DK144178B - PURIFICATION ADDITIVE MIXTURE AS ADDITIVE TO DISTILLED CARBON HYDRADIC FUELS - Google Patents

Description

(19) DENMARK

6 (12) PUBLICATION OF 1441 78 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 4379/73 (51) lnt.CI.3 G 10 L 1/22 (22) Filing Day 9 * Aug. 1973 (24) Race day 9 · Aug. 1973 (41) Aim. available Feb 12 1974 (44) Submitted Jan 4 1982 (86) International application # - (86) International filing day - (85) Continuation day - (62) Master application no -

(30) Priority Aug 11 1972, 279891, US

(71) Applicant ROHM AND HAAS COMPANY, Philadelphia, US.

(72) Inventor Warren H. Machleder, US: Robert Roland Kuhn, US.

(74) Clerk Th. Ostenfeld Patentbureau A / S.

(54) Purification additive mixture as additive for distilled hydrocarbon fuels.

The present invention relates to a purifying additive composition as an additive for distilled hydrocarbon fuels, the majority of which is constituted by a hydrocarbon material which distils in the distillation range of gasoline.

Construction of modern internal combustion engines has changed in important areas and is still changing to meet stricter standards for engine and exhaust gas emissions. An important change in the design of engines is the supply or recycling of combustion gases, the so-called "blow-by" gases, from the crankcase in the engine to the carburettor's air intake instead of discharging these gases into the atmosphere, as has happened before. These gases -tf contain a substantial amount of substances which cause deposits, and it is known that they form deposits in and around the area Q where the carburetor throttle is located. These deposits prevent the flow of air through the carburetor at idle and at low speeds, so that 2 mm results in a bold fuel mixture. This condition produces uneven idling as well as engine shutdown and also causes too much hydrocarbon and carbon monoxide to be released through the exhaust to the atmosphere.

In addition to the changes that have already been made, additional requirements are expected for modern combustion engines and their fuels upon the emergence of new exhaust control devices, such as exhaust gas recirculation systems and catalytic exhaust silencers. Use of certain fuel additives, such as the purifying alkyl ammonium phosphates, must be restricted or eliminated, as catalytic exhaust silencers using metal catalysts will be poisoned by the phosphorus-containing compounds.

British Patent No. 1,258,549 discloses a motor fuel cleaning additive containing an amine salt of a phosphoric acid ester and a polybutene having a molecular weight of 400 to 3000. From US Patent No. 3,399,982 and British Patent No. 796,427 Furthermore, it is known that certain primary amines with tertiary alkyl counteract fuel deposition.

It has now been found that by combining (1) certain primary amines containing tertiary alkyl having a further branched carbon chain and a total of 6 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and (2) one or more surfactants ammonium carboxylates of a trimer or dimer acid (as hereinafter defined) ethoxylated and / or propoxylated alkyl phenol esters can obtain a purifying additive mixture which possesses not only carburetor purity but also hair rust inhibiting effect.

Accordingly, the present invention provides a purifying additive composition as an additive for distilled hydrocarbon fuels, the majority of which is constituted by a hydrocarbon material distilling in the gasoline distillation range, which purifying additive comprises a mixture of (1) 20 or 250 parts by weight. several amines of the general formula: R2 R1 - C - NH7 '3 R · 5 wherein R1, R2 and R3 are alkyl groups whose total content of carbon atoms is from 5 to 23 and of which at least one is branched, (2) 10 to 100 parts by weight of one or more surfactant alkyl ammonium carboxylates of a timer or dimer, ethoxylated and / or propoxylated alkyl phenol esters of the formula: Θ ®NH 3 R 6] y wherein - in the case of a single compound - n is a number between 1 , 5 and 12.5, or in the case of a mixture of compounds, n is an average value of 1.5 to 12.5 and wherein x represents 1 or 2 and y 1 or 2, the sum n of x + y is 3, in the case of a salt ester derived from a trimeric acid, and wherein both x and y represent 1, in the case of a salt ester derived from a dimer acid, A represents ethylene oxide or propylene oxide. represents an alkyl group containing 4-12 carbon atoms, represents H or an alkyl group containing 4-12 carbon atoms, R 4 represents an alkyl group containing 2-24 carbon atoms, which group may be straight or branched or be an amine-substituted alkyl group of 2-24 carbon atoms, and wherein Z represents a saturated or unsaturated hydrocarbon residue, the hydrocarbon residue having from 34 to 51 carbon atoms.

If, in addition to carburetor purity and rust inhibitory action, particular attention is paid to the control of deposits in the intake system, the purifying additive mixture can be further added to a polybutene. Thus, according to a preferred embodiment of the invention, the purifying additive mixture further contains (3) 150-650 parts by weight of hydrocarbon soluble polybutene having a number average molecular weight (Mn) of 700 to 3000. The polybutene preferably has a viscosity of 9000 to 900,000 S.U.S. at 38 ° C and a viscosity of 300 to 20,000 S.U.S. at 99 ° C.

Therefore, the compositions in question are usually liquid mixtures for addition to distilled hydrocarbon fuels, the majority of which are constituted by a hydrocarbon material which distils in the distillation range of gasoline, e.g. gasoline containing lead in normal or low quantity, or unleaded gasoline.

An advantageous combination of effect and price is obtained for component (1) when present in an amount of 50 - 100 parts by weight, for component (2) when present in an amount of 4 T44T78 25 - 50 for parts (3), when present in an amount of 200-400 parts by weight.

The additive mixture of components (1) and (2) can at the concentration at which the treatment takes place, i. in the concentration applicable to gasoline is added or used in the gasoline at a total concentration of 30 to 350 ppm (weight basis). When both components (1), (2) and (3) are included in the additive mixture, it can be added or used at a total concentration of 180 to 1000 ppm (weight basis).

For the purposes of the present disclosure, the primary amine component of t-alkyl or tertiary (tertiary) alkyl is defined as a compound comprising one or more amines of the general formula (I): R1

2 I

R - C - NH9 (I)

I L

1 3 R-5 in 2 3 wherein R, R and R are alkyl groups whose total carbon atom content is from 5 to 23 and at least one alkyl group is branched. It is preferred that two of the R groups, e.g. R and R in the primary amine containing tertiary alkyl are methyl groups.

The primary amines containing tertiary alkyl, which amines can be used in the present composition, comprise e.g. t-octylamine, t-nonylamine, t-dodecylamine, t-tetradecylamine, t-octadecylamine, t-docosylamine, t-tetracosylamine, and mixtures of two or more of these. These amines are generally prepared by known reactions such as reacting nitriles with alkenes or secondary or tertiary alcohols in highly acidic medium. According to the invention, it is preferred that the primary amine containing tertiary alkyl (1) has a carbon atom content of 12 to 22 carbon atoms, since such amines are readily available commercial products. Commercially available primary tertiary alkyl amines are often mixtures, t-octylamine having a branched structure having the formula: CH, CH, I 3 in 3 3 I 2 in 2 ch 3 ch 3 and the alkyl group of this amine will hereinafter be referred to as t . A form of t-nonylamine is prepared as a mixture containing 5144178 C6H13C2 CH3 ^ 2NH2 and C7H1SCiCH3) 2NH2 and has a neutralization equivalent of approx. 142. A commercial product useful in the present invention is available under the trademark "Primene 81-R", which is a mixture of t-dodecyl, t-tridecyl and t-tetradecylamines, or substantially a mixture of of tC- ^ 2 ^ 25 ^ 2 t-C14 ^ 29 ^ 2 amines with a neutralization equivalent of ca. 191. Another commercial product useful in the present invention is available under the trademark "Primene JM-T" which is essentially a mixture of t-ClgH37NH2 to ^ - ^ 2 ^ 45 ^ 2 'and having a neutralization equivalent of approx. 315. It is important here that the NH 2 group in a primary amine containing tertiary alkyl is always attached to a carbon atom which does not contain hydrogen atoms, and in accordance with the present invention is at least one of the alkyl groups attached to the carbon atom, branched.

The alkyl ammonium salt of the ethoxylated and / or propoxylated alkyl phenol esters of the trimers or dimers has the formula (II); ,> · «> .- <gr ·; λ VCO 2 ® ® NH 3 R 6 / y wherein - in the case of a single compound - n represents a number between 1.5 and 12.5, or in the case of a mixture of compounds, n represents an average number from 1.5 to 12, 5, where n is preferably from 3 to 10, and in the case of a salt ester derived from a trimeric acid x represents 1 or 2, and y 1 or 2, the sum of x + y being 3, and in the case that the salt ester is derived from a dimeric acid, both x and y represent 1; A represents ethylene oxide or propylene oxide, represents an alkyl group containing 4 to 12 carbon atoms, R 5 represents H or an alkyl group containing 4 to 12 carbon atoms, R 2 represents an alkyl group containing 2 to 24 carbon atoms, with 2-24 carbon atoms (preferably R 1 contains 12-22 carbon atoms), and Z represents a saturated or unsaturated hydrocarbon group, the hydrocarbon group having from 34 to 51 carbon atoms.

Due to the availability of the materials, it is preferred that n represents 3-10, especially 3, x represents 2, y represents 1, and Z represents a hydrocarbon residue of 51 carbon atoms in the formula for component (2).

This product is primarily incorporated to provide protection against rust and corrosion, although it also has a modest carburetor cleansing activity.

The alkyl ammonium carboxylate ester, i.e. component C2), can be used as a derivative of exclusively trimeric acid or as a derivative of only dimeric acid, or any mixture of dimeric and trimeric acid derivatives can be used.

Presence of C ^ g monocarboxylic acids or the like in ester or salt form or mixtures of both ester and salt form can be tolerated in minor amounts, i.e. ca. 5¾ or less.

Examples of some of the salt esters which can be used in additive compositions of the invention are listed in the following Table I.

Table I

alkylammonium

carboxylate ester n R X Y

A 1.5 t "C12_i4 1 2 B 1.5 t_c12-i4 2 1 C 3 ^ ~ ^ 12-14 1 2 * * - £." * *. E · 5 t_ci2-i4 1 2 7.5 t-C12_i4 1 2 G 9.5 t-C12_14 1 2 H 9.5 t "c12_i4 2 1 I 12.5 t-C12_i4 1 2 J 3 CH2CH2NH2 2 1 K 3 (CH3CH2NH) 2H 2 1 L 3 (CH2CH2NH) 3H 2 1 M 1.5 t-C12_,. 1 1 "3 t-Ci2-14 1 1 0 9.5 t- ^ l2-14 1 1 7 144178

The polybutene component (if present) comprises substantially polyisobutenes (i.e., polybutene in which each monomer unit in the polymer chain is derived from isobutene) or polybutene wherein the butylene units are derived from 1-butene or 2-butene, or copolymers of various butenes under provided that the polybutene is a liquid at normal temperatures and has a molecular weight and preferred viscosity as previously stated. For the sake of availability and overall characteristics, polyisobutenes are preferred. The term polyisobutylene (or the equivalent term polyisobutylene), as used herein, encompasses polymers which in the polymer chain may have incorporated smaller amounts of 1-butene and 2-butene units. The polyisobutylene is conveniently obtained by polymerizing the isobutylene or mixtures of the isobutylene with small amounts of 1-butene and / or 2-butene in accordance with known methods. The polybutenes which can be used in accordance with the present invention are commercially available. Further examples and descriptive literature relating to the useful polybutene can be found in British Patent Specification No. 1,258,549.

The molecular weights referred to above are the number average molecular weights determined by vapor pressure osmometry in accordance with ASTM-D - 2503. Accordingly, in accordance with the present invention, the polybutene component has molecular weights in the range of from 700 to 3000 and is mixtures of polybutene molecules having an average of about 12 to about 10. 54 C 2 Hg units in the polymer chain, each molecule containing an olefinic double bond which can be determined analytically by titration with bromine in accordance with common methods such as ASTM-D-1159.

The molecular weight and molecular weight distribution among the polybutene molecules in these mixtures are such that the viscosities of these normally liquid materials are in the range of 9000 S.U.S. at 38 ° C and from 300 S.U.S. at 99 ° C for the low molecular weight polymers (700) to 900,000 S.U.S. at 38 ° C and 20,000 S.U.S. at 99 ° C for the high molecular weight polymers (3000), the viscosities determined in accordance with ASTM D-445 and 446.

Among polybutzenes useful in accordance with the present invention, those having a molecular weight in the range of 950 to 1400 and viscosities in the range of 1050 to 2990 S.U.S. at 99 ° C and in the range of 40,000 to 123,000 S.U.S. at 38 ° C as they are readily available commercial products. Preferably, the polybutzenes are primarily (80¾ or more) polyisobutylene or polyisobutylene. Mixtures of two or more of the various polybutenes may be used if desired.

The polybutenes are the preferred additive for controlling deposits in the intake system (ISD). However, the polybutene can be completely or partially replaced by mineral oil for ISD control, or the polybutene or mineral oil can be completely omitted where ISD control is not considered necessary or where other additives are used for ISD control. The alkyl ammonium carboxylate ester can e.g. in the case of the diester mono salt, is known in the art by acid-catalyzed esterification of a suitable trimer or dimer acid with two molecules of a suitable ethoxylated alkyl phenol followed by conversion of the residual carboxylic acid function to an alkyl ammonium carboxylate by the addition of a suitable amine.

The trimeric acid may be the product resulting from the trimerization of a Clg unsaturated fatty acid; An example of a suitable trimeric acid is the acid available under the trademark "Empol 1041". A general reaction scheme for the preparation of the alkylammonium carboxylate ester is shown below.

/ 1) acid c5l (c ° 2H) 3 + 2H0 (CH2CH2O) n- / QA ->. \ 2) -2H90

Trim acid \ Λ ώ 1) acid // C02tCH2CH20) n- (Q Λ - »C \ 7 ^ -R5

2) -2H20 51 ^ CO2H

^ 02tCH2CH20) 3- (0VR J

C51 \ p 5 CO2e ® NH3R6 wherein k, R3, and R4 have the meanings previously defined and are the hydrocarbon group of the hydrocarbon group.

In the following examples which illustrate the preferred embodiments of the present invention, all percentages and percentages are by weight unless otherwise noted. The ability of the additive compositions of the present invention for purification and purification of an internal combustion engine carburetor is illustrated by the carburetor purity engine test described below. The gasoline used in the engine tests illustrated in Tables II and III (an MS-08 gasoline) has the following characteristics.

Density 59.7

API

Specific density at 15.6 ° C 0.74

ASTM D-86 distillation, ° C

Initial boiling point 34 10¾ 51 50¾ 96 90¾ 176

Final boiling point 207 ¾ recovered 98% residue 1% loss 1% sulfur 0.11

Lead, g / liter 0.81 FIA composition

Aromatics,% 23.1

Olefins, ¾ 20.0 Saturated Compounds, ¾ 56.9

Oxidation stability, minutes 600 + ASTM Gum (greasy), mg / 100 ml 1.0 "Research" octane number 95.5 ° SH 13.10 IC 86.61 H / C 1.80 10 144178

Assessment of multi-function carburetor cleaners through engine testing _________ A. Carburetor cleanup test for "blowby" gases throttle clean and performed on a 1970 "Ford" 351 CID V-8 engine equipped with two single-chambered carburetors using a special "Y" intake manifold, which carburetors can be independently adjusted and activated. By means of this arrangement, a separate test of fuel can be carried out by means of each carburetor which feeds four of the eight cylinders via unrelated intake manifolds. The carburetors are modified with removable aluminum linings to facilitate the weighing of the deposits which accumulate in the throttle area. The load on the test is set to an appropriate level by recirculating the entire amount of gases from the bottom vessel, approximately 90-110 CFH, to the top of the air filter so that each carburetor receives the same amount of these gases. During the first hour of operation, the flow of suction mixture in the two carburetors is adjusted to the same value by means of the differential pressure in the suction manifold and analysis of CO in the exhaust gas. The following test cycle and operating conditions were used:

Attempts Cycle:

Phase I 650 rpm minute for 8 minutes

Phase II 3000 rpm minute for 1 minute

Trial duration, hours 10

Suction temperature ° C 135 in 10 Cooling water ° C 190 t 10

Bottom temperature ° C 99 t 6% CO in exhaust gas 3.0 iol 0.2 Blowby gas CFH 90 - 110 The weight (mg) of the deposits collected in the aluminum lining was measured and the average value for each additive or additive mixture was given. for four tests.

11 144178

Table II

Carburetor clean-up test for "blowby" gases

Example Additive Concentration of Deposition weight in additive ppm (in gasoline) mg (average of _ _ ___ 4 measurements) _

Control Untreated - 15.9 gasoline 1 I + II2 ^ 50/25 2.3 21 50 1.7 3 II 50 8.6 4 I + II + III 50/25/440 2.6 5 IV 50 3.3 v The additive component I is a tertiary C12-CU alkylamine having a highly branched carbon chain as well as a molecular weight substantially in the range of 185-213, and the component has a neutralization equivalent of 191; the additive component II is essentially a alkylammonium carboxylate ester of formula (III): ³² / CO₂ (CH₂CH₂O) ³ (O / C8H17 - 2 Z1 \ - (ΠΙ) ³CO₂) NH3 t-c from the trimerization of an unsaturated C ^g fatty acid, the trimeric acid being, for example, "Empol 1041". It is assumed that "Empol 1041" is a mixture of about 90a trimeric acid (Cg The additive component III is a hydrocarbon soluble polyisobutylene having a number average molecular weight (Mn) of about 1000, the additive component IV is a tertiary C 1-6 alkylamine having a highly branched carbon chain and a molecular weight, as in the molecular weight, e ranges from 269 to 325 and this amine has a neutralization equivalent of 315.

It can be seen from Table II that the additive mixture of Example 1, which contains 50 parts of Component I admixed with 25 parts of Component II, is as effective a carburetor cleaning agent as the mixture of Example 4. The effectiveness of the carburetor cleaning is shown by the weight of the deposits, of deposits denotes a more effective carburetor cleanser. Thus, the untreated MS-08 12 144178 gasoline gave a deposition weight of 15.9 mg in the purity test, whereas the mixture of Example 1 gave only 2.3 mg and the mixture of Example 4 gave only 2.6 mg of deposits, the latter results being significant better than that obtained by the untreated gasoline. It is also apparent from Table II that Component II has carburetor cleansing properties in addition to the fact that, as will be shown below, it has rust inhibitory properties.

B, Carburetor purification test for "blowby" gases

To measure the ability of gasoline additives to clean deposits in a carburetor's throttle area, a carburetor purge test is performed in connection with "blowby" gases (BBCDT-Clean Up). The process is similar to that used for the "BBCDT-Keep Clean" process, except that the carburetor's aluminum liners are first soiled by running with untreated MS-08 gasoline, and then purified by running with additive-treated gasoline. The test results are recorded as the weight in mg of the deposits that are collected and then removed from the linings and are reported as percentage purification.

Table III

Carburetor cleaning test in connection with "blowby" gases

Example Additive Component (s) Concentration Percentage Purification ppm (average of 4 of- (_____________ _______ tests) _ 6 Ι + ΙΙχ) 50/25 19.5 71 50 16.3 8 I + II + III 50/25/300 19 , 6 9 IV 50 23.9 x · ^ The additive components I, II, III and IV are the same as previously stated. In the purification test, the efficiency of the additive mixtures is higher the higher the percent purification. It is therefore clear from Table III that considerable purification is provided in Examples 6 and 8. The untreated MS-08 gasoline, ie. gasoline without additives, gave a value of -22.3¾ purification, ie. a further soiling of 22.3¾.

13 144178 C. Carburetor Cleaning Test Using Auxiliary Engine __________

The carburetor purity test using auxiliary engine ('sECDT') is similar to the "BBCDT11 sample except that the severity of the sample is adjusted to an appropriate level by dosing a proportion of the exhaust gases from the" Labeco "auxiliary engine to the top of the" Ford engine carburetor air filter. . It is intended to simulate the use of exhaust gas recirculation (EGR) systems, such as the systems developed by the automobile industry to facilitate exhaust pollution control.

Table IV

Carburetor cleaning test using auxiliary motor

Example Additive Component (s) Concentration Deposits _ ______ ppm (in gasoline) weight in mg control untreated gasoline ^ - - 10.0 10 1 + II 50/25 1.9 11 I 50 2.4 12 IIx) 25 4.1 x ) Additive components I and II are the same as previously stated.

^ The gasoline used in the test listed in Table IV is unleaded gasoline and has the following characteristics: "Research" octane number (RON) 91.2-91.0

Distillation 0 C_

Initial boiling point 31.1-32.2 10¾ 52.2-54.4 50¾ 101.1-106.7 90¾ 172.8-175.0

Final boiling point 196.1-212.2

FIA

¾ aromatics 23.9-25.9 ¾ olefins 18.7-15.8 ¾ saturated compounds 57.4-58.3% by weight of natural sulfur 0.088-0.084 mg Gum (washed) 0.8

Lead ppm 0.8-1.8 14 144178

It can be seen from Table IV that the mixing of components I and II provides at least the deposits expressed in mg in this test of the carburetor's ability to keep clean.

D. Intake system deposition sample 1. Procedure of the sample

The intake system deposition test (ISDT), which is used to assess the ability of gasoline additives or gasoline additive mixtures to control deposits in the intake system, is performed for each test using a 2.5 horsepower feriggs and Stratton "air-cooled single-cylinder 4-stroke engine. for 150 hours at 3000 rpm and a load of 0.58 kgm with a 1 hour break for every 10 hours to check the oil level.Each hourly measurements of carbon monoxide emissions in the exhaust gas to ensure a constant ratio of air and fuel (A / F).

At the end of a series of tests, the engine is partially disassembled and the intake valve and valve seat are visually assessed, after which deposits on valve and valve seat are collected and weighed.

Table V

Indsugningssystemaflejringsprøve

Example Additive Concentration Valve and valve - ppm Ci gasoline) seed rings in mg 13 untreated gasoline ^ - 475. 14 I + II 250/25 977 15 I + II + IIIX) 250/25/300 446

The additive components I, II and III are the same as previously mentioned.

* · The untreated gasoline was the same one used for the sample referred to in Table IV. Example 15 comprises the mixing of Components I, II and III and shows improved control of deposits in the intake system, recalling that Components I and II must be added for carburetor cleansing and rust inhibition.

15 144178

Table VI

Rust Inhibition Test (ASTM-D-665)

Example Additive Concentration Rusted area,% _ _ red_ _ 16 Isooctane (control) - 80 17 I + II 250/20 1 18 I 250 65 19 II 20 2

Additive components I and II are the same as previously stated.

The above Table VI shows that the mixture of I and II provides good rust inhibition and provides a very pronounced improvement over the component (I), ie. only 1% rusted area compared to 65¾ rusted area in the above ASTM test.

As previously stated, the polyisobutylene (or polybutene) component may be completely omitted (where control of deposits in the intake system is not deemed necessary), or may be replaced in whole or in part by mineral oil to control deposits in the intake system. However, where mineral oil is used, it must generally be used at a greater concentration for suction system deposition control, e.g. in a concentration which is approx. 2-5 times as high as the required polybutene component concentration.

The fuel mixtures may also contain one or more of the following normal fuel additives:

Anti-banking agents, ignition accelerators, combustion enhancers, power enhancement agents, cold start assistants, self-ignition inhibitors, antioxidants, gum inhibitors, corrosion inhibitors, sludge inhibitors, color stabilizers, other cleaners, metal deactivators, stabilizers, stabilizers, stabilizers, stabilizers, stabilizers, , stabilizers for metal carbonyls, surfactants, modifiers or antifouling agents, resin inhibitors, upper barrel lubricants, neutralizers, octane booster requirements, surface ignition inhibitors, spark plug coke inhibitors, foam inhibitors, evaporative and solubility enhancers, fragrance inhibitors, fragrance marking agents, anti-icing agents, decolorizers, fragrances, identification markers, freezing agents point, means for lowering flammability.

Claims (2)

It is sometimes desirable to incorporate a smaller amount of alcohol such as n-butanol, e.g. 5-15% by weight, in the additive mixture of the three components to form a non-distinct solution of the three combined components to improve the use properties. 1. Purification additive composition as an additive for distilled hydrocarbon fuels, the majority of which is a hydrocarbon material distilling in the distillation range of gasoline, characterized in that it comprises a mixture of (1) 20-250 parts by weight of one or more amines of the general formula: R2 in · R 1 - C - NH 7 13 12 wherein R, R and R are alkyl groups whose total carbon atoms are from 5 to 23 and at least one of which is branched, (2) 10 to 100 parts by weight of one or more surfactant alkyl ammonium carboxylates of a trimer or dimer ethoxylated and / or propoxylated alkyl phenol ester of the formula: z ^ cc (a) n _ <^ E5] χ "Nco Θ © NH, R6] 2. y