high sulfur content, especially when exposed to heat, In some cases, diesel fuel is more prone to forming insolubles than substantially sulfur-free diesel fuel. It may be easy to discolor. Sulfur is a naturally occurring organic sulfur-containing compound. present in fuels derived from Sulfur reacts in middle distillate fuels to produce one or more sulfur in refined middle distillate fuel is removed during the refining process. May be present as an unintended by-product. Typically, middle distillate fuels If c) is considered a problem, this problem is determined based on the weight of this middle distillate fuel. Due to the presence of sulfur at O,lppm~20,000ppm are doing.

In any case, the final customer will decide whether the fuel will form insolubles due to discoloration or not. Since there is no way of knowing, the present invention aims to obtain a product with minimal coloration. Guarantee.

The next aspect of the invention provides aromatic compounds substituted with hydrocarbyl and hydroxy groups. It is in the study of compounds. This hydrocarbyl group and hydroxy group-substituted aromatic The aromatic compound can be a mononuclear aromatic compound or a polynuclear aromatic compound. Mononuclear aroma Aromatization in which aromatic compounds are substituted with hydrocarbyl and hydroxy groups Preferably, it is a compound base.

Hydroxy groups typically exist as monohydroxy groups in mononuclear aromatic compounds do. At least one hydroxy group is present per aromatic nuclear group is desirable. Aromatic compounds substituted with this hydrocarbyl group and hydroxy group The hydrocarbyl substituent of the product typically contains up to 150 carbon atoms, preferably is from 2 to about 30 carbon atoms, more preferably from about 3 to about 20 carbon atoms. , most preferably having about 6 to about 18 carbon atoms.

The hydrocarbyl substituent can be saturated or unsaturated, with saturated being preferable. Branched-chain hydrocarbyl substituents are preferred by straight-chain hydrocarbyl substituents. is also preferable. Polyisopropylene and polyisobutylene are the preferred hydrocarbons. It is a rubyl substituent.

In one aspect of the invention, substituted with hydrocarbyl groups as indicated in the Summary The moiety containing an aromatic hydroxyl group has R as previously described, and m is 0-2, preferably 1. R1 and R2 are independently hydrogen or hydro It is a carbyl group. When R1 and R2 are other than hydrogen, this hydrocarbon A rubyl group typically has 1 to 5 carbon atoms. Therefore, R+also R2 is conveniently a methyl or ethyl group. X is (R3)2N- , hydroxyl (-0H), or OR3. Here, R3 is A hydrocarbyl group as defined for R. The value of n is 1 to 3. Yes, preferably 1. The sum of n+m is 5 or less, for example, for mononuclear This is the remaining valence of aromatic phenols.

The second component of the reaction product (B) is an aldehyde or ketone. This aldehyde is represented by the formula Ra(C-0)H. In contrast, this ketone has the formula Rs ( It is represented by C=O)Re. R4 is hydrogen or hydrocarbyl group in aldehyde It is. R5 and R6 are each a hydrocarbyl group in the ketone. It is something. The foregoing hydrocarbyl group typically contains 0 to 10 carbon atoms. and is preferably a saturated group.

Typical examples of aldehydes or ketones include formaldehyde, acetaldehyde, Propanal, dimethyl ketone, diethyl ketone, methyl isobutyl ketone, etc. is included. Preferably, the aldehyde is formaldehyde; Any form can be used such as phosphorus or paraformaldehyde.

The alkylene polyamine used in the present invention typically has the following formula: H2N(CnH2nNH)X ((sH21NH)bcOH2ONH2 where, n is an integer, a is an integer, b is an integer, and C is an integer. Typically, this ingredient Then, X, a and b are all zero, and C is 2.

The preferred polyamine is ethylene diamine or propylene diamine. It is based on Preferred species in the present invention include ethylenediamine or its like. Polymers of triethylenetetramine, tetraethylenepentamine or pentae Chiren has beef samin.

An example of the preparation of reaction product (B) is shown below as Example IA.

Upper left m two people Polypropylene phenol (polypropylene) containing 74% rose-polypropylene substituents 5,300 g of propylene molecular weight: 168).

1.912 g of tetraethylenepentamine and 1.775 g of toluene 1,686g of 36% formaldehyde aqueous solution was added to the reactor over 90 minutes. Add. The reaction mixture is refluxed for 11 hours. During this time, 1,440 Separate ml of water. The reaction mixture is agared with diatomaceous earth.

The net recovered product has a nitrogen content of 4.5% by weight. Theoretical value is 4.6% nitrogen elemental content.

amines containing different amounts of benzyl groups, prepared using methods substantially as described above. Some of the benzyl polyamines substituted with alkyl and hydroxy groups are: Shown below.

In each case, polypropylene phenol, formaldehyde and By appropriate selection of the molar ratio of reamin, the desired product is obtained. This port Lipropylene phenol (molecular weight of polypropylene; 16 g) is 60% polypropylene. It has a polypropylene group in the la position.

Polypropylene phenol: ) IC) 10: Molar ratio of polyamine Polyamine preparation B 2 :2:1 Ethylenediamine preparation c 1:l:1 ) Liethylenetetramine Preparation D 2:2:1 Triethyl Lentetramine Preparation E 3:3:1) Liethylenetetra Min preparation F 4:4:1) Liethylenetetramine preparation G l:1:1 Tetraethylenepentamine preparation H2:2: 1 Tetraethylenepentamine Preparation I 3:3:1 Tetraethylenepentamine Preparation J 5:5:1 Tetrae Tyrenepentamine preparation K 5:10:1) Liethylenetet Lamin generally molar ratio of aromatics, aldehydes and alkylene polyamines are about 1:1:1 to about 5:10:1, respectively. Preferably 2:l:1-3 :3:1, most preferably 2:2:1. For example, hydrocarbyl Aromatic compounds substituted with groups and hydroxy groups; aldehydes or ketones; The molar ratio of and alkylene polyamine is 2:2:1.1:l:1.2+1:2 ．． For example, 1:2:2.

Typical reaction conditions are to combine this alkylene polyamine with a suitable solvent and hydrochloride. Pre-mix with aromatic compounds substituted with carbyl and hydroxy groups That's true. Suitable solvents include xylene, toluene or benzene . The aldehyde or ketone is easily added as a suitable aqueous mixture thereof. can be added.

The reaction is carried out at reflux for a period sufficient to ensure the desired reaction is complete. Proceed as follows. Typically, reaction times vary from 1 hour to 24 hours.

Desirably, the aldehyde or ketone can be added intermittently. perform the reaction The preferred method of The water formed may be removed from the reactants.

The product may conveniently be recovered in a solvent and filtered through a suitable filter material.

! Belly Blood Rinori The products of the present invention are typically based on all middle distillate fuels processed. Used in very small quantities. The amount of (B) used simply depends on the color of the resulting fuel. The amount is sufficient to stabilize against degradation. Typically, the reaction product (B) The amount of is from about 5 ppm to about 2000 pp+e of the fuel being treated. reaction generation The preferred range for utilizing substance (B) in fuel is 50 ppm to 1.5 ppm of the fuel. 00 ppm.

Conveniently, the reaction product (B) is mixed directly into the fuel in the refinery. . Component (B) has very low solubility with fuel, so mixing is required. component (B) can be fed directly to the fuel stream in fixed amounts. Preferably, the reaction product (B) contains a certain amount of a suitable solvent (which contains middle distillate fuels or their components) may be pre-mixed with the fuel to be treated) and then diluted with the fuel to be treated. child Conveniently, the solvent of is the solvent used to prepare (B).

The following is an example of the treatment of diesel fuel according to the present invention.

i fruit Obtain diesel fuel and blend/facilitate mixing with the active material of Example I-A. To do this, the active substance is first diluted with xylene. For solvents of active substances The weight ratio is 4:1. This active substance was added at a rate of 115 pp+g of fuel. Add to fuel.

This product is then tested for storage stability. At the final stage of the exam, color and and the formation of insoluble matter. The products described here are passed the evaluation.

165 ppm, 330 ppm, 495 ppm, 742.5 ppm and Substantially similar results are obtained using active agents at a ratio of 100pp. child Using a higher amount of activator will provide a longer period of fuel protection. In addition, Similar results are obtained using product B-K.

international search report 1"""""'1""""60F'F/+Ie QQ/I'1QA11S A 33156

Claims (1)

[Claims] 1. A composition containing (A) and (B): (A) a middle distillate fuel; and (B) an aromatic compound substituted with a hydrocarbyl group and a hydroxy group; Reaction product of a dehyde or ketone with at least one alkylene polyamine . 2. The composition of claim 1, wherein the aromatic compound is a monohydroxy aromatic compound. thing. 3. 2. The composition of claim 1, wherein (B) uses an aldehyde. 4. 2. The set of claim 1, wherein the hydrocarbyl substituent of the aromatic compound is saturated. A product. 5. The composition of claim 1, wherein the alkylene polyamine is ethylene diamine. . 6. 5. The set of claim 4, wherein said hydrocarbyl substituent is a propylene oligomer. A product. 7. The composition of claim 1, wherein the aromatic compound is monohydrocarpyl substituted. thing. 8. The molar ratio of the aromatic compound; aldehyde; and alkylene polyamine is 2. The composition of claim 1, wherein the ratio is about 1:1:1 to 5:10:1, respectively. 9. (B) is used in an amount of about 5 ppm to about 2000 ppm based on component (A). , the composition of claim 1. 10. The hydrocarbyl substituent of the aromatic compound has from 2 to about 30 carbon atoms. The composition of claim 1, comprising: 11. 4. The composition of claim 3, wherein the aldehyde is formaldehyde. 12. The alkylene polyamine is diethylene triamine and triethylene The composition of claim 1 selected from the group consisting of tetramine. 13. A composition containing the following (A) and (B): (A) middle distillate fuel; and Beauty (B) monohydrocarbyl-substituted phenol; formaldehyde; Reaction product with diamine. 14. A composition containing the following (A) and (B): (A) middle distillate fuel; and Beauty (B) Compound of the following formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R where R is at least one hydrocarbyl substituent, and Ph(OH) is an aromatic hydrocarbyl substituent. It is a part containing a xyl group. 15. 15. The composition of claim 14, wherein R is a polypropylene oligomer. 15. 15. The method of claim 14, wherein R is a single hydrocarbyl substituent of said aromatic group. Composition. 17. 15. The composition of claim 14, wherein R is a saturated hydrocarbon. 18. 15. The composition of claim 14, wherein R has about 6 to about 18 carbon atoms. 19. (B) exists at about 5 ppm to about 2000 ppm based on component (A). 15. The composition of claim 14, wherein the composition comprises: 20. Aromatic compounds substituted with hydrocarbyl groups and hydroxy groups; A sufficient amount of the reaction product (B) of the dehyde or ketone; and the alkylene polyamine. A method of preventing coloration in a middle distillate fuel by adding (A) to the middle distillate fuel. 21. 21. The method of claim 20, wherein the fuel is diesel fuel. 22. 21. The method of claim 20, wherein (B) uses formaldehyde. 23. (B) is present at 5 ppm to 2000 ppm based on component (A). 21. The method of claim 20. 24. A method for preventing coloration in middle distillate fuel, the method comprising: , filling of a compound of formula RPh(OH)CH2HHC2H4NHCH2Pb(OH)R wherein R is a hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxy moiety. 25. 25. The method of claim 24, wherein the fuel is diesel fuel. 26. A composition containing the following (A) and (B): (A) middle distillate fuel oil; call (B) a compound of [R]mPh(OH)[C(R1)(R2)X]n; Reaction products with polyamines: Here, Ph(OH) is a phenol residue, R is at least one hydrocarbyl Substituent; R1 is hydrogen or hydrocarbyl group; R2 is hydrogen or hydrocarbyl group; building group; X is (R3)2N-, OH or OR3, where R3 is hydrogen locarbyl group; n is 1 to 3; m is 0 to 2, where n+m does not exceed 5. stomach. 27. 27. The composition of claim 26, wherein the alkylene polyamine is ethylene diamine. thing. 28. 26. The hydrocarbyl substituent is a propylene oligomer. Composition of. 29. The weight ratio of (B) is about 5 ppm to about 2000 ppm based on (A) 27. The composition of claim 26. 30. A method for preventing coloration in middle distillate fuel, the method comprising: , [R]mPh(OH)[C(R1)(R2)X]n; alkylenepo contacting the reaction product (B) with reaamine; Here, Ph(OH) is a phenol residue, R is at least one hydrocarpyl Substituent; R1 is hydrogen or hydrocarbyl group; R2 is hydrogen or hydrocarbyl group; building group; X is (R3)2N-, OH or OR3, where R3 is hydrogen locarbyl group; n is 1-3; and m is 0-2, where n+m is 5. Here, the amount of (B) is sufficient to prevent coloring in (A). be. 31. 31. The method of claim 30, wherein said alkylene polyamine is ethylene diamine. 32. the hydrocarbyl substituent R is a propylene oligomer, and m is 31. The method of claim 30, wherein: 1. 33. [R]mPh(OH)[C(R1(R2)X]n for the polyamine 31. The method of claim 30, wherein the molar ratio of each of the two is about 1:1 to about 3:1. 34. The weight ratio of (B) is about 5 ppm to about 2000 ppm based on (A) 31. The method of claim 30.