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Publication numberUS3486866 A
Publication typeGrant
Publication dateDec 30, 1969
Filing dateJan 5, 1966
Priority dateJan 5, 1966
Publication numberUS 3486866 A, US 3486866A, US-A-3486866, US3486866 A, US3486866A
InventorsDavid B Guthrie, Verner L Stromberg
Original AssigneePetrolite Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Quaternary ammonium iodide stabilized fuels
US 3486866 A
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Description  (OCR text may contain errors)

United States Patent ABSTRACT OF THE DISCLOSURE A distillate fuel composition comprising a major amount of distillate fuel having a distillation range between about 100 F. and about 750 F- and boiling sub.- stantially continuously throughout said distillation range and distillate fuel soluble quaternary ammonium iodide additive in a [minor amount suflicient to inhibit oil de terioration with the attendant formation of. color and :sludge.

This invention relates to'improved fuel oil compositions. More particularly, it is concerned with'th provision of fuel oils which have been stabilized against the formation of color and sediment therein duringstorage. "Fuel oils' in general are contemplated by the invention. The fuel oils with which this invention is especially concerned 'are'hydrocarbon' fractions havingan initial boiling point of at"lea'st"about 100 *F. andan end point not higher than about 750 .F., and boiling substantially continuously throughout their distillation range. Such fuel oils are generally known as distillate fuel oils. It will be understood, however, that this term is not restricted to straight-run distillate fractions. Thus, as is wellknown to "ice zles, etc., as is explained further herein. An important economical factor is also involved in the problem of oil deterioration in storage, viz, customer resistance. Thus, customers judge the quality of an oil by its color and they oftentimes refuse to purchase highly colored oils. It will be appreciated then that since fuel oils of necessity are generally subject to considerable periods of storage prior to use, the provision of a practical means for preventing the deterioration of the fuel oil during storage would be a highly desirable and important contribution to the art.

I The problem of the formation of color bodies and sludge is further aggravated because fuels, such as diesel and jet fuels, are often preheated for some time before consumption, thus introducing the additional problem of thermal instability.

We have now found that oil deterioration, with attendant formation of color and sludge in the oil, can be outstandingly inhibited by employing the quaternary ammonium iodide systems of this invention in the oil. In general, one employs a minor amount of the additive which is sufficient to inhibit oil deterioration with the attendant formation of color and sludge.

The amount of additive employed will vary depending on various factors, for example the particular oil to be stabilized, the conditions of storage, etc. The stability of an oil depends largely on the nature of the crude oil from which it is made, the type of processing involved during refining, etc., and therefore some oils will require .more additive to stabilize them than others. For example,

caustic-treated oil will, in general, require less additive than untreated oil of similar character. In practice, one

those skilled in the art, the distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillates, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with'well known commercial methods, such as acid or caustic'treatment, solvent refining, clay treatment, etc. a

The distillate fuel oils are ch'aracterized' by their rela- :tively low viscosities, low pour points,--and the like. The principal property which characterizes the contemplated hydrocarbon fractions, however, is the distillation range.

As mentioned herein, this range will lie between about 100 Fvand about 750"-'.F. Obviously, the 'distillation range of each individual'fue'l'oil will cover a narrower irange falling, neverthelessywithin the above-specified limits. Likewise, each fuel oil will boil substantially co'ntinuously throughout its distillation range.

-Especially contemplated her'einare Nos. 1', 2 and 3 fuel oils usedin dor'nestic 'h'eating and as diesel fuel oils, particularly those-made up chiefly or entirely of' cracked distillate stocks. The domestic heating oils generally conon the characteristics of the oil,'particularly on the ignition and burning qualities thereof; It is also a contributory factor, along with the presence of other impurities in the oil, such as rust, dirt and moisture, in causing clogging of the equipment parts, such as screens, filters, nozgenerally employs at least about .0001% (1 p.p.m.), such as from about .0001 to .1% (1-1000 p.p.m.), for example about .0002 to .05 (2500 p.p.m.), but preferably about .0003 to .03% (3-300 p.p.m.) based on weight of oil. Larger amounts, such as 1% or higher, can be employed but in general there is usually no commercial advantage in doing so.

The quaternary ammonium iodides of this invention can be prepared by any conventional means, but should be soluble in the fuel. For example, one can prepare an oil soluble quaternary ammonium iodide by'the alkylation of an oil soluble tertiary amine with any alkyl, benzyl, etc., iodide; the iodide, for example, contains at least one carbon atom and may contain up to thirty carbon'atoms or more per molecule. However, to convert an oil insoluble' amine to an oil soluble quaternary ammonium iodide one must use an alkyl iodide of sufiicient molecular weight to accomplish this. For economic'reasons, it is usually preferred to start with an oil soluble tertiary amine.

The quaternary ammonium iodide systems of this invention include those derived from tertiary monoamines. A monoamine suitable'for the ultimate conversion to a quaternary ammonium iodide of this invention may 'be defined by the formula R N, where the Rs, which may be the same or different, are hydrocarbon or, substituted hydrocarbon groups, for example, alkyl, cycloalkyl, aryl, a'lkenyl, substituted aryl, aralkyl, ogygen-containing, sulfur-containing, heterocyclic radical including cyclic amino wherein the nitrogen is part of the ring,- etc. Each R group on the amine can vary widely, for example from l-30 or more carbons. However, to provide the amine with sufiicient hydrocarbon content to render it soluble in the fuel, the monoamines most advantageously employed are those which have a total carbon content of at least 8 atoms per molecule; and where at least one R group is as follows: hexyl, heptyl, octyl, isoctyl, t-octyl, nonyl, decyl, undecyl, dodecyl, t-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl octadecyl, eicosyl, docosyl, octadecenyl, octadecadienyl, octadecatrienyl, mixtures of the foregoing radicals, radicals as derived from tallow, soybean, coconut oil and other animal and vegetable oils, and hydrocarbon radicals derived from" the acids of rosin and tall oil, such as abietic acid, dehydroabietic acid and tetrahydroabietic acid, petroleum, etc.; one or more of the Rs in the amine may be a lower hydrocarbon radical, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc. or isomers analogues thereof etc., for example, isopropyl, isobutyl, secondary butyl, etc. An example of a quaternary ammonium iodide of this invention derived from a tertiary monoamine is:

Examples of commercially available tertiary monoamines which can be employed in the preparation of quaternary ammonium iodides of this invention are those based on fatty amines sold under the Armeen trademark manufactured and sold by Armour & Company of Chicago, Illinois, such as Armeen DM12D, Armeen DM14D, Armeen DM16D, Arme'en DM18D, Armeen DMCD, Armeen DMSD, Armeen DMHTD, Armeen M2HT, and N-coco-morpholine. The code for these compounds is DM for dimethyl, M for methyl, CD for distilled coconut oil amine, SD for distilled soybean oil amine, 2HTD for distilled dihydrogenated tallow amine and the 12D, 14D, 16D and 18D are distilled fatty amines containing predominantly the number of carbon atoms specified in the code number.

In addition to the quaternary ammonium iodides of tertiary monoamines, other suitable systems of this invention include the product of a mixture of an alkyl iodide or aralkyl iodide with the derivatives of primary amines such as, for example, the Schiffs base or 2120- methine of a Primene.

CH CH These Schiif bases or azomethine compounds are described in US. Patent 2,701,187 which is by reference incorporated into the present application.

Quaternary ammonium iodides of this invention also include those systems derived from tertiary monoamines which are hydroxylated monoamines. The hydroxylated monoamines employed as precursors for the quaternary ammonium iodides of this invention are monoamines containing at least one hydroxy group, usually in the form of an alkanol group (ROH) and may contain as many of these groups as there are available positions in the molecule, particularly at the amino positions. Thus, they may be:

and the like, where R is a hydrocarbon, or a substituted hydrocarbon group, for example alkenyl, alkyl, cycloalkyl, aryl, aralkyl, substituted aryl, oxygen-containing group, heterocyclic group, including the R groups which may be joined together so as to form a heterocyclic ring with the nitrogen, and the like; and Where R is a hydrocarbon group, for example, (CH (where x is a whole number, preferably 2-8),

and other members of the homologous series. Thus, any primary or secondary amine may be oxyalkylated to form dihydroxy tertiary amines or monohydroxy tertiary amines, respectively.

The quaternary ammonium iodide systems of this invention contain at least one quaternary ammonium group and are represented symbolically, for convenience, as:

where v I i V Y represents a quaternary ammonium moiety. These include mono-, diand polyquaternaries. Not all of the amino groups in the molecule need to be quaternized. A more specific formula canbe expressed by the general formula:

1'1 6B [Brad-R2 1 L s where N' represents the quaternary ammonium'nitrogen atom; R R R R may be alkyl, aryl, aralkyl, cycloalkyl, alkenyl, substituted aryl, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, heterocyclic groups, etc. The Rs may be the same or dilferent. Two of the R groups may be joined together so as to form a nitrogen containing ring.

A preferred class of commercial monoamines that can be hydroxylated to a suitable precursor amine for conversion to quaternary ammonium iodides of this invention are those sold under the trademark Primene by Rohm & Hass, which are described in their Technical Bulletin SP-33, dated December 1951 and in their other bulletins. A Primene is a tertiary alkyl primary monoamine which is characterized by the terminal structural unit.

0 C-( JN It may also be expressed by the formula CH3 CH2 where n is for example 0-5.

Specific tertiary alkyl primary monoamines for preparing suitable precursor amines for conversion to quaternary ammonium iodides contemplated by the invention are, for example: tertiary butyl primary amine, tertiary octyl primary amine, tertiary decyl primary amine, tertiary dodecyl primary amine, tertiary tetradecyl primary amine, tertiary hexadecyl primary amine, tertiary octadecyl primary amine, tertiary eicosyl primary amine, tertiary docosyl primary amine and tertiary tetracosyl primary amine, and mixtures of tertiary alkyl primary amines having from about 4 to about 24 carbon atoms; a typical mixture of amines, for example, is one comprised of tertiary alkyl primary amines of from about 12 to 15 carbon atoms, said mixture averaging about 12 carbon atoms per amine molecule. This mixture, designated hereinafter as mixture 1 contains, by weight, about of tertiary dodecyl amine, about 10% of tertiary pentadecyl amine and relatively small amounts, i.e., less than about 5% of amines having less than 12 or more than 15v carbon atoms; Another mixture of tertiary alkyl primary, amines is composed of tertiary alkyl primary amines of from about 18 to 24 carbon atoms and averaging about 20 carbon atoms per molecule. This latter mixture, designated hereinafter as mixture B, contains the C C tertiary alkyl primary amines in about the following proportions: 1

Percent Tertiary octadecyl amine 40 Tertiary eicosyl amine 30 Tertiary docosyl amine 15 Tertiary tetracosyl amine 10 Other amines and non-amine 5 Amine mixtures, such as mixture A? and mixture-B, as well as other suitable mixtures of tertiary alkyl primary amines of 4 to 24 carbon atoms, can be prepared by methods within the knowledge of those skilled in the art. For example, such mixtures may be preparedfrom polypropylene or polybutyleneiractions or mixtures thereof. Thus, a selected polymer fraction composed of mixed polyolefins within a desired molecularweight range can be converted to' thegorresporiding tertiary alkyl primary amines as follows: The selected polyolefin fraction is first hydrated bymeans of sulfuric acid and water to convert it to the cor-responding alcohols. The alcohol mixture is then convertedto alkyl chlorides by reaction with dry hydrogen chloride. Finally, the alkyl chloride mixture is condensed under pressure with ammonia to produce the tertiaryalkyl primary amine mixture. -Specific methods of preparing the tertiary alkyl primary amines are disclosed in the Journal of Organic Chemistry, vol. 20 (1955), page 295 et.'seq.

' The Primene type primary monoamine may be readily converted to a tertiary hydroxylated monoamine by reaction with alkylene oxide" and alkylation as necessary. This type 'of' suitable precursor'amine now contains'another functional group (the hydroxy group) besides the amino group. Thus, for example, a N,N-bis(hydroxyalkyl) tertiary alkyl mono-amine'and N-alkyl-N-(hydroxyalkyl) tertiary alkyl monoamine, such as, N,N-bis(2 -hydroxyethyl) tertiary octyl amine and N-ethyl-N-(Z-hydroxyethyl) tertiary octyl, amine and N-methyl-N-(2-hydroxy- I ethyl) tertiary-octyl amine, respectively, can be used for subsequent conversion to a quaternary ammonium iodide. The hydroxylated monoamines so'described can be treated with additional alkylene oxide, for example,

ethylene oxide, propylene oxide, butylene oxide, octylene oxide and other aliphatic oxides, glycide as well as aromatic oxides suchas styrene oxide and similar compounds to .form, hydroxylated amines having repetitious ether linkages. Such resulting hydroxylated amines may be described by the formula V X M g wherein, X, Y and Z are either hydrocarbon groupsor {-RO) H groups (where z isa'whole' number, for example l-lQ'or higher and where R is the hydrocarbon moiety derived from thealkyleneoxidep I These monoamines' contain at least one hydroxyl group, but may have two' or three or even more. For'example, a tertiary'amine compound havingfour hydroxyl radicals can be prepared from a primary amine such as octylamine, dodecylamine, 'octadecylamine or the like by reaction with two moles of glycide. Similarly, if a mole of triethanol, tripropanol or tributanol amine is reacted with three moles of glycide, one obtains a'monoamine having as many as six hydroxyl radicals; In addition, one or more of the terminal OH groups in the" molecule maybe blocked by an ether 0r an ester linkage, for example, as in compounds of the type:

Quaternary ammonium iodides of this invention also include those derived from hydroxylated polyamines and non-hydroxylated polyamines which contain at least one tertiary amine; A wide variety of polyamines can be employed as long as there is at least one tertiary amino .group which is capable of forming the quaternary ammoniuni group. The polyamines prior to their formation as tertiary polyamines includealiphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, heterocyclic polyamines and polyamines containing one or more of the above groups. Thus, the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group as the heterocyclic radical as'in the case of the following formulae: J


' Polyamines' are available commercially and can be prepared by well-known methods. It is well-known that olefin dichlorides, particularly those containing from ,2 to 10 carbon atoms, can be converted to alkylene'polyamines by reaction with ammonia or amines such as ethylamine, propylamine, butylamine, octylamine, dccylamine, cetylamine, dodecylamine, etc. Cycloaliph'atic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also use alpha-omega dialkyl ethers such as ClCH OCH Cl, C1CH CH OCH CH CL and the like. Furthermore, compounds derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines or a mixture of two diflerent amines are useful.

' In using such polyalkylene polyamines it is preferred [0 use the polyethylene-polyamines, because of their greater commercial availability. These compoundshave theformula: 1

In numbering the main carbon atom chain, the carbon atom attached to a terminal -NH radical is designated as the carbon atom in the 1-position. Similar alkylene groups recur throughout the molecule. Non-limiting examples of the polyalkylenepolyamine reactants are diethylenetriamine; triethylenetetramine; tetraethylenepentamine; di-(methylether) triamine; hexapropylene-heptamine; tri(ethylethy1ene) tetramine;

pental-methylpropylene) -hexamine;

7 tetrabutylenepentamine; hexa-(1,1-dimethylethylene) heptamine;

dil-methylbutylene) triamine; pentamylenehexamine;

tri( 1,2,2-trimethy1ethylene) tetrarnine;

di-( l-methylamylene) triamine; tetra-(1,3-dimethylpropylene) pentamine; penta(1,5-dimethamylene)-hexamine;

dil-methyl-4-ethylbutylene) triamine pen ta- 1 ,Z-dimethyll-isopropylethylene) hexamine; tetraoctylenepentamine tri- 1,4-diethylbuty1ene) tetramine; tridecylenetetramine;

tetra-(1,4-dipropylbutylene) pentamine didodecylenetriamine; tetratetradecylenepentamine;

penta( 1 methyl-4-nonylbutylene) hexamine;

tri-j( I l S-diinethylpentadecylene) tetramine; trioctadecylenetetramine;


di- 1,2-dimethyl-14-nonyltetradecylene) triamine; di-(1,18-dioctyloctadecylene) triamine;

penta-( l-methyl-2-benzylethylene) hexamine; tetral-methyl-3-benzylpropylene) pentamine; tri- 1-methyll-phenyl-3 propyl-propylene) tetramine; and tetra-(1-ethyl-2-benzylethylene) pentamine.

Cyclic aliphatic polyamines such as piperazine, etc. can also be employed.

Polyamines of Armours Duomeen type may be employed, for example of the formula The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from 8-30 or more carbon atoms, a typical example of which is where the aliphatic group is derived from any suitable source, for example, from compounds of animal, vegetable, petroleum, etc., origin, such as coconut oil, tallow, tall oil, soya, etc., are very useful as starting materials. In addition, the polyamine can contain other alkylene groups, fewer amino groups, additional higher aliphatic groups, etc. Compositions of this type are described in US. Patent 2,267,205.

Polyamines containing aromatic groups in the main part of the chain, for example, N,N-dimethyl-p-xylylenediamine, are useful as starting materials.

In order to use many of the above alkylene polyamines in the invention, the alkylene polyamines must be converted as necessary to a product containing at least one tertiary amino group for subsequent conversion to quaternary ammonium iodides. The desired tertiary polyamine can be characterized by the general formula:

R R R C nHZnN C DHZDN 8 Suitable tertiary polyamines also include tertiary polyamines wherein the alkylene groupvor groups are interrupted by an oxygen radical, for example,

R R R N CnH2nOCnH2uI I CnHZnOOnHZn R /x R or mixtures of these groups and alkylene groups, for example,

N cnnaocn'mnN cnmnN where R, n and x has the meaning previously stated for the linear polyamine. Polyamines may be converted to tertiary amines by any suitable introduction of hydroxylated groups. One can use any one of a number of wellknown procedures such as alkylation, involving a chlorohydrin, such as ethylene chlorohydrin, glycerol chlorohydrin or the like. Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides to be subsequently described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type of reaction just referred to is well known and results in the introduction of a hydroxylated or polyhydroxylated radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarb-on atom; for instance, instead of using the chlorohydrin corresponding to ethylene glycol, one employs the chlorohydrin corresponding to the diethylene glycol. Similarly, instead of using the chlorohydrin corresponding to glycerol, one employs the chlorohydrin corresponding to diglycerol.

Polyalkylene polyamines having the general formula H N( --RNH) H (wherein R is an alkylene radical or a hydrocarbon radical-substituted alkylene radical, and x is an integer, there being no upper limit to the number of alkylene groups in the molecule) can be alkylated with any alkyl halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule.

Such polyamines can be alkylated in the manner commonly employed for alkylating monoamines. Such alkylation results in products which are symmetrically or nonsymmetrically alkylated. The symmetrically alkylated polyamines are most readily obtainable. For instance, alkylated products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reaction results in the formation of hydrochloric acid, and hence the resultant product is an amine hydrochloride. The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain which is interrupted at least once by an oxygen atom. In other words, alkylation is accomplished by compounds which are essentially alkoxyalkyl chlorides, as, for example, the following:

It is especially preferred to use alkyl halides having between about eight and about eighteen carbon atoms per molecule. Those having between about twelve and about eighteen carbon atoms are more particularly preferred. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Some non-limiting examples of the akyl 9 halide reactant are n-butyl bromide; n-butyl chloride; secbutyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2-ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethy1-2-methy1-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride and triacontyl chloride.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and monochlorinated kerosene. Methods for the preparation of mono-chlorowax have been set forth in United States Patent 2,238,790.

The quaternary ammonium iodides of this invention, also, include those derived-from cyclicamidines which may be converted directly into quaternary ammonium iodides by reaction with alkyl iodides and aralkyl iodides. Suitable cyclic amidines include the following:

GE -CH2 where x: 1-5.

2-undecylimidazoline '2-heptadecylimidazoline 2-oleylimidazoline l-N-decylaminoethyl, 2-ethylimidazoline 1-hexadecylaminoethylaminoethyl, 2-methylimidazoline 1-dodecylaminopropylimidazoline l-(stearoyloxyethyl) aminoethylimidazoline 1-stearamidoethylaminoethylimidazoline Z-heptadecyl, 4-5-dimethylirnidazoline l-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazoline l-methylaminoethyl, Z-heptadecyl tetrahydropyrimidine l-methylaminoethylaminoethyl, 2-dodecyl, 4-methyl tetrahydropyrimidine.

Cyclic amidines such as imidazoline and tetrahydropyrimidine are well known. See U.S. Patents, 2,466,517, 2,488,163, Re. 23,227 which are by reference incorporated into the present application.

Polymeric amines can also be employed in this invention. Examples of this invention include those disclosed in the Ser. No. 442,793, filed Mar. 25, 1965; Ser. No. 502,447, filed on Oct. 22, 1965 (Docket #5-32); and Ser. No. 502,636 filed on Oct. 22, 1965 (Docket #5 16), all assigned to the same assignee as the present invention.

It should also be realized in the preparation of the cyclic amidine compounds that amides as well as cyclic amidines may be formed. By controlling the reaction of the carboxylic acids with polyamines so that one rather than two moles of water are removed, one obtains amides rather than cyclicamidines. Examples of amidopolyamines are shown in U.S. Patent 2,598,213.

The preferred system of this invention is a quaternary ammonium iodide system such as a bis oxyalkylated Primene, or a polyoxyalkylated polyamine.

The particular amine employed can vary widely provided the derived quaternary ammonium iodide system is sufliciently soluble in the fuel to perform its function in the concentrations employed. Certain quaternary ammonium iodides which may be insoluble or only slightly soluble in the fuel when employed alone, may be rendered soluble by being employed in conjunction with other amines and/or quaternary ammonium iodide systems. Stated another way, it is not the individual quaternary ammonium iodide, but the total quaternary ammonium iodide system whose solubility must be determined.

As is quite evident, new quaternary ammonium iodides will be constantly developed which could be useful in this invention. It is, therefore, not only impossible to attempt a comprehensive catalogue of such compositions, but to attempt to describe the invention in its broader aspects in terms of specific chemical names of its components used would be too voluminous and unnecessary.

since one skilled in the art could by following the description of the invention herein select a useful agent. This invention lies in the use of suitable quaternary ammonium iodides as stabilizers for petroleum distillates, and the individual compositions are important only in the sense that their properties can affect its function. To precisely define each specific useful quaternary ammonium iodide in light of the present disclosure would merely call for chemical knowledge within the skill of the art in a manner analogous to a mechanical engineer who prescribes in the construction of a machine the proper materials and the proper dimensions thereof. From the description in this specification and with the knowledge of a chemist, one will know or deduce with confidence the applicability of specific quaternary ammonium iodides suitable for this invention by applying them in the process set forth herein. In analogy to the case ofamachine, wherein the use of certain material of construction or dimensions of parts would lead to no practical useful result, various materials will be rejected as inapplicable where others would be operative. One can obviously assume that no one will wish to employ a useless quaternary ammonium iodide nor will be misled because it is possible to misapply the teachings of the present disclosure to do so. Thus, any quaternary ammonium iodide that can perform the function stated herein can be employed.

The following diesel fuel test is a standard test for diesel fuel stability and is regarded as a rapid screening test for discovering new systems which can be used to stabilized petroleum distillate fuels.

DIESEL FUEL TEST minutes 300 F.

In the operation of a dieselengine, a portion of the fuel sent to the fuel injection system is injected and burned; the remainder is circulated back to the fuel reservoir. The injection system is located on the engine such that the fuel being returned to the reservoir is subjected to high temperatures. Consequently, diesel fuels should exhibit good thermal stability as well as good storage stability. Since the fuels used as diesel fuel are interchangeable with furnace oils, the following procedure is used to screen the thermal stability of fuel oils in general.

The test involves exposing 50 ml. samples of fuel, containing desired quantities of fuel additives, to the test where a bath is held at 300 F. and the samples are exposed for 90 minutes.

After cooling to room temperature the exposed fuel is passed through a moderately retentive filter paper and the degree of stain on the filter paper noted. The filter paper pads are compared according to a rating of 0, or where is the amount of insoluble matter collected from the oil containing no additive, is good stability and indicates a reduction in the formation of insoluble matter, is superior stability and indicates a substantial reduction in the formation of insoluble matterand is excellent stability and indicates essentially no formation of insoluble matter.

In the following examples, the fuel employed was a South Central US. Oil containing 70% light cycle oil and 30% range oil. The following quaternary ammonium iodides were tested for their ability to stabilize fuel oil in the diesel fuel test. They are presented as examples to illustrate (rather than limit) the applicability of the invention.

Additive: Composition as reaction product of- A 2 moles cH l-l-ethoduomeen T/13. B 1 mole cH I-l-ethoduomeen T/l5. C 2 moles CH I+ethoduomeen T/ 12. D 1 mole CH Iethoduomeen T/ 20. E 2 moles CH I+ethoduomeen T/ 15. F 2 moles CH Iethoduomeen T/ 25 G 1 mole CH I+N-(' -dilaurylamino propyl) morpholine. H 2 moles CHfl-l-N-(methyl-cocoaminopropyl)morpholine.

Ethoduomeens are commercial diamines derived from fatty amines and are available from Armour and Company. They have the general formula:

T is a code for the R-N group and is a designation for tallow amine. The numbers 12, 13, 15, 20 and 25 is a code for moles of ethylene OXide and represent the 2, 3, 5, and moles of ethylene oxide which were used to oxyalkylate the tallow diamine. In other words, the numbers (12, 13, 15, and represent 10 more than the sum of x+y+z.

The data in Table 1 shows that excellent stability was achieved in the 90-minute 300 F. diesel fuel test.

TABLE 1DIESEL FUEL TEST RESULTS [After 90 minutes at 300 F.] [Oil='1exas light cycle oill Results after Total wt. Wt. of iodine heating filter Additive (p.p.m.) (p.p.m.) pad rating None. 0 0 O A 13 4. 3 14. 4 2. 6

Although quaternary ammonium iodides are useful as fuel additives, their performance can be enhanced by employing certain auxiliary chemical aids. Among these chemical aids are dispersants, for example acrylic polymers or copolymers which can be employed in conjunction with the quaternary ammonium iodide systems of this invention.

One such auxiliary chemical component is the copolymer derived from an acrylic ester ofthe formula:

and N-vinyl-2-pyrrolidone, for example, a copolymer containing the following units:

having a molecular weight for example of at least 50,000, for example 50,000-500,000, or higher, but preferably 100,000-400,000 with an optimum of 300,000-400,000 of which vinyl pyrrolidone comprises at least 1% by weight, of the polymer, for example l30%, but preferably 315% with an optimum of 510%; where Y is hydrogen, a lower alkyl group such as methyl, ethyl, etc., Z is an hydrocarbon group having, for example, 130 carbon atoms, but preferably 8 to 18 carbon atoms. These polymers are preferably acrylic or methacrylic polymers, or polymers derived from both in conjunction with vinyl pyrrolidone. The Z group on the polymer, which can be the same throughout or mixed, can be octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, etc. Lower alkyl groups can also be empoyed such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc., but they preferably are employed as copolymers of the higher Z groups, for example a copolymer of dodecyl methacrylate and methyl acrylate, etc. The acrylic ester units may be derived from one or more acrylic type monomers and may be fully acrylic or fully methacrylic or both acrylic and methacrylic. The polymer may be random, block, graft, etc.

Also, Z may also be an alkylated aromatic group such as butyl phenyl, amyl phenyl, etc., or a cycloaliphatic group such as cyclohexyl. Thus, non-limiting specific examples of suitable monomeric esters are: methyl acrylate, ethyl acrylate, propyl methacrylate, amyl acrylate, lauryl acrylate, cetyl acrylate, octadecyl acrylate, amyl methacrylate, lauryl methacrylate, cetyl methacrylate, octadecyl methacrylate, amylphenyl methacrylate, cyclohexyl methacrylate, etc., including the analogous acrylate or methacrylate esters. Copolymers of the above and other acrylic esters may be used, for example, a copolymer of methyl or ethyl acrylate and dodecyl methacrylate in conjunction with vinyl pyrrolidone. However, it should be understood that this description does not preclude the presence of small amounts of unesterified groups being present in the polymer, i.e. approximately 5% or less of where Z=H.

It should be understood, of course, that when the above compounds are polymerized, the polymerization should not be carried to such an extent as to form polymers which are insoluble or non-dispersible in the petroleum hydrocarbon used. The polymerization may be carried out by methods known to-the art, such as by heating mildly in the presence of a small amount of benzoyl peroxide, but the method of polymerization is not part of this invention. For examples of acrylic-vinyl pyrrolidone copolymers see French Patent 1,163,033.

4 -Examples of vinyl pyrrolidone-acrylic ester typeresins are presented in Table II. 1 I

r 14 4-hydroxyquino1ine-a1dehyde-3 7-hydroxyquinoline-aldehyde-8 '3 TABLE IL-VINYL PYRROLIDONE-ACRYLIO ESTER TYPE RESINS Vinyl pyrroli- 1 done, percent M01 ratio Av.mol Example Monomer 1 v Monomer 2 Monomer 3 by wt. 1:2. weight Tridecylmethaerylate Octadecyl methacrylate 7.5 1 1 300,000 Dodecyl methacrylatea 3-. .Dodecyl methaorylate.- Butyl aerylate- 4" Ootadecyl methacrylate- 5-- Trideeyl methaerylate. 6-. Ootadeeyl methacrylate Methyl methaeryla 7-- Dodecyl methaerylate. Ethyl aerylate Cetyl methacrylate Ootadecyl methacrylate Butyl methacrylate Another auxlliary chemical component is a metal de- POLYAMINES act vator for example those conveniently employed in de Ethylenedlamme activating copper, ll'OIl and other metals from hydrocarbon systems. Typical examples are those described in US. Patent 2,282,513. Of course, one skilled in the art is aware that many other metal deactivators are known and can be employed.

The compounds employed as metal deactivators are preferably of the type of Schiff bases and may be represented by the formulae wherein A and B each represents an organic radical and preferably a hydrocarbon radical. In Formula 2 A and B each preferably represents an aromatic ring or an unsaturated heterocyclic ring in which the hydroxyl radical is attached directly to a ring carbon atom ortho to the -CH=N-group. R represents an aliphatic radical having the two N atoms attached directly to different carbon atoms of the same open chain.

Typical examples of aldehyde and polyamines employed in preparing these Schiff bases include the followmg:

ALDEHY DES Benzaldehyde Z-methylbenzaldehyde 3-methy1benzaldehyde 4-methylbenzaldehyde Z-methoxybenzaldehyde 4-methoxybenzaldehyde 2-naphthaldehyde l-naphthaldehyde 4-phenylbenzaldehyde Propionaldehyde n- Butyraldehyde Heptaldehyde Aldol 2-hydroxybenzaldehyde 2-hydroxy-6-methylbenzaldehyde 2-hydroxy-3-methoxybeuzaldehyde 2-4-dihydroxybenzaldehyde 2-6-dihydroxybenzaldehyde 2-hydroxynaphthaldehyde-1 l-hydroxyuaphthaldehyde-Z Anthrol-Z-aldehyde-l 2-hydroxyfluorene-aldehyde-1 4-hydroxydiphenyl-aldehyde-3 3-hydroxyphenanthrene-aldehyde-4 I-3-dihydroxy-Z-4-dialdehyde-benzene 2-hydroxy-S-chlorobenzaldehyde 2-hydroxy-3-5-dibromobenzaldehyde 2-hydroxy-3-nitrobenzaldehyde 2-hydroxy-3-cyanobenzaldehyde 2-hydroxy-3-carboxybenzaldehyde 4-hydroxypyridine-aldehyde-3 1-2-propy1enediamine 1-3-propylenediamine 1-6-hexamethylenediamine 1- IO-decamethylenediamine Diethylenetriamine Triethylenetetramine Pentaerythrityltetramine 1-2-diaminocyclohexane Di-(b-aminoethyl)ether Dib-aminoethyl) sulfide The ratio of the quaternary ammonium iodide to the metal deactivator can vary widely depending on the particular system, the fuel, etc. employed. Thus, the weight ratio of quaternary ammonium iodide to metal deactivator may be from about 0.1 to 20 or more, such as from about 8-15, but preferably from about 10-12.

The weight ratio of the quartenary ammonium iodide to the acrylic type polymer can also vary widely from about 0.1-20 or more, such as from 8-15, but preferably from about 10-12.

Having thus described our invention and what we claim as new and desire to obtain by Letters Patent is:

1. A distillate fuel composition comprising a major amount of distillate fuel having a distillation range between about F. and about 750 F. and boiling substantially continuously throughout said distillation range and a minor amount, sufficient to improve stability of said fuel during storage, of distillate fuel soluble quaternary ammonium iodide additive selected from the group consisting of (1) N,N bis(2 hydroxyethyDtertiary octylamine iodide,

(2) N ethyl N-(2-hydroxyethy1)tertiary-octylamine iodide,

(3) N methyl-N-(Z-hydroxyethyl)tertiary-octylamine iodide,

(4) N,N bis(2 hydroxyethyl) tertiary-dodecylamine iodide,

(5) N ethyl N (Z-hydroxyethyl)tertiary-dodecylamine iodide, (6) N methyl N (2-hydroxyethyl)tertiary-dodecylamine iodide, (7) an oxyalkylated diamine iodide of the formula (Tallow-N-CHi(JH20H2N--(tnitioHio)x e omcmonrr momm 1 where the sum of x, y and z is 2-15,

(8) an oxyalkylated diamine iodide of the formula where the sum of x, y and z is 2-15, (9) N-(y-dilaurylaminopropyl)morpholine iodide, and (10) N-(methyl-cocoaminopropyl)morpholine iodide.

15 2. The distillate fuel composition of claim 1 wherein the quaternary ammonium iodide additive is N,N-bis(2- hydroxyethyl) tertiary-dodecylamine iodide.

3. The distillate fuel composition of claim 1 wherein the quaternary ammonium iodide additive is (Tallow-N-CH2CH2cH2-N--((JHzCHzO)x 6B (omomomi .(omcmm n 1 4. The distillate fuel composition of claim 1 wherein the quaternary ammonium iodide additive is an oxyalkylated diamine iodide of the formula where the sum of x, y and z is 2 -15.

16 5. The distillate fuel composition of claim 1 wherein the quaternary ammonium iodide additive'is N-(v-dilaurylaminopropyl)morpholine iodide. I q I 6. The distillate fuel composition of claim l wherein the quaternary ammonium iodide additive is N-(methylcocoaminopropyl)morpholine iodide.

I References Cited UNITED STATES PATENTS 2,321,517 6/1943 Rosen' 252 51 3,102,797 9/1963 Udelhofen 4472 3,317,291 5/1967 Marsh et a1.' 44-72 DANIEL W m ry Examiner Y H. SMITH, Assistant Examiner Patent No. 3,486,866 Dated December 30, 1969 Inventor) Verner L. Stromberg and David B. Guthrie It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1 4, line l9, after "additive", there should be inserted --derived from an alkyl iodide, the alkyl having 1 to 30 carbon atoms, and a tertiary amine or a ditertiary diamine--; column 1 4, line 52 delete "iodide"; column 1 line 54 "iodide"; column l t, line 56, delete "iodide"; column 15, line 58, delete "iodide"; column 14, line 60, delete "iodide"; column 14, line 62 delete "iodide"; column 1 line 63, delete "iodide"; column 1 the formula after line 63 should read Tallow N CH CH CH N (CH CH O) (CH CH 0) H (CH CH O) H delete column 14, delete lines 69-73, inclusive; column l l, line 7 "(9)" should read --(8)-- and delete "iodide"; column 1 4, line 75, "(10)" should read --(9)-- and delete "iodide".

Column 15, line 3, "amine" should read --alkyl ammonium--; column 15, the formula after line 5 should read alkyl (9 l Tallow N CH CH CH -N (CH CH O) (cn cn m li (cH CH O) I6 FORM po'wso uscoMM-oc scan-Pan UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3 3 Dated December 30, 1969 Verner L. Stromberg and David B. Guthrie P 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

column 15, lines 10 and 11, delete "an oxyalkylated diamine iodide of the formula" and the formula directly thereafter should read alkyl alkyl 2 (cn cn m n (cn cn m n 21G Column 16, line 2, "is" should read -is alkyl--; column 16, line 3, "morphopholine" should read --morpholinium--; column 16,

line 5, "is" should read --is alkyl--; column 16, line 6, "morpholine" should read --morpholinium--.

SIG D I9 an k9) Anon:

ml. sdaumm, .13 W omuqmr of Patents FORM PC4050 (10-69) uscomwoc 80376-P69

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2321517 *Jan 2, 1941Jun 8, 1943Standard Oil Dev CoLubricant composition
US3102797 *Jul 28, 1960Sep 3, 1963Standard Oil CoFuel oil composition
US3317291 *Jul 16, 1963May 2, 1967Armour & CoNonclogging fuel oil compositions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4065499 *Sep 15, 1975Dec 27, 1977Ethyl CorporationPolyalkylene ammonium chloride
US4871374 *Jan 14, 1988Oct 3, 1989Petrolite CorporationFuel oils stabilized with imine-enamine condensates and method thereof
US4978366 *Jan 14, 1988Dec 18, 1990Petrolite CorporationDistillate fuels stabilized with diaminomethane and method thereof
US6727387May 6, 2002Apr 27, 2004Rohm And Haas CompanyQuaternary ammonium salts having a tertiary alkyl group
EP0151621A1 *Jul 23, 1984Aug 21, 1985Chevron ResQuaternary deposit control additives.
EP1258472A2 *May 8, 2002Nov 20, 2002Rohm And Haas CompanyQuaternary ammonium salts having a tertiary alkyl group
U.S. Classification44/334, 44/336, 44/342, 44/422, 44/335
International ClassificationC10L1/22
Cooperative ClassificationC10L1/2335, C10L1/223, C10L1/2225, C10L1/2222, C10L1/22, C10L1/2283, C10L1/232
European ClassificationC10L1/22