EP2751236A1

EP2751236A1 - Additive composition for burning-kerosene-type liquid fuel and uses thereof

Info

Publication number: EP2751236A1
Application number: EP12751348.9A
Authority: EP
Inventors: Bénédicte Amblard; Laurent Germanaud; Christian Vermorel
Original assignee: Total Raffinage Marketing SA
Current assignee: TotalEnergies Marketing Services SA
Priority date: 2011-09-02
Filing date: 2012-08-30
Publication date: 2014-07-09
Also published as: FR2979633A1; FR2979633B1; WO2013030295A1

Abstract

The invention relates to additive compositions that improve the combustion qualities of liquid fuel containing same, said liquid fuel being of the burning kerosene, burning oil, lamp oil or heating gas oil type. The aforementioned additive-containing liquid fuels are suitable for use as fuels for heating appliances, in fixed energy-production devices, in devices used to supply power required for cooking or for any type of heating system: domestic boilers (atomising burner), vaporising stoves, in particular those operating with a sleeve burner and, more specifically, AGA® or Rayburn® boilers, cookers and cooking and/or heating devices.

Description

COMPOSITION OF BURNING KEROSENE LIQUID FUEL ADDITIVES AND USES THEREOF

Technical area

The present invention relates to a high quality fuel consisting of a Burning Kerosene or Burning Oil type liquid fuel or kerosene or domestic fuel oil and an additive composition. This high quality fuel can be used for energy production, heating or cooking for family or collective use.

Burning Kerosene type fuels (BUK) are liquid fuels with distillation temperatures between those of gasoline and those of diesel and properties rather similar to those of diesel fuel. They are very present on the Anglo Saxon market.

There are two BUK categories available on this market:

the class C2 BUK according to the British standard BS 2869 (BUK C2 or

Kerosene Regular) which is a standard kerosene for conventional heating systems

- Class C1 BUK according to the British standard BS 2869 (BUK C1 or Prermium Oil), which is a deflavored BUK C2, it has characteristics similar to those of an aviation fuel.

BUK C1 or C2 type liquid fuels or lamp oils can be used in heating appliances, or in stationary energy-producing appliances, or in appliances for supplying the energy necessary for cooking food. . These fuels are suitable for any type of heating system: domestic boilers (equipped with a spray burner), spray boilers, especially those operating with a sleeve burner (continuous burner), such as cooking and / or heating appliances , stoves, AGA ^® or Rayburn ^® boilers.

As examples of fuels, there may be mentioned C2 BUK type of liquid fuel marketed by the applicant under the name ^® KetruI and the liquid fuel marketed by the applicant under the name ^® Kerdane which has properties equivalent to those of BUK C1 or aviation kerosene. State of the art

In some combustion appliances such as spray stoves or ranges and / or hand-operated burner boilers, the liquid fuel passes through a small diameter feed pipe, usually metal, to reach the combustion chamber. . The walls of this duct closest to the combustion chamber are subjected to very high temperatures for residence times which can be significant, more particularly for appliances where the fuel flow is low. This greatly increases the risk of thermal degradation of the fuel and can lead to the formation of solid deposits on the walls of the conduit, resulting in a reduction in the diameter available for the passage of the fuel and a possible reduction of the flow, or an interruption of the supply of the combustion chamber. Then, in some heaters or cooking, the fuel reaches a combustion pot in which it stays at high temperature (250 ° C to 380 ° C), a few minutes to 1 hour before being vaporized and burned. Under such conditions thermal cracking can occur which results in the formation of solid deposits which lead to degradation of the combustion.

To avoid too much degradation of the quality of combustion over time, the manufacturers of these devices recommend maintenance of the combustion system every 6 months. In some cases, more frequent maintenance is required even before 6 months of use.

To solve these problems and increase the time interval between two maintenances, EP 2 147 966 has proposed a liquid fuel additive composition which comprises

a) at least one anti-oxidant agent of phenol or phenol / amine type, preferably of phenol / amine type,

b) at least one metal passivator,

c) at least one metal sequestering agent such as N, N'-disalicylidene 1, 2-diaminopropane, especially a copper sequestrant,

d) at least one anti-corrosion agent. These additive compositions, although having under certain conditions of use very good performance to maintain the quality of combustion, can in some cases undergo thermal cracking at high temperature which inhibits the effectiveness of the additive and leads to a potential clogging of the feed circuit of the sleeve burner or and / or the burnpot by the formation of residues during thermal cracking.

Presentation of the invention

The present invention provides a liquid fuel additive with an additive composition having excellent combustion properties and which avoids the problems stated above. The liquid fuel additive according to the invention can be used in particular as fuel for thermal appliances and in particular for appliances where the fuel flow is low; the problems of plugging the supply ducts from the fuel storage tank to the combustion chamber are avoided but also the fuel ensures excellent combustion quality while limiting solid deposits at the burner, i.e. unburned. This has the effect of significantly increasing the time interval between two maintenances.

A first object relates to a high quality liquid fuel BUK, kerosene or domestic fuel oil, adapted to energy production devices and / or heating and / or for cooking food. This high quality fuel has improved properties over a standard fuel. For the purposes of the present invention, several properties of the fuel are improved, in particular the oxidation stability, the quality of the combustion, and possibly the odor. Can also be improved: cold resistance, corrosion resistance ...

The invention also proposes an additive composition for liquid fuel of the BUK or kerosene and / or domestic fuel type comprising the following components:

a) at least one hindered phenol type antioxidant agent (alkyl phenol), b) at least one metal sequestrant, in particular copper, or chelating agent,

and preferably c) at least one perfuming and / or masking odor and / or re-odorant agent, and / or

d) at least one marker or tracer additive.

The compositions according to the invention may also contain one or more of the following additives:

e) at least one biocidal additive,

f) one or more additives improving the cold-holding properties: cloud point, filterability limit temperature (TLF), pour point and / or antisedimentation,

g) at least one lubricant additive,

h) at least one anticorrosive additive.

Depending on the nature and miscibility of additives a) and b), c) and / or d) possibly present, but also any other additives, such as those defined below from e) to h), the additive composition according to the invention may also contain a hydrocarbon organic solvent and optionally a cosolvent or compatibilizer which may be selected from organic solvents, especially those derived from petroleum fractions.

Preferably, the additive composition according to the invention comprises at least one hydrocarbon organic solvent and / or at least one compatibilizer or co-solvent.

The antioxidant (s) a) may contain or consist of at least one compound comprising at least one hindered phenol group (mono- or polysubstituted phenol); as an example of hindered phenol type antioxidants, mention may be made of 2,6-di-tert-butyl-4-methyl-phenol (BHT) (CAS No. 128-37-0), tert-butyl hydroquinone (TBHQ) (CAS No. 1948-33-0), 2,6-di-tert-butyl phenol (CAS No. 128-39-2) and 2,4 di-tert-butyl phenol (CAS No. 96-76-4), 2,4-dimethyl-6-tert-butyl phenol CAS No. 1879-09-0), pyrogallol (CAS No. 87-66-1), tocopherol (CAS No. 7616 -22-0), 4,4'-methylene bis (2,6-di-tert-butylphenol) (CAS No. 118-82-1), alone or in admixture.

The metal sequestrant (s) b) may be chosen from amines substituted with Ν, Ν'-disalicylidene groups, such as Ν, Ν'-disalicylidene 1, 2-diaminopropane (CAS No. 94-91-7). The optional scenting and / or masking odorant (s) and / or odorant (c), preferably present in the additive compositions according to the invention, can be chosen for example from:

the organic tricyclic compounds defined in EP-A-1591514, in paragraphs [0010] to [0013] by the formula (I), in particular the organic tricyclic compounds described in paragraphs [0018] to [0022] and 'verdyl acetate corresponding to the additive A of Example 1 (paragraph [0057] of EP-A-1591514), as well as

aliphatic or aromatic aldehydes such as vanillin,

aliphatic or aromatic esters, such as benzyl acetate,

alcohols, such as terpene alcohols such as linalool 3,7-dimethyl-1,6-octadiene-3-ol), or else phenylethyl alcohols,

* ketones, such as crystallized camphor, maltol or ethylmaltol, * essential oils, such as essential oils derived from citrus, alone or in mixtures.

Organic tricyclic compounds defined by the formula (I) in EP-A-1591514 have the following formula:

(I)

wherein the cyclopentane ring is saturated or unsaturated, and

R1, R2, R3, which may be identical or different, are chosen from hydrogen and hydrocarbon radicals comprising from 1 to 10 carbon atoms and optionally comprising one or more heteroatoms, in particular from 1 to 3 heteroatoms; the hydrocarbon radicals can be linear or branched.

By heteroatom is meant here oxygen atoms, nitrogen and sulfur.

According to one embodiment, the organic tricyclic compounds as described in paragraphs [0018] to [0022] of application EP-A-1591514 have formula (Γ): in which :

R1 and R2, identical or different, are chosen from:

hydrogen,

alkylcarboxylate radicals of formula R-COO,

alkylcarbonyl radicals of formula R-C = O,

alkoxy radicals of formula R-O,

with R saturated or unsaturated hydrocarbon-based radical containing from 1 to 4 carbon atoms, linear or branched.

Preferably, R3 is selected from hydrogen and radicals

alkylcarboxylate of formula R'-COO with R 'linear or branched C1-C4 alkyl radical.

Preferably, R 1 or R 2 is hydrogen. Preferably, R3 is

hydrogen. Even more preferably, R 1 is chosen from alkylcarboxylate radicals of formula R'-COO with R 'linear or branched C 1 to C 4 alkyl radical.

As examples of additives of formula () that are particularly preferred in the context of the present invention, mention may be made of the compounds in which:

R2 = R3 = H and R1 = CH ₃ -COO;

R2 = R3 = H and R1 = C ₂ H ₅ -COO;

R2 = R3 = H and R1 = CH (CH ₃₎ ₂ -COO;

or the acetate of Verdyle of formula:

Advantageously, a mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, a hydroxide, a ketone, an essential oil, is preferably used as perfume, odor masking or reodorant c). as defined above. The optional marker (s) d), preferably present in the additive compositions according to the invention may be chosen in particular from the following aliphatic or cycloaliphatic esters:

^■ 3a, 4,5,6,7,7a-hexahydro-4,7-methano-1H-inden-5 (or 6) -yl isobutyrate (CAS No. 67634-20-2)

Tricyclodecenyl propionate (CAS No. 17511-60-3)

^■ cis-hexenyl acetate (CAS No. 3681-71-8)

^■ ethyl linalool (CAS No. 10339-55-6)

^■ prenyl acetate (CAS No. 1191-16-8)

Ethyl myristate (CAS No. 124-06-1)

Para-tert-butyl cyclohexyl acetate (CAS No. 32210-23-4)

^■ butyl acetate (CAS No. 123-86-4),

^■ 4,7-methano-1H-inden-6-ol, 3a, 4,5,6,7,7a-hexahydro-acetate (CAS No. 5413-60-5)

■ ethyl caprate (CAS No. 110-38-3)

Preferred additive compositions according to the invention comprise:

from 2 to 50, preferably from 5 to 30, parts by weight of anti-oxidant agent (s) of hindered phenol type or mono or polysubstituted phenol a),

from 2 to 20, preferably from 2 to 10, parts by weight of metal sequestrant (s) b),

from 3 to 20, preferably from 5 to 15, parts by weight of perfume agent (s) and / or odor masking (s) and / or odorant (s) c),

from 0 to 15 parts by weight of tracer (s) d),

from 20 to 70 parts by weight of organic solvent (s) hydrocarbon (s).

In addition to the above components, the preferred compositions may also contain:

up to 20, preferably from 5 to 15, parts by weight of organic co-solvent (s) or compatibilizing agent (s),

from 0 to 30 parts by weight of other additives, such as, for example, additives e) to h). The additive compositions according to the invention have the additional advantage of being storage-stable for at least several months at room temperature (-15 ° to + 40 ° C.) and can therefore be stored in a deposit before mixing with the fuel. Burning Kerosene type or kerosene.

A second subject of the invention relates to a process for preparing the additive compositions as defined above, by mixing, preferably at room temperature, in one or more steps according to any suitable mixing means:

· Components or additives a) and b) as described above,

And preferably also components c) and / or d), as described above,

• and eventually

One or more of components e) to h) as described above, and / or one or more other additives,

A hydrocarbon organic solvent an organic co-solvent.

The liquid fuel according to the invention of higher combustion quality can be prepared by mixing in one or more steps generally at room temperature:

- liquid fuel,

the additive composition or compositions according to the invention (additives a) and b), and preferably additives c) and / or d),

optionally the solvent (s) and / or co-solvent (s),

and the optional additive (s), such as additives e) to h).

It would not be departing from the scope of the invention by mixing the liquid fuel, the components of the composition or compositions of the invention one by one.

A third subject of the invention relates to a liquid fuel composition comprising:

a major part comprising a liquid fuel which is a mixture of liquid hydrocarbons having distillation temperatures of between 180 and 370 ° C., preferably between 180 and 280 ° C. and more particularly between 180 and 260 ° C. These mixtures are generally derived from cuts of the middle distillate type, from refineries and / or agrofuels and / or biofuels and / or biomass and / or synthetic fuels, and in particular kerosene cuts; these cuts from petroleum refineries generally contain a few percent of aromatic compounds and can be used as liquid fuels or can be subjected to dearomatization, in particular by hydrogenation, having the effect of very strongly reducing the concentration of aromatic compounds (typically less than or equal to at 2% by volume); deflavored mixtures having better combustion properties than mixtures with higher aromatic content; the liquid fuels may also have a composition close to that of the middle distillates of diesel or domestic fuel type.

a minor portion comprising at least one additive composition as defined above, and optionally one or more other additives not forming part of the additive composition or compositions according to the invention.

Preferably, the liquid fuel composition according to the invention comprises from 150 to 3,000 mass ppm of additive composition (s) as defined above, and advantageously from 250 to 1,500 ppm m / m.

A fourth object of the invention relates to the use of liquid fuel compositions as defined above as fuels for the production of energy, for heating and / or for cooking.

The high quality liquid fuel according to the invention, ie additive with at least one additive composition according to the invention can advantageously be used as a fuel for certain types of thermal apparatus and in particular for apparatus where the fuel flow is low. Preferably, the additives e) to h) additive compositions according to the invention, such as additives a) to d), are not sensitive to thermal cracking which occurs under the combustion conditions of the thermal appliances and cooking appliances, and in particular thermal cracking which occurs in the combustion conditions of the heaters and / or cooking of the types of appliances equipped with sleeve burner (for example the stoves and / or boilers of the type AGA ^® or Rayburn ^® Example 1 - Preparation of additive compositions

An additive composition called composition A according to the invention is prepared by mixing at room temperature the following components:

8 parts by weight of a commercial mixture of hindered phenol-type antioxidants (comprising as a major component 2,6-di-tert-butyl phenol (CAS No. 129-39-2): 30-60 2,4,6-tri-tert-butylphenol (CAS No. 732-26-3): 5-10%; 2-tert-butyl-phenol (CAS # 88-18-6): 0% 1-5% 2,4-di-tert-butyl phenol (CAS No. 96-76-4): 0.01-0.1%),

3 parts by weight of N, N'-disalicylidene 1, 2-diaminopropane (CAS No. 94-91-7) (metal sequestering agent b),

6 parts by weight of resorant agent c),

10 parts by weight of 2-ethyl hexanol (compatibilizing agent),

the complement to 100 parts by weight of Solvarex 10 (heavy aromatic organic solvent) marketed by the applicant.

By way of comparison, an additive composition according to the teaching of EP 2 147 966 and designated Composition B is prepared according to the following procedure:

At room temperature, mix:

15 parts by weight of phenol / amine antioxidants,

7 parts by weight passivator of copper of the benzotriazole type,

3 parts by weight of anti-corrosion (mixture of oleic, linoleic and linolenic acid dimer esters),

6 parts by weight of resorbing agent,

10 parts by weight of 2-ethyl hexanol (compatibilizing agent)

the complement to 100 parts by weight of Solvarex 10 (heavy aromatic organic solvent) marketed by the applicant. Thermal stability

The thermal stability of the additive compositions according to the invention was evaluated by using the standard methods JFTOT ^® (Jet Fuel Thermal Oxidation Tester) and Conradson carbon.

Thermal stability - JFTOT® measured according to ASTM D3241 modified (test temperature 350 ° C instead of 260 ° C)

One practical thermal stability measurements according to the JFTOT ^® Test (Jet Fuel Thermal Oxidation Test) of D3241 ASTM modified (temperature of test 350 ° C instead of 260 ° C) on different samples of Burning Kerosene type of liquid fuel ( BUK) additive or not with the additive composition according to the invention A or with the comparative composition B. The test is hardened by working with a treatment rate equivalent to 5 times the nominal dose called here "d" (with d = 500 ppm m / m).

The results are summarized in Table 1 below.

Table 1

These results show that at a temperature representative of that of the burn pot or the fuel supply pipe upstream of the burn pot (typically 350 ° C.), the liquid fuel additive with composition A according to the invention forms a great deal less deposits than additive with composition B. Combustion quality - measurement of Conradson Carbon according to NF-T60-1 16 standard (test temperature 350 ° C instead of 550 ° C)

This standardized test was adapted to the temperature conditions encountered in the burner before combustion, the tests were carried out at 350 ° C instead of 550 ° C.

This test involves burning the volatile effluents as they form while pyrolyzing the residue under a non-inert atmosphere; the residue is weighed. The result of the test corresponds to the mass proportion of residue obtained relative to the initial mass of burned fuel.

The test is hardened by working with a treatment rate equivalent to 5 times the nominal dose called here "d" (here = 500 ppm m / m).

Table 2 shows the results of the modified Conradson Carbone test at 350 ° C.

Table 2

The difference observed between the results obtained on the liquid fuel additive with the composition A according to the invention and that additive with the comparative composition B is significant: the amount of residue obtained for the first product is much lower than for the second. When the BUK fuel is additive with the composition A, it forms much less solid residues at 350 ° C. than in the presence of the composition B.

Claims

1. Additive compositions for Burning Kerosene type liquid fuel or kerosene or domestic fuel oil comprising:

a) at least one hindered phenol type antioxidant (mono- or polysubstituted),

b) at least one sequestering agent of metals, in particular of copper,

and preferably

c) at least one perfuming and / or masking odor and / or re-odorant agent, and / or

d) at least one marker or tracer.

2. Compositions according to claim 1 further containing at least one hydrocarbon organic solvent, and optionally at least one co-solvent or compatibilizing agent, and optionally other additives.

Compositions according to claim 1 or 2, comprising one or more additives:

e) at least one biocidal additive,

f) one or more additives improving the cold-holding properties, g) at least one lubricating additive,

h) at least one anticorrosive additive.

4. Compositions according to one of claims 1 to 3, comprising

a) at least one antioxidant chosen from molecules containing at least one phenol group, such as di-tert-butyl-2,6-methyl-4-phenol (BHT), tert-butyl hydroquinone (TBHQ), 2,6 or 2,4 di-tert-butyl phenol, 2,4-dimethyl-6-tert-butyl phenol, pyrogallol, tocopherol, 4,4'-methylene bis (2,6-di- tert-butyl phenol), alone or as a mixture;

b) at least one metal sequestrant chosen from compounds having at least one Ν, Ν'-disalicylidene group, such as N, N'-disalicylidene 1, 2-diaminopropane;

and preferably c) at least one scenting and / or odor-masking and / or re-scouring agent, preferably chosen from

The organic tricyclic compounds defined in Application EP-A-1591514, in paragraphs [0010] to [0013] by the formula (I), in particular the organic tricyclic compounds described in paragraphs [0018] to [0022] and verdyl acetate corresponding to the additive A of Example 1 (paragraph [0057] of EP-A-1591514). as well as

Aliphatic or aromatic aldehydes such as vanillin, aliphatic or aromatic esters, such as benzyl acetate,

• alcohols, such as linalool, phenylethyl alcohols,

Ketones, such as crystalline camphor, ethylmaltol,

• essential oils, such as essential oil derived from citrus fruits

· Their mixtures,

And advantageously the mixture of at least one organic tricyclic compound and at least one aldehyde, an ester, an alcohol, a ketone, an essential oil;

and or

d) at least one tracer or label, preferably chosen from the following aliphatic or cycloaliphatic esters:

> 3a, 4,5,6,7,7a-hexahydro-4,7-methano-1h-inden-5 (or 6) -yl isobutyrate

> tricyclodecenyl propionate

> cis-hexenyl acetate

> ethyl linalool

> prenyl acetate

> ethyl myristate

> para tertio butyl cyclohexyl acetate

> butyl acetate

> 4,7-methano-1H-inden-6-ol, 3a, 4,5,6,7,7a-hexahydro-, acetate

> ethyl caprate;

and optionally at least one solvent and / or a co-solvent and / or one or more other additives.

Compositions according to any one of claims 1 to 4 comprising:

from 2 to 50, preferably from 5 to 30, parts by weight of hindered phenol-type antioxidant (s) or mono or polysubstituted phenol a),

from 2 to 20, preferably from 2 to 10, parts by weight of sequestrant (s) of metals b),

from 3 to 20, preferably from 5 to 15, parts by weight of perfume agent (s) and / or masking (s) of odor and / or odorant (s) c),

from 0 to 15 parts by weight of tracer (s) d),

from 20 to 70 parts by weight of organic solvent (s) hydrocarbon (s).

Compositions according to claim 5 further comprising

from 0 to 30 parts by weight of other additives, such as, for example, additives e) to h).

7. Process for the preparation of a composition as defined in any one of claims 1 to 6, by mixing, preferably at room temperature, components of said composition in one or more steps.

8. Liquid fuel composition comprising

a major part of a mixture based on liquid hydrocarbons of Buming Kerosene type or kerosene or domestic oil having distillation temperatures of between 180 and 370 ° C., preferably between 180 and 280 ° C. and particularly between 180 ° C. C and 260 ° C, an aromatic compound content of up to 20%, preferably less than or equal to 1%, said liquid hydrocarbon-based mixture comprising cuts of the middle distillate types, originating from refineries and / or agrofuels and / or biofuels and / or biomass and / or synthetic fuels; a minor portion of at least one additive composition as defined in any one of claims 1 to 6.

9. Composition according to claim 8 comprising from 50 to 3,000 ppm, preferably from 250 to 1,500 ppm m / m of at least one additive composition as defined in any one of claims 1 to 6.

Use of a liquid fuel composition as defined in claim 8 or 9 as fuel for energy production, for heating and / or for cooking, and especially for cooking and / or heating in sleeve burner apparatus.

11. Use of a composition according to claim 8 or 9 as fuel for heating apparatus, boilers and spray stoves.

12. Use of a composition according to claim 8 or 9 as fuel stoves equipped with sleeve burner.