FR2505867A1 - IMPROVED FUEL, GASOIL-BASED, CONTAINING WATER AND ALCOHOL - Google Patents

Abstract

GASOIL FUEL CONTAINS 100 TO 5000 PPM OF WATER IN THE FORM OF A MICELLAR SOLUTION, CLEAR, CLEAR AND STABLE OVER TIME, OBTAINED BY ADDITION OF ONE OR MORE SURFACTANTS, ASSOCIATED WITH ONE OR MORE COTENSIO AGENTS -ACTIVE. THE SURFACTANT IS A SALT OF N-ACYL A-AMINE ACID.

Description

The invention relates to a method for improving combustion properties.

diesel fuel, by adding

  diesel with appropriate amounts of water and one or more

  several surfactants possibly associated with one or more co-surfactants, the latter being

  posed likely to form with water hydro-

  The diesel oil, treated according to the invention, has a perfectly clear and limpid appearance, the water is there

  perfectly dissolved and does not decant.

  It is known to use organometallic salts

  that of Ca ++, Ba ++, Mn ++, Fe + and others, to improve the combustion of gas oils Such additives, incorporated

  for diesel fuel at levels of the order of 10 to 1000 ppm, per-

  reduce the emission of soot, solid unburnt,

  CO and unburnt hydrocarbons, initiating the formation

  tion of free radicals However, these additives have a certain number of drawbacks, in particular: toxic exhaust emissions, in particular in the case of Ba ++ salts, and, generally, formation in the combustion chambers of oxides that can

exert an abrasive action.

  The beneficial effect of water on the combustion of hydrocarbons is known. Thus, as early as 1954, it was proposed, in French patent No. 1,100,551, to incorporate into the

  liquid fuels of small quantities of water in pre-

  sence of wetting agents, for example

  densification of fatty alcohols, phenols or fatty acids,

  with ethylene oxide However, in practice we do not arrive

  not to obtain stable emulsions, and the incorporated water separates in the long term, leading to disadvantages in the storage tanks: corrosion, bacterial proliferation In addition, water droplets, entrained

  in the filters caused swelling and clogging

  tage, of untimely stops of the supply from the tank, seizure of the pumps, etc. The presence of water drops caused the formation of ice crystals in cold weather, with icing and clogging of the filters of the

motor supply circuit.

  More recently, attempts have been made to remedy the shortcomings of the prior art by the use of mixtures

  special surfactant compounds, to give

  stable emulsions, containing water in the form of very fine particles, dispersed in the hydrocarbon It is

  as well as patent U S n 3 876 391 describes the incorporation

  tion of 6 to 16% of water with auto gasoline, in the presence of 3 to 8% of a fatty acid ester, optionally polyethoxylated, and as much of a surfactant based on amine, on alkyl polyethoxylated phenol, a polyethoxylated fatty acid amide or a fatty ester of polyethoxylated sorbitol; and still are we

  forced to add 0.5 to 10% of an amide or a hy-

  drosoluble, such as acetamide, formamide, mono-

  ethanolamine, ethylenediamine, etc. The proposed solution

is therefore very complicated.

  The issue has remained as complex over the past

  n recent years, as can be seen from U.S. Patent No. 4,083,698 which further advocates mixtures of fatty acid salts with nonionic surfactants,

  polyethoxylated, to obtain very fine emulsions, sta-

  0.1% to 10% water and 1% to 10% lower alcohol in a fuel When the latter is relatively heavy, in particular a Diesel fuel, i.e. diesel, the combination generally no longer suffices, and the patent explains (columns 24 and 25) that

  add up to about 15% cyclohexanol and / or cyclohe-

xanone.

  The present invention provides an improvement

  marked in this technique, in that it improves

  considerably improve the combustion of diesel fuels, that is to say hydrocarbons boiling between 200 and 425 C, in a much simpler, more economical and easier to carry out, than does

known technique.

  This invention results from two unexpected observations: 1 the desired improvement in a diesel can be obtained by incorporating small proportions of water, namely from 0.01 to 0.5%, unlike the several% used in the prior art ; 2 the water can be emulsified completely clear and very stable by means of certain specific surfactant compounds which have never been used for this purpose,

in the past.

  The new process, according to the invention, which consists in emulsifying 100 to 5,000 parts per million of water in diesel oil, in the presence of a surfactant,

  is characterized in that the surfactant is

  killed by one or more compounds of formula: COOH

R-CH (1)

  N% NHCO Rt o each of the radicals R and Rt is an aliphatic group, in particular alkyl or alkenyl, R being in C 2 to C 28 and R 'in

C 1 to C 10.

  The radical R is preferably a relative alkyl

  strongly heavy, that is to say containing at least 6 carbon atoms, and especially in C 8 to C 24 The acyl group can be lower, such as acetyl, propionyl, butyryl, etc., but it can also derive from 'a fatty acid, R' being C 6 or more, but it is preferably C 1 to C 4 Although the radicals R and R 'are most commonly alkyls, they can nevertheless be constituted by hydrocarbyls

  unsaturated, especially alkenyls.

  By way of nonlimiting examples, here are some-

  some of the salts according to the invention, which are suitable for

  as emulsifiers and microemulsifiers: N-acetyl a-ami-

  no potassium caprylate, sodium N-butyryl a-amino decanoate, diethylamine Npropionyl a-amino dodecanoate, sodium N-acetyl a-amino dodecanoate, ammonium N-octanoyl a-amino dodecanoate, Nacetyl a-amino tetradecanoate potassium, N-caproyl a-amino pyridinium tetradecanoate, di- (N-propionyl c-amino hexadecanoate) ethylene diamine, N-ac 6 tyl amiin QL-sodium, N-acetyl c-amino octadecanoate-N isobutylamine acetyl a-amino linoleate, sodium acetyl a-amino tetradecanoate, sodium N-oleyl a-amino octadecanoate, potassium N-linoleyl a-amino hexanoate, etc.

  The salts of the acids according to formula (1), used

  readable according to the invention, derive from any mineral base

  organic or organic, provided you are at least a little bit

  soluble in water, in the chosen hydrocarbon or in the

  two Practically suitable alkali metal salts

  linens, especially those of potassium and sodium, and possibly-

  alkaline earth salts ammonium salts

  wind suit, like those of amines, primary, secondary or tertiary, in particular methyl-, ethyl-, propyl-, butyl-,

  hexyl-, etc, amines, ethylene diamine, diethylene-tria-

  lead, propylene diamine, hexamethylene diamine, mono-, di-

  or tri-ethanolamine, pyridine, piperidine, piperazine, etc. The surfactant co-agent, solvent or / and stabilizer of the salt according to the invention, can be chosen from those of

  known art, in particular among different alcohols So has

  there is a wide choice in the class of alcohols like iso-

  propyl, butyl, isobutyl, amyl, isoamyl,

  hexyl, heptylic, octyl, nonyl, decyl, do-

  decyl, mono-butyl ether of ethylene glycol, dibutyl-

  ethylene glycol ether, various ethoxylated alcohols, cyclo-

  hexanol, methylcyclohexanol, benzyl alcohol or the like;

  this list is given by way of illustration only-

  ment, without any limiting nature.

  The invention is carried out with the use of

  joint of one of these co-surfactants of types known per se for this kind of emulsions; lower alcohols, such

  as methanol, ethanol, propanol, isopropanol and bu-

  tanols are generally suitable.

  The proportion of co-surfactant is, like that of surfactant itself, of the order of 10 to 5,000 ppm, and

  especially from 25 to 2000 ppm, or 0.0025 to 0.2% of diesel.

  Depending on the case, the weight of co-surfactant is generally

  0.1 to 1 part and often 0.5 to 1 part for 1 part

tie by weight of surfactant.

  The amount of surfactant to be used is

  proportional to the amount of water to be dissolved

  general, aromatic gas oils, having an aro-

  more than 25%, require less amounts of surfactant than paraffinic gas oils,

  the aromatic content is of the order of 10 to 15%.

  The addition of the surfactant, possibly as-

  association with cotensio-active, allows to greatly reduce the interfacial water-diesel tension by a value

of the order of 30 to 40 dynes cm 1.

  The system obtained is in the form of a disper-

  liquid ion, the external continuous phase of which is diesel, while the dispersed phase consists of water in droplets or micelles of size less than 0.4 microns the whole of the dispersion has an appearance transparent to light The system formed is thermodynamically stable

  and, unlike conventional emulsions, water does not

  not even after a very long time

several months.

  In general, the method of the invention is practiced by adding 100 to 5,000 ppm of water to the gas oil, 10 to 5,000 ppm of surfactant and 10 to 5,000 ppm of co-compound. surfactant, the weight ratio of the latter to the agent being from 0.1 to 1 However, very good results can be obtained with 100 to 1000

  ppm water and 25 to 2,000 ppm of surfactant compound

  gained from 0.5 to 1 part of its weight of co-surfactant compound.

  The nonlimiting examples which follow, illus-

  trent invention in some of its achievements

  with specific surfactants.

  In these examples, a diesel engine is operated with diesel oil containing no additives and

  on the other hand with gas oils treated according to the invention.

  We start from a diesel with the characteristics

  following ques s -density relative to 15 e C relative to water at 4 e C 0.831 -Distillation point at 50% 255 e C

"" at 90% 363 C

  "t" n final 340 * C - viscosity at 20 OC 4 1 cst - initial water content 75 ppm

  The water used is demineralized.

  The test vehicle is placed on a

  dynamometric chassis The room in which

  slow testing is air-conditioned, so it is possible

  ble to place itself under perfectly known conditions

  and reproducible (20 C) We proceed in a first é-

  tap at a 45 minute trial period, at steady speed

  stabilized, the engine operating at approximately two-thirds of its nominal power The vehicle's tank

  contains the diesel used for the tests.

  know when a good thermal equilibrium of the engine has been obtained. A completely similar procedure was also

  performed on an engine on the test bench.

  The tests are carried out in accordance with the

  Criteria of the Official Journal of the French Republic for the reception by the EEC of the vehicles, namely: Tests at stabilized speed: the engine being brought to full load, measurements are carried out uniformly between the mode corresponding to the maximum power of the engine and the largest of the following speeds: (10) 45% of the rotation speed corresponding to the maximum power, and (20) 1,000

revolutions / minute.

  Free acceleration tests: the vehicle speed boot is placed in neutral and the engine is engaged; with the engine idling, we operate

  quickly, but without brutality, the order of the ac-

  accelerator, so as to obtain the maximum flow rate of the injection pump; this position is maintained until the regulator intervenes; as soon as this

  speed is obtained, the accelerator is released until

  until the engine resumes idling speed.

  The operation is repeated at least six times to clean

  the exhaust system and if necessary carry out the

gliding devices.

  The measures consist in determining the opacity of the fumes collected at the vehicle exhaust.

  used is an opacimeter whose type and mode of use

  sation conform to the description published in the Journal

  Official of the French Republic from March 21, 1974 year-

nexes 7 and 8.

  The test vehicle is equipped with a 3.3 liter displacement engine, developing a power of 56 kW at

3,200 rpm.

EXAMPLES 1 to 4

  Engine speed tests, stabilized at 1,500, 2,000, 2,500 and 3,200 rpm, were carried out, on the one hand with diesel fuel without additive, and on the other with

  the various additives indicated in Table I of the results

states.

  These are expressed by the absorption coefficients

  tion in m-1 found for exhaust gases as a result of the opacity measurement mentioned above. Each result is an average of 4 determinations, including

the differences do not exceed 5%.

  For comparison, tests were carried out with,

  1 a k Iben ên ,,, me additives, S fona e Se Ba designated by "SB" and a conventional tepsioactive agent based on polyoxyethylenated alcohols (UKANYL 36 from the company Péchiney-Ugine-Kuhlmann), designated

by "UK".

  Microemulsions of water and methyl-3

  butanol-1 in diesel fuel are prepared by means of

  cosyl-1 acetamide-1 acetate Na C 22 H 45? H-COO Na

NHCOCH 3

as a surfactant.

  The diesel used has a distillation point of 255

  C at 50%, 363 C at 90% and an end point of 3400 C; his te-

neur in initial water is 75 ppm.

  Microemulsions, formed with this fuel, are

  yées in a diesel engine of 3.3 liters of displacement,

  with a power of 56 Kw at 3,200 rpm, the tests

  both performed at four different regimes, ranging from

1,500 to 3,200 rpm.

  During these tests, the opacity of the exhaust gases is measured.

  engine exhaust by regulatory method, fran-

  çaise (Official Journal of the French Republic, March 21, 1974, Appendices 7 and 8) The absorption coefficients

  of light, thus determined in m 1, are indicated below

  afterwards for the treated diesel, as well as for the same waste

  soil without any adjuvant, tried for comparison.

  (See Table on the next page).

  Water content% added Me-butanol content% À

Agent content

sioactive Regimen: rpm t 500

2,000

2,500 3,200

Tee Example

less ple

0 0.1

Example "UK" "SBU ple 3 4

0.5 0.1 0.1

0 0.05 0.2 0.06

0 0.05

Coefficients

1.94 1.45

1.47 1.00

2.61 1.60

4.45 3.10

0.2 0.06

absorption,

1.25 1.70

0.90 1.35

1.20 2.20

3.10 3.70

  0.1 0.01 m-1 1.40 0.5 1 50 3.50 We see that improvements, i.e. reductions in the opacity of the exhaust gases, from around 30% to more

  50% are obtained by using the following microemulsions

  before the invention; thus at 2,500 rpm at 0.5% water

  we have, compared to the control, an improvement of (2.61 -

1.20): 1.20 = 54%.

  On the other hand, the results of Examples 1 and 2, following

  the invention are better than those of the conventional surfactant

  that, polyethoxylated ("UK" example 3); they are practi-

  similar to those of alkyl benzene sulfo-

Ba nate (Example 4).

EXAMPLE 5

  The operations of Example 2 are repeated with 0.2% of N-acetyl amino-oleated Na as a surfactant The results are equivalent to those of

Example 2.

EXAMPLE 6

  0.3% water is micro-emulsified with 0.1% iso-

  propanol and 0.1% di-butyryl a-amino-dodecanoate

  thylamine, in m 4 gas oil than in the previous examples.

  The exhaust gas absorption coefficient is

  lowered by 40% compared to the control, at 2500 rpm.

EXAMPLES 7 and 8

  Gas oils containing water, according to respec-

  examples 1 and 2 are tried in acceleration

  free compared with untreated diesel.

  The following results are found: 2 Examples: 7 8 Control% water in microemulsion 0.1 0.45 O% butanol-n 0.07 0.25 O% N-propionyl aamino-stearate Na 0.06 0 , 20 O Absorption coefficient m-1 0.91 0.85 1, 20 1-1

Claims (6)

Claims   1 Advanced fuel, consisting of a micro-   emulsion of water and an alcohol or an amine, in a gas oil, containing a surfactant, characterized in   that this agent is a salt of an N-acyl-a-amino acid.   2 Fuel according to claim 1, in which the surfactant is R-CHCOOM   NH Cc R 'o R and R' are linear or branched alkyls or alkenyls, R comprising 2 to 28 carbon atoms and R'1 to   , while M is an ammonium or amine cation.   3 Fuel according to claim 2, characterized in that one or both radicauk R and R 'contain a or more aromatic nuclei.   4 Fuel according to claim 2 or 3, charac-   terized in that R is C 8 alkyl or alkenyl to   C 24, Rt being C 1 -C 6 alkyl.   Fuel according to one of the preceding claims, characterized in that the surfactant is a sodium salt.   6 Fuel according to one of the preceding claims.   teeth, characterized in that the microemulsion which comprises it   laying contains 0.001 to 0.5% by weight of surface-active agent, 0.01 to 0.5% of water, 0.01 to 0.5% of an alcohol, the rest being a diesel.   7 Fuel according to claim 6, characterized in that its content, by weight, of surfactant is 0.1 to 0.5%, in water from 0.1 to 0.5 fet in alcohol of 0.1 at 0.5%.