DE1271455B - Motor fuels - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

X13k

GERMAN MS9Wl PATENT OFFICE Int. Cl .:

ClOl

EDITORIAL

C 07 c German KL: 46a6-7 12O-10 Number: 1 271455 File number: P 12 71 455.5-44 Registration date: April 22, 1960 Ausleeetas: June 27, 1968

The invention relates to motor fuels used in spark ignition internal combustion engines can be used.

The resistance of fuels to detonation phenomena is known to be increased by the addition of anti-knock agents such as tetraethyl lead (TEL) and, more recently, methylcyclopentadienyl manganese tricarbonyl. However, to the extent that the octane number of modern petrol-based fuels has been increased, there has been a concomitant reduction in the sensitivity of such fuels to an octane improvement due to the addition of organometallic anti-knock agents. It is therefore no longer economical to improve the resistance to knocking in fuels with higher octane numbers by such additives. It must also be incorporated in the motor fuels amount of tetraethyl lead are kept within narrow limits because of the toxicity of Bleitetraäthyls, to it is added that organometallic antiknock additives are difficult to synthesize and are quite expensive. Fuels containing such additives also have the disadvantage that they form large amounts of deposits in the combustion chamber of the engine.

The subject of German patent 1144 971 are hydrocarbon fuels that are made from hydrocarbons With an octane number of more than 80 and a content of at least 10% olefins or aromatics and an organic lead anti-knock agent and 0.1 to 5 percent by volume of monocarboxylic acids, tert-alkyl esters, ether acids, ketonic acids, acid anhydrides or contain aldehydes as additives.

The invention now relates to motor fuels for internal combustion engines with spark ignition, containing

a) a major portion of a gasoline with a research octane number of at least 90, consisting from at least two different types of hydrocarbons from the group of paraffins, naphthenes, Olefins and aromatics, and

b) a tetraalkyl lead in an amount equal to at least 1 cc / 3.7851 of the fuel, if as Anti-knocking agent tetraethyl lead is used,

Motor fuels

Applicant:

Shell

International Research Maatschappij N.V.

The hague

Representative:

Dr. E. Jung, patent attorney,

8000 Munich 23, Siegesstr. 26th

Named as inventor:

Hubert Teamon Henderson, Pleasant Hills, Calif .; Lawrence Bruce Scott, Lafayette, Calif .;
William de Acetis, Berkeley, Calif. (V. St. A.)

Claimed priority:

V. St. v. America April 24, 1959 (808 578),

dated September 21, 1959

(841004)

and

R - C -

2 η

- C —R '

which are characterized in that they
c) another hydrocarbon-soluble anti-knock agent is a diketone of the formulas

00

1 Ι

- C - C - CHo

where η denotes the numbers 1 or 2 and R and R 'denote identical or different monovalent radicals with 1 to 10 carbon atoms from the group consisting of alkyl, aryl, cycloalkyl, alkylaryl, arylalkyl and alkyl radicals with 1 to 3 fluorine atoms are selected on the terminal carbon atom in an amount of not more than 1.0 weight percent carbonyl, based on the fuel.

It has surprisingly been found that the motor fuels according to the invention have improved octane numbers exhibit. In contrast, an improvement in the octane number could not be observed if the Motor fuels contain the diketone additive, but not the organometallic anti-knock agent.

The motor fuels according to the invention not only determine the research octane number (RON),

809 567/535

but also the engine octane number (MOZ) improved. Regarding the research or motor method To determine the octane number, refer to the two ASTM test methods D-908-55 and D-357-53 referenced.

The content of tetraethyl lead in the compositions according to the invention can be up to 12.0 ecm / 3.7851 of the fuel.

It should be noted that some were used in the fuel blends of the present invention Anti-knock agents also have certain properties that suppress the phenomena of detonation exhibit. At the low concentrations considered according to the invention, this is used However, only a negligible increase in octane number is achieved, especially when the fuels are used already have a high octane number, d. H. a research octane number of at least 90 or preferably at least 95. The invention particularly relates to the improvement of such high octane Fuels.

The anti-knock agents used according to the invention have a particular effect in commercially available Gasolines that contain two or more different types of hydrocarbons, as in gasoline products the usual refining processes is the case, for example from a catalytic Reforming, catalytic cracking, olefin alkylation or thermal cracking originating products.

Gasoline obtained by direct distillation of a crude oil can also be used as one of the fuel components be used. The compounds additionally used as anti-knock agents have however, in general, they have not been found to be effective on fuels consisting of virtually a single fuel There are hydrocarbons, especially when it comes to paraffins or naphthenes. Therefore, strongly paraffinic or essentially naphthenic gasolines, such as a Directly distilled gasoline, blended with one or more types of gasoline that originate from conversion or synthesis processes.

The anti-knock agents used according to the invention are preferably in concentrations of at least 0.1 percent by volume applied. The limit above which there is practically no further improvement one of the two octane numbers (engine or research method) is more possible, fluctuates depending on the Type of anti-knock compound additionally used and the special composition of the hydrocarbon fuel considerably. The new anti-knock agents are preferably used in quantities which correspond to a carbonyl content of 0.1 to 0.5 percent by weight. It has been shown that the The additional effect achieved is small if one uses an amount that is more than 1.0 percent by weight Contains carbonyl.

The following examples illustrate the invention:

Contained 60 additional mixture. This additional mixture had the following composition:

Weight percent

Pure tetraethyl lead 61.48

Ethylene dibromide 17.86

Ethylene dichloride 18.81

Dye 0.06

Luminous oil and impurities 1.79

The octane numbers of those containing the diketone, determined by the research and motor methods Mixtures were then made with the numbers for the leaded catalytic reformate without such Diketone addition compared. The increase in octane number resulting from the additional anti-knock compound used is listed in Table I below.

Table I.

As an additional anti-knock agent
carbonyl compound used
Volume name percent
added

improvement

the octane number

by co-used

Carbonyl compound

Δ RON I zlMOZ

2,3-butanedione 0.3 +0.2 +0.3

2,4-pentanedione .... 0.3 +0.7 +1.2

2,5-hexanedione 1.0 +0.2 +0.4

l-phenyl-l, 3-butane

dione 0.8 +0.2 +1.5

1,3-diphenyl

1,3-propanedione ... 0.8 0.0 0.7

2,3-pentanedione 1.0 negative negative

l _s 3-butanedione 1.0 negative negative

Diketones with the formula

O O

It Il

Rp η TJ r * "D V ^ - Ksfiiify γι vv -tv

in which R is a monovalent alkyl radical having 1 to 3 carbon atoms and η 1 or 2 are preferably used. Particularly favorable results are achieved with diketones of the above formula in which η is 1, such as 2,4-pentanedione (acetylacetone).

Further fuel mixtures according to the invention are:

Example 2

Catalytic reformate. 98.5 percent by volume

Tetraethyl lead 1.5 ccm / 3.7851

(as an additional mixture) 4,7-Hendecandione 1.5 percent by volume

example 1

Several diketones were commercially available in varying small quantities from different samples catalytic reformate with a research octane number (RON) of 97 added, which contains 3 ecm of tetraethyl lead each 3.7851 of the reformate in the form of one

Example 3

Catalytic reformate. 48.5 percent by volume Catalytic cracking gasoline 50.0 percent by volume

Tetraethyl lead 2.0 ccm / 3.785 1

(as an additional mixture) 2,2-diethyl-5,8-nonanedione 1.5 percent by volume

1

Example 4

Catalytic cracking gasoline 70.0 percent by volume

Directly distilled gasoline 21.5 percent by volume

Normal butane 7.5 percent by volume

Tetraethyl lead 2.5 ccm / 3.7851

(as an additional mixture) bis (2,3-dimethylbutane) -

1,3-propanedione 1.0 percent by volume

Example 5

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 2.5 ccm / 3.785 1

l ^ -Diphenyl-l ^ -butane

dion 1.0 percent by volume

Example 6

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 2.0 ccm / 3.7851

l-phenyl-1,4-hexanedione .. 1.0 percent by volume

Example 7

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 1.5 ccm / 3.7851

l ^ -dicyclohexyl-l ^ pen-

tandion 1.0 percent by volume

Example 8

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 1.5 ccm / 3.7851

l-Cyclopentyl-l ^ -butane

dion 1.0 percent by volume

455

Example 9

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 1.5 ccm / 3.785 1

l-phenyl-2,4-pentanedione .. 1.0 percent by volume

Example 10

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 2.5 ccm / 3.785 1

l-phenyl-3,5-hexanedione .. 1.0 percent by volume

Example 11

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 3.0 ccm / 3.785 1

Bis (3,5-dimethylphenyl) -

1,3-propanedione 1.0 percent by volume

Example 12

Catalytic reformate .. 99.0 percent by volume

Tetraethyl lead 3.0 ccm / 3.7851

Bis- (2-methylphenyl>

1,4-butanedione 1.0 percent by volume

Example 13

Both trifluoro and hexafluoroacetylacetone various samples of a catalytic reformate were added, which contained 3 ecm of tetraethyl lead each 3,785 1 of the reformate contained. Subsequently, the Octanzahien of the fuel were added with the addition determined on the fluorine-substituted diketones by means of the motor and the research method and compared with the value for the catalytic reformate, which only contained the lead compound.

The following results were obtained:

Table II

Carbonyl compound used as an additional anti-knock agent Volume percentage
added improvement
by co-used the cetane number
Carbonyl compound Structural formula -dROZ ZlMOZ OHO
Il I 0.2 I! I.
F ₃ CCCC-CF ₃ 0.0 +0.3 H OHO 0.2 F ₃ -CCCC-CH ₃
I. +0.6 +1.3 I.
H

It follows that both fluorine-substituted diketones have favorable properties as anti-knock agents have, although trifluoroacetylacetone is much better works.

Example 14

To check whether the anti-knock agents additionally used according to the invention for all possible Tetraethyl lead concentrations are effective, were each 0.4 percent by volume of acetylacetone, which is a Content of about 0.28 percent by weight of carbonyl corresponds to various samples of a lead-containing one added catalytic reformate, which contains between 0.5 and 6 ecm of tetraethyl lead in the form of an additional mixture contained on each 3.7851 of the reformate. The octantanes for those containing the acetylacetone Samples were then compared to the numbers for the same leaded platform, but which was the second anti-knock agent did not contain.

The results obtained are summarized in Table III below.

Table ΙΠ

Continuation of the table above

Acetylacetone improvement / IMOZ Tetraethyl lead concentration the octane number 0 concentration by co-used -1.0 Volume percentage Carbonyl compound -o, i cc / 3.7851 0.4 ZfROZ +1.5 0 0.4 0 +1.4 0.5 0.4 -1.2 +0.3 2.0 0.4 +0.8 +0.4 3.0 0.4 +0.6 4.0 0.4 +0.8 5.0 0.4 +0.7 6.0 +0.8

15 From these results it can be seen that the

Additional anti-knock agents in such fuels are no longer effective, which are less than about 1.0 ecm tetraethyl lead each contain 3.7851. In fuels, which contain less than 1.0 ecm of tetraethyl lead per 3.7851, it can even deteriorate the octane number. Therefore, fuel mixtures are preferably used which are at least 2.0 ecm tetraethyl lead each contain 3.7851.

Furthermore, anti-knock compounds are generally shown in the table above Obviously, that the selected upper limit for the pure compounds from the gasoline boiling range or Tetraethyl lead is not critical and that only one type of hydrocarbon is used in mixtures of compounds are not effective. It turns out, however, that the additional tapping agent in both 2-Me-30 thylbutene-1 as well as in butylene polymer was effective. These two olefins are in proportion to the Molecular size extremely branched. This means that a high degree of branching of the Olefins contained in the fuels, the anti-knock

Fuel Name of the connection Verbs
the Oc
through with
Carbonyl
Λ RON utterance
t number
used
link
Λ MOZ Mono
olefine Heptene-3 -1.4 +1.1 Mono
olefine Octene-2 -8.2 -1.6 Mono
olefine Butylene polymer +0.4 +0.8 Diolefins Octadiene -4.4 +0.2 Naphthenes Cyclopentane -ο, ι -0.1 Naphthenes Cyclohexane -2.1 +0.1 Aromatics sec-amylbenzene 0.0 -0.5 Aromatics Mixture of
Xylenes 0.0 +0.7

These data show that the additional

Tetraethyl lead content is not critical and has favorable results with regard to the anti-knock effect can be achieved even with much higher concentrations of lead compounds.

Example 15

This example shows the influence of the type of fuel on the effect of the additionally used anti

knocking agent. A number of samples were promoted for the effect of the diketones. For this reason

Manufactured in which the fuel on the one hand from practically pure hydrocarbons and on the other hand consisted of only one type of hydrocarbon. For each sample 3 ecm of tetraethyl lead were added to 3.7851 each in the form of an additional mixture (motor mix) and 0.4 percent by volume of acetylacetone added, what a Carbonyl content of about 0.28 percent by weight. The octane numbers of these samples were determined and compared with those of samples of the same fuel, which was also 3 ecm Tetraethyl lead each contained 3.7851, but no additional anti-knock agent. The results were as follows obtain:

Table IV

fuel Name of the connection Verbs
the Oc
through with
Carbonyl
JROZ sserung
t number
used
/ attachment
/ IMOZ Paraffins 3-methylpentane -2.4 -1.2 Paraffins 2,2,4-trimethyl
pentane -1.8 -1.1 Paraffins Butene isobutane
Alkylate -0.9 -2.3 Mono
olefine 2-methylbutene-1 +1.6 +1.8 Mono
olefine Witches-1 -0.8 +0.4 Mono
olefine Hepten-2 -1.8 +1.4

branched olefins are preferred over unbranched olefins, if olefins at all Fuel mixtures according to the invention are to be used. Furthermore, certain alkyl-substituted Aromatics such as toluene or xylenes can be used, at least within a narrow range Range in relation to the concentration of the anti-knock agent additionally used. The extraordinary and often abnormal sensitivity of the additional anti-knock agent used compared to the hydrocarbon species disappears when these additives are in such fuels are used, which consist of a mixture of hydrocarbons of various types. This fact is confirmed by the results of the following example.

Example 16

Acetylacetone was used in an amount which corresponds to a carbonyl content of about 0.28 percent by weight, added to various samples of the following base fuels:

60

1. A commercially available platform.

2. A butylene polymer in the gasoline boiling range.

3. A mixture of the platform and the butylene polymer.

4. A standard mixture of the platform and the butylene polymer, the increase normal butene had been added to the vapor pressure.

ίο

3 ecm of tetraethyl lead, 3.785 l each, were added to these samples in the form of an additional mixture. The octane numbers of each sample were determined by the engine and research methods.

Table V

Composition of the base fuel polymer n-butane Acetylacetone Improvement of the octane number by Λ MOZ Platform format Volume percentage Volume percentage concentration used carbonyl compound +1.9 Volume percentage _ _ Volume percentage Δ RON +1.5 100 50 - 0.4 +0.4 +1.5 50 45 10 0.4 +1.0 +0.8 45 100 - 0.4 +0.7 - 0.4 +0.4

These base fuels not only show unexpectedly favorable results due to a non-linear increase the octane number, but the improvement of the research octane number of the platform is also directly favored by the presence of the olefinic polymer. In addition, the The presence of 10% normal butane also only slightly reduces the research octane number of the mixture, although one would expect the acetylacetone to be strongly antagonistic because it is at the η-butane is an unbranched paraffin of low molecular weight. The research octane number of the mixture of platform, butene polymer and butane is unexpected still larger than that of the platform alone. This surprising mixing effect also occurs when such base fuels are blended with one another, their octane rating normally occurs is improved by adding small amounts of a diketone as an anti-knock agent. In order to explain a commercial catalytic reformate and a high olefinic, light catalytic cracking gasoline mixed together in different concentrations. To each a sample of these duplicate samples were 0.4 percent by volume of acetylacetone and 3 ecm of tetraethyl lead each 3.7851 added.

Table VII Table VI

composition
of the base fuel catalytic improvement
the octane number
by co-used Δ MOZ pl η * fnrtn n t Split gasoline Carbonyl compound +0.7 JrIcImJJLlHCiL _ Δ RON +0.9 100 20th +0.2 +1.1 80 40 +0.6 +1.0 60 50 +0.8 +1.0 50 60 +0.6 +0.8 40 80 +0.8 +0.9 20th 100 +0.3 - +0.4

50

55

60

The properties and the hydrocarbon analysis of the catalytic reformate as well as the catalytic Fission fuel is shown in the following table.

Research 'Octane Number
with 3 ecm TEL *
each 3.7851

Engine octane number
with 3 ecm TEL *
each 3.7851

Analysis of hydrocarbons

Paraffins

Olefins

Naphthenes

Aromatics

Distillation ASTM:
Initial boiling point.,
Final boiling point

*) TEL = tetraethyl lead.

Catalytic
Split gasoline

99.7

84.7

17.0%

75.0%

6.0%

2.0%

64, O ⁰ C
85, O ⁰ C

Catalytic reformate

27.0%

15.0%
58.0%

47.4 ° C
193, O ⁰ C

The data in Tables VI and VII further show that when using diketones as additional anti-knock agents harmful to fuels from a single hydrocarbon species Effects are overcome if one small amounts of a second gasoline in question Type of hydrocarbon admixed. For this reason, the fuel mixtures according to the invention should be preferred from at least two different types of hydrocarbons exist, some of which do not exceed 90 percent by volume of the total gasoline matters. Furthermore, when using lead-containing hydrocarbons, at least 10 percent by volume should be used of the fuel from aromatics, olefins or mixtures of these two types of hydrocarbons exist. Within the stated limitation that the fuel does not exceed 90% of a given Should contain hydrocarbon species, it may be composed of three or more hydrocarbon species. However, if there are only two different types of hydrocarbons, the fuel should be preferably from paraffins and olefins, from olefins and naphthenes, from olefins and aromatics or composed of naphthenes and aromatics.

809 567/535

Although in the fuels of the above examples, the tetraethyl lead as an organometallic Contained anti-knock agents, the tetraethyl lead used in the form of a commercially available additive mixture are the anti-knock agents additionally used in the motor fuels according to the invention also effective in those bleached gasolines which only contain pure tetraethyl lead and no halogenated hydrocarbons Dish soap included. That the effect of the new additional anti-knock agents not adversely affected by the presence of other additives such as detergents is also evident from the following example.

Example 17

Various samples of the previously used commercial platform were used up to one Content of 3 ecm of tetraethyl lead per 3.7851 lead. Two of these samples were made with pure tetraethyl lead modified without further additives, while two other samples made use of a commercially available one Additional mixture (engine mix) were weighted. Each sample was then 0.4 volume percent Acetylacetone added. When determining the octane number of these samples, it was found that the the increase in octane number caused by the addition of the diketone was the same in all cases.

In addition to the halogen-containing lead detergent already mentioned in the additive mixture, the inventive Fuel mixtures also contain other known additives, such as dyes, Agents that prevent spark plug fouling, such as tricresyl phosphate, dimethyl xylyl phosphate and diphenyl cresyl phosphate, as well as combustion modifying substances, e.g. B. alkyl boronic acids, lower alkyl phosphates or phosphites, also oxidation inhibitors such as N, N'-di-tert-butyl-4-methylphenol, or metal deactivators, e.g. B. N, N'-disalicylal-1,2-propanediamine, and rust inhibitors, z. B. polymerized linolenic acids and N, C-disubstituted imidazolines or similar compounds.

Claims (3)

Patent claims: 1. Containing motor fuels for internal combustion engines with spark ignition a) a larger proportion of a gasoline with a Research octane number of at least 90, 45 consisting of at least two different types of hydrocarbons from the group of Paraffins, naphthenes, olefins and aromatics, and b) a tetraalkyl lead in an amount which is at least 1ccm / 3.7851 of the fuel, if tetraethyl lead is used as an anti-knock agent, characterized in that they c) as a further hydrocarbon-soluble anti-knock agent a diketone of the formulas O O 1 Il CH3 - C - C - CH ₃ and Il - C * - where η denotes the numbers 1 or 2 and R and R 'denote identical or different monovalent radicals with 1 to 10 carbon atoms from the group consisting of alkyl, aryl, cycloalkyl, alkylaryl, arylalkyl and alkyl radicals with 1 to 3 fluorine atoms are selected on the terminal carbon atom in an amount of not more than 1.0 weight percent carbonyl, based on the fuel. 2. Motor fuels according to claim 1, characterized in that acting as an anti-knock agent Compound c) is a diketone with alkyl radicals linked to the carbonyl groups and have 1 to 3 carbon atoms. 3. Motor fuels according to claim 2, characterized in that the anti-knock agent is acetylacetone or trifmoracetylacetone. Older Patents Considered: German Patents No. 1144 971,1236 854. When announcing the application, there are two priority documents and two transfers of priority rights has been laid out. 809 567/535 6.68 © Bundesdruckerei Berlin