CA1193257A

CA1193257A - Compositions for use in alcohol and alcohol containing fuels

Info

Publication number: CA1193257A
Application number: CA000420515A
Authority: CA
Inventors: Casper J. Dorer, Jr.
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1982-02-03
Filing date: 1983-01-28
Publication date: 1985-09-10
Also published as: IN162820B; AU1082483A; ES519482A0; BR8300381A; ES8403491A1; JPS58134191A; JPH0238119B2; EP0085510A2; IN158319B; AU552631B2; ZA83683B; EP0085510B1; DE3362984D1; MX163706B; EP0085510A3

Abstract

Abstract of Disclosure Corrosion inhibiting additive compositions for use in alcohol and alcohol containing normally liquid hydrogen fuels derived by the reaction of at least one phosphoric acid reactant and at least one amine selected from the group consisting of morpholines and alkanolamines and alcohol and alcohol containing normally liquid hydrocarbon fuels con-taining said additive compositions are disclosed.

Description

~ . L-2100B
~3;~

Compositions for Use in Alcohol and Alcohol Containing Fuels Field of the Invention This inv~ntion relates to corrosion inhibiting compositions for u e in alcohol and alcohol containing nor~
mally liquid hydrocarbon fuels. This invention further re-lakes to alcohol and alcohol containing normally liquid hydrocarbon fuels containing said corrosion inhibiting com-po~itions and characterized by improved corrosion inhibi-tio~, Alcohol fuels and alcohol containing normallyliquid hydrocarbon fuels for use in spark-ignited and com-pression-ignited internal combustion engines possess a high degree of corrosive activity. This higher activity is attributable to the reactive nature of alcohols in general and in some instances, such as for example ethenol, to the presence of acidic and halogen ion containing contaminants.
Thus, ~lcohols are particularly destructlve to various nonferrous metals and metal coati~, such as tin/lead alloy coatings employed on internal surfaces of fuel tanks and to zinc/aIuminum alloys employed in the construction o c~r-buxetors. As a result, motox vehicles employing alcohol and alcohol containing normally liguid hydrocarbon fuel~ have shown a greater propensity toward corro~ion in ~he fu~l tank, fuel linel and fuel induction system areas~
Two patent~ which are specifically directed toward corrosion inhibition in alcohol or alcohol containing h~dro-carbon fuel, e.g., gasohol, are U.S. Pa~ents number~

~3~

4,282,007 and 4,282,008~ In the former are disclosed addi-tives comprising the reaction products of aminotriazoles and polyisobutenyl succinic anhydride and in the lat-ter reaction products of an amineotriazole, isatoic anhydxid~ and ~L~-alkylpropylenediamine.
It is an object of this invention to provide other corrosion inhibiting additives for use in alcohol and alco-hol normally liquid hydrocarbon fuels. It is a further object of this invention to provide alcohol and alcohol containing normally liquid hydrocarbon fuels containing said additives. It is yet a further ob~ect o this lnvention to pxovide alcohol and alcohol containing normally liquid hydrocarbon fuels characterized by improved corrosion in-hibition~ These and other objects are accomplished in accordance with the invention described hereinbelow.
Su~mar of the Invention In its broadest sense, the present invention relates to compositions for use in alcohol and alcohol containing normally hydrocarbonaceous petroleum distillate fuels, said compositionq comprising a corrosion inhibiting reaction product of (A) at leas~ one phosphoric acid com-pound having the formula \ POOH

wherein Rl i~ a hydrocarbon based radical containing from about 8 to about 18 carbon atoms and R2 is hydrogen or a hydrocarbon based radical containing fro~ about 8 to about 18 c~rbon a~oms and (~) at least one amine compound selected from a group con~isting of morpholines of the formula Q~ ~7 ~32~7 wherein R3, R4, R5, and R6 are irldependently hydrogen or alkyl radicals containing from 1 to about 3 carbon atom6 and R7 i5 hydroyen or a radical selected rom the group consi~t-ing of hydrocarbon hased radicals containing from 1 to about 20 carbon atoms ~nd ~R8O~R9 radicals where R8 i.5 divalent alkyl radical conta.ining from 1 to about 20 carbon atoms, x is a number ranging from 1 to about 10 and R9 is hydrogen or aliphatic radicals containing from 1 to about 6 carbon atoms a~d alkanolamines having the formula (Rlo )~

/ 3-(m+n) (Rll ~/
wherein R10 is a hydrocarbon based radical containing from 2 to about 10 carbon atoms, said radical R10 further contain-ing at least hydroxyl group, Rll is a hydrocarbon based radical con~aining from 1 to about 20 carbon atoms, m is a numbex equal to 1, 2, or 3, n is a number equal to 0, 1, or

2 and the sum of m~n is a number ransing from 1 to 2 to provide alcohol and alcohol co~taining normally liquid hydrocarbonaceous petroleum di~taillate fuels with improved corrosion inhibition.
The invention further relates to compositions for use in internal combustion engines comprising (A) a major portion of a fuel containing (i) from about 2 to 100 percent by volume of an alcohol co~taining from 1 to about 5 carbon atoms and ~ii) from about 98 to 0 volume percent of a nor-mally liquid hydrocarbonaceous petroleum distillate fuel and (B) a minor portion of ~he corrosion inhibiting products generally described hereinabove.

The corrosion inhibiting additives comprising one aspect of thi~ invention are amine salts ~repared by the reaction of phosFhoric acids and msnoamine~, both of which are defined in detail below~

3~57 As used herein, the term "hydrocarbon based" or "hydrocarbon based radicals" denotes a radical having a carbon atom directly attached to the remainder of the mole-cule and naving predominantly hydrocarbon character within the context of this invention. Such radicals include 'che following:
1. Hydrocarbon radicaLs; that is, aliphatic, (e,g. alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic aliphatic- and alicyclic substi-tued aromatic, aromatic substituted aliphatic and alcyclicradicals, cyclic radicals wherein the ring is cornpleted through another portion of the molecule ~i.e., an~ two indicated ubstitutents may together form an alicyclic xadical) and the like as well as two or more used benzene nuclei. Such radicals are know to those skilled inthe art, represented examples of which include methyl, ethyl, propyl, butyl, octyl, decyl~ dodecyl, cyclohexyl, phenyl, tolyl, benzyl, napthyl, anthryl, phenanthryl and the like, and 2, Substituted hydrocarbon radicals; that is radicals containing non-hydrocarbon substitu~ent which, in the context of this invention do not alter the predominantly hydxocarbon character of the radical. Those skilled in the art will b~e aware of suitable substituents (hydroxyr alkoxy, carbalkoxy t etc.).
The phosphoric acids which are useful in the pre-paration of the amine salts in this invention are partially esterified orthopho~phoric ac~ds having the formula RlQ~
POOH
R2~
wherein Rl is a hydrocarbon based radical containing from about 8 to about 18 carbon atoms and R2 is hydrogen or a hydrocarbon radical containing from about 8 to about 18 carbon atoms. Thus, i~ is com~emplated that the phosphoric acids may be monoesters or diesters of orthophosphoric acids ~3257 or mixtures thereof represented by the formulae R~ Rl Q~
,POOH and POO~
R2 ~ HO /
wherein Rl and R2 are hydrocarbon based radicals as defined above. For reasons of economy a mixture of mono- and di-phosphate esters is preferred. Such a mixtuxe can be pre~pared by the reaction of one mole of phosphorus pentoxide with three moles of a hydrocarbon alcohol having from about 8 to about 18 carbon atoms. The xeaction may be illus~rated by the following equation:
3ROH~P205------~(RO)2POOH ~ (RO) ~ ~)2 Alternatively, from abou~ two to four moles of the hydro-carbon alcohol or a mixture of such alcohols can be employed per mole of the phosphorus pen~oxide.
G~nerally, Rl will be un~ubstituted aliphatic radicals and preferably unsubstituted alkyl radicals such as, e.g~, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, and oc~adecyl and R~ will be hydrogen or Rl For ~he prepaxation of the phosphoric acids, the alcohol will be primary alcohol and preferably branched primary alcohol having from about 8 to about 18 caxbon atom~. Examples of such alcohol are the normal alcohols derived from coconut kernel oil One such commercially available fraction consists mainly of th~ n-octyl and n-decyl alcohols. Another consists largely of n-dodecyl alcohol, but contains others alcohols having from abou~ 10 to about 18 carbon atoms~ Preferably, the alcohol will be a mixture of branched-chain primary alcohols such as those praduoed by the well known "Oxo" process. Examples of such alcohols include the 1'OX3 1l octyl, decyl, tridecyl, and octyldecyL aLcohols, all of which are mixture~ co~sisting predominantly o branched-chain primary alcohols obtained ~3~S~

from propylene-butylene dimPr, tri-propylene, tetra-pro-pylene, and penta~propylen~, respectively.
The amines, which are useful in preparing the corrosion inhibiting additive compositions which comprise one aspect of the present invention are monoamines selected from the group consisting of the group morphylenes of the formula /~ 7 ~ ~!J- R

~R6 wherein R3, R4, R5, and R6 are independently hydrogen or alkyl radicals containing from 1 to abou~ 3 carbon atoms and R7 is hydrogen or a radical selected from the group con-sisting of hydrocarbon based radicals containing from 1 to about 20 carbon atoms and ~R8O~R9 radicals where R~ iS a divalent aliphatic hydrocarbon radical containing from 1 to ahout 20 carbon atoms, x is a number ranging from 1 to about 10, and R9 is hydrogen or an aliphatic hydrocarbon radical con~aining from 1 to about 6 carbon atoms, and akanolamines having the formula (Rlo ~
3-(m+n) (Rll ~/
~herei~ R10 is a hydxocarbon based radical containing from about 2 to about 10 carbon atom~, said radical R10 further containing at least one hydroxyl group, Rll is a hydrocarbon based xadical containing from 1 to about 20 carbon atoms, m is a number e~ual to 1, 2, or 3~ n is a number equal to 0, ~5 1, or 2, and the ~um of m+n is a number ranging from 1 to 3O
In a preferred embodiment, the amine compounds useful in preparing the additive composition described herein are se-lected rom the group con~isting morpholines of the above formula wherein R3, ~4 J R5, and R6 are all hydrogen atoms and R7 is hydrogen or a radical selected from the group ~3325~

consisting of hydrocarbon based radicals containing from 1 to about 10 caxbon atoms and tR8O~R9 radicals where p,8 is a divalent alkyl radical containinq from 1 to about 10 carbon atoms, x is a number ranging from 1 to about 6 and R9 is hydrogen or alkyl radical containing from 1 to about 3 car-bon atoms and alkanolamine~ of the above formula wherein R10 is an aliphatic hydrocarbon radical containing from about 2 to 5 carbon atoms, said radical R10 containing at least one hydroxyl grsup, Rll is a hydrocarbon based radical contain-ing from l to about 10 carbon atoms, and m and n and the sumof m+n axe as set forth above. The most preferxed amine compounds is useful in preparing the additive compositions of this invention are morpholines having the following formula ~ 7 O N-R
~.

wherein R is hydrogen or a radical selected from the group consi~ting of straight-chain or branched-chain alipha~ic radicals containing from l to about 5 carbon atoms and ~R8O~R9 radical~ where R8 is a divalent alkyl radical co~-taining from 1 to a~out 6 carbon atoms, x is a number rang-ing from 1 to about 4, and R9 is hydrosen or alkyl radicals containing from l to about 3 carbon atoms and alkanolamine of the oxmula above wherein RlO is a straight-chain or branched~chain alkyl radical con~aining from about 2 to 3 carbon atoms, said radical RlO fur~hex containing one hy-droxyl group, Rll is a straight-chai~ or branched-chain alkyl radical containing from l to about 3 carbon atoms and m and n and the sum of m~n are the same as set forth abov~.
Representative, but non-limlted examples of amine compound~ useful in the preparation of the additive compo-~itions compri~ing o~ one aspect of this invention and falling wi~hin the description of the amines set forth above are Morpholine, 4-methylmorpholine, 4-ethylmorpholine, 4-propylmorpholine, 4-butylmorphol.ine t 2-methylmorpholine, ~3~7 2-ethylmorpholine, 2,5-dimethylmorpholine, 2-ethyl-5-methyl-morpholine, 2,6-diethylmorpholine, 4-heptylmorpholine, 4-dodecylmorpholine, 4-hexyldecylmorpholine, 4-cyclohexyl-morpholine, 4-cyclohexyl-2,6-dimethylmorpholine, 4-cyclo-pentylmorpholine, 4-(3-butenyl)morpholine, 4-(1-hexenyl)-morpholine, ~(2 ethylhexyl)morpholine, 4-eicosylmorpholine,

4-(2-methoxy)morpholine, 4-(2-cyclohexyloxyethyl)morpholine, 4-(2-methoxymethyl)morpholine, 4-(2~methylpentyl)morpholine, 4-(3-methylthenyl)morpholine, 4~phenylmorpholine, 4-(2-phenylethyl)morpholine, monoethanolamine, diethanolamine,triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, mono-sec-butenylamine, di-sec-butenyl-amine, di-methylethanolamine, di-methylisopropanolamine, di ethylethanolamine, methylethanolamine, butylethanolamine, phen~lethanolamine, phenylethylethanolamine, methyldie-thanolamine, tris(hydroxy methyl) methylamine, and the like.
The most preferred amines for use in preparing the additive compositions of this invention are selected from the group consisting of morpholine, ethylmorpholine, diethanolamine, and triethanolamine.
The amine salts comprising the corrosion inhibit-ing additive compositions of the present invention can be prepared simply by mixing the organic substituted phosphoric acid and the amine reactant at a temperature below about 100C. The xeaction in most instances is slightly exo-thermic and i3 preferably carried out in the presence of a solvent. Solvents which have been found to be useful are the hydrocarbons or polar salts t such as, benzene, naptha, oluene, xylene, n-hexane, dioxane, chlorobenzene, kerosene, or a fuel oil. Ordinarilyf the xelative proportions of the reactants used to prepare the salts are one equivalent of the phosphoric acid compound and one eguivalent of the amine so that all of the free amino groups are converted to salts.
In some in~t~nces, however, only one acidic hydrogen on a mono-organic substituted phosphoric acid may be utilized to fonm a salt. Thus, amine salts which axe useful in this ~3~

g invention are prepared ~y reacting the amine with one to two e~uivalents of the phosphoric acid.
The following examples illustrate the preparation of the additive composition~. comprising one aspect o~ thi~
invention and improved corrosion characteristics of alcoho]
or alcohol containing normally liquid fuels containing these compositions~ In the following examples, all parts are by weight unles~ otherwise specified~
Example 1 A reac~ion vessel equipped with a stirrer, ther-mometer and reflux conden~er is charged with 1000 parts (5.0 moles~ tridecyl alcohol. The vessel is purged with nitrogen while the alcohol is heated to 35C. Phosphoru~ pentoxide, 248 parts (1.74 moles), is added in increments over a period of 5 hoursO The reaction is exothermic and the temperature is allowed to rise to 50C. during the addition. The ma-terials are then reacted at 60C. for 8 hours. The reac~ion mixture is then filtered and collected, The product ob-tained contains 8~5 percent phosphorus.
~
To a solution of 14.8 paxts of diethanolamine in 50 paxts of xyle~e i~ added, over a period of one hour, 35.2 parks o the product o Example lc The temperature of the reaction mixture rises exothermically from room temperatu~e ~o 50C. during the addition. The materials are -then stirred for an additional 0.25 hour at 50C.

To 18.7 parts of triethanolamine is added, over a period of o~e hour, 31~3 parts of the product of Example 1.
The tempera~ure rises exothermically from room temperatur2 to 51C. duri~g the addition. Xylene, 50 parts, is then added and the materials are mixed at 50C. for an additiGnal 0.25 hour.

Following t~e procedure of Fxample 3, 9.85 parts of ethanolami~e i~ reacted with 40.15 parts of ~he product of Example 1, and dlluted with 50 parts xylene.

3~57 Example 5 Following the procedure of Example 2, a solution consisting of 12.95 parts of morpholine and 50 parts xylene is reacted with 37.05 parts of the product of Example 1.
Example 6 A series of alcohol fuels are prepared by blending from 10 to 450 parts by weight of one of the reaction pro-~ucts of examples 2 through 5 with one million parts by weight of hydrated ethanol containing about 7.5 percent by 1~ weight water~
A series of alcohol containing gasoline fuels is prepared by blending from 10 to 450 parts by wei~ht of one of the reaction products of examples 2 through 5 with one million par~s by weight of a gasohol which comprise~ 20 percent by volume of hydrated ethanol containing 7.5 percent by weight of water and 80 percent by volume of gasoline having an ASTM distillation xange of from about 60C at the 10 percent distillation point to about 205C a~ the 90 pexcent distillation point.
The corrosion inhibiting effectiveness of the additlve compositions were te~ted in accordance with Method K, Test C of the Brazilian Association of Technical Norms (ABNT)~ In this test, various metal specimens (e.g., s~eel, 2~ brass, zinc/aluminum alloys) are immersed in commercially available hydrated ethanol fox a continuous period of 144 hours at a temperature of 50C + 3C. At the end of the test period each test specimen is then rinsed first with water and then with a ketone or other suitable solvent and dried. After drying, each test specimen is weighed and its visual appearance ~oted. The weight loss~ if anyl and visual appearance of the specimens axe then compar~d to those of specime~s txeated in the same manner in a control or reference gasoli~etalcohol blend comprised of 78 to 82 percent by volume of gasoline and 22 to 18 percent by volume of 100 percent ahsolute ethanol. Fox a corrosion inhibit.ing 32~ii7 additive composition to be considered effective, neither the weight loss nor the visual appearance of specimens te~ted with additive containing hydrated ethanol can vary from those treated in the controlled or referenced gasohol/alco-

5 hol blend by more than 10 percent. The corrosion inhi~itingadditive compositions described in examples 2 through 5 above are found to be affective when tested in accordance with this Brazilian method.
Another aspect of this invention comprises fuel 10 compositions for use in internal combustion engines com-prising (A) a major portion of a fuel containing (i) at least one alcohol having from 1 to about 5 carbon atoms and (îi) a normally liquid hydrocarbonaceous petroleum distil-late fu~l and (B) ~ minor portion of a corrosion inhibiting 15 reaction pxoduct as de5cribed hereinabove, i.e., the reac-tion product of (i) at least one phosphoric acid reac~ant having the formula as set forth hereinabove, and (ii) a~
least one amine reactant selected from the group consisting of morpholines and alkanolamines corresponding to the form-ulae also set forth hereinabove.
Alcohol fuels useful in combination with thecorrosion inhibiting reaction products of phosphoric acids and amin~s as defind herein to provide fuel compositions having improved corrosion inhibiting characteristics include such commercially available alcohols as methanol, ethanol, propanol, isopropa~ol, butyl alcohol and its isomers and amyl alcohol and its isomers and mixtures of these various alcohols. As produced commercially~ the pre-Eerred alcohols for use in the present invention are methanol and ethanol.
The hydrated forms of the above alcshol are particularly suited or accomplishing the objectives of this invention.
The normally liquid hydrocar~onaceous petroleum distillate fuels which are useful in combination with al-cohols and ~he corrosion inhibitng reaction product as de~
scribed hereinabove include motor ga~oline as defined by 3~

(ASTM) Specification D439 and diesel fuel or fuel oil as defined by ASTM Specification D396. A particularly pre-ferred petroleum distillate fuel, however, is gasoline, that is, a mixture of hydrocarbons having an ASTM distillation range of from about 60C at the 10 percent distillation point to about 205C at the 90 percent distillation point.
The fu~l portion of the fuel compGsition of this invention comprise of about 2 to 100 percent by volume of at least one alcohol containing 1 to about 5 carbon atoms, and from ahou~ 98 to 0 percent by volume of the normally liquid hydrocarbonaceous petroleum distillate fuel. In a preferred embodimen~, this fuel portion will comprise from about 10 to 190 percent by volume of at least one alcohol containing from 1 to about 5 carbon atoms and from 90 percent to 0 percen~ by volume of the petroleum distillate fuel. In a more preferred embodiment, the ranges of the alcohol and petroleum distillate fuels employed in the fuel compositions of this invention will be from about 20 to 100 p rcent by volume and from about 80 to 0 percent by volume respec-tively. Par~icularly useful fuel compositions are thosebased on a mixture of alcohol, especially methanol or ethanol, and a petroleum distillate fuel~ especially gaso-line, in which mixture -the alcohol component component xanges from abou~ 10 to abou~ 20 percent by volume and the petroleum di3tilla~e fuel ranges from about 90 to 80 percent by volume.
The amount of the corro~ion inhibiting reaction products disclosed herein, to be added to the above de-scribed fuel portion to provide the fuel compositions of this invention will be an amount sufficient to impart im-proved corrosion inhibitng characteristics to these fuel compoqitio~s. Broadly this amount will arrange from about 10 to 1,000 parts by weight of said additives reaction product per million part by weight of said fuel portion.
Preferably this amount will range from about 10 to about 450 parts by weight with a range from about 175 to about 450 ~3f~7 parts by weight of said additive reaction product per mil-lion parts by weight of said fuel portion being the most preferred. It is to be understood that these amounts are based on additive in pure form and not in a diluted form such as in a concentrate form as described below.
The fuel compositions of this invention can be prepared by merely adding the reaction product of the phos-phoric acid and amine directly to the fuel portion or it can be diluted with a substantially inert normally liquid diluent such as naptha, benzene, toluene, xylene, or a petroleum distillate fuel as described above to form a concentrate of said reackion product which is then added to th~ fuel portion. These concentrates which constitute yet another embodiment of the invention generally contain from about 20 pexcent to about 90 pPrcent of the additive reac-tion productsc The fuel compositions described hereinabove, may also contain additional materials normally added to liquid fuels to obtain specific benefitsO Thereore, th~ fuel composi~ions which represent one aspect of this invention may also contain additional materials normally added to liquid fu~Ls to obtain specific benefitsJ Therefore the fuel compo~itions which represe~t one aspect of this in-ven~ion may contain anti-knock agents such as tetraalkyl lead compounds, lead scaveng~rs such as halo alkanes (e.g., ethylene dichloride and ethylen dibromide) deposit pre-venters or modifiers such as triaryl phosphates, dyes, octane improvers, antioxidants such as 2,6 di-tertiary-butyl-4-methylphenol, bacterio~tatlc agents, gum inhibitors, metal deactivatoxs, demulsifiers, di~persants, detergents, uppex cylinder lubricants and anti-icing agents.
The compositions for use in alcohol and alcohol containirlg normally liquid hydrocarbonaceous petroleum dis tillate fuels and th~ fuel compositions based thzreon as well as their methods of preparation have heen ~pecificall~
set forth abova to as-~ist those skilled in the art in under~

3~

standing and practicing the invention. Based on the teach-ings herein, many various and departures from these specific disclosures will be obvious to those skilled in the art.
Such varions and departures are contemplatPd as beiny within ~he scope and spirit of the present invention as defin~d by the appendic claims~

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. Compositions for use in alcohol and alcohol containing normally liquid hydrocarhonaceous petroleum dis-tillate fuels comprising reaction products of (A) at least one phosphoric acid compound having the formula wherein R1 is a hydrocarbon based radical containing from about 8 to about 18 carbon atoms and R2 is hydrogen or a hydrocarbon based radical containing from about 8 to about 18 carbon atoms and (B) at least one amine compound selected from the group consisting of morpholines of the formula wherein R3, R4, R5 and R6 are independently hydrogen or alkyl radicals containing from 1 to 3 carbon atoms and R7 is hydrogen or a radical selected from the group consisting of hydrocarbon based radicals containing from 1 to about 20 carbon atoms and radicals where R8 is a divalent aliphatic hydrocarbon radical containing from 1 to about 20 carbon atoms, x is a number ranging from 1 to about 10 and R9 is hydrogen or an alipnatic hydrocarbon radical contain-ing from 1 to about 6 carbon atoms and alkanolamines having the formula wherein R10 is a hydrocarbon based radical containing from 2 to about 10 carbon atoms said radical R10 further containing at least one hydroxyl group, R11 is a hydrocarbon based radical containing from 1 to about 20 carbon atoms, m is a number equal to 1,2 or 3, n is a number equal to 0, 1 or 2 and the sum of m+n is a number ranging from 1 to 3 to pro-vide alcohol and alcohol containing normally liquid hydro-carbonaceous petroleum distillate fuel with improved cor-rosion inhibition.
2, The compositions of Claim 1 wherein the phos-phoric acid reactant (A) is a mixture of compounds having the formulae and wherein R1 and R2 are aliphatic hydrocarbon radicals con-taining from about 8 to about 18 carbon atoms and the amine reactant (B) is selected from the group consisting of mor-pholines having the formula wherein R3, R4, R5 and R6 are hydrogen and R7 is hydrogen or a radical selected from the group consisting hydrocarbon based radicals containg from 1 to about 10 carbon atoms and radicals wherein R8 is a divalent alkyl radical con-taining from 1 to about 10 carbon atoms, x is a number ranging from 1 to about 6 and R9 is hydrogen or an alkyl radical containing from 1 to about 3 carbon atoms and alkanolamines having having the formula wherein R10 is an aliphatic hydrocarbon radical containing from 2 to about 5 carbon atoms, said radical R10 containing at least one hydroxyl group, R11 is a hydrocarbon based radical containing from 1 to about 10 carbon atoms, m is a number equal to 1,2 or 3, n is a number equal to 0,1 or 2 and the sum of m+n is a number ranging from 1 to 3.
3. The compositions of Claim 2 wherein the amine reactant (B) is selected from the group consisting of mor-pholines having the formula wherein R7 is hydrogen or a radical selected from the group consisting of straight-chain or branched-chain aliphatic hydrocarbon radicals containing from 1 to about 5 carbon atoms and radicals where R8 is a divalent alkyl radical containing from 1 to about 6 carbon atoms, x is a number ranging from 1 to about 4 and R9 is hydrogen or alkyl radical containing from 1 to about 3 carbon atoms and al-kanolamines having the formula wherein R10 is a straight-chain or branched-chain alkyl radical containing from 2 to about 5 carbon atoms, said radical R10 further containing one hydroxyl group, R11 is a straight-chain or branched-chain alkyl radical containing from 1 to about 4 carbon atoms, m is a number equal to 1, 2 or 3, n is a number equal to 0, 1 or 2 and the sum of m+n is a number ranging from 1 to 3.
4. The compositions of Claim 3 wherein the amine reactant (B) is morpholine.
5. The compositions of Claim 3 wherein the amine reactant (B) is an alkanol amine having the formula wherein R10 is a straight-chain alkyl radical containing from 2 to 3 carbon atoms, said radical R10 containing one hydroxyl group, R11 is a straight-chain alkyl radical containing from 1 to about 3 carbon atoms, m is a number equal to 1, 2 or 3, n is a number equal to 0, 1 or 3 and the sum of m+n is a number ranging from 1 to 3.
6. The compositions of Claim 5 wherein the amine reactant (B) is selected from the group consisting of monoethanolamine, di-ethanolamine and triethanolamine.
7. The compositions of Claim 2, 3 or 4 wherein the phosphoric acid reactant (A) is a mixture of mono- and di-tridecyl phosphoric acids.
8. Fuel compositions for use in internal combustion engines comprising (A) a major portion of a fuel containing (i) from about 2.0 to 100 percent by volume of at least one alcohol containing from 1 to about 5 carbon atoms and (ii) from about 98.0 to 0 percent by volume of a normally liquid hydrocarbonaceous petroleum distillate fuel and (B) a minor portion of a corrosion inhibiting reaction product of (i) at least one phosphoric acid compound having the formula wherein R1 is a hydrocarbon based radical containing from about 8 to about 18 carbon atoms and R2 is hydrogen or a hydrocarbon based radical containing from about 8 to about 18 carbon atoms and (ii) at least one amine compound se-lected from the group consisting of morpholines of the formula wherein R3, R4, R5 and R6 are independently hydrogen or alkyl radicals containing from 1 to 3 carbon atoms and R7 is hydrogen or a radical selected from the group consisting of nydrocarbon based radicals containing from 1 to about 20 carbon atoms and radicals where R8 is a divalent aliphatic hydrocarbon radical containing from 1 to 20 carbon atoms, x is a number ranging from 1 to about 10 and R9 is hydrogen or aliphatic hydrocarbon radical containing 1 to about 6 carbon atoms and alkanolamines having the formula wherein R10 is a hydrocarbon based radical containing from to about 10 carbon atoms, said radical R10 further con-taining at least one hydroxyl group, R11 is a hydrocarbon radical containing from 1 to about 20 carbon atoms, m is a number equal to 0, 1 or 2 and the sum of m+n is a number ranging from 1 to 3, said fuel compositions being charac-terized by improved corrosion inhibition.
9. The fuel compositions of Claim 8 wherein the phosphoric acid reactant (B) (i) is a mixture of compounds having the formulae and wherein R1 and R2 are aliphatic hydrocarbon radicals con-taining from about 8 to about 18 carbon atoms and the amine reactant (B) (ii) is selected from the group consisting of morpholines having the formula wherein R3, R4, R5 and R6 are hydrogen and R7 is hydrogen or a radical selected from the group consisting hydrocarbon based radicals containing from 1 to about 10 carbon atoms and radicals where R8 is a divalent alkyl radical containing from 1 to about 10 carbon atoms, x is a number ranging from 1 to about 6 and R9 is hydrogen or an alkyl radical containing from 1 to about 3 carbon atoms and al-kanolamines having the formula wherein R10 is an aliphatic hydrocarbon radical containing from 2 to about 5 carbon atoms, said radical R10 containing at least one hydroxyl group, R11 is a hydrocarbon atom containing from 1 to about 10 carbon atoms, m is a number equal to 1, 2 or 3, n is a number equal to 0, 1 or 2 and the sum of m+n is a number ranging from 1 to 3.
10. The fuel compositions of Claim 9 wherein the amine reactant (i) is selected from the group consisting of morpholines the formula wherein R7 is hydrogen or a radical selected from the group consisting of straight-chain or branched-chain aliphatic hydrocarbon radicals containing from 1 to about 5 carbon atoms and radicals where R8 is a divalent alkyl radical containing from 1 to about 6 carbon atoms, x is a number ranging from 1 to about 4 and R9 is hydrogen or alkyl radical containing from 1 to about 3 carbon atoms and alkanolamines having the formula wherein R10 is a straight chain or branched-chain alkyl radical containing from 2 to about 5 carbon atoms, said radical R10 further containing one hydroxyl group, R11 is a straight-chain or branched-chain alkyl radical containing from 1 to about 4 carbon atoms, m is a number equal to 1, 2 or 3, n is a number equal to 0, 1 or 2 and the sum of m+n is a number ranging from 1 to 3.
11. The fuel composition of Claim 10 wherein the amine reactant (B) (ii) is morpholine.
12. The fuel compositions of Claim 10 wherein the amine reactant (B) (ii) is an alkanol amine having the formula wherein R10 is a straight-chain alkyl radical containing from 2 to 3 carbon atoms, said radical R10 containing one hydroxyl group, R11 is a straight-chain alkyl radical containing from 1 to about 3 carbon atoms, m is a number equal to 1, 2, or 3, n is a number equal to 0, 1 or 3 and the sum of m+n is a number ranging from 1 to 3.
13. The fuel compositions of Claim 12 wherein the amine reactant (B) (ii) is selected from the group consisting of monoethanolamine, diethernolamine and triethanolamine.
14. The fuel compositions of Claims 9, 10 or 11 wherein the phosphoric acid reactant (B) (i) is a mixture of mono- and di-tridecylphosphoric acids.
15. The fuel compositions of Claim 9 wherein the fuel portion (A) of said compositions comprises (i) from about 10 to 100 percent by volume of an alcohol containing from 1 to about 5 carbon atoms and (ii) from about 90 to 0 percent by volume of a normally liquid hydrocarbonaceous petroleum distillate fuel.
16. The fuel compositions of Claim 15 wherein said fuel portion (A) the alcohol component (A) (i) is selected from the group consisting of methanol and ethanol and the normally liquid hydrocarbonaceous petroleum distillate fuel component (A) (ii) is gasoline.
17. The fuel compositions of Claim 16 wherein said fuel portion (A) the alcohol component (A) (i) is ethanol.
18. The fuel compositions of Claim 17 wherein the phosphoric acid reactant (B) (i) is a mixture of mono- and di-tridecyl-phosphoric acids.
19. The fuel compositions of Claim 9 wherein the fuel portion (A) of said compositions comprises (i) from about 20 to 100 percent of an alcohol containing from 1 to about 5 carbon atoms and (ii) from about 80 to 0 percent by volume of a normally liquid hydrocarbonaceous petroleum distillate fuel.
20. The fuel compositions of Claim 19 wherein said fuel portion (A) the alcohol component (A) (i) is selcted from the group consisting of methanol and ethanol and the normally liquid hydrocarbonaceous petroleum fuel component (A) (ii) is gasoline.
21. The fuel compositions of Claim 19 wherein said fuel portion (A), the alcohol component (A) (ii) is ethanol.
22. The fuel compositions of Claim 21 wherein the phosphoric acid reactant (B) (i) is a mixture of mono- and di-tridecylphos-phoric acids.
23. Fuel compositions for use in internal combustion engines comprising (A) a major portion of a fuel containing (i) 10 percent by volume of ethanol and (ii) 90 percent by volume of gasoline and (B) a minor portion of a corrosion inhibiting reaction product of (i) a mixture of mono- and di-tradecylphos-phoric acid and (ii) at least one amine selected from the group consisting of morpholine and mono-, di- and triethanolamine.
24. Fuel compositions for use in internal combustion engines comprising (A) a major portion of a fuel containing (i) 20 percent by volume of ethanol and (ii) 80 percent by volume of gasoline and (B) a minor portion of a corrosion inhibiting reaction product of (i) a mixture of mono- and di-tridecylphos-phoric acids and (ii) at least one amine selected from the group consisting of morpholine and mono-, di- and triethanol amine.