DE2050071A1 - Liquid hydrocarbon preparations - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

β MUNICH 2. HILBLESTRASSE 2O

Dr. Mountain ΡίρΙ.-lng. Stapf, 8 Mönchen 2, HllblestraBe 20 Our sign date

Oct 12, 1970

Attorney's file 20 058 Be / A

ESSO Hesearcn and Engineering Company Linden, N. J. (USA)

"Liquid hydrocarbon preparations"

This invention relates to certain liquid hydrocarbon fuels. Fuel preparations (fuels), also referred to as "heating oils" and in the following for simplification Fuels are called and oil preparations that contain a blackberry in order to reduce their pour point.

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109818/1872

to improve the flow rate of the fuel or oils »

Various flow improvers or pour point depressants are known, but many of them appear when you use them Fuels or lubricating oils admits to have a limited effect insofar as that after a certain period of time the pour point moves towards that of the untreated fuel or oil. This so called regression or regression is obviously a disadvantage and limits the value of these flow improvers and pour point depressants a. The applicant has now found flow improvers and pour point depressants which have essentially no regression, at least for fuels containing residues, shale oils or flash distillate fuels exhibit.

According to this invention contains a liquid hydrocarbon preparation of a larger proportion by weight of a fuel containing residue, a flash distillate fuel, a shale oil or a crude oil and a lower weight fraction, sufficient to improve the flow properties of the preparations, reaction product of (a) an alcohol or amine having at least 16 carbon atoms atoms per molecule, with (b) a copolymer of comonomers (1) an ethylenically unsaturated dicarboxylic acid or their anhydride or derivative and (2) little-

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1098 18/1872

at least one alpha-olefin having at least 20 carbon atoms per molecule. In the case of crude oils, the reaction product can also be from an alpha-olefin with 18 or Carbon atoms per molecule.

It is particularly desirable in accordance with the invention that the hydrocarbon be a residue-containing fuel. The residue-containing fuel is defined as being a fuel that contains residue from the distillation of crude oil or shale oil or mixtures thereof. In general, the can Residue containing fuel from about $ 10 to $ 100, e.g. B, about 35 to 100 wt "contain # residue, preferably about 315 C (600 F) boiling at atmospheric pressure, and usually it will have kinematic viscosities in the range from 10 to 3500 cS at 37.8 ⁰ C (100 ⁰ F) . However, it may be difficult to measure the viscosity of some particularly wax-containing fuels exactly at 37.8 ⁰ O (10O ⁰ F), and it is generally known that the viscosity of such fuels is measured as the viscosity at a higher temperature. The viscosity at 37.8 C (100 F) is then obtained by extrapolating using a REFUIASo Viscosity Temperature Sheet. The extrapolated kinematic viscosity can then fall in the desired range of 37.8 ⁰ C (100 ⁰ F). The ReE.FUToA.S. temperature viscosity index was determined by CI Kelly M.Sc. Tech *; FICj M ₀ Inst ", Pet .;

10 9 8 18/1872 " ⁴ ~

BATH ORIGINAL.

-A-

AMIAE Copyright reserved in Great Britain and US "A" by Baird and Tatlock (London) Limited, 14-17 Cross Street, Hatton Garden, London, E.C1. Fuels with kinematic viscosities 15-1500 cS at 37.8 ⁰ C (10O ⁰ F) are preferred, and as fuel, wherein at least

Boiling 30% and preferably at least 60% by weight above 260 ° C (500 ° F) at atmospheric pressure are particularly suitable.

To the residue containing fuels to which the invention relates, are therefore lightweight, medium, heavy and bunker fuels or fuel oils or oven, and their viscosities in the range of about 15 to 2,000 cS at 37.8 ⁰ C ( 10O ⁰ F), however, the maximum viscosity is usually around 1500 cS at 37.8 ⁰ C (100 ⁰ F). Examples of suitable fuels are described in Pt, 3 Industrial and Marine Fuels of BS 2689, 1957 »

Suitable fuels also include "flash distillate fuels", which are defined as distillate fuels that are obtained by flash distillation under reduced pressure from the residue, which in turn results from the distillation under reduced pressure from the residue, which in turn is obtained from the distillation of crude oil at atmospheric pressure «, Such fuels become by distilling a crude oil at a soil temperature

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at about 350 ° C. under atmospheric pressure to give an atmospheric residue which is then separated into a "flash" distillate and a vacuum residue by "flash" treatment under substantially reduced pressure. In "Hash ¹¹ " or equilibrium distillation, the preheated feed is continuously introduced into a "Plash" chamber, where evaporation takes place under constant equilibrium conditions. Gaseous and liquid products are continuously removed. Fractionation does not occur in the "Piaah" treatment Significant role "The temperature at which the" plash "treatment is carried out is limited by potential cracking and carburization. These side reactions start to occur when the temperatures exceed 400 0" The "plash" treatment is carried out at significantly reduced pressure performed to ensure the high distillate yield from a given atmospheric residue «,

Shale oils can also be used, as can the crude oils themselves. Usually the pour point of the crude oils is higher than -23 ° C (-10 ⁰ P).

Suitable ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, mesaconic acid, citraconic acid, Itaconic acid, trans- and cis-glutaconic acids. The corresponding anhydrides (if they are present) can also be used.

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However, it is preferred to maleic anhydride or a To use derivative of the same »

Such derivatives include those of the general formula

O = C C = O

wherein the radicals R .. and Rp are hydrogen, halogen or a C. to Cg-alkyl group, (e.g. methyl, ethyl or Butyl), and X is oxygen, NH or KU, where R, an alkyl group, preferably a Cj to C, Q alkyl group is. Suitable examples of such derivatives include methyl maleic anhydride, dimethyl maleic anhydride, Ethyl maleic anhydride, N-ethyl maleimide, N-hexyl maleimide, N-dodecyl maleimide, N-tetradecyl maleimide, N-eicosyl maleimide, N-tetracosyl maleimide, chloromaleic anhydride or dichloromaleic anhydride another maleic anhydride derivative, that can be used is maleic acid.

The ethylenically unsaturated dicarboxylic acid or its anhydride or derivative is with an alpha-olefin with at least 20 carbon atoms per molecule converted · Although there is no upper limit on the number of carbon atoms per

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Molecule can be given, olefins which contain between 20 and 50, ζ, Β _β between 22 and 30 carbon atoms per molecule should preferably be used in practice. Mixtures of ^ -olefins can be used, e.g. a C ₂₂ -CPg-Ge ¹¹ IiSChO Suitable \, - 01efins include Cos-1-en, Docos-1-en, Tetracos-1-en, Hexacos-1 -en and octacos-1-en «, If the additive is added to a crude oil, one can also use octadec-1-en or nonadec-1-en or mixtures containing these olefins»

The reaction between the dicarboxylic acid, its anhydride or derivative and the <* - olefin can suitably by mixing the - ^ - olefin with at least 0.5 moles, preferably 1 to 2 moles of the acid, its anhydride or derivative and heating the mixture to a temperature of at least 100 ⁰ C, preferably at least HO ⁰ C can be performed ,, a catalyst such as t-butyl hydroperoxide or di-t-butyl peroxide is normally used · The final product has etc after esterification · a number-average-molecular weight from 500 to 50,000 , usually from 500 to 20,000 and suitably from 1,000 to 1,500.

The reaction product so prepared is treated with an alcohol or an amine of at least 16, suitably up to Contains 26 carbon atoms per molecule, converted · The Alcohol can be straight or branched sei.i, however aliphatic, essentially straight, monovalent alcohol

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hole with 20 to 26 carbon atoms per molecule preferred »Such alcohols include eicosanol, Cpp-oxo alcohol, Tetracosanol, and may further include mixtures of such alcohols as, for example, behenyl alcohol. That Amine can be acyclic or a primary or secondary monoami " with at least 16, suitably up to 26, preferably between 20 and 26 carbon atoms per molecule.Examples of such amines are 1-docosylamine, 2-tetracosylamine, 1-octadecylmethylamine or 1-docosylethylamine.

The ratio of the reaction product, i.e. h _e additive to the fuel or oil is added, should preferably zwischenO, 0001 # and 10 #, z. B. between 0.0005 and 0.5 wt _e $, based on the weight of the residue-containing fuel, flash distillate fuel, shale oil or crude oil.

Manufacturing 1

In a 500 ml 5-neck polymerization flask equipped with a water condenser, stirrer and control thermometer were placed: 56 parts of maleic anhydride and 200 parts of a C _22-28 1-olefin fraction having an iodine value of 76 g / 100 g. The reactants were added at 145 ° G, and di-t-butyl peroxide at a rate of Ή2 part per hour for a period of 1V4 hours _e. The reaction was terminated after 1.5 hours by adding 1000 parts of xylene. The copolymer was by adding

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358 parts of alcohol (behenyl alcohol) of the following composition: CQ 16 $>, OpQ 15 # »Cgp 69 # and 5 parts of p-toluenesulfonic acid diesterified. The solution was refluxed for 8 hours and the water of reaction was removed using a Dean and Stark water trap. The product was isolated under reduced pressure while removing the xylene solvent.

Manufactures 2 and 3

The following copolymers were prepared in a manner similar to preparation 1 (Table 1) »

Table 1 Manufacturing 2 2 1-olefin type ^G 30+ ° 18 Weight (g) 200 28.6 Maleic anhydride weight (g) 32.8 11.2 Response time at 145 ° C (hours) 14th 5 Rate of addition of di-t-
peroxide ml per hour 2 1 during (hours) 13 3/4 1

The copolymers were di-esterified under similar conditions as in the preparation 1

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Xylene added (g) 1000 1000

Alcohol *) added (g) 210 70

p-Toluenesulfonic acid (g) 11 5

*) C ₁₈ 16 #, C ₂₀ 15 *, C ₂₂ 69 +.

Manufacturing 4

Monoesters of all copolymers were prepared under similar reaction conditions, except that half the amount of alcohol was used in the esterification step and no p-toluenesulfonic acid was added.

example 1

The additives produced in the production method 1, 2, 3 and 4 were contained in two residual fuel oils A and B mixed by stirring at 82 ° C (18O ⁰ P). The pour point of the mixtures was then determined (Admiralty method 7)

The fuel oil (fuel oil) A was a residual fuel, which was prepared from a North African crude oil by distillation using a Enddampftemperatür of 377 ° C (710 ⁰ F). It contained $ 100> residue and had a melting point of about 40 ⁰ C (105 ⁰ F).

The fuel oil B was a residue fuel made from

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30% by weight of gas oil and 70% by weight of residue from the distillation of lybisehem crude oil to a final vapor temperature of 343 C (65O ⁰ F). The heating oil had a pour point of 35 ⁰ C (95 ° F) "

The following results were obtained:

Fuel A

Additive (marked concentration pour point ⁰ C ( ⁰ F) is characterized by the d _e additive (Admiralty process «in the production (weight, #) 7)
1-olefin used)

40 (105)

0.10 26 (80)

0.10 35 (95)

0.15 24 (75)

0.15 32 (90)

0.10 32 (90)

0.10 40 (105)

0.15 32 (90)

0.15 40 (105)

^C 22-28 Diester Monoester ^C 18 Diester Diester ^C 22-28 Diester Diester ^C 18 Diester ° 30 + Monoester ° 18 Monoester ⁰ 3Ot Monoester ° 18 Monoester Fuel B ° 3O + ° 22-28 ^C 18

- 35 ( 95) 0 , 20 26th ( 80) 0 , 20 21st ( 70) 0 , 20 32 ( 90)

The pour point or pour point for rucks χ adölo, .admiralty Method 7, is a modified pour point developed by

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The test consists of initially heating the sample to 93 ° C (20O ⁰ P), dividing it into smaller samples, air cooling and then shock quenching. Followed by a WJ ^r iererhitzen the separate samples to different reheating temperatures "The upper pour point of each sample is then determined and the maximum value is the yield point," The process is described in the Journal of the Institute of Petroleum, 1960, Volume 46, page 189 _f «

The table shows that the results obtained even with monoesters of the additives in the context of the present invention are often significantly superior to the results obtained with diesters of the C .. "product.

This is a surprising advantage that can be obtained by selecting and using the additives according to the present invention Another advantage is that, if desired, one is able to use a few long chain esterifying agents to use

Example 2

The table below summarizes the results obtained with the implementation of "Upper Pour Point Tests (Inst · Pet, Method 15/67)" on various residual fuels “A mono-

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behenyl ester of a 22p8

misciipolymerisats, produced according to the manufacturing process drive 1 and 4 »used

Residual oil

"Upper Pour Point" G ⁰

without additive 0.1 wt

North Africa Libya Eastern Europe

Light African heating oil

15 18

27 15

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Claims (2)

205007 Ί - H claims: 1 ο Liquid hydrocarbon preparation characterized by that they have a larger weight fraction of a Flash distillate fuel, an eon or shale oil or, preferably, fuel containing a residue and $ 0.0001 to 10, preferably $ 0.0005 to 0.5 on the weight of the fuel or oil of the reaction product (a) an alcohol or amine of at least 16 and preferably 20 to 26 carbon atoms per molecule, with (B) a copolymer of co-monomers (1) of an ethylenically unsaturated dicarboxylic acid or its anhydride or derivative and (2) at least one alpha-olefin having not less than 20, preferably 20 to 50 carbon atoms per molecule contains ο 2. Liquid hydrocarbon preparation according to claim 1 characterized in that the co-monomer (2) has at least one alpha-olefin with 22 to 30, preferably 22 to 28 Carbon atoms per molecule is » 10 9818/1872 Liquid hydrocarbon preparation according to Claim or 2, characterized in that the co-monomer (1) is maleic acid, fumaric acid or, preferably, maleic anhydride. Liquid hydrocarbon preparation according to one of the preceding claims, characterized in that the alcohol is an aliphatic, essentially straight, monohydric Alcohol, preferably behenyl alcohol. Liquid hydrocarbon preparation according to claim 4, characterized in that the reaction product is a Behenyl ester, preferably the monoester of a maleic anhydride / Cpp 2 «~ Alpha-01efin copolymer is. 109818/1872 BAD ORIGJNAL