FR2576908A1 - HIGH-DETERGENT / DISPERSANT ADDITIVE FOR LUBRICANT FOR INTERNAL COMBUSTION ENGINES BURNING ALCOHOL-BASED FUEL, LUBRICANT CONTAINING THE SAME AND ITS OBTAINING, AND ITS APPLICATION TO INHIBIT THE CORROSION AND EXCESSIVE WEAR OF AN ENGINE - Google Patents

Abstract

THE INVENTION RELATES TO A HIGH DETERGENT-DISPERSANT ADDITIVE FOR LUBRICANT FOR INTERNAL COMBUSTION ENGINES BURNING ALCOHOL-BASED FUEL, A LUBRICANT CONTAINING THIS ADDITIVE AND ITS OBTAINING, AND ITS APPLICATION TO INHIBIT CORROESS AND EXCIVE WEAR A MOTOR. THE LUBRICANT CONTAINS 89.5 TO 98.75 BY WEIGHT OF A MINERAL OR SYNTHETIC OIL (SAE 5 TO 50) AND 1.25 TO 10.5 BY WEIGHT OF AN ADDITIVE INCLUDING 68.75 TO 75.0 BY WEIGHT OF AN ORGANIC AMINE COMPONENT CHOSEN FROM AROMATIC PRIMARY OR SECONDARY AMINES, ALIPHATIC PRIMARY OR SECONDARY AMINES, CYCLOALIPHATIC PRIMARY AMINES AND THEIR MIXTURES, AND 25.0 TO 31.25 BY WEIGHT OF A SELECTED PAR PHOSPHORIC ACID ESTER ORTHO-, META- OR TRICRESYL PARAPHOSPHATE, DIBUTYL PHENYL PHOSPHATE, TRIBUTYL PHOSPHATE, TRIS- (2-ETHYLHEXYL PHOSPHATE, TRIOCTYL PHOSPHATE, DIBUTYL PHOSPHATE, DIBUTYL DIPHOSPHATE DE , TRILAURYL AND OR TRISTEARYLE APPLICATION TO INTERNAL COMBUSTION ENGINES BURNING ALCOHOL OR AN ALCOHOL BASED FUEL.

Description

The present invention aims at a formulation

  additive with a high detergent / dispersant content

  designed to be used with conventional engine lubricants

  internal combustion engine to provide a suitable lubricant

  for use in internal combustion engines burning fuels consisting of one or more alcohols, or containing one or more alcohols, such as fuels based on methanol or ethanol. The present invention also provides a lubricating composition containing said lubricant additive, a process for preparing said composition

  of lubricant and a method for inhibiting, with the aid of

  so-called lubricant composition, corrosion and wear

excessive motor.

  Lubricants commonly used for

  are not efficient in combustion engines.

  alcohol, which is evidenced by excessive motor wear and rates, gradually increasing, consumption of lubricant. One reason is the great difference in chemical reactivity of the products from the combustion of gasoline and those from the

  combustion of fuels based on alcohol (s) porautomobile.

  In a fuel based on alcohol (s), a certain amount of

  number of lubricant degradation reactions not found in gasoline

  fuel. These chemical reactions cause corrosion.

  increased use of alcohol-based fuels). For example, methanol oxidizes easily to form formaldehyde and formic acid. This reaction is represented in equation 1:

CH 3 OH H HCHO.HCOOH (1)

  (methanol) (formaldehyde) (formic acid).

  Most vehicles using methanol fuel suffer from excessive cylinder corrosion and excessive bearing wear due to

  with formic acid produced by the combustion of methanol.

  Formic acid reacts with organic amines which are conventional lubricant additives for automobiles and

  who play the role of antioxidants, corrosion inhibitors

  and anti-wear agents. Amine additives neutralize formic acid. However, the additives

  are unable to neutralize adequately

  quate the amount of formic acid formed during the com-

  busting of methanol. These reactions are represented in equations 2 and 3: neutralization

RNH2 + 2HCOOH - RNH2.2HCOOH (2)

  (amine (primary acid) formic) neutralization

R2NH + HCOOH R2NH.HCOOH (3)

  (formaldehyde) Formaldehyde is highly reactive with amine additives. Formaldehyde reacts with amines that are used as antioxidants, antacids and ashless dispersants. These reactions of formaldehyde, represented by equation (4), strongly contribute to a degradation of the oil present in a methanol fuel formulation: Basic catalysis-type aldol 2 condensation

2RNH2 + HCHO> RNHCH2NHR (4>

  (amine) (formaldehyde) We need a lubricant additive that

  minimizes the oxidation of methanol to formaldehyde

  dehyde and formic acid and reduces to a minimum the

  excessive formaldehyde and formic acid

  in order to extend the possible service life of

  lubricants that are rapidly depleted by reaction with formaldehyde and formic acid. Likewise, you need a lubricant additive that reduces to a minimum

2S76908

  the oxidation of ethanol to acetaldehyde and acetic acid and minimizes the excessive reactions of these components. Another important problem in a system

  using alcohol-based fuel is a dialkyl-

  zinc dithiophosphate, which is a multifunctional additive-

  In most conventional lubricants, it is easily transesterified and thus loses many of its antiwear properties. The trans-esterification reaction involves the mutual exchange of a group

  of an alcohol, such as methanol or ethanol.

  nol, with that of an existing ester, like a dialkyldi

  zinc thiophosphate, to form a new ester. A transesterification reaction is represented in equation 5: reaction catalyzed by RPOO (OH) R '+ CH 3 OH an acid RPOO (OH) CH 3 + R'OH (5) (ester ex- (m <thanol)) (new ester ) so much)

  The trans-esterification reaction is catalytic

  lysed by an acid and therefore occurs after exhaustion

  additives formed by basic amines in the lubricant

  a reaction with aldehydes and acids formed during the combustion process. Trans-esterification is not a major mechanism for degradation of

  oils in systems using hydrogen fuels

  but it is a primary mechanism of oil degradation in systems using fuels based on methanol and other alcohols. For example, when mixing methanol and ethanol with gasoline, the magnitude of the transesterification reaction is

  proportional to the amount of alcohol in the mixture.

  Another cause of increased corrosivity in a motor burning alcohol is the increased solubility:

  carbon dioxide in alcohol. For example, the dio-

  Carbon dioxide is much more soluble in methanol than in water. Water and methanol are usually present in the colder parts of the crankcase as combustion products. The water reacts with the fuel combustion products as SO3, NO2 and CO2, to form the corresponding acids, sulfuric acid, nitric acid and carbonic acid as shown in Equations 6, 7 and 8:

S03 + H2 - H2SO4 (6)

'(sulfuric acid)

NO2 + H20 NO (7)

2- 2 (nitric acid)

CO2 + H2O H2CO3 (8)

  (carbonic acid) By reacting with the motor metals, these acids are one of the major causes of corrosion in an internal combustion engine. Lubricants commonly used in a hydrocarbon fuel formulation effectively neutralize these acids with basic additives such as organic amines and alkali metal compounds. However, due to the increased solubility of CO2 in alcohols, the

  of carbonic acid are significantly higher in a

  using methanol or another alcohol as a

  only in a system using gasoline as fuel. This is also true for nitric acid

  formed from NO2 combustion products.

  The absorption of carbon dioxide seems to be a reason

  of the surprisingly high corrosivity of car-

alcohol based fuels.

  Lubricant analysis indicates that the

  Corrosion bitters composed of sulfonates, naphthenes

  or other alkali metal salts, are largely exhausted by reaction with carbonic acid, which causes the precipitation of insoluble carbonates.

  alkali metals. The precipitation reaction is

  presented in equations 9 and 10.

  (RSO3) 2Ba + H2C03 <> BaCO3 + 2RS03H (9) (RSO3) 2 Ca + H2Co3 <- -> CaCO3 + 2RSO3H (10) (RS3) 2Ca H + H 2 C 03 <

  This precipitation reaction comes into

  with the neutralization of carbonic acid by organic amines. Although neutralization is

  faster and more likely to occur, the reaction

  with alkali metal salts increases as organic amines are depleted. Thus, a lubricant additive is needed in which depletion of the organic amine additives, due to neutralization of formic acid or acetic acid and carbonic acid, occurs less rapidly, thereby decreasing the likelihood that alkali metal salts will be depleted by the precipitation reactions represented

in equations 9 and 10.

  A general object of the present invention is to provide a lubricant additive for use in an engine

  internal combustion engine burning one or more alcohols as

  burdens, an additive that confers protection against ef-

  corrosive and engine wear due to alcohol.

  Another object of the present invention is

  to provide a lubricant additive having a high content

  detergent / dispersant, to emulsify

  liquids of liquid alcohol such as methanol or ethanol,

  introduced into the lubricant by leakage gases through

  crankcase ventilation during combustion, and for

thus reduce engine wear.

  Another object of the present invention is to provide a lubricant additive having a greater

  ability to neutralize acids.

  Another object of the present invention is to provide a lubricant additive comprising an agent

  anti-wear that is not degraded by methanol or ethanol.

  nol. The invention also relates to a lubricant composition containing a major amount of a conventional lubricant for an internal combustion engine and a quantity

  minor of a lubricant additive according to the invention.

  The invention also relates to a method for pre-

  a lubricant for an internal combustion engine, which inhibits corrosion and excessive wear of the engine, by

  a mixing operation of a major quantity of a

  conventional lubricant for an internal combustion engine and a minor amount of a lubricant additive according to the invention. The invention also relates to a method for reducing corrosion and excessive wear of the engine, in an internal combustion engine burning alcohol or a fuel containing alcohol, according to which is added in the engine a conventional lubricant for internal combustion engine, and which contains an additive for

lubricant according to the invention.

  The present invention therefore provides a lubricant additive, which can be added to conventional motor vehicle lubricants and meets the minimum requirements of the American Petroleum Institute (API) for oils of severe service quality ( "HD" oil; SF / CD) or the minimum requirement of the Common Market Autobuilder Committee (CCMC) for service grade 2.2 oils, and other internal combustion engine lubricants selected from the group consisting of mineral oils and synthetic oils having a single viscosity condition and / or multiple viscosity conditions (multigrade oil) having an SAE of S to, to produce a lubricant suitable for use in a burning engine a fuel consisting of one or more alcohols or containing one or more alcohols, the additive

  comprising a major amount of a selected organic amine

  in the group consisting of aliphatic primary amines, aliphatic secondary amines, cycloaliphatic primary amines, aromatic primary amines, aromatic secondary amines and mixtures thereof, and a minor amount of a phosphoric acid ester. Preferably, the lubricant additive of the present invention comprises about 68.75 to 75.0% by weight.

  weight of an organic amine selected from the group

  above and about 31.25 to 25.0% by weight of a

phosphoric acid.

  The amine component of the lubricant additive of the present invention may be an aliphatic amine, a cycloaliphatic amine, a primary aromatic amine, a secondary aromatic amine, or any mixture of these amines. Preferably, the amine component is a

  primary or secondary aliphatic amine; a primary amine

  cycloaliphatic mayor; a mixture of a primary amine

  or aliphatic secondary or cyclic primary amine

  aliphatic with an aromatic primary amine, an aromatic secondary amine or both: a mixture of an aliphatic primary or secondary amine and a cycloaliphatic primary amine; or a mixture of an aromatic primary amine and an aromatic secondary amine. An amine

  primary or secondary aliphatic, used alone,

  the most preferred amine component.

  Preferred aromatic primary amines include

  take ortho-phenylenediamine, meta-phenylenediamine

  mine and para-phenylenediamine, orthotoluidine, metha-

  toluidine and paratoluidine, aniline, xylidine, naphthylamine, benzylamine, toluenediamine and naphthalenediamine. A primary aromatic amine

  preferred is ortho-phenylenediamine. Secondary amines

  Preferred aromatic compounds include N-phenyl-2-naphthyl-

  amine, phenyl-alpha-naphthylamine, phenyl-beta-naphthyl-

  amine, tolylnaphthylamine, diphenylamine, ditolyl-

  amine, phenyltolylamine, 4,4'-diaminodiphenylamine and N-methylaniline. An aromatic secondary amine

  more preferred is N-phenyl-2-naphthylamine.

  The preferred aliphatic amines are the aliphatic amines

  ticks having 10 to 30 carbon atoms. An aliphatic amine

  More preferred is 12 to 30 carbon atoms. The most preferred aliphatic amine is octadecylamine. Preferred cycloaliphatic amines

  include cyclohexylamine, and methylcyclohexylamine.

  Preferred esters of phosphoric acid

  include tricresyl orthophosphate, metaphosphate

  tricresyl phage or tricresyl paraphosphate, the

  dibutyl phosphate and phenyl phosphate, triphosphate

  butyl, tris- (2-ethylhexyl) phosphate, phos-

  trioctyl phate, diphenyl orthophosphonate, dicrésyl orthophosphonate, trilauryl orthophosphonate and tristearyl orthophosphonate. An ester

  phosphoric acid which is more preferred is

tricresyl phosphate.

  A preferred composition of the additive for

  of the present invention comprises about 68.75 to 75.0% by weight of octadecylamine and about 31.25 to

  0% by weight of tricresyl paraphosphate.

  Another preferred composition of the lubricant additive of the present invention comprises about 68.75 to 75.0% by weight of the octadecylamine and about 31.25 to

  0% by weight of mixed isomers of tricrephosphate

syle.

  All chemicals above are dis-

  available in the trade. The additive for

  brifiant of the present invention by mixing together

  a minor amount of a lubricant additive, including

  a major amount of an organic amine selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, amines

  primary cycloaliphatics, the aromatic amines

  mayors, secondary aromatic amines and their

  and a minor amount of a phosphoric acid ester

  phoric, with a major amount of a blend of lubricant base oils meeting the API minimum requirements for SF / CD grade oils or CCMC for service grade 2.2 oils, or any which mixture of lubricant base oils selected from the group consisting of mineral oils and

  synthetic materials which satisfy a single condition of visco-

  sity and / or meeting multiple conditions of

  (Preferably, the lubricant additive of the present invention is prepared by mixing together about 1.0 to 8.0% by weight of said amine, about 0% by weight). 25 to 2.5% by weight of the phosphoric acid ester, and about 89.5 to 98.75% by weight of the lubricant base oil mixture.

  The lubricating composition thus obtained

  therefore holds about 1.25 to 10.5% by weight of the additive

for lubricant according to the invention.

  The lubricant additive of the present invention can be used by adding about a portion

  lubricant additive to 5 parts of oil. The D-

  lubricant according to the present invention will

  to provide effective protection against the effects of corro-

  engine wear and tear due to methanol, ethanol or

  to other fuels consisting of alcohols or

  holding alcohols, for emptying intervals

  more than 6400 km of oil and in some cases

  valleys up to 9600 km.

  The phosphoric acid ester, preferably the

  tricresyl paraphosphate or the mixed isomers of phosphorus

  tricresyl phate, plays the rattle of a solubilizer of methanol or ethanol and an ashless detergent / dispersant for the droplets of alcohol, such as methanol or ethanol, in the lubricant. A solubilizer of this type is required to dissolve or disperse the relatively large amounts of alcohol, such as methanol or ethanol, introduced into the lubricant at the same time.

  during the combustion process in a combustion engine

  burning burning alcohol fuel. The ester

  of phosphoric acid solubilises and disperses the droplets

  methanol or ethanol, which prevents the formation of

  dry points on the moving parts of the internal combustion engine. In the absence of the phosphoric acid ester, methanol or ethanol is insoluble in hydrocarbon lubricants and dry spots may occur which results in excessive engine wear. Phosphoric acid ester also plays the role

  anti-wear agent and, when used in a car-

  based on methanol or ethanol, it is superior

  to the conventional anti-wear agent of the dialkyldithiophos-

  zinc phate. A zinc dialkyldithiophosphate is used

  almost universal in lubricants for

  tomobiles for engines burning gasoline, but

  quickly loses its anti-wear properties in

  burning methanol or ethanol because it is

  easily trans-esterification with alcohols.

  The amine component plays the role of an additive influencing the base number to neutralize the formic or acetic and carbonic acids formed by the oxidation of methanol or ethanol and by the reaction of water and carbon dioxide. carbon, respectively. The amine component also plays the role of an antioxidant, which minimizes the oxidation of methanol or ethanol to

  their respective aldehydes and acids.

  The presence of rather large quantities (approximately

  68.75 to 75.0% by weight) of organic amines in the additive

  The lubricant of the present invention makes it possible to prepare a lubricant containing about 1.0 to 8.0% by weight of organic amines, in comparison with about 0.25% by weight.

  by weight of organic amines in lubricants containing

  conventional additives for lubricants; this pre-

  minimizes the exhaustion of metal salts.

  alkaline levels such as naphthenates and sulfonates. Alkali metal salts run out when they react

  with carbonic acid to form insoluble carbonates

  lubles, competing with the neutralization of carbonic acid. The neutralization reaction is

  faster and more likely to happen, but the reaction

  Precipitation becomes a problem when the organic amines are exhausted. With the presence of a

  more organic amines, there is

  more carbonic acid, so there is less carbonic acid available to react with

of alkali metals.

  The analysis of the lubricant after use in the engine of an automobile provides a convenient and reliable indication of engine wear during an interval, between oil changes, as brief as a few thousand

kilometers.

  A lubricant additive can be evaluated based on the amounts of elements present as a result of wear, such as iron, lead, copper, chromium, nickel, tin, aluminum and aluminum. molybdenum, which is detected by spectrochemical analysis in an oil sample after the car has been driven for a

  number of kilometers after an oil change.

  These metals or elements due to wear appear in the lubricant as a result of excessive corrosion or failure of certain engine components consisting of

  this metal, as well as as a result of normal mechanical wear

male.

  Since the building materials of the

  There is a great deal of variation in the degree of wear in the components of a used oil analysis which is indicative of excessive wear of the engine. However, there are generalized criteria for the evaluation of

  results concerning the elements due to wear and

  These criteria are presented in Table I. The primary and secondary source in the engine of each element due to wear is given as well as the average amount, in parts per million (ppm) of each element. due to wear, which one could find

  in the oil at the point of "break-in" and at the point of "post-

  The wear rates of the engine during the break-in period tend to be relatively high and, after the engine has been burned down, the wear rates reach a plateau.

  and remain stable for approximately 80 000 km, depending on the vehicle

  and the degree of maintenance. The "break-in" point is generally for an average engine in the range of 0 to 16,000 km. The evaluation criteria found in Table I will be used to

  evaluate the results presented in examples 1 to 13.

  The most useful indication of excessive engine wear is obtained by sudden deviations in the wear-related content of a given element in a used oil analysis which has been previously established.

  for a given engine performing a given service in use

reading a specific oil.

  The basic index is a measure of the detergent action of the oil and its ability to inhibit the

  corrosion. New automotive oils have

  a basic index of 4 to 5. For an oil of some

  conch, a reading equal to or less than 1 indicates a

  dangerous depletion of additive reserves.

257'6908

  A basic index 2 is generally considered to be

  denying an adequate margin of protection in an engine

burning gasoline.

TABLE I

  Criteria for Evaluating Results for Lubricant Wear Content in Lubricant Evaluation Criteria, ppm S o u r c e Before e After break-in Items of Matter Content Grade Primary Secondary Wear Average Mo yen

Excess-

  sive sive Iron (Fe) 200-400 400 10-100 200 Cylinder wall Blocks, crankshaft, piston pin, segments, rings, valves, oil pump, fuel tank Pblybdenum (Mo) 2-4 5 0-2 3 Cylinder wall Blocks, crankshaft, piston pin, rings, rings, valves, oil pump, fuel tank

  Pl! Cb (Pb) 100-300 300 5-100 150 Plunging bearings plamb-_.

  tetraethyl in fuel Copper (Cu) 50-150 150 5-75 100 Bearings Bushings, rings, rings, cams, valves, thrust washers, oil pump Tin (Sn) 20-50 50 1-10 15 Bearings Chrome ( Cr) 2-10 10 1- 5 5 Rings Crankshaft, exhaust valves Nickel (Ni) 3-5 5 1-2 4 Valves, vile- Rings Aluminum (Al) 30-100 100 1-15 30 Pistons, blocks in aluminium

Example 1

  An oil sample comprising about 98.68% by weight of "Kendall" automotive lubricant 40 and about 1.32% by weight of the lubricant additive of the present invention, comprising about 75.0% is taken. by weight of octadecylamine and about 25.0% by weight of tricresyl paraphosphate, on the crankcase of a Chevrolet Citation 1981 engine, running on a methanol fuel and traveling 146,900km with an oil change which was carried out about 450 km before the sampling. The methanol fuel that was used is a mixture of 88.0% methanol and 12% unleaded regular gasoline, index

octane 87.

  The oil sample has a base number of 3.14, which is well above the acceptable value

  for the basic index of 2, and indicates that octadecyl-

  amine is not sold out and is still available for

  neutralize acids to prevent oxidation of metha-

  in formic acid and formaldehyde.

  The spectrochemical analysis reveals that the quantities

  The following items of wear elements are present in the oil sample: 25 ppm iron; 49 ppm of

  lead; 83 ppm copper; 1 ppm of chromium; 3 ppm of aluminum

  minium; 1 ppm nickel; 15 ppm tin and 2 ppm molybdenum. Since the engine has traveled 146,900 km, the "after break-in" criteria in Table I are used for

* evaluate the content of elements due to wear.

  Referring to Table I, we see that the

  iron, lead, chromium, aluminum, nickel and molyb-

  are within the average wear element content interval, for these wear elements observed at one mileage traveled after break-in. Content

  copper is above average, but is not ex-

  cessive. According to Table I, the tin content is

2Z576908

  excessively, but the tin content in the oil sample taken from the crankcase during the oil change of 6450 km before the present oil change is 14 ppm, which indicates that There is no significant variation in the tin content, and therefore no excessive wear of the engine. As previously mentioned, a sudden deviation of the wear element content in a used oil analysis indicates more excessive engine wear than the generalized criteria presented in Table I. Exemole 2

  We take from the crankcase of the same engine, -ali-

  in Example 1, an oil sample comprising 98.68% by weight of the lubricant used in Example 1 and 1.32% by weight of the lubricant additive. used in example 1. The engine has traveled 153 100 km and the previous oil change

  of oil occurred for 6200 km previously.

  The oil sample has a base number of 2.8, which is well above the acceptable value

  of 2 for the basic index, which indicates that the octa-

  decylamine has not been depleted.

  The spectrochemical analysis reveals that the quantities

  The following items of wear components are present in the oil sample: 34 ppm iron; 72 ppm of

  lead; 95 ppm copper; 0 ppm of chromium and 4 ppm of aluminum

  minium; 1 ppm nickel; 19 ppm tin and 3 ppm molybdenum. The criteria in Table I correspond to

  spawning one kilometer traveled, "after break-in".

  Referring to Table I, we see that the

  levels of iron, lead, chromium, aluminum and nickel

  in the mean interval of the levels of elements due

  to wear, for these elements due to wear at this mil-

  trage traveled "after break-in". The copper content is

  below average, but it is not excessive and has not varied markedly with respect to the above copper content described in Example 1. It is considered that the tin and molybdenum contents are excessive according to Table I, but there is no significant difference with respect to the previous content of tin and molybdenum described in Example 1, this

  which does not indicate excessive motor wear.

Exempt 3

  We take from the crankcase of the same engine,

  methanol fuel, used in Examples 1 and 2, which ran 159,255 km, an oil sample comprising about 98,68% by weight of the lubricant used in Examples 1 and 2 and about 1, 32 % in

  the weight of the lubricant additive used in the

  ples 1 and 2. Thus, the previous oil change occurred when the mileage traveled was about

  6156 km to that corresponding to the present oil change.

  The sample has a base index of 3.02, which is

  which indicates that octadecylamine is not exhausted.

  The spectrochemical analysis reveals that the quantities

  The following items of wear elements are present in the oil sample: 20 ppm iron; 49 ppm of

  lead; 97 ppm copper; 1 ppm of chromium; 2 ppm of aluminum

  minium; 2 ppm nickel; 19 ppm tin and 2 ppm molybdenum. The sample is evaluated using the criteria

of Table I "after break-in".

  Referring to Table I, we see that the

  iron, lead, chromium, aluminum, nickel and molyb-

  This is within the range of the average wear element content due to wear due to "after break-in" mileage. The copper content is above average but not excessive. The tin content is considered as

  according to Table I, but there is no

  at all compared to the previous oil change,

  and there is therefore no indication of excessive engine wear.

Example 4

  We take from the casing of a car engine

  "ChevroletS-10", powered by a fuel based

  thanol, which traveled about 128,334 km, with an oil change of about 6,504 km less traveled, an oil sample of about 98.68% by weight of lubricant for car at% of 'endall' and approximately 1.32% by weight of the additive

  lubricant of the present invention, including

  75.0% by weight of octadecylamine and 25.0% by weight

  of tricresyl paraphosphate. Fuel based on

  thanol used is a mixture of 88.0% methanol / 12.0% unleaded natural gasoline (octane number 87). v The base index of the sample is 2.52,

  indicating that octadecylamine is not exhausted.

  The spectrochemical analysis reveals that the quantities

  The following items of wear elements are present in the oil sample: 96 ppm iron; 27 ppm of

  lead; 49 ppm copper; 3 ppm of chromium; 14 ppm of aluminum

  minium; 2 ppm nickel; 5 ppm of tin and 7 ppm of

  molybdenum. The criteria in Table I are used after

  "car 128 334 km represents one kilometer traveled

after break-in.

  Referring to Table I, it can be seen that iron, lead, copper, chromium, aluminum, nickel and tin contents are within the normal range of wear element content, for these elements due to wear at such mileage after break-in. The molybdenum content is considered to be excessive according to Table I but, as shown in Examples 5 and 6 below, there is no sudden difference in the molybdenum content at the various oil changes and it does not there is no indication of wear

excessive motor.

Example 5

  We take from the crankcase of the same engine,

  mented into a methanol fuel, used for

  FIG. 4, which has traveled 135,119 km, an oil sample comprising approximately 98.68% by weight of the lubricant used in Example 4 and approximately 1.32% by weight of the lubricant additive used in the example 4. Thus, the previous oil change occurred for a mileage traveled

  approximately 6785 km below that corresponding to the ac-

a change of oil.

  The oil sample has a base number of 1.93, which is very close to the acceptable value for the basic index, which is 2, which indicates the presence of sufficient quantities of octadecylamine for

  neutralize the acids and reduce to a minimum the oxidation

methanol.

  The spectrochemical analysis reveals that the quantities

  The following elements of wear elements are present in the oil sample: 57 ppm iron; 26 ppm of

  lead; 42 ppm copper; 2 ppm of chromium; 16 ppm of aluminum

  minium; 2 ppm nickel; 0 ppm tin and 18 ppm of

  molybdenum. The criteria in Table I correspond to

  spawning at one kilometer traveled after break-in.

  Referring to Table I, it can be seen that iron, lead, copper, chromium, nickel and tin contents are well within the mean range of wear element levels for these elements. due to wear at one kilometer traveled after break-in. Aluminum content is slightly above average

  but: is not excessive. The molybdenum content is

  considered excessive according to Table I, but it did not

  not at all varied with regard to the content in the last

  oil, which indicates that there is no

excessive wear of the motor.

Example 6

  From the crankcase of the engine, fed with a methanol fuel, used in Examples 4 and 5, and which has traveled the equivalent of 142 382 km, an oil sample comprising about 98.68% by weight of lubricant used in Examples 4 and 5 and about 1.32% by weight of the lubricant additive used in Examples 4 and 5. Thus, the previous oil change occurred for a mileage less than about 7 263 km.to that corresponding to the current oil change.

  The basic index of the sample is approximately

  ron 1.62, which is slightly lower than the value of 2, more acceptable for the base index, but is still

  greater than 1.0, indicating that there is a quantity

  sufficient quantities of octadecylamine.

  The spectrochemical analysis reveals that the quantities

  The following items of wear elements are present in the oil sample: 71 ppm iron; 22 ppm lead; 41 ppm copper; 1 ppm of chromium; 16 ppm aluminum; 1 ppm nickel; 0 ppm tin and 34 ppm

  of molybdenum. it is appropriate to use the criteria for

  I corresponding to "after break-in" to evaluate the oil sample, since 142 382 km constitute a

  mileage considered to be done after break-in.

  Referring to Table I, we see that the

  the contents of elements due to wear: iron, lead, copper

  vre, chrome, nickel and tin, are well

  average value of the contents in elements due to wear for

  mileage traveled after break-in. The alumni content

  nium is above average but not excessive.

  The molybdenum content is considered excessive according to

  Table I, but this molybdenum content did not clearly

  varies with the content of the two previous oil changes, indicating that there is no wear

excessive motor.

Example 7

  A crankcase motor is taken from the crankcase.

  1982 S-10 "vrolet, fueled with a methanol fuel, which traveled 123,307 km with an oil change at a mileage of 5,215 km, an oil sample of about 98,68 % by weight of 30% by weight automotive lubricant "Kendall" and about 1.32% by weight of the lubricant additive of the present invention, comprising about 75.0% by weight

  weight of octadecylamine and about 25% by weight of

  tricresyl phosphate. The methanol fuel used is a mixture of 88.0% methanol / 12.0%

  unleaded natural gasoline (octane number 87).

  The oil sample has a base number of 3.3, which is well above the acceptable value of 2 for the base number, indicating that octadecylamine is not

  not exhausted and is still available to neutralize

  acid and minimize the oxidation of methanol.

  The spectrochemical analysis reveals that the quantities

  The following items of wear elements are present in the oil sample: 50 ppm iron; 10 ppm of

  lead; 56 ppm copper; 2 ppm of chromium; 9 ppm of aluminum

  minium; 0 ppm nickel; 0 ppm tin and 3 ppm

  molybdenum. The criteria after "break-in" of the

  I to evaluate the oil sample, since a mileage of 123 307 km represents a mileage

after break-in.

  Referring to Table I, it can be seen that iron, lead, copper, chromium, aluminum, nickel and tin contents are well within the average range of wear element contents, for these elements due to wear at one kilometer-traveled after break-in. The molybdenum content is considered as

  in Table I, but, as indicated in the examples

  8 and 9 below, there is no sudden change in the molybdenum content at the various oil changes,

  which indicates that there is no excessive wear of the

tor.

Example 8

  The crankcase of the same engine, fueled with methanol fuel, used in Example 7, is taken from the crankcase.

  and who traveled 130,646 km, a sample of

  taking about 98.68% by weight of the lubricant used in Example 7 and about 1.32% by weight of the lubricant additive used in Example 7. Thus, the previous oil change occurred at about 7,339 km less

that the present oil change.

  The basic index of the oil sample is

  3.64, which is well above the acceptable value.

  table of 2 for the basic index and indicates that the octahedron

decylamine is not exhausted.

  The spectrochemical analysis indicates that the quantities

  The following items of wear elements are present in the oil sample: 39 ppm iron; 9 ppm lead; 27 ppm copper; 2 ppm of chromium; 7 ppm aluminum;

  0 ppm nickel; 0 ppm tin and 11 ppm molybdenum.

  The contents of iron, lead, copper, chromium, aluminum

  Minium, nickel and tin are well within the framework of the average interval of contents in elements due to wear, for these elements due to wear at one kilometer traveled after running-in. The molybdenum content is considered as

  according to Table I, but there is no

  sudden change from the content at the time of the pre-

  oil change, described in Example 7, and this

  therefore does not indicate excessive wear of the motor.

EXAMPLE 9

  We take from the crankcase of the same engine, food

  mented into a methanol-based fuel used for

  examples 7 and 8, which traveled 137,330 km, an exchange of

  of about 98.68% by weight of the oil.

  A car refiner used in Examples 7 and 8 and

  about 1.32% by weight of the lubricant additive used

  Example 7 and 8. Thus, the previous oil change occurred at a mileage traveled 6684 km below that corresponding to the present oil change. The base index of the oil sample is 3.36, which is well above the value of 2,

  acceptable for the basic index and indicates that octadec

cylamine is not exhausted.

  The spectrochemical analysis reveals that the quantities

  The following items of wear elements are present in the oil sample: 39 ppm iron; 9 ppm of

  lead; 94 ppm copper; 2 ppm of chromium; 7 ppm of aluminum

  minium; 1 ppm nickel; 0 ppm tin and 12 ppm

  molybdenum. The sample is evaluated using the criteria

  Table I, corresponding to the mileage

after break-in.

  Referring to Table I, the iron, lead, chromium, aluminum, nickel and tin contents are well within the mean wear element content range for these elements. due to wear, for a distance traveled after break-in. The copper content is above average but not excessive. The molybdenum content is considered excessive according to Table I, but it increased only 1 ppm compared to the previous oil change described in Example 8, which indicates that there is no had

excessive wear of the motor.

  Extmple 10 On the -carter of a motor "Chevrolet S-10" 1982, powered by a methanol fuel, which ran the equivalent of about 12C 487 km, with a previous oil change to a lower mileage of

  approximately 6848 km, an oil sample comprising

  98.68% of 30% by weight automotive lubricant of "Kendall" 30 and about 1.32% by weight of the additive

  lubricant of the present invention, comprising

  75.0% by weight of octadecylamine and about 25.0% by weight of tricresyl paraphosphate. The methanol fuel used is a mixture of 88.0% methanol / 12.0%

  unleaded natural gasoline (octane number 87).

  The base index of the oil sample is about 3.02, which is well above the value

  acceptable by 2 for the basic index and indicates that the

tadecylamine is not used up.

  The spectrochemical analysis reveals that the quantities

  The following elements of wear elements are present in the oil sample: 130 ppm iron; 15 ppm of

  lead; 69 ppm copper; 4 ppm of chromium; 14 ppm of aluminum

  minium; 2 ppm nickel; 5 ppm tin and 11 molybdenum ppm. The oil sample is evaluated using the criteria of Table I corresponding to a mileage traveled "after break-in", since mileage of 126 487km

  represents a distance traveled after break-in.

  Referring to Table I, it can be seen that the contents of lead, copper, chromium, aluminum, nickel and tin are well within the mean range of wear element contents, for these elements due to wear at one kilometer traveled after break-in. Content

  iron is above average but is not excessively

  The molybdenum content is excessive according to the

  I but, as shown in examples 11 and 12, the

  Molybdenum does not vary suddenly from previously established values during any of the various oil changes, indicating that there is no

excessive wear of the motor.

Example 11

  We take from the crankcase of the same engine,

  methanol-based fuel, which is used, for example, in

  FIG. 10, which has traveled 131,872 km, an oil sample comprising about 98.68% by weight of the lubricant used in Example 10 and about 1.32% by weight of the additive.

  for lubricant used in Example 10. Thus, the preceding

  oil change occurred at mileage

  about 5385 km to that corresponding to the pre-

oil drain.

  The base index of the oil sample is 3.36, which is well above the acceptable value of 2 for the base index and indicates that octadecylamine

is not exhausted.

  The spectrochemical analysis reveals that the quantities

  The following elements of wear elements are present in the oil sample: 63 ppm iron; 10 ppm lead; 83 ppm copper, 3 ppm chromium; 9 ppm aluminum;

  2 ppm nickel; 0 ppm tin and 31 ppm molybdenum.

  The "after break-in" criteria in Table I are used for

evaluate the oil sample.

  Referring to Table I, we see that the contents of iron, lead, chromium, aluminum, nickel and tin

  fall within the average intervals of the

  in elements due to wear, for these elements due to

  wear observed at one kilometer traveled after break-in.

  The copper content is above average but not excessive. The molybdenum content is considered as

  excessive in Table I, but it does not vary

  compared to the previous molybdenum content, when

  of the previous oil change, as described in the example

  10. Thus the molybdenum content does not indicate excessive wear of the motor. In addition, the content of iron, lead,

  chromium, aluminum and tin decreases when we go from the example

  10 to 11, which indicates that the lubricant additive of the present invention effectively inhibits corrosion.

and engine wear.

Example 12

  We take from the crankcase of the same engine,

  mented into a methanol fuel, that

  10 and 11, which traveled 138,781 km, an oil sample comprising about 98.68% by weight of the lubricant used in Examples 10 and 11 and about 1.32% by weight of the lubricant additive used. Examples 10 and 11. Thus, the previous oil change occurred for a mileage less than 6909 km

  to that corresponding to the present oil change.

  The base index of the oil sample is approximately 2.91, which is well above the acceptable value of 2 for the base number and indicates that octadecylamine is not exhausted and is still available

  to neutralize the acids and prevent oxidation of the

  thanol to formaldehyde and formic acid.

  The spectrochemical analysis reveals that the quantities

  The following elements of wear elements are present in the sample: 70 ppm iron; 8 ppm lead; 22 ppm copper; 1 ppm of chromium; 12 ppm aluminum; 0 ppm nickel; 0 ppm tin and 17 ppm molybdenum. The oil sample is evaluated using the "after break-in" criteria in Table I. Referring to Table I, the iron, lead, copper, chromium, aluminum, nickel and tin contents are found in Table 1. inside the mean interval

  the contents of elements due to wear, for these ele-

  wear due to mileage after lapping. The molybdenum content is considered excessive according to Table I, but it has decreased since the previous oil change described in Example 11;

  which indicates that the lubricant additive effectively inhibits

  corrosion and prevent excessive wear and tear on the

  tor. In addition, lead, copper, chromium and

  nickel decreased in relation to the evaluation of the pre-

  the oil change described in Example II and the

  iron, lead, copper, chromium, nickel and tin decreased from the previous oil

  example 10, indicating that the lubricating additive

  of the present invention effectively inhibits corrosion and prevents excessive motor wear in

  an engine burning a fuel based on methanol.

Example 13

  The average base number in the evaluations of the oil samples described in Examples 1-12 is 3.15, which is well above the acceptable value of

2 for the basic index.

  The average content of wear elements in the evaluations of the oil samples described in Examples 1 to 12 is as follows: 57.8 ppm iron; 25.5 ppm of lead; 63.2 ppm copper; 1.8 ppm of chromium; 9.4 ppm aluminum; 1.2 ppm nickel; 5.25 ppm tin and

12.5 ppm molybdenum.

  All of the above results for wear element values representing the average results from the previous twelve examples are well within the average elemental content range.

  the wear and tear shown in Table I for one kilogram

  footage traveled after break-in, except for molybdenum.

  However, the excessive amounts of molybdenum, described in the previous twelve examples, do not indicate a

  excessive engine wear as there has never been any change

  abrupt comparison with a previous assessment for

the oil used.

  The average values of the basic index and the contents of elements due to wear described here

  illustrate that the lubricant additive of the present invention

  This invention effectively inhibits corrosion and prevents excessive wear of the engine in internal combustion engines burning fuels consisting of or containing

one or more alcohols.

Claims (29)

  1. Additive for lubricant for serving   in internal combustion engines burning fuel   based on alcohol (s) or containing one or more alcohols, an additive characterized in that it comprises a major proportion of an organic amine component (s) selected from the group consisting of   aromatic primary amines, the secondary amines aro-   aliphatic primary amines; the amines   secondary aliDhatics; cycloalkyl primary amines   pests, and their mixtures, and a minor proportion a phosphoric acid ester.   2. Lubricant additive according to claim   cation 1, characterized in that the amine content (s) is between about 68.75 and 75.0% by weight, and in that the phosphoric acid ester content is between about 25.0 and 31.25% by weight.   3. Additive for lubricant according to the   expansion! i, characterized in that the amine component is a mixture comprising an aliphatic primary amine   and an amine selected from aromatic primary amines   aromatic secondary amines and their mixtures.   4. Additive for lubricant according to the claim   1, characterized in that the amine component (s) is a mixture comprising an aliphatic secondary amine and an amine selected from aromatic amines,   aromatic secondary amines and mixtures thereof.   5. Additive for lubricant according to the claim   1, characterized in that the amine component (s) is a mixture comprising a cycloaliphatic primary amine and an amine chosen from aromatic primary amines,   aromatic secondary amines and mixtures thereof.   6. Additive for lubricant according to the claim   1, characterized in that the amine component is a primary amine aliphatic.   7. Additive for lubricant according to the claim   1, characterized in that the amine component is a aliphatic secondary amine.   8. Additive for lubricant according to the claim   1, characterized in that the amine component (s) is a mixture comprising an aliphatic primary amine and a cycloaliphatic primary amine.   9. Additive for lubricant according to the claim   1, characterized in that the amine component (s) is a mixture comprising a secondary-aliphatic amine and a cycloaliphatic primary amine.   10. Lubricant additive according to claim   cation 1, characterized in that the amine component (s)   takes a cycloaliphatic primary amine.   11. Lubricant additive according to claim   cation 1, characterized in that the amine component (s) is a mixture comprising an aromatic primary amine and a aromatic secondary amine.   12. Lubricant additive according to claim   cation 1, characterized in that the primary aromatic amine   tick is selected from ortho-phenylenediamine,   meta-phenylenediamine, para-phenylenediamine, ortho-   toluidine, metatoluidine, para-toluidine, animal   line, xylidine, naphthylamine, benzylamine,   toluenediamine and a naphthalenediamine   13. Lubricant additive according to claim   12, characterized in that the primary aromatic amine   tick is ortho-phenylenediamine.   14. Lubricant additive according to claim   cation 1, characterized in that the secondary aromatic amine   is selected from N-phenyl-2-naphthylamine, phenyl-alphanaphthylamine, phenyl-beta-naphthylamine, tolylnaphthylamine, diphenylamine, ditolylamine, phenyltolylamine, 4,4'-diaminodiphenylamine and N-methylaniline.   15. Lubricant additive according to claim   cation 14, characterized in that the secondary amine aro-   is N-phenyl-2-methylamine.   16. Lubricant additive according to claim   cation 1, characterized in that the aliphatic amine is   an aliphatic amine having 10 to 30 carbon atoms bone.   17. Lubricant additive according to claim   cation 16, characterized in that the aliphatic amine is octadecylamine.   18. Lubricant additive according to claim   cation 1, characterized in that the cycloaliphatic amine   is selected from cyclohexylamine and methylcyclo hexylamine.   19. Lubricant additive according to claim   cation 1, characterized in that the phosphoric acid ester   is selected from tricresyl orthophosphate,   tricresyl metaphosphate, triphosphate paraphosphate   cresyl, dibutyl phenyl phosphate, phos-   tributyl pte, tris (2-ethylhexyl) phosphate,   trioctyl phosphate, diphenyl orthophosphonate   nyle, dicrésyl orthophosphonate, orthophosphonate   of trilauryl and tristearyl orthophosphonate.   20. Lubricant additive according to claim   cation 19, characterized in that the phosphoric acid ester   Phoric is tricresyl paraphosphate.   21. Process for inhibiting corrosion and a   Excessive engine wear in an internal combustion engine   dye burning alcohol or fuel containing alcohol, characterized in that it comprises the step of adding to said engine a lubricant for an internal combustion engine selected from mineral oils and synthetic oils meeting a specific viscosity condition and meeting multiple conditions of   viscosity, having an SAE index of about 5 to 50, this   lubricant containing a lubricant additive comprising a major proportion of an organic amine component (s) selected from aromatic primary amines, amines   aromatic secondary, aliphatic primary amines   aliphatic secondary amines, primary amines   cycloaliphatic mayors and their mixtures, and a   minor portion of a phosphoric acid ester.   22. The method of claim 21, wherein   characterized in that the amine content (s) of the lubricant additive is between about 68.75 and 75.0% by weight and the phosphoric acid ester content of the lubricant additive is between approximately 25.0 and 31.25% by weight. -   23. The method of claim 21, wherein   in that the lubricant contains about 1.25 to   5% by weight of the lubricant additive.   24. Process for preparing a lubricant for an internal combustion engine, which inhibits corrosion and   excessive wear of the internal combustion engine   drinking alcohol or fuel containing alcohol,   characterized in that it comprises the step of   to mix a major proportion of a lubricant for an internal combustion engine, selected from mineral and synthetic oils meeting a single condition   viscosity and those meeting   viscosity ples, having an SAE value of about 5 to 50, and a minor proportion of a lubricant additive comprising a major proportion of an organic amine component, selected from aromatic primary amines, aromatic secondary amines, amines aliphatic primers, aliphatic secondary amines, cycloaliphatic primary amines and mixtures thereof, and   a minor proportion of a phosphoric acid ester.   25. The method of claim 24, wherein   characterized in that the amine content (s) of the lubricant additive is about 68.75 to 75.0% by weight and the phosphoric acid ester content of the additive for   lubricant is about 25.0 to 31.25% by weight.   26. The method of claim 24, wherein   in which about 89.5 to 98.75% by weight of the lubricant and about 1.25 to 10.5% by weight of the additive for lubricant.   27. A lubricant composition which inhibits corrosion and excessive wear of an internal combustion engine burning alcohol or a fuel containing alcohol, characterized in that it comprises   a major proportion of a motor lubricant to com-   internal combustion, selected from mineral and synthetic oils with a single viscosity condition   and those meeting multiple conditions of visco-   site, having an SAE index of about 5 to 50, and a proportion   minor addition of a lubricant additive comprising a major proportion of a 1-amine component; (s) selected organiqoe (s)   among the primary aromatic amines, the secondary amines   aromatic amines, aliphatic primary amines,   aliphatic secondary amines, the primary amines cy-   cloaliphatic drugs and their mixtures, and a half   of a phosphoric acid ester.   28. Lubricant composition according to the   in which the amine content (s) of the lubricant additive is about 68.75 to 75.0% by weight and the phosphoric acid ester content of the lubricant additive is from about 25.0 to 31.25% by weight.   29. Lubricant composition according to the   cation 27, characterized in that the lubricant content   is about 89.5 to 98.75% in weight and the additive content   for lubricant is about 1.25 to 10.5% by weight.