DE1144971B - Hydrocarbon fuel from the gasoline boiling range - Google Patents

Description

GERMAN

PATENT OFFICE

T15730 IVc / 46a6

REGISTRATION DAY:

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:

OCTOBER 8, 1958

MARCH 7, 1963

The invention relates to a hydrocarbon fuel in the gasoline boiling range with a high octane number.

The recent increases in compression ratios of automotive engines are putting on petroleum refining plants great demands inasmuch as fuels with the one required for these engines Octane number must be produced. Premium fuels currently have research octane numbers between 97 and 100. To produce first-class fuels with octane numbers of 97 and more, one was previously on catalytic manufacturing processes, z. B. the liquid catalytic cracking, catalytic Reforming, alkylation and catalytic isomerization.

The catalytic cracking and reforming processes produce considerable amounts of aromatic compounds. The catalytic cracking also leads to the formation of a substantial one Amount of olefins. It is known that olefins and aromatics, despite their high octane numbers, are based on organic lead compounds, such as tetraethyl lead, are less responsive than saturated aliphatic gasoline components. Since the content of aromatics and olefins in petrol has risen to the extent of the modern Automotive engines with high compression ratios to achieve required octane levels has the response to lead is reduced in these fuels. In other words, the addition an organic lead compound achievable octane value increase decreases to the extent to which the The aromatic and olefin content of the base fuel increases.

It has now been found that the octane value of leaded motor fuels is a substantial amount high octane components; d. H. Contain aromatics, olefins and their mixtures, can be increased significantly by adding certain octane improvers described below can.

The invention relates to a hydrocarbon fuel with the boiling range of gasoline, which contains an organic lead anti-knock agent and at least 10% of components of olefinic or aromatic hydrocarbons or their mixtures with a high octane number (80 and more), characterized by a content of at least 0, 1 percent by volume, but not more than 5 percent by volume, of one or more monocarboxylic acids of the general formula R — COOH, in which R denotes a hydrocarbon radical with 1 to 29 carbon atoms, or the following compounds: t-alkyl esters of the general formula hydrocarbon fuel
from the gasoline boiling range

Applicant:

Texaco Development Corporation,
New York, NY (V. St. A.)

Representative:

Dr. W. Beil and A. Hoeppener, lawyers,
Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority

V. St. v. America from October 2nd, December 2nd,
December 23, 1957, March 7, March 10, April 14, June 19

and June 27, 1958

(No. 689 466, 699 942, 699 943, 699 944, 704303, 719 750, 720 014, 728 089, 743 001 and 744929)

George Walter Eckert, Wappingers Falls, N.Y.,

Howard Vincent Hess, Glenham, NY,
and Edwin Chandler Knowles, Flower Hill,
Poughkeepsie, NY (V. St. A.),
have been named as inventors

2

RCOOR ', where R is a hydrogen atom or a hydrocarbon radical with 1 to 29 carbon atoms and R' is a hydrogen atom or a tertiary aliphatic hydrocarbon radical with 4 to 18 carbon atoms; Etheric acids of the general formula R ² OR ³ COOH, in which R ^{2 is} a monovalent hydrocarbon radical with 1 to 18 carbon atoms and R ^{8 is} a divalent hydrocarbon radical with 1 to 12 carbon atoms; Keto acids of the general formula R ⁴ COR ⁵ COOH, in which R ^{4 is} a monovalent hydrocarbon radical with 1 to 27 carbon atoms and R ^{5 is} a divalent hydrocarbon radical with 1 to 18 carbon atoms; Acid anhydrides of the formula

RC;

:O

RC

in which R is a hydrocarbon radical with 1 to 29 carbon atoms

309 538/217

3 4

The new fuel mixtures should be at least

30 carbon atoms per molecule, and aldehydes have 10 percent by volume of aromatic and / or olefin constituents Formula RGHO, in which R contains a hydrocarbon part. The aromatic and / or olefin radical with 1 to 29 carbon atoms is part of the engine power according to the invention

Effective sweet number improvers of the above formulas S substances can make up up to 100 percent by volume, are: Monocarboxylic acids with 1 to 30 carbon atoms are usually 20 to 80 percent by volume, as well as urn anhydrides, ketocarboxylic acids, ether- The minimum content of 10% is for the monocarboxylic acids of the invention , t-alkyl esters of the monocarbo-proper octane number improvers considered necessary, acidic and -aldehydes with 2 to 30 carbon atoms. The one to achieve a significant increase in octane number. T-alkyl esters generally decompose while the engine is working. The aromatic constituents of the new engine are converted to olefins and monocarboxylic acids. The aldehydes oxidize in situ during the kung process. The catalytic reformied of the operation of the engine to the monocarboxylic acids. tion product has a particularly high content. The octane improver can also be used as a syn- 15 in aromatics. The olefin constituents of the new ergistic additive mixture with at least engine fuel are obtained either by mixing 0.1 percent by volume of one or more arylamines or by using catalytic cracking or by using the general formula R ³ NHR *, polymerization.

where R ^{3 is} a mono- or acyclic aryl or organic lead reagent that is used for the invention

If an alkaryl radical with 6 to 16 carbon atoms is required and an improvement in the octane number is required, R ^{4 is} hydrogen or a hydrocarbon radical with a tetraalkyl lead compound. Almost always 1 to 12 carbon atoms. It has been found that tetraethyl lead is used as an anti-knock agent, primary and secondary arylamines synergistically but also have other tetraalkyl compounds that react with octane improvers of the above formulas such as tetramethyl lead, tetrabutyl lead, tetraamyl lead or, and thus the octane value, leaded petrol with the prescribed tetrapropyl lead and can have anti-knock properties Improve content of aromatics and / or thus in the new fuel mixtures in connection with olefins. used with monocarboxylic acids and derivatives

The effect of the octane number according to the invention will be.

improved on increasing the octane value of the commercially available tetraethyl lead mixtures

Gasoline is notable for its various types of unusual 30 for motor vehicles as an engine detergent borrowed features. The first characteristic consists of an ethylene chloride-ethylene bromide mixture to the lead in that the octane improvers take an increase out of the combustion chamber in the form of volatile the octane value of gasolines only then causes lead halides to be removed. The following in the appear when an organic lead anti-knock agent used illustrative examples Usually tetraethyl lead, part of petrol 35 The term "tetraethyl lead liquid" denotes this mixed is. - Commercial product made from tetraethyl lead, ethylene

The second unusual feature, which consists of the active chloride and ethylene bromide, the two effects of the octane improvers according to the invention, the latter reagents being contained in a theoretical amount of 1.0 and 0.5 to increase the knock resistance of gasolines. What matters is that equal amounts of the 40 "theoretical amount" are the stoichiometric amount of additive above an octane number of 100 that is required for the reaction with the lead containing the anti-knock properties more than below a lead containing tetraethyl lead.
Octane number of 100. For example, the organic lead reagent is in the new

Base fuel with an octane number of 105 contain a fuel mixture in quantities of 0.13 cm ³ / l up to an increase in the octane number on the research scale by 45 to the legally stipulated limit, 3.9 units with 0.5 percent by weight of 2-ethylhexane at the moment for motor vehicle fuel 0.8 cm ³ / l acid achieved, while in a base fuel with and for aircraft fuel is 1.22 cm ³ / l. The octane number of 96.6 usually used with the same amount of tetraethyl lead in 2-ethylhexanoic acid is only an increase of 2.3 one for motor vehicle gasoline 0.3 to 0.8 cm ³ / l and was achieved for units. The third surprising 50 aircraft gasoline 0.5 to 1.2 cm ³ / !.
Feature that the effect of the invention The effect of the octane number according to the invention

Octane improver distinguishes, is that improver is obviously based on a function this has no significant effect on the octane number of the carboxylic acid residue - COOH, since it is aliphatic one consisting essentially of saturated aliphatic monocarboxylic acids, aryl monocarboxylic acids, cyclo-hydrocarbons existing gasoline remain, 55 aliphatic monocarboxylic acids and compounds, even if this is an organic lead anti-knock agent, which is in situ while the engine is working in this contains. Since organic lead anti-knock agents are the largest converted, such as t-alkyl esters of mono-octane number increases in predominantly saturated carboxylic acids and aldehydes, an increase in the Hydrogen fuels based on paraffin and the octane value of leaded fuels with the previous Octane number of gasolines with a high content of 60 written content of aromatics and / or ole-aromatics and least affect olefins, effect finen.

The present invention simply complements the lead examples of effective monocarboxylic acids are: Amei-

tetraethyl as an octane improver. Monocarboxylic acid, acetic acid, propionic acid, caproic acid, acids and derivatives of the prescribed formula 2-ethylhexanoic acid, capric acid, lauric acid, stearin have Then the least effect is when lead tetraic acid, behenic acid, cumic acid, benzoic acid, cinnamon ethyl exerts the greatest effect, and then have acid, cyclohexanecarboxylic acid, phenylacetic acid and the greatest effect on the octane number when the the anhydrides derived from it. Examples more effective Effect of tetraethyl lead is the least. Ether and ketomonocarboxylic acids are: methoxy

acetic acid, ethoxyacetic acid, phenoxyacetic acid, 3-ethoxypropionic acid, o-ethoxybenzoic acid, levulinic acid, 4-ketostearic acid, 3-oxo-n-hexanoic acid and Si-phjenyl-3-oxopropanoic acid.

t-Alkyl esters of monocarboxylic acids are special preferred oetane number improvers for industrial consumption, as they are made from readily available materials, i.e. H, from olefins and monocarboxylic acids and because they are essentially non-corrosive Add ester. However, the new rule according to the invention is missing for these fuels! being in the rest the amount of aromatics added is not specified, d. that is, the amount of the particular additive 0.1 to 5 percent by volume must be in order to increase the octane value above that previously achieved To produce maximum values.

Table I shows the effect of the oetane number improvers according to the invention on the octane number of an example of effective t-alkyl esters are: t-butyl fuel with a high content of acetate, t-butyl formate, t-amyl propionate, t-amyl capro aromatics. Cinnamon t-octyl ester and t-butyl benzoate are added as base gasoline to which the various at, t-butyl laurate, cyclohexanecarboxylic acid t-amyl ester * compounds are added in the specified amount. The preferred was a catalytically reformed crude petrol added t-alkyl esters made from aliphatic and containing 0.8 cm ³ / l lead tetraethyl liquid (BTÄ) aromatic monocarboxylic acids with 1 to 14C-15 and an initial boiling point of 54 ^P C and atoms had a final boiling point of 201 ⁰ C of a t-aliphatic hydrocarbon. Derived from the basic residue with 4 to 12 carbon atoms. fuel had a research octane examples of effective aldehydes are: benzaldehyde, number (RON) of 96.6 and an aromatic content of n-butyraldehyde, isobutyraldehyde, propionaldehyde, 48 percent by volume, as indicated by »fluorescence indicator acetaldehyde, paraldehyde, the one Trimer of the acetal analysis (FIA) method «was measured,
dehyds is, laurylaldehyde and tolylaldehyde.

The octane number improvers according to the invention must in the new, leaded mixtures containing aromatics and / or olefins in an amount of at least 0.1 volume percent to achieve a significant increase in octane number. Is the Amount of the octane improver less than about 0.1 volume percent will be in the leaded gasolines the composition prescribed here

Table I.

Octane improver

Research octane numbers in

Base fuel with a

original octane value

of 96.6 percent acid

0.05 I 0.1

no increase in octane number achieved. The preferred formic acid
The added amount of octane improver is 0.2 acetic acid
up to 1.5 percent by volume, with a maximum increase
the octane number is generally achieved at a concentration of about 0.5 to 1.0 percent by volume.

In the case of most octane improvers, the increase in the octane value decreases when the concentration increases exceeds about 1.5 percent by volume. The oetane number improver can be used in an amount of 5.0 percent by volume can be used, but the use of such concentrations is not only for economic reasons Considerations rejected out, but it adds that at these higher concentrations a slight decrease in the octane number occurs.

Examples of aryl amines with tertiary alkyl esters form anti-knock additives that act synergistically from monocarboxylic acids are: aniline, N-methylaniline, N-ethylaniline, N-isopropylaniline, N-t-butylaniline, N-n-butylaniline, o-toluidine, p-toluidine, m-toluidine, N-methyl-o-toluidine, N-ethyl-o-toluidine, N-tert-butyl-p-toluidine, diphenylamine, amine, di- (o-methylphenyl) -amine.

The arylamines must be used in an amount of at least 0.1 percent by volume in order to achieve a significant synergistic increase in the octane value at the prescribed concentration of the octane improver to achieve. The preferred concentration of the synergistic effect in the inventive The arylamine anti-knock additive used is 0.2 to 1.0 percent by volume. Although can arylamine concentration of up to 5 percent by volume as a synergistic additive with tertiary alkyl esters can be used, but for economic reasons, such concentrations in the im Commercial fuel blends rejected. So is the upper limit of the arylamine concentration set at approximately 2.0 percent by volume.

It is already known to leaded, aromatic fuels organic acids, their anhydrides or

Propionic acid

Caproic acid

n-heptanoic acid

Pelargonic acid

Capric acid

Lauric acid

Myristic acid

Palmitic acid

Stearic acid

Behenic acid

2-ethylbutyric acid

4-methylvaleric acid

2-ethylhexanoic acid

C ₁₀ acid, obtained by oxidation of the carbonylation product of trimer

Propylene

a-naphthyl- 50 2- (2 ', 2'-dimethyl) propyl-4,4-dimethyl- valeric acid

2-methyl-2-t-butyl-4,4-dimethylvaleric acid

Oleic acid

Coconut Fatty Acids ..

Snodotte acids (mixture of C ₁₄ -C ₂₂ fatty acids, obtained by hydrogenating fresh oils)

Cyclohexanecarboxylic acid

Phenylacetic acid

Cinnamic acid

Benzoic acid

t-butyl 2-ethylhexanoate

96.6

97.2 97.4

98.5

0.25 I 0.50 I 0.75

97.3

98.0 97.1

97.2 96.8

98.5 98.9

97.5 97.8 97.9 98.4 97.8 97.8 97.6 97.2 98.0 97.6 97.5 97.4 97.6 98.6 98.9

98.0

98.8

98.4 97.5 98.2

97.5 97.9 97.9 97.9 99.0

97.7

Table I continued

Octane improver

Research octane numbers in

Base fuel with a

original octane value

of 96.6 percent acid

0.05 I 0.1 I 0.25 I 0.50 I 0.75

t-butyl benzoate ...

Benzaldehyde

n-butyraldehyde ... isobutyraldehyde .. propionaldehyde ..

paraldehyde

2-ethylhexaldehyde

Levulinic acid.

4-ketostearic acid methoxyacetic acid ethoxyacetic acid.

The data in the table above shows the octane increase in leaded gasoline with the prescribed content of aromatics is achieved by the specified amount of octane improver. Monocarboxylic acids, keto acids, ether acids, t-alkyl esters and aldehydes cause a considerable

97.6 97.9 97.6 97.2 97.2 98.6 97.3 97.2 97.7 97.2 97.4 97.2 97.6 97.0 97.2 97.2 97.8 97.2 98.0 98.1

increase the octane number of catalytically reformed. Raw gasoline.

The data in Table I further indicate that an amount of at least 0.1 percent by volume must be used in order to achieve a measurable increase in the octane number of the leaded, aromatic-containing fuel to reach. By adding 0.05 percent by volume of 2-ethylhexanoic acid, one of the most effective Acids, there was no measurable increase in octane number

ίο scored while improving by almost 2 units was achieved by adding 0.1 volume percent of this acid to the leaded fuel.

Table II shows what increase in the octane value of leaded gasoline with a Reseaich octane number

of 100 is achieved by adding the octane improvers according to the invention. As a base fuel a mixture of about 5% butane, 38% light, liquid, catalytic was used in the experiments in Table II cracked petrol and 57% catalytic

ao refonned raw gasoline applied. The base fuel contained 0.8 cm ³ / l tetraethyl lead and approximately 24 volume percent aromatics as measured by the FIA method.
The basic fuel with an octane rating of 100

had an initial ^{boiling point of 36.6 0} C and an end boiling point of 186.8 ⁰ C.

Table Π

0.1 research octane numbers in gasoline with an original octane number

of 100 volume percent acid in the fuel
0.25 I 0.50 I 1.0

2.0

Lauric acid

Capric acid

2-methyl-2-tert-butyl-4,4-dimethylvaleric acid

Cumic acid

Cyelohexanecarboxylic acid

2-ethylhexanoic acid

Benzoic acid

t-butyl 2-ethylhexanoate

t-butyl benzoate

100.3

100.1 100.5

100.1 100.4 99.6 100.5 100.4 100.9 99.7 100.7 100.8 101.9 101.2 . 102.1 (0.2%) 100.9 100.5 100.4 100.8 101.1

101.8 101.3

101.2 101.4
100.4
102.0

100.8
101.2

100.9

98.6

100.1
100.1

Table ΠΙ shows which octane number increase in liquid, catalytic reforming product. This a gasoline with an octane number of 105 by the 50 fuel with a research octane number of 105 is achieved octane improver according to the invention. The base fuel contained 0.8 cm ³ / l "lead tetraethyl liquid" and consisted of approximately 10% n-butane, 40% isobutane-isobotylene-alkylate, 10% pentenes

had an aromatic content of approximately 35%
an olefin content of approximately 6%, an initial boiling point of 32 ° C and an end boiling point of 186 ° C.

Table III

Research octane numbers in a fuel with an original octane number

of 105 volume percent additive in the fuel
0.1 I 0.25 I 0.50 I 0.75 I 1.0 I 2.0

t-butyl acetate

t-butyl benzoate

t-butyl-2-ethylhexanoate cyelohexanecarboxylic acid 2-ethylhexanoic acid benzoic acid ...;

106.9 106.4 107.8 107.0 106.1 106.4 107.6 107.1 107.5 106.0 106.5 107.0 106.6 105.8 107.6 107.8 106.7 107.9 109.2 106.0 108.6 107.4

106.4

Table III (continued)

10

Research octane numbers in a fuel with an original octanzahi

of 105 percent by volume of additive in the fuel 0.1 0.25 0.50 0.75 1.0 | 2.0

0.25 0.50 0.75 1.0 105.3 105.7 106.9 105.8 105.8 107.0 106.7 106.2 105.9 106.0 105.5 107.2 107.6 107.2 107.8 108.0 107.9 107.2 107.9

Benzaldehyde

n-butyraldehyde

C _e aldehyde (carbonylation of

C ₈ -OIeBn)

C ₈ aldehyde (carbonylation of

C ₇ -OMn)

Acetic anhydride

Propionic anhydride

n-butyric anhydride

Isobutyric anhydride

The octane number increases in the base fuel with an original octane number of 105, the obtained by adding the octane improvers according to the invention are particularly important. Of particular interest is the fact that using equal amounts of octane improver in the base fuel with an octane number of 105 a greater increase in the octane value is achieved than in the base fuels with lower octane numbers in Tables I and II.

The data in Table IV show that the presence of an organic lead anti-knock agent in one Fuel containing aromatics and olefins for the effect of the octane improvers according to the invention necessary is. As the base fuel A of Table IV, that used in Table I became catalytic reformed petrol used. Base fuel B of Table IV consisted of 40% isobutane isobutylene alkylate, 20% propylene polymer and 40% heavy platforming product.

Table IV

Base fuel A 87.7 96.7 Base fuel A + 0.5 % By volume 2-ethyl- hexanoic acid 87.4 98.9 Base fuel A + 0.5 percent by volume Benzoic acid 88.0 98.5 Pentene-2 95 1 98.6 Pentene-2 + 0.5 volume per cent benzoic acid 94.6 99.4 Heavy, catalytically refor- formed raw gasoline .. 103.4 105.6 Heavy, catalytic reform mated raw gasoline + 0.5 percent by volume Benzoic acid 102.9 108.0 Base fuel B 98.8 104.0 Base fuel B + 0.7 percent by volume t-butyl acetate 98.6 106.8

Research octane numbers without lead ^! with 0.8 cm ³ / l organic anti-knock

middle

Tetraethyl lead liquid

From the above data it can be seen that the prescribed amount of the octane improver was absent of an organic lead anti-knock agent, either the octanzahi of the fuel are not worth mentioning affects or actually reduces the Octanzahi somewhat.

The data listed in Table V show that no increase in the octane value is achieved by the octane improvers in a saturated aliphatic hydrocarbon fuel. In the tests in this table, isobutane isobutylene alkylate is used as the base fuel. Base fuel D consists essentially of 2,4-dimethylpentane. A light, directly distilled off crude gasoline with a boiling range from 34 to 97 ^° C. is used as the base fuel E.

Table V

60

40 Base fuel C Octane numbers
Lead tetraeth
Research
Octane number with 0.8 cm ³ / l
oil fluid
Engine-
Octane number 97.8 Base fuel C
⁴⁵ + 0.7 percent by volume
t-butyl acetate 107.4 98.1 Base fuel D 86.8 Base fuel D
50 +0.5 percent by volume
2-ethylhexanoic acid 107.4 86.8 Base fuel E. Base fuel E.
55 + 0.5 percent by volume
2-ethylhexanoic acid

The above values show that with predominantly saturated aliphatic! Gasoline the octane improver of the present invention has essentially no effect on the octane number of the leaded fuel to have.

Table VI shows that the effects of the octane improvers both increase the research octane number as well as the engine octane number of leaded gasoline with the prescribed content of aromatics and / or olefins is improved. The basic force used in Table VI

309 538/217

Il

Fabric F was a commercial gasoline per liter of 0.8 cm and containing ⁸ Bleitetraäthylflüssigkeit consisted approximately 26% of aromatics zti to 16% ^of olefins and 60% of saturated hydrocarbons. Basic fuel G contained 0.8 cm ³ tetraethyl lead liquid per liter and consisted of approximately 7.1% butane, 63% ^of catalytically reformed raw gasoline and 30.6% of light, liquid, catalytically cracked raw gasoline. The content of the base fuel B of aromatics, measured by the FIA analysis method, 46 percent by volume was, and its boiling range was 32-177 ⁰ C.

Table VI Table VE

Octane numbers when used Engine- of 0.8 cm ³ tetraethyl lead Octane number liquid per liter 88.5 Research Octane number Base fuel F ....... 97.0 89.5 Base fuel F + 0.1 percent by volume 2-ethylhexanoic acid 97.4 89.7 Base fuel F + 0.2 percent by volume 2-ethylhexanoic acid .... 97.5 - Base fuel F + 0.5 percent by volume 2-ethylhexanoic acid .... 98.2 89.5 Base fuel F + 0.1 percent by volume Benzoic acid 97.7 90.0 Base fuel F 91.3 + 0.2 percent by volume Benzoic acid 98.0 Base fuel G 101.3 92.6 Base fuel G + 0.5 percent by volume t-amyl acetate 101.9 92.1 Base fuel G + 0.5 percent by volume t-butyl acetate 102.5 92.4 Base fuel G + 0.5 percent by volume t-butyl propionate 102.1

30th

35

40

45

50

Table VII compares the effect of the octane improvers of the present invention on the octane numbers of three different types of knock-resistant gasoline blends. The “aromatic gasoline mixture” had a boiling range from 110 to 190 ^° C. and consisted of 84% aromatics, 15% saturated aliphatic hydrocarbons and 1% olefinic hydrocarbons. The "olefinic gasoline mixture A" consisted essentially of a mixture of propylene dimers and trimers and had a boiling range of 40 to 165.degree. The "olefinic gasoline mixture B" consisted of 50% iso-octene and 50% isohepten. The "isoparaffinic gasoline" contained 10% isopentane, 5% n-heptane and 85% isooctane. The data presented in Table VII also show that the octane improvers of the present invention require a substantial amount of aromatics and / or olefins in the gasoline to be effective.

Research Octane numbers at a Salary of 0.8 cm ³ Tetraethyl lead liquid per liter Aromatic gasoline 108.3 Aromatic gasoline + 0.5 volume percent benzoic acid 110.6 Aromatic gasoline + 0.5 volume percent 2-ethylhexanoic acid 110.0 Olefin gas mixture A ... 98.6 Olefin gasoline mixture A + 0.5 Volume percent benzoic acid 99.6 Olefin gasoline blend B 100.4 Olefin gasoline mixture B + 0.5 Volume percent benzoic acid 101.1 Olefin gasoline mixture B + 0.5 Volume percent 2-ethylhexanoic acid .. 101.3 Isoparaffinic gasoline mixture 105.3 Isoparaffinic gasoline mixture + 0.5 Volume percent benzoic acid 105.4 Isoparaffinic gasoline mixture + 0.5 Volume percent 2-ethylhexanoic acid .. 105.1

The values given in Table VIII show that oxymonocarboxylic acids are halogen-substituted Monocarboxylic acids, mercaptomonocarboxylic acids and their esters, apart from the t-alkyl esters, none Increase the octane number of leaded gasoline. The base fuel H in this table is the catalytically reformed raw gasoline mentioned in Table I with an octane number of 96.6 with lead. The base fuel I in Table VIII corresponds to the fuel used in Table III a research octane number of 105.

Table VIII

Research Octane number Base fuel H 96.6 Base fuel H + 0.5 percent by volume Ricinoleic acid 96.6 Base fuel H + 0.5 percent by volume Salicylic acid 96.6 Base fuel H + 0.5 percent by volume Monochloroacetic acid 87.0 Base fuel H + 0.5 percent by volume Heptafluorobutyric acid 89.3 Base fuel H + 0.5 percent by volume 2-bromohexanoic acid 96.3 Base fuel H + 0.5 percent by volume α-chloropropionic acid 94.0 Base fuel H + 0.5 percent by volume Mercaptoacetic acid 96.0 Base fuel I 105.0 Base fuel I + 0.75 percent by volume Methyl caproate 104.3

Table VIII (continued)

Base fuel I + 0.75 percent by volume

n-amyl salicylate

Base fuel I + 0.75 percent by volume

Methyl salicylate

Base fuel I + 0.75 percent by volume

Benzyl acetate

Base fuel I + 0.75 percent by volume

2-ethylbutyl-2-ethylhexanoate

Base fuel I + 0.75 percent by volume diethylene glycol di-2-ethylhexanoate

Research Octane Number

103.4 103.0 104.7 104.2 104.3

In addition to the above acid derivatives, amino acids are also ineffective as octane improvers because they are in Petrol are not soluble enough.

Table IX shows the synergistic anti-knock effect of monocarboxylic acids and arylamines of the type described in a leaded gasoline with the prescribed content of aromatics and / or olefins. The base fuel used in the experiments of Table IX was a very good commercial gasoline with an octane rating of 99, which contained about 7 to 10% butane, 25 to 30% light, catalytically cracked raw gasoline, 10 to 15% light, solvent-refined gasoline, Contained 50% catalytically reformed raw gasoline and 0.8 cm ³ tetraethyl lead per liter. This base fuel had an aromatic content of approximately 31 volume percent (measured by the FIA method), an initial boiling point of 32 ° C and a final boiling point of 21O ⁰ C.

Table IX

Research 1Π1 A Octane number J. Ul, Η · Base fuel 99.0 Base fuel + 0.5% Cyclohexanecarboxylic acid 99.8 Base fuel + 0.5% 2-ethylhexanoic acid 100.0 Base fuel + 0.5% aniline 99.2 Base fuel + 0.5% diphenylamine 99.2 Base fuel + 0.5% α-naphthylamine 99.3 Base fuel + 0.5% o-toluidine .. 99.2 Base fuel + 0.5% N-methylaniline 99.4 Base fuel + 0.5% 2-ethylhexanoic acid 1 100.7 Base fuel + 0.5% aniline J Base fuel + 0.5% 2-ethylhexanoic acid L 1ΠΠ R Base fuel + 0.5% > ιυυ, ο α-naphthylamine I. Base fuel + 0.5% 1 2-ethylhexanoic acid } 100.8 Base fuel + 0.5% diphenylamine J Base fuel + 0.5% I. 2-ethylhexanoic acid } 100.8 Base fuel + 0.5% o-toluidine .. J Base fuel + 0.5% Cyclohexanecarboxylic acid Base fuel + 0.5% N-methylaniline

The values listed in Table IX show the synergistic anti-knock effect of a combination from monocarboxylic acids and arylamines in leaded fuels with the required aromatic content and / or olefins. Those using the combinations of arylamines and monocarboxylic acids The increase in octane number achieved is almost 2 units, while the acids alone only have one Increase by one unit and the arylamines only

ίο an increase of less than half a unit cause.

Table X shows the synergistic effect of arylamines and the octane improvers according to the invention in a gasoline with a research octane number of 105. The base fuel contained 0.8 cm ^{3 of} tetraethyl lead per liter and its composition corresponded to the fuel specified in Table III with the research octane number 105.

Table X

Increasing the octane number with mixtures of octane improvers and N-methylaniline in gasoline der Octane number 105

Octane improver
Concentration in percent by volume

Without improvers

t-butyl benzoate

0.5%

1.0%

t-butyl 2-ethylhexanoate

0.5%

1.0%

, ₀ t-butyl acetate

0.5%

1.0%

Benzoic acid, 0.5%

2-ethylhexanoic acid, 0.5%
Isobutyraldehyde, 1.0%.

Increasing the octane number

(in units

Research octane number)

Concentration of

N-methylaniline

in percent by volume

0.0 1 0.25 0.50 1.0

1.5
1.6

1.1

2.2

1.5
1.7
3.6
3.0
1.1

0.4

1.7
2.4

0.8
1.5

0.7
1.5

0.7

2.5
2.6

1.5
2.1

1.5
2.1
5.3
4.4
1.9

The synergistic anti-knock effect of mixtures is clear from the values given in Table X. from N-methylaniline and the octane number converters according to the invention improve in gasoline with an octane number of 105 to recognize. The octane increases that can be achieved with the synergistic additional mixtures around 3 to 5 units are exceptional.

Claims (3)

PATENT CLAIMS: 1. Hydrocarbon fuel from the gasoline boiling range, which contains an organic lead anti-knock agent and at least 10% of components of olefinic or aromatic hydrocarbons or their mixtures with a high octane number (80 and more), characterized by a content of at least 0.1 percent by volume, but not more than 5 percent by volume of one or more monocarboxylic acids of the general formula R — COOH, in which R is a hydrocarbon radical with 1 to 29 carbon atoms, or the following compounds: t-alkyl esters of the general formula RCOOR ', where R is a hydrogen atom or a Hydrocarbon radical with 1 to 29 carbon atoms and R 'is a hydrogen atom or a tertiary aliphatic hydrocarbon radical with 4 to 18 carbon atoms; Ether acids of the general formula R ² OR ³ COOH, in which R ^{a is} a monovalent hydrocarbon radical with 1 to 18 carbon atoms and R ^{3 is} a divalent hydrocarbon radical with 1 to 12 carbon atoms; Keto acids of the general formula R ⁴ COR ⁵ COOH, in which R ^{4 is} a monovalent hydrocarbon radical with 1 to 27 carbon atoms and R ^{5 is} a divalent hydrocarbon radical with 1 to 18 carbon atoms; Acid anhydrides of the formula , 0 RC R is a hydrocarbon radical with 1 to 29 carbon atoms. 2. Hydrocarbon fuel according to claim 1, characterized in that the octane improver is present in a synergistic additive mixture with at least 0.1 percent by volume of one or more arylamines of the general formula R ³ NHR ⁴ , in which R ^{3 is} a mono- or bicyclic aryl or alkaryl radical with 6 to 16 carbon atoms and R * denotes hydrogen or a hydrocarbon radical with 1 to 12 carbon atoms. 3. hydrocarbon fuel according to claim 1 or 2, characterized in that it is 0.2 to Contains 1.5 percent by volume of the octane booster. in which R is a hydrocarbon radical with 1 to 29 carbon atoms, the etheric and keto acids having a maximum of 30 carbon atoms per molecule, and aldehydes of the formula RCHO, in the publications considered:
German Patent Nos. 659 210, 833 732, so 964279, 941 946, 885 500, 678 222, 339 989, 341 162; German Auslegeschriften Nos. 1 008 958, 1 011 222; Swiss Patent No. 206 436;
U.S. Patents Nos. 2,228,662, 2,800,400, 672,450, 2,721,846, 2,207,163, 2,635,042, 2,002,645; French patent specification No. 1,064,316. © 30Ϊ 538/21? 2.