DE1147799B - Petroleum distillate propellant or fuel - Google Patents

Description

GERMAN

PATENT OFFICE

E 19712IVd / 46a ⁶

REGISTRATION DATE: AUGUST 3, 1960

NOTICE DEB. SIGN UP AND ISSUE OF EXPLAINING PUBLICATION 25 A P RIL 1963

The invention relates to improving the flowability at low temperatures and the pour points of hydrocarbon propellants and fuels boiling between about 120 and 400 ° C, namely especially heating oils and diesel fuels, luminous oil, turbine jet fuels for aircraft and others Fuels that are exposed to low temperatures.

With the increasing use of hydrocarbon fuels of all kinds, in areas where The low temperatures exposed to a serious difficulty arose affecting the behavior of the Fuels and fuels in the cold. Particularly serious problems exist with heating oils, Diesel and jet fuels that have too high pour points and therefore cause distribution problems and operational difficulties or both types of trouble. So z. B. the distribution of heating oils impossible by pumping or siphoning off at temperatures in the region of the pour point of the oil. In addition, the flow of the oil through the filter can no longer be maintained at such temperatures, which leads to the failure of the system in question.

Furthermore, the low-temperature behavior of petroleum distillate propellants and fuels boiling in the range of about 120 to 400 ° C in recent years the increasing demand for such propellants and fuels in subarctic areas and as a result of the Development of turbine jet planes that can fly at altitudes where temperatures are as low as -45 ° C or below, received increasing attention.

The invention is of particular importance for jet fuels that are a luminous oil-like gas oil and contain a heavy gasoline fraction.

It is known to add pour point depressants to lubricating oils in order to lower their pour points. These Lubricating oil additives, usually by alkylating benzene or naphthalene or derivatives thereof, by polymerization of low molecular weight methacrylic acid esters or by condensation polymerization produced organic compounds are of high molecular weight, are medium for distillates Settling position or lighter fuels not satisfactory. The unfavorable behavior of these additives is possibly explained by the structural differences between the waxes used in lubricating oils and in so-called distillates of middle settlements occur.

A large number of compounds have proven effective as pour point depressants for lubricating oils Petroleum distillate fuel

Applicant:

Esso Research and Engineering Company, Elizabeth, N.J. (V. St. A.)

Representative:

E. Maemecke and Dr. W. Kühl, patent attorneys, Hamburg 36, Esplanade 36 a

Claimed priority:

V. St. v. America of August 3 and September 23, 1959 (No. 831244 and No. 841664)

Stephan Ilnyckyj and Charles B. Rupar,

Sarnia, Ontario (Canada) have been named as the inventor

proven. The best known pour point depressants for lubricating oils are condensation products made of chlorinated wax and naphthalene, methyl polymethacrylate as well as modifications thereof. In general, it is believed that the effect of these pour point depressants is based on the fact that the Cooling the oil containing the additive, the hydrocarbon chain of the additive compound is in the The crystal lattice of the wax which is deposited is embedded, while the other part of the molecule of the pour point depressant prevents the crystals from sticking together and forming a gel structure. the The fact that these additives are ineffective for distillates of medium boiling point may at least in part on the fundamental differences in composition between those contained in lubricating oils Waxes and the waxes contained in distillates of medium boiling point.

The invention relates to a petroleum distillate Treibbzw. -Fuel with a boiling range between about 120 and 400 ⁰ C, which is characterized by the fact that it is an oil-soluble copolymer with a molecular weight between about 1000 and 3000 of ethylene and an olefinically unsaturated aliphatic monomer with 3 to 5 carbon atoms each

309 577/178

3 4

Molecule which accounts for about 1 to 40 percent by weight of the thermal degradation of polymers of high

the latter component has, in amounts molecular weight or the treatment of poly

contains up to about 1.0 percent by weight. merisates of high molecular weight with ozone to

Among the fuels that are invented to break the polymer chains, according to by the addition of this pour point depressant 5 A very advantageous method consists in the Improvements that can be made include using turbine nozzle polymerization in solution in benzene fuels for aircraft, light oil, diesel fuels of di-tert.-butyl peroxide as pathogens at a temperature and heating oils. The jet fuels boil normally in the range of about 138 to 171 ° C between about 120 and 288 ° C, the luminous and lead. The preferred temperature is about 150 ° C. Heating oils between about 150 and 400 ° C. OK The pressure is in the range from about 48 to 136 atü,

To the olefinically unsaturated aliphatic mono- preferably at about 55 atm. The autoclave or the

mers with 3 to 5 carbon atoms in the molecule other device that the solvent, the

Include vinyl acetate, vinyl propionate, methacrylic acid pathogens, and the vinyl acetate it contains will be about three times

methyl ester, allyl ethyl ether, divinyl ether, acrylonitrile and rinsed with nitrogen and twice with ethylene and vinyl acetonitrile. 15 then charged with so much ethylene that when heated

The polymeric pour point depressants can in accordance with the reaction temperature, the desired pressure

appropriately together with the most diverse other- arises. During the polymerization, each time

Renal additives are used, which are more common - when the pressure has dropped by about 6.8 atmospheres, further

wise added to the abovementioned propellants or fuels ethylene. The polymerization is considered complete. Typical additives of this type are rust inhibitors considered continuously when the hourly pressure drop

gates, anti-emulsifying agents, corrosion inhibitors, oxy- is less than 3.4 atmospheres. The product is made of solid

dation retarders, dispersants, dyes, dyes freed, and the unreacted vinyl acetate

Fabric stabilizers, turbidity inhibitors and antista- is driven off in a vacuum.

table means. It is often advisable to use additional concentrates for the preparation of the polymers would have to produce and in this way not claim any protection for the relevant 25 of the present invention.

Propellant or fuel all additives at once.

to add. Typical distillate fuels from a boiling point

The pour point depressant is a copolymer rich between 120 and 400 ° C, which the invention Ethylene and vinyl acetate. It should preferably be possible to add the appropriate additives Copolymer approx. 60 to 99 percent by weight of 30 heating oils of medium boiling point. These fuels are from Ethylene and about 40 to 1 percent by weight vinyl technical grade and have the following acetate included. An advantageous mixed polymer with typical characteristics: from ethylene and vinyl acetate contains about 15 to 25 ". z. B. about 20 weight percent vinyl acetate. composition

__ The molecular weights of the copolymers from 35 distillate gas oil 40

Ethylene and vinyl acetate are critical and should be used in the catalytically cracked gas oil 60

Range from about 1000 to 3000, preferably from

about 1500 to 2200. The molecular weights are parameters

according to the method of K. Rast (reports of the specific gravity 0 8811

German Chemical Society, 55 [1922], p. 1051 40. ¹ L ,. _Cj . ,,. , ". _o _, '

and 3727). ASTM pour point without addition, ° C .. -6.7

The mixed polymer of ethylene and vinyl acetate Flash point according to Pensky-Martin, ° C 89

is the fuel in concentrations in the ASTM distillation range, ° C

from about 0.001 to 0.5, preferably from 0.005 to the beginning of boiling point 203

0.1 percent by weight added. 45 jqo / 255 5

Surprisingly, these copolymers have '

sate of low molecular weight no effect '°' '

on the pour points of lubricating oils, which is on the 90% ■ 322

Difference in structure between the ones in lubrication boiling end 340

oils and waxes contained in distillates

medium-sized settlements. By adding the additives according to the invention

The copolymers of low molecular weight achievable advantages result from the following

Weight can be calculated using any method with a table. All pour points given therein are

Using peroxides to be produced. Under Um- determined according to ASTM test standard D-97-47,

It may be advantageous to first use a polymer. 55 A number of tests are carried out with different

cation product of higher average molecular polymers in a mixture of equal proportions

produce weight and from this then a product of unsplit and split gas oil is executed. That

to obtain, which boils a molecular weight in the range of unbroken gas oil in the range of about 177 to

from about 1000 to 3000. Since such polymer is 371 ° C, the cleaved range from about 177 to

cation products usually from mixtures of 60 343 ° C. The mixture has a pour point of

There are polymers whose molecular weights are above -6.7 ° C. The various polymers are at

are distributed over a wide area, there is a good various pressures and other different

Process for obtaining that part of the working conditions established. As already mentioned,

Product, the molecular weights in the range of are the critical factors with regard to the poly-

1000 to 3000 has therein, the product having a 65 merisate its molecular weight and concentration

Solvents such as n-heptane or methyl ethyl ketone on vinyl acetate in the polymer. The results of this

to extract. Other methods of obtaining experiments are summarized in the following table.

Low molecular weight polymers are provided.

Table I Synthesis of copolymers from ethylene and vinyl acetate

Polymerization conditions: 149 ° C, di-tert-butyl peroxide as pathogen, benzene as solvent

Attempt no.

Concentration of vinyl acetate, percent by weight in benzene ...

in the product ...

Pressure, atü

Yield,
g / g peroxide

ASTM pour point, ° C *

0.05%

0.1%

0.25%

0.5%

7.5

-17.8 -31.7 -45.5 -40

0 0

51 19

-15 -17.8 -31.7 -56.7 0.53
3.0

51
18th

-15
-17.8
-45.5
<-56.7

2.1
8.4

51

17.5

-17.8

-23.3

<-56.7

<-56.7

8.5
28.1

51
22.5

-12.2

-31.7

<-56.7

<-56.7

2.1
5.8

61.3
23

-17.8

-28.9

<-56.7

-51.1

2.1 17.9

27.2

-9.4 -12.2 -12.2 -17.8

*) Mixture of equal parts of cracked and non-cracked gas oil, ASTM Stokpunkt -6.7 ° C.

Table I (continued)

Attempt no.
11

12th

13th

Concentration of vinyl acetate, percent by weight in benzene ...

in the product ..

Pressure, atü

Yield,
g / g peroxide

ASTM pour point, 0.05% .. 0.1% ...

0.25% 0.5% ...

C *

2.1 12.1

40.8 14

-9.4 -15 -26.1 -56.7

21.0 53.8

51

31

-6.7

-6.7

-6.7

-12.2 14.8
44.7

51
26th

-9.4

-9.4

-12.2

-12.2

11.7
35.2

51
23.5

-12.2
-12.2
-51.1
-56.7

6.3

24.3

51

18th

-12.2

-45.5

<-56.7

-51.1

6.3
20.4

57.8
23

-40
<-56.7
<-56.7

-40

*) Mixture of equal parts of cracked and non-cracked gas oil, ASTM pour point -6.7 ° C.

The above values show that a copolymer containing 3% vinyl acetate behaves much more favorably than a polymer of ethylene which does not contain vinyl acetate (experiment no. 3 versus experiment no. 2). It can also be seen that a concentration of vinyl acetate of about 28% ^{senr is} effective (test No. 5) and that the effectiveness of the additive decreases sharply when the concentration of vinyl acetate exceeds about 40% (tests No. and 10).

The luminescent oil fraction used as jet fuel has a boiling range of about 93 to 316 ° C and a mid-boiling point in the range of about 215 to 238 ° C.

A typical one used in the following examples Jet fuel from the luminous oil sector has the following characteristics:

Type of analysis (F.I.A.) Jet fuel

Paraffins,%

Aromatics,%

6.3 14.7

109 29.5

-12.2 <-56.7 <-56.7 <-56.7

Jet Fuel 43

Flash point (T. C. C), ° C

: 5 distillation, ° C
Beginning of boiling 102

2.5%

5.0%
10.0%
50.0%
85.0%
90.0%
95.0%

148 165 178 225 258 264 272

End of boiling 277

Residue,% 3.0

In a number of attempts, the luminous oil fraction becomes a copolymer of ethylene and vinyl acetate added. The molecular weight of the copolymer is about 800 and its content of Vinyl acetate about 8 percent by weight.

The influence of this copolymer on the pour point of the jet fuel results from the following Tabel:

Table II
Influence of the copolymer on the pour point

Table IV (continued)

Mixed polymer
Weight percent

Heavy fuel,
Boiling range
60 to 104 ⁰ C

ASTM pour point, ⁰ C

Heavy fuel,

Boiling range

104 to 160 ⁰ C

Heavy fuel,

Boiling range

154 to 199 ° C

one Jet fuel Mixed polymer,
Weight percent 0
0.1
0.2
0.5 ASTM pour point, ° C -42.8
-42.8
-42.8
-53.9

(b) 10 percent by volume heavy fuel

These values show that the copolymer to be used according to the invention has the pour point of the jet fuel is only influenced in concentrations in the range of about 0.5%.

Further investigations are carried out with a jet fuel made from a luminous oil fraction according to Table II and different amounts of heavy gasoline from different boiling ranges. The results of these tests are given in Table III.

Table III

Influence of the heavy benzine content of the luminescent oil fraction on the pour point

0 (C) 0 -42.8 -42.8 -45.5 -53.9 -48.3 0.1 0.1 -45.5 -48.3 -45.5 -76.1 -62.2 0.2 0.2 -53.9 -56.7 -45.5 -78.9 -65 40 percent by volume heavy fuel -53.9 -65 -76.1

Heavy fuel BRANCH
Heavy fuel, M-pour point, '
Heavy fuel, ^! C.
Heavy fuel, V Ul Ulli " Boiling range Boiling range Boiling range percent 60 to 104 ⁰ C 104 to l60 ° C 154-199 ° C 0 -42.8 -42.8 -42.8 5 -42.8 -42.8 -45.5 10 -42.8 -42.8 -45.5 20th -45.5 -42.8 -45.5 40 -53.9 -53.9 -48.3

The above values show that a jet fuel contains various heavy fuel fractions in addition to luminous oil contains, does not have a significantly lower pour point, even if it is considerable Adds amounts of heavy gasoline.

In further experiments, the copolymer to be added according to the invention is used in various proportions Added to fuels, which are composed of various amounts of light oil and heavy fuel are. The results can be found in Table IV.

Table IV

Influence of the copolymer on the ASTM pour point of mixtures of a luminous oil fraction (end of boiling point 277 ° C) with different amounts of heavy gasoline

Mixed ASTM pour point, Heavy fuel, ° C polymer Heavy fuel, Boiling range Heavy fuel, Weight Boiling range 104 to 160 ⁰ C Boiling range percent 60 to 104 ⁰ C 154 to 199 ° C

(a) 5 percent by volume heavy fuel

0 -42.8 -42.8 -45.5 0.1 -45.5 -45.5 -45.5 0.2 -45.5 -45.5 -45.5

It can be seen that by adding relatively small amounts of copolymer when using a jet fuel, which is composed of a luminous oil fraction and a heavy gasoline fraction, reaches significantly lower pour points.

The drawings show a series of curves that relate to the relationship between various factors the composition, the production and the effect of the copolymers illustrate.

Fig. 1 shows that at constant pressure, the amount of vinyl acetate in the copolymer increases with The concentration of vinyl acetate in the solvent increases. Here, the copolymerization is at a pressure of 51 atm and a temperature of 149 ° C using benzene as a solvent and di-tert-butyl peroxide carried out as a polymerization agent.

Fig. 2 shows that with a constant concentration of vinyl acetate in the solvent, the quantitative proportion of vinyl acetate in the copolymer decreases when the ethylene pressure increases. The concentrations of vinyl acetate in the solvent are as follows: 0.2, 2.1, 6.3 percent by weight. The other test conditions are the same as in the test according to FIG. 1.
Fig. 3 shows the effectiveness of the copolymers as pour point depressants for distillates of medium boiling point. The middle boiling distillate here is the same as that according to Table I. Curves A, B, C, D, E and F correspond to experiments No. 9, 10, 2, 3, 1 and 13 of Table I. It is It should be noted that the copolymer of curve F, which contains about 20% vinyl acetate, is very effective.

4 illustrates the relationship between the effectiveness of the copolymer as a pour point depressant and its vinyl acetate content. The oil according to curve A contains 0.05%, that of curve fi 0.1% pour point depressant. It can be seen that the most effective pour point depressant is obtained by copolymerization at a pressure of 57.8 atmospheres if the copolymer contains about 80% ethylene and 20% vinyl acetate. 4 shows that copolymers which contain more than 20% vinyl acetate show a marked decrease in the effectiveness of the pour point lowering effect. This is particularly pronounced at lower additional concentrations. At a concentration of 0.05%, the effectiveness of the pour point depressant is irrelevant if the copolymer contains about 24% vinyl acetate. At a concentration of 0.1%, the copolymers show

a certain pour point lowering effectiveness, up to the vinyl acetate content of about 35% of the total amount of the copolymer is.

FIG. 5 explains the influence of the pressure at which the copolymer is produced on its effectiveness as a pour point depressant. The curves shown in the diagram relate to copolymers, which are made at the following pressures and the following molecular weights exhibit:

Addition is effective. This can be seen clearly from Table V.

Table V

Influence of the copolymer of ethylene and vinyl acetate on the pour point and viscosity of

light gas oil
ASTM pour point of the oil: -3.9 ° C

Mixed
polymer Polymerization
pressure
atü Molecular weight A.
B.
C. 27.2
40.8
57.8 500
560
750

It can be seen that the polymers produced at pressures lower than 40.8 atmospheres hardly prove to be Pour point depressants are suitable. Since the molecular weight increases with the pressure applied in the synthesis, this also means that the copolymer has a certain minimum molecular weight must in order to be effective as a pour point depressant.

6 illustrates the effectiveness of the copolymers prepared according to the invention as pour point depressants compared to polyethylene. The two referred to as "polyethylene A" and "polyethylene B" Types of polyethylene are extracts from commercially available polyethylene. All three polymers own Molecular weights of about 1300.

The pour point depressant according to the invention for distillates with a medium boiling point has only a low level Influence on the viscosity of the oil, especially in those concentration ranges in which the

Mixed poly Pour point Viscosity of the ίο mensat *)
Weight
percent humiliation
at ⁰ C Oil at 37.8 ⁰ C,
SUS 0 38.27 15 0.01 11.1 38.21 0.03 27.8 38.30 0.05 36 38.24 0.1 44.5 38.36 0.3 30.5 38.54 20 1.0 2.8 39.37

*) Molecular weight 800, determined by Rast's method.

It should be noted that the pour point lowering effect with added amounts in the order of magnitude of 1% is considerably less than with smaller additional amounts of, for example, about 0.1%. This is unfavorable Effect of the copolymer of ethylene and vinyl acetate on the lowering of the pour point at higher additional concentrations is probably due to the fact that the copolymer, if it is present in large quantities, it forms a gel structure with the oil on cooling.

A large number of other polymers have been tested for their pour point-lowering effect on distillates investigated middle settlement area. As Table VI shows, none of these were for the specified one Purpose effective.

Table VI
Hydrocarbons, which are ineffective as pour point depressants for distillates with a medium boiling point

Hydrocarbon Weight
percent
in the oil Pour point
humiliation
around ⁰ C *) Remarks Microcrystalline waxes 0.001 1.1 Melting point 82 ° C ■ 0.01
0.1 0.55
-3.3 1.0 -4.4 0.001
0.01 0
-3.3 Melting point 84 ° C J 0.001 -0.55 0.01
0.1 -1.1
-2.8 1.0 -5.5 Melting point 46 ° C 0.001 -1.7 0.01
0.1 -1.1
-3.9 1.0 -6.1 Melting point 48 ° C

*) (-) = increase in pour point.

309 577/178

11

Table VI (continued)

Hydrocarbon

Weight Pour point insoluble in oil 0 Remarks ic > 34.9 percent lowland insoluble in oil 42.80 in oil around ⁰ C *) 0.1 viscosity 118.9 at 37.8 ° C, SUS - 563.0 0.1 +0 fixed; Molecular 0.1 +2.8 weight range 0.1 +2.8 10,000 to 30,000 0.1 +1.4 0.1 + 1.4 ASTM stick 0.2 + 1.4 point, ⁰ C 0.5 +1.4 -54 1.0 +7 -37 2.0 +1.4 -31.7 -17.8 -15 0.1 +1.4 -6.7 0.1 0 +1.7 0.1 +2.8 Oil from lower 0.1 0 viscosity 0.1 +1.4 0.1 0 Viscosity at 0.1 +2.8 37.8 ° C, 1269 SUS 0.1 +2.8 Viscosity at 0.5 0 37.8 ⁰ CSUS 0.1 + 1.4 54.0 0.1 +4.2 78.10 841.2 1496.0 0.1 +2.8 0.1 +2.8 0.1 0 0.1 +1.4 0.001 0 0.01 +1.7 0.1 0 1.0 0 0.001 0 Viscosity at 0.01 0 - 0.1 0 57.8 ° C, 6340 SUS

Polypropylene

Solution of linear polypropylene in n-heptane

Polybutene,

Molecular Weight 330 Molecular Weight 420 Molecular Weight 470 Molecular Weight 660 Molecular Weight 700 Molecular Weight 780 Molecular Weight 940

Polybutene!

Polybutene-2

Polyisobutylene
Molecular weight 23

Molecular weight 100

Molecular weight 200 molecular weight 300 polycylopentane

Polystyrene

*) (+) = Lowering of the pour point, none of the different species examined was in Soluble in oil.

1 \ ΑΊ

It has already been stated that this is in distillates The wax contained in the middle boiling point differs from the wax contained in lubricating oils and that the pour-point-lowering ones effective in one case Additions are ineffective in the other case. Two known pour point depressants are shown in Table VII for lubricating oil with a copolymer of ethylene and vinyl acetate of one molecular weight compared from about 1750.

Table VII

Influence of various additives on the ASTM pour point and the stable pour point of an uncleaved one Gas oil with a boiling range of 180 to 361 ° C.

additive I. Weight
percent ASTM
Floor-
Point,
⁰ C none f -3.9 Condensation product
chlorinated wax
and naphthalene I. 0.2
0.5
1.0 -6.7
-9.4
-15 Polymethacrylic
acid methyl ester 0.2
0.5
1.0 -9.4
-12.2
-17.8 Mixed polymer
Ethylene and vinyl acetate
(Molecular weight 1750) * 0.5
0.1
0.25
0.5 -40
> -56.7
> -56.7
-40

*) Determined by Rast's method.

These values clearly show the superiority of the copolymers of ethylene and vinyl acetate from low molecular weight versus pour point depressants for lubricating oils. If these copolymers on the other hand, lubricating oils are added, they are ineffective in them.

Table VIII

Weight
percent
Mixed polymer
(Molecular weight 800)

0.1

0.5

ASTM cloud point / pour point, ° C

MCT-10 *) j MCT-30 *) I MCT-60 *)

45

- 12.27-15
-2; 2 / -9.4
+ 8.9 / -9.4

- 1.1 / —1.1-

0 / 1.1
+ 4.4 / -3.9

+ 10 / + 7.2 + 13.3 / + 4.4

*) Paraffinic oil, obtained from a Leduc crude oil tacif Distillation, dewaxing, extraction with phenol and treatment with adsorbent earth.

The various effects of these copolymers on the pour point of Lubricating oils at least partially due to the structural differences between those in distillates Siedelage (η-paraffins) and the in deparaffmized Lubricating oils (isoparaffins and naphthenes) contained waxes.

Not all oils respond to the additive in the same way. Catalytically cracked gas oil speaks considerably stronger than uncleaved gas oil. However, as Table IX shows, both are in terms of their Pour point improved.

Table IX

Response of non-split and split gas oil to the pour point-lowering effect of the copolymer made of polyethylene and vinyl acetate

Average molecular weight 800 *

Type of gas oil
IO Mixed
poly
merisat
Weight
percent ASTM
Floor-
Point
⁰ C More stable
floor
Point Unsplit ** ... j
Catalytic Γ
split *** ■ · ■ \
₂₀ 50 7o unsplit
+50 7o cataly
table split .. J 0
0.1
0
0.1
0
0.1 -3.9
-17.8
-12.2
<-64.4
-9.4
-40 -9.4
-15
-15
-37.2
-12.2
-37.2

*) Determined according to the method of R as t.
**) Boiling range 228 to 357 ° C.
***) Boiling range 201 to 337 ° C.

The effectiveness of the copolymers of ethylene and vinyl acetate of low molecular weight than Pour point depressants for jet fuels are shown in Table X. Jet fuels are exceptional exposed to sharp changes in temperature, and it is very important that they have low freezing points own. For comparison purposes, the values for known pour point depressants are given. The jet fuels are selected hydrocarbon fractions in the boiling range of heavy gasoline and des Luminous oil.

Table X
Pour point depressants for jet fuels

f Mixed poly
merisat * I. Condensa floor
Point Freezer tion product
from chlorination ⁰ C Point
(FSM) tem wax -53.9 ⁰ C Jet fuel and until -49.7 naphthalene -56.7 Jet fuel <-78.9 + 0.5 / ο -70.6
-67.8 -51.1 + o, i7o
+0: 05-%. -62.2 -50
-51.1 +0.0257 ₀ -59.4 -50.6 +0.01257 « -50.6 -70.6 -65
-53.9 -50 -59.4 -59.4 -48.9 Jet fuel -53.9
-53.9 + 17ο -48.9 +0.5 7o
+ 0.25% + 0.1% + 0.05% + 0.025%
+0.0125 7o

*) Molecular weight 800, determined by Rast's method.

Table X (continued)

Jet fuel

+ 1%
+ 0.75%
+ 0.5%
+ 0.25%
+ 0.125%

Jet fuel

Polymethacrylic acid methyl ester

+ 1%
+ 0.5%
+ 0.25%
+ 0.125%

Mixed polymer
Fumaric acid alkyl ester and
Vinyl acetate

-59.4 -56.7 -53.9 -53.9 -56.7

-56.7 -59.4 -59.4 -59.4

Freezing point (FSM) ⁰ C

The effectiveness of the copolymers according to the invention of ethylene and vinyl acetate to improve the filterability arises from the table below. Various amounts of different substances were added to one fuel oil, and the filterability was determined by the Hagemann and Hammerich test method in accordance with DIN-51770 (Determination of the filterability of diesel fuels). For this purpose a sieve of 0.42 mm was used Mesh size used.

Table XI

Base oil -3.9 ° C

+ 0.5% polymethacrylic acid methyl

ester -9.4 ° C

+ 2.0% condensation product

chlorinated wax and naphthalene -33.3 ° C + 0.1% copolymer of ethylene and vinyl acetate, molecular weight

about 1000 -38.3 ° C

Claims (9)

PATENT CLAIMS: 45 1. Petroleum distillate propellant or fuel from .ein boiling range between about 120 and 400 ° C, characterized in that it is an oil-soluble copolymer with a molecular weight between about 1000 and 3000 of ethylene and an olefinically unsaturated aliphatic mono- 35 40 mers with 3 to 5 carbon atoms per molecule, which is about 1 to 40 percent by weight of the has the latter component, in amounts up to about 1.0 percent by weight. 2. propellant or fuel according to claim 1, characterized in that the copolymer is a copolymer of ethylene and a vinyl ester, such as vinyl acetate. 3. propellant or fuel according to claim 1, characterized in that it is the copolymer in a concentration between about 0.001 and 0.5 percent by weight, in particular between about 0.005 and 0.1%. 4. propellant or fuel according to claim 1, characterized in that the copolymer has a molecular weight between about 1500 and 2200. 5. propellant or fuel according to claim 1, characterized in that the oil-soluble copolymer about 60 to 99 percent by weight ethylene and about 1 to 40 percent by weight vinyl acetate and is contained in the oil base in amounts of about 0.005 to 0.1 percent by weight. 6. jet fuel according to claim 1 to 4, characterized in that the fuel base consists of consists of a mixture of a luminous oil fraction and a heavy gasoline fraction. 7. jet fuel according to claim 6, characterized in that the luminous oil fraction one Boiling range of about 93 to 343 ° C and the heavy gasoline fraction a boiling range of about 60 to 160 ° C. 8. jet fuel according to claim 6, characterized in that it contains the heavy gasoline fraction Contains in amounts of about 10 to 40 percent by volume. 9. jet fuel according to claim 1 to 6, characterized in that it is about 10 to 40 percent by volume from a heavy gasoline fraction and about 90 to 60 percent by volume from one Luminous oil fraction and a copolymer of ethylene and an olefinically unsaturated one aliphatic monomers with 3 to 5 carbon atoms in the molecule, which contains the latter Contains monomers in amounts of about 1 to 40 percent by weight and a molecular weight from about 700 to 3000. Considered publications:
German Auslegeschrift No. 1 014 785;
U.S. Patent No. 2,800,453. For this purpose 2 sheets of drawings © 309 577/178 4.63