DE3218294A1 - FUEL BASED ON GASOEL WITH A CONTENT OF WATER AND ALCOHOL - Google Patents

Description

4167 B.256 3

The invention relates to a method for improving the properties of gas oils by adding to the gas oil suitable amounts of water and one or more surfactants, optionally together with one or more co-surfactants, wherein the latter are compounds that are suitable for hydrogen bonding with the water. That according to the invention Treated gas oil has an extremely clear and transparent appearance, the water that is in it is extremely soluble and is not decanted.

It is known to use organometallic salts of Ca ⁺⁺ , Ba ⁺⁺ , Mn ⁺⁺ , Fe ⁺⁺⁺ and others to improve the combustion of gas oils. Such additives, which are incorporated into gas oils in amounts of the order of magnitude of 10 to 1000 ppm, enable the emission of soot, unburned solids, GO, and unburned hydrocarbons to be reduced by initiating the formation of free radicals. However, these additives have numerous disadvantages, in particular toxic emissions on leakage, especially in the case of Ba ⁺⁺ salts and, in general, the formation of metal oxides in the combustion chambers, which can have an abrasive effect.

The beneficial effect of water on the combustion of Hydrocarbon is known. Since 1954 ic the FR-PS 1 100 551 recommended in liquid fuels to incorporate small amounts of water in the presence of wetting agents, for example of condensation products of fatty alcohols, phenols or fatty acids with ethyloxide. However, in practice it was not possible to produce stable emulsions and the incorporated

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Water separated out over time, which led to disadvantages in the storage containers: corrosion, bacterial proliferation. In addition, the water droplets, • that were dragged along into the filter, to a flatulence of the deposits, resulting in unpleasant interruptions of the Feeding from the container, the seizure of pumps, etc. resulted. The presence of water droplets led to the formation of ice crystals at cold times with icing and clogging of the filters Motor feed circuit.

More recently, attempts have been made to address the drawbacks of the booth the technique to compensate by using special mixtures of surface-active compounds that are stable Emulsions are said to result in and the water in the form of very fine particles that are dispersed in the hydrocarbon are, include. For example, in US Pat. No. 3,876,391 Incorporation of 6 to 16% water in automotive gasoline in the presence of 3 to 8% of a fatty acid ester, the is optionally polyethoxylated, described and, moreover, a surface-active agent on the Based on amine, polyethoxylated alkylphenol, a polyethoxylated fatty acid amide or a polyethoxylated one Sorbitol fatty esters; one is also forced to 0.5 to 10% of an amide or a water-soluble one Amines such as acetamide, formamide, monoethanolamine, ethylenediamine, etc. add. The recommended Solution is therefore very complicated.

The question has remained very complicated over the past year, as described in US Patent No. 4 083 698, which still mixtures of fatty acid salts with ^3i> polyethoxylated nonionic surfactants provides for very fine stable emulsions of 0.1

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• up to 10% water and 1 to 10% of a lower alcohol to achieve in a fuel. Since the latter is relatively heavy, especially a diesel fuel, i. H" ein.Gasöl, the proposed combination is generally no longer sufficient, and in the patent specification it is explained (columns 24 and 25) that up to about 15% cyclohexanol and / or cyclohexanone are added have to.

By the invention, a considerable improvement of this Technik'bereitgestellt since they von.Brennstoffen a considerable improvement in the combustion enables the gas oil type, ie of hydrocarbons boiling at about 200-425 ⁰ C, in a substantially simplified and more economical manner, the easier is to be carried out than with the known technology.

The invention is based on two surprising findings. First: The sought-after improvement in a gas oil can be achieved by incorporating small amounts of water, ie from 0.01 to 0.5%, as opposed to several percent which are used in the prior art; Secondly: The water can be emulsified completely clear and very stable by means of certain special surface-active agents that have not been used for this purpose up to now.
".

The new process of the invention is to emulsify 100 to 500 parts per million starter in the gas oil in the presence of a surfactant and is characterized in that the surface-active agents ^ ⁵ of one or more compounds of the formula

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4167 B.256

COOH

(D

NHCOR ¹

consists in which each of the radicals H and R ^{1 is} an aliphatic group, in particular alkyl or alkenyl, and EC ₂ to C ₂₈ and R ^{1 has} C ^ to C ^ ₀ .

The radical R is preferably a relatively heavy alkyl radical, ie with a content of at least 6 carbon atoms and in particular Cg to Co ₂ . The acyl group can be low, such as acetyl, propionyl, butyryl, etc., but it can also be derived from a fatty acid, where R ^{1 is} CV or more, but preferably C _x . to C. is. Although the radicals R and R ^{1 are} most frequently alkyl radicals, they can, however, also consist of unsaturated hydrocarbons, in particular alkeny].

Some salts according to the invention are listed as examples, which are used as emulsifying agents and microemulsifying agents are suitable:

Potassium N-acetyl-a-aminocaprylate,
Sodium N-butyryl-a-aminodecanoate

Diethylamine N-propionyl-oc-aminododecanoate Sodium N-acetyl-a-aminododecanoate, Ammonium N-octanoyl-a-aminododecanoate, Potassium N-acetyl-a-aminotetradecanoate, Pyridinium-N-caproyl-a-aminotetradecanoate, Diethylenediamine di- (N-propionyl-oc-aminohexadecanoate) Sodium N-acetyl-oc-aminooleate,

Sodium N-acetyl-ct-aminooctadecanoate,

Isobutylamine-N-acetyl-a-aminolinoleate, 3b sodium N-acetyl-oc-aminotetradecanoate,. : ■ Sodium N-oleyl-oc-aminooctadecanoate,

· ■ "Ö ^mmm

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Potassium N-linoleyl-oi-aminohexanoate, etc.

B The salts of the acids of formula (1), according to the invention vex 'are applicable, derive yich from any inorganic or organic base, on condition that they are at least a little in water, the chosen Hydrocarbon or both. Practically suitable are the salts of alkali metals, especially of potassium and sodium, and optionally the alkaline earth salts. The salts of ammonium can be suitable, such as those of primary, secondary or tertiary Amines, especially methyl, ethyl, propyl, butyl, hexyl, etc. amines, ethylenediamine, diethylenetriamine, Propylenediamine, hexamethylenediamine, mono-, di- or triethanolamine, pyridine, piperidine, piperazine, etc.

The co-surface-active agent, solvent and / or stabilizing agent of the salt according to the invention can be selected from those of the prior art, in particular from various alcohols. So you have a wide choice in the class of alcohols, such as isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, monobutyl alcohol, ole ethyl alcohol, monobutyl alcohol, methyl alcohol, cyclohexyl ethers of ethylene glycol, methyl alcohol, cyclohexyl ether, various alcohol, cyclohexyl ether, methyl alcohol, cyclohexyl ether, methyl alcohol, cyclohexyl ether, various ethyl alcohol, isobutyl alcohol, amyl alcohol, isobutyl alcohol, , Benzyl alcohol or ³ ^ others; this list is intended to include only examples without representing a restriction.

The invention is practiced using one of the co-surfactants together of types known for this type of emulsions; whereby lower alcohols such as methanol, ethanol,

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Propanol, isopropanol, and butanols generally good are suitable.

The proportion of co-surfactant, such as that of the surfactant itself, is on the order of 10 to 5000 ppm and especially from 25 to 2000 ppm, which corresponds to 0.0025 to 0.2% gas oil. The weight of the co-surfactant depends on the particular pail Means generally at 0.1 to 1 part and often at 0.5 to 1 part per 1 part by weight of the surfactant.

The amount of surfactant to be used is proportional to the amount of water to be solubilized. In general, aromatic gas oils with an aromatic content of over 25% require lower amounts of surface-active substances Medium than the paraffinic gas oils, the aromatic content of which is of the order of 10 to 15%.

The addition of surfactants, if necessary together with the co-surfactant, enables the very large reduction in interfacial tension Water-gas oil to a value on the order of JO to 40 dynes cm

The system obtained is in the form of a liquid dispersion, the outer continuous phase of which

the gas is oil, while the dispersed phase consists of water in droplets or micelles of smaller size to 0.4 ma or micron; the entire dispersion is translucent. The system formed is thermo ^{3 £>} stable and, unlike conventional emulsions, the water does not deposit or not decanted

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even over a long period of time on the order of several months.

In a general way, the process according to the invention is carried out by adding to the gas oil from 100 to 5000 ppm water, 10-5000 ppm surfactant and 10-5000 ppm co-surfactant, the weight ratio of the latter to the agent being 0.1 to 1. However, very good results can be achieved are obtained with 100 to 1000 ppm of water and 25 to 2000 ppm of the surface-active compound together with 0.5 to 1 part of their weight of co-surface

15 active connection.

The following examples, which are not intended to be limiting, serve to illustrate the invention in the form of some embodiments with specific surfactants.

In these examples, a diesel engine is run on gas oil that does not contain any additive and on the other hand with gas oils which have been treated according to the invention.

One assumes a gas oil with the following properties:

relative density at 15 ° C,
related to water at 4 ⁰ C 0.831

30 distillation point at 50 % distillation point at 90 % final distillation point
Viscosity · at 20 ^° C

35 original water content

The water used is demineralised.

255 ⁰ C 363 ⁰ C 340 ⁰ C 4.1. 10 ~ ⁶ m ² / s (4.1 CSt) 75 ppm

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The vehicle used for the tests is placed on a dynamometric chassis. The location at which the experiments are carried out is air-conditioned in such a way that known and reproducible conditions (20 ^° G) are possible. Work at a stabilized speed for an initial test period of 45 minutes with the motor running at twice its normal power. The tank of the vehicle contains gas oil intended for the tests. You work until the engine is thermally well stabilized.

A motor is operated on the trainer in a comparable way.

The experiments are carried out according to the regulations of the Journal Officiel de la Republique Francaise pour la reception described par la GEE des vehicules, that is;

- Experiments with stabilized speed: The engine is brought to full load and one leads Measurements evenly divided in the area of maximum engine power

^<w 25 and the largest of the following ranges: (i) 45% of the range of rotation corresponding to the maximum force, and (2) 1000 rpm.

- Experiments with free acceleration: the gearbox is brought to idle and the engine is engaged. Operated when the engine is slowing down quickly, but gently, the accelerator so that the maximum flow rate of the injection pump is achieved will. This position is maintained until the controller intervenes; when this speed is reached, there

3k you free the accelerator until the engine slows its down Speed resumes.

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The procedure is repeated at least six times, to clean the exhaust system and the fixtures possibly adjust.

The measurements consist in determining the opacity of the exhaust gases collected at the exhaust of the vehicle determine. The device used is an opacimeter, the type and method of use in the Journal Officiel de la Republique Pramfaise of March 21, 1974 - 1 annexes 7 and 8, will be described.

The test vehicle is with an engine of 3> 3 1 cubic capacity equipped with an output of 56 Kw at 3? 00 RPM developed.

Examples 1 to 4-

Tests with motor ranges, stabilized at 1500, 2000, 25OO and 32OO rpm were on the one hand with gas oil carried out without addition and on the other hand with the various additives indicated in Table I of the results.

—1 The latter are the absorption coefficients in m indicated, which are found for the exhaust gases in the course of the turbidity measurement, as mentioned above.

^3U Each result is the mean of four determinations, the deviations of which do not exceed 5% °.

For comparison purposes, experiments are carried out with Ba-alkylbenzenesulfonate, which is referred to as "SB" ³ ^ and a conventional surfactant based on polyoxyethylene alcohols (Ukanyl 36 der

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Societe Pechiney-Ugine-Kuhlmann), referred to as "UK".

The micro emulsions of water and 3-methyl-butanol (i) in gas oil are produced using Na-i-docosyl-1-acetamide acetate

NHCOCH,

_w as a surfactant.

The gas oil used has a distillation point of 255 ° G at 50%, 363 ⁰ C at 90% and a final distillation point at 3 ^ 0 ⁰ C; its original water content is 75 ppm.

The microemulsions formed with this fuel are examined in a diesel engine of 3 »3 1 cubic capacity with an output of 56 Kw at 3200 rpm, with the Investigations in four different areas from 1500 up to 3200 rpm.

^ 25 In the course of the investigations, the turbidity of the Exhaust gases from the engine according to regulated French methods, Journal Officiel de la ßepublique Prancaise, March 21, 1974, Appendices 7 and 8. The absorptive coefficients of light, which are so determined in m, are similar to those for the treated Gas oils, as well as for the same gas oil without additives that was used as a comparison (see the following Table), given below.

35

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Kon example

trol- 1 2 3 4-

Ie

Content of ^ added water Content of me-butanol

Surfactant content

Range2_rpm 1500 2000 2500 32OO

0 0.1 0.5 0.1 0.1

0 0.05 0.2 0.06 0.1
0 0.05 0.2 0.06 0.01

" ¹

1.94-1.4-5 1.25 1.70 1.40

1.47 1.00 0.90 1.35 0.95

2.61 1.60 1.20 2.20 1.50

4.45 3.10 3.10 3.70 3.50

It can be seen that improvements, ie lower opacities of the exhaust gases, by about 30% to more than 50 % are achieved using the microemulsions according to the invention, so that at 2500 rpm with 0.5% water is obtained, based on the control sample , an improvement of (2.61 - 1.20): 1.20 = 54%.

On the other hand, the results of Examples 1 and 2 according to the invention are better than those of the conventional polyethoxylated surfactant (UK Example 3); they are practically comparable to those who do that Ba-alkylbenzenesulfonate (Example 4) gives.

Example 5 ; ·

The procedure of Example 2 is carried out with 0.2% Na-N-acetyl-A-amino-oleate repeated as a surfactant. The results are the same as in the example 2.

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• β bold * «« * · * · t *

41 ί> 7 -B.256 14

Example 6

0.5% water is microemulsified with 0.1 % isopropanol and 0.1% diethylamine-N-butyryl-ot-aniinododecanoate in the same gas oil as in the previous examples. The absorption coefficient of the exhaust gases, based on the control sample, is reduced by 40% at 25ΟΟ rpm.

Examples 7 and 8

Gas oils containing water according to the examples 1 and 2, are compared with free acceleration investigated with untreated gas oils. The following results are obtained:

Examples 2 8 control

% Water in the microemulsion 0.1 0.45 0 % n-butanol 0.07 0.25 0

% Na-N-propionyl-α ~ aminostearate 0.06 0.20 0

Absorption coefficient m " ¹ 0.91 0.85 1» 20

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Claims (6)

I \ i1i ntiiimäJU · ·! '. Ornpcun Patent .Mt ^(II "5-'y ^s * ·. * ..." * ·. *.! ». W. Λ1> ΐ (/ I> ι Inc. I) .F. Morf I) r. Dipl .- (lit-m. M. Gritschneder Dipl.-Phys. Abu ?. Morf. Grilsihnctkr, from WillivnMcin. P.O. Box 86 01 09, 8000 Munich 86 A. Frhr. from Wittgenstein Postal address P.O. Box 86 0] 09 D-8000 Munich 86 May 14, 1982 4167 B.256 ELl · ¹ ΪΕΑΝΟΕ rue de 1'Universite 75ΟΟ7 Paris, France Fuel based on gas oil with a content of Water and an alcohol - Patent claims MJ fuel consisting of a microemulsion of water and an alcohol in a gas oil containing a surfactant composed of a salt of a K-acyl-oc-amino acid ' R-CH-GOOM "consists in which R and R ^{1 are} linear or branched alkyl or alkenyl, where R 2 to 28 carbon atoms and R ^{1 has} 1 to 20, M is a cation of an alkali metal or alkaline earth metal, of ammonium or an amine, 4167 B-256 characterized in that the microemulsion, based on weight, consists of 98.5 to 99.98% gas oil, 0.01 to 0.5% water, 0.001 to 0.5 % of the salt of N-acyl-tf-amino acid and 0.001 up to 0.5% of an alcohol. 2. Fuel according to claim 1, wherein H is alkyl or an alkenyl with Co to Gp ₁ , and E ^{1 is} an alkyl with C. to G _c .
b 3 · Fuel according to claim 1, characterized in that one of the residues or the two residues E and E ' contain one or more aromatic nuclei. 15th 4. Fuel according to one of claims 1 to 3> characterized in that its content, based on weight, of surfactant 0.1 to 0.5%, 0.1 to 0.5% of water and 0.1 to 0.5% of alcohol. 5. Fuel according to one of the preceding claims, characterized in that the weight fraction of the surfactant is 0.5 "to 1 per liter of water. 6. Fuel according to one of the preceding claims, characterized in that the weight fraction of Alcohol is 0.5 to 1 per 1 surfactant .. ■