ES2245872A1 - Composition of gas oil or fuel disposal stabilized means. (Machine-translation by Google Translate, not legally binding) - Google Patents

Abstract

A composition of diesel fuel or middle distillate fuel stabilized by the addition of a combination of a metal deactivator and at least one other compound selected from dispersants, antioxidants and light stabilizers, as well as the use of said composition as heating gas oil a process of obtaining said composition. (Machine-translation by Google Translate, not legally binding)

Description

Composition of diesel or distilled fuel stabilized medium

Field of the Invention

The present invention relates to a medium stabilized diesel or distilled fuel composition by adding a combination of a deactivator of metals and at least one other compound selected from dispersants, antioxidants and light stabilizers, as well as the use of said composition as heating oil and a process of obtaining said composition.

State of the art

Diesel is a fuel widely employed, both for combustion in industry and in homes. Diesel is obtained from the refining of crude oil. The refining comprises a series of separation processes, transformation and purification, whereby crude oil It is converted into useful products with countless uses, which go from simple combustion in a lamp to the manufacture of intermediate products, which in turn are the raw material for Obtaining other industrial products. The different oil fractions are separated into columns called columns of fractionation. Each fraction of oil is a mixture of hydrocarbons, which vary from "heavy" to light. Depending the degree of boiling, the order of obtaining or leaving the Products is as follows: liquefied gas, gasoline, kerosene and diesel oil.

There are many types of diesel, depending on their origin and way of obtaining. Due to the incorporation of new processes of crude oil treatment, the formulation of diesel Heating is very variable; the combined presence of direct distillation and conversion currents, at different Hydrotreatment levels, further increases this variability. By Therefore, the composition of diesel can vary widely intervals, for example, may have a greater or lesser content in olefins, metals, etc.

The evolution of diesel formulations heating has also been accompanied by the evolution of facilities where it is burned. It has opted for the massive incorporation of copper pipes in these facilities, which can cause the incorporation of copper into diesel, to which a high recirculation rate is added to the deposit of fuel. In addition, the use of translucent materials for storage tanks, which allows the incidence of light on diesel. All this entails an increase in the instability of diesel. In addition, the systems injection have been progressively sophisticated, which converts diesel stability into a critical feature for the proper functioning of them.

As can be seen in Figure 1, the Diesel instability mechanisms are complex. The biggest part of the routes lead to insoluble products, so the dispersant products are usually effective in relieving the trouble. However, there are also rubber formation routes that They require an antioxidant to avoid them. Additives stabilizers affect neutralizing the acids product of the oxidation. Metals (Zn, Cu) are also known to accelerate the oxidation mechanisms, so it is usual to use metal deactivators if they are present. These metals may be present in diesel from the refinery, or, however, have their origin in the typical facilities of the market for diesel heating, which in many cases incorporate pipes or other parts of the installation made in copper. Another additional destabilizing factor is the incidence of light on heating oil.

There are numerous additives on the market that they try to solve these instability problems, which incorporate antioxidants, metal deactivators, stabilizers, detergents, dispersants and neutralizers, individually or in Mix of two or more of them. However, due to the high variability in the composition of diesel, its response to Stabilizing additives is unpredictable and distinct in each case. After years of use, these known additives have demonstrated acceptable effectiveness in most types of diesel; no However, in general they only serve a certain type of diesel, being ineffective for other diesel, or even counterproductive, even worsening the stability of the same. That is, none of these additives exist in the market really solves favorably the problem of instability of diesel, since so far it is necessary adapt the addition of these stabilizing additives to each diesel of heating, according to its composition. In addition, due to mentioned variations in the composition of the diesel that is producing by incorporating new processes, these additives, in fact, do not have adequate efficacy to increase The stability of diesel.

In addition, there are a number of interactions unpredictable among the different compounds to additive: by for example, the use of metal deactivators, necessary for passivating copper can cause a worsening of stability in front of the light The use of dispersants is also critical, since that these enhance the dissolution of copper.

The concept of using anti-polymerizers to improve the stability of conversion products It is very common in residual fuels. The GB 2 026 publication 025 A describes the use of acrylonitrile copolymers or alkylacrylonitrile. However, the doses used of these products are very high (0.1% weight) and its purpose (avoid getting worse viscosity after thermal instability) do not conform to needs of a diesel or medium distilled fuel. Some additives based on this concept have adapted to distillates media (additive 1050 in patent tests 1 and 2) but its Efficacy is not always satisfactory.

Manich bases have been used as dispersants, as in US 5,026,495, and in literature they come to advocate its effectiveness to stabilize the currents unstable diesel. This type of product has been evaluated but its  effectiveness has been far from satisfactory, as shown in test 1 later in this document (additive "141").

It has been described that amines improve stability of hydrocarbons, including medium distillates (US 3,516,806, ES 2 199 696). However, its effectiveness is not mentioned to improve stability in the presence of copper or subjected to incidence of light. It is not strange to check its lack of effectiveness in tests 1 and 2 (additive 2146).

Sulfomono- and sulfodiimines have been described as dispersants of residual fuels (US 4,867,753), but have not been considered suitable for heating diesel, given the expected reduction in sulfur content of this Fuel for the next few years.

To improve the stability of diesel in presence of cracking components salts have also been used guanidino (EP 0 388 236 B1). However, its use in packages it is less widespread than polybutensuccinimides, so that its Marketing cannot compete with these. The search for a additive for an extensive fuel such as diesel heating should consider without avail the availability and the price.

Polyisobutenes Multifunctional are commonly used as detergents to avoid fouling of diesel and gasoline engines (EP 0 629 641 B1). However, by themselves, they are not able to avoid the deposit formation when the fuel is in contact with a catalyst metal; rather the opposite, facilitating the dissolution of the catalyst metal and seriously worsening the final stability (tests 1 and 2, additive 2111).

The use of esters to stabilize diesel Diesel is mentioned in several patent publications (DT 25 59 480 A1, DT 25 22 014 A1) and has advantages over others products, since they can provide anti-rust advantages. Without However, they are not effective in preventing oxidation catalysis in presence of metals, whose deposit formation can overflow the dispersive capacity of the additive, as with the product according to the present invention.

The combined use of dispersants based in succinimides and amines, along with document deactivator FR 2 839 315 A1. However, this document does not demonstrate nor does it describe the use of combinations of this type to improve oxidation stability, neither in the presence of catalytic metals (copper) or in the presence of light.

The use of combinations with deactivators of Metals are mentioned in US Patent 4,744,801. Stabilizes diesel using a mixture of 20-40% of a polyphenol, a sulfured polyphenol and a sterically hindered phenol, together with a 80-60% of a cyclic amide. Check that the Adding a metal deactivator does not improve stability. This result is a consequence of not considering a system where the diesel is in contact with a catalyst metal, as in the case of  most domestic heating oil installations in Spain.

There was, therefore, the need to provide some additive or mixture of stabilizing additives that solve the instability problems of all types of diesel heating, without the need to adapt its composition to each individual case, and that also inhibited the effect of copper, while improving stability against light, from the point of view of deposit formation. Additionally, the variation of the formulation of diesel due to the incorporation of new processes, discussed above, has also caused a variation in your response to additives. The combined presence of direct distillation and conversion currents, at different hydrotreatment levels, is a challenge for additives that It is also one of the objectives to be resolved by the present invention.

Description of the invention

It has now been found that the incorporation of a certain ratio of additives, basically a combination of a metal deactivator and at least one additional compound selected from dispersants, antioxidants and stabilizers against to ultraviolet (UV) light, to a diesel or distilled fuel oil medium, solve the indicated problems previously.

In accordance with the present invention, it has been found that as a metal deactivator it is especially effective he N, N'-disaliciliden-1,2-diaminopropane, of formula

one

as dispersant, the poly-isobuten-succinimide, from formula

2

where R is an isobutene polymer from formula

3

as antioxidants, a mixture that understands 2,6-diterc-butyl-phenol and, optionally mono and isomers triterc-butylphenol, and the N, N'-disecbutyl-paraphenylene diamine;

4

5

and as UV light inhibitors, the 2-hydroxy-n-oxyalkyl benzophenone

6

Y 2- (2'-hydroxyphenyl) benzotriazoles, by example 2- (3 ', 5'-diterbutyl-2'-hydroxyphenyl) benzotriazole:

7

These light inhibitors have come usually using for uses very different from that of stabilize diesel or fuels, such as for polymer stabilization. So far its description has not been described use in the stabilization of diesel or fuels.

Therefore, according to a first aspect, the The present invention relates to a diesel oil composition or medium distilled fuel characterized in that it comprises, by each kg of diesel or fuel:

-

from 6 to 50 mg of N, N'-disalicyliden-1,2-diaminopropane;

-

from 0 to 75mg of poly-isobuten-succinimide;

-

from 0 to 10 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono isomers and triterc-butylphenol;

-

from 0 to 15 mg of N, N'-disecbutyl-paraphenylene diamine;

-

from 0 to 15 mg of 2-hydroxy-n-oxyalkyl benzophenone; Y

-

from 0 to 15 mg of 2- (2'-hydroxyphenyl) benzotriazoles.

It has been found that the optimal relationship between amount of dispersant and deactivator of metals added to diesel or fuel is a very relevant aspect to improve the Critical stability of diesel or fuel in the market. From this way, it has been found that the weight ratio of poly-isobuten-succinimide with about N, N'-disalicyliden-1,2-diaminopropane it should preferably be between 1: 4 and 1: 8.

According to a preferred embodiment, the Composition of diesel or medium distilled fuel according to The present invention incorporates 30 to 50 mg of poly-isobuten-succinimide and 10 to 30 mg of N, N'-disaliciliden-1,2-diaminopropane,  respectively for each kg of composition or fuel.

According to another preferred embodiment, the composition or the fuel according to the present invention incorporates from 10 to 20 mg of N, N'-disaliciliden-1,2-diaminopropane, from 25 to 45 mg of poly-isobuten-succinimide, from 3 to 6 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono and triterc-butylphenol isomers, and from 6 to 12 mg of N, N'-disecbutyl-paraphenylene diamine, respectively for each kg of composition or fuel.

According to an embodiment additional, composition or fuel according to the invention incorporates 3 to 9 mg of N, N'-disaliciliden-1,2-diaminopropane, from 3 to 12 mg of 2-hydroxy-n-oxyalkyl benzophenone and from 3 to 12 mg of 2- (2'-hydroxyphenyl) benzotriazoles, respectively for each kg of composition or fuel.

The diesel composition according to the present The invention has a high utility as heating oil; therefore, the present invention also relates, according to a second aspect, to the use of the diesel or fuel composition medium distillate as defined above, as diesel fuel heating.

Also, according to a third aspect, this invention refers to a method of obtaining a Composition of diesel or medium distilled fuel, characterized because it includes adding, for every kg of diesel composition or Medium distilled fuel, the following components:

-

from 6 to 50 mg of N, N'-disalicyliden-1,2-diaminopropane;

-

from 0 to 75 mg of poly-isobuten-succinimide;

-

from 0 to 10 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono isomers and triterc-butylphenol;

-

from 0 to 15 mg of N, N'-disecbutyl-paraphenylene diamine;

-

from 0 to 15 mg of 2-hydroxy-n-oxyalkyl benzophenone; Y

-

from 0 to 15 mg of 2- (2'-hydroxyphenyl) benzotriazoles.

Preferably, in the previous procedure Is added poly-isobuten-succinimide in a ratio between 1: 4 and 1: 8 with respect to N, N'-disalicylicidene-1,2-diaminopropane.

According to another preferred embodiment, add 30 to 50 mg of poly-isobuten-succinimide and 10 to 30 mg of N, N'-disaliciliden-1,2-diaminopropane,  respectively for each kg of composition or fuel.

According to another preferred embodiment, add 10 to 20 mg of N, N'-disaliciliden-1,2-diaminopropane, 25 to 45 mg of poly-isobuten-succinimide, from 3 to 6 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono and triterc-butylphenol isomers, and 6 to 12 mg of N, N'-disecbutyl- paraphenylene diamine, respectively for every kg of composition or fuel

According to an embodiment additionally, 3 to 9 mg of N, N'-disaliciliden-1,2-diaminopropane, from 3 to 12 mg of 2-hydroxy-n-oxyalkyl- benzophenone and 3 to 12 mg of 2- (2'-hydroxyphenyl) benzotriazoles, respectively for each kg of composition or fuel.

Next, the invention will be described. additionally, by means of a series of examples, merely to Illustrative title and in no way limiting.

Examples

Examples 1-8

Several samples of the stabilizing composition for heating oil according to present invention; these samples will be called from now on forward A-H. For this they have mixed different component quantities, as specified in the table next. All data is in mg.

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8

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Examples 9-20

Twelve stabilizing compositions are taken known for its use for the stabilization of diesel heating; They have been named as follows. Then you It also details its respective composition:

" 1050 ":

30-60% xylene

10-30% n, n'-disaliciliden-1,2-diaminopropane

10-30% polymer methacrylate

5-10% ethylbenzene

1-5% propan-2-ol

<1% cresol

0.28% phenol

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" 1049 ":

60-100% N, N'-disalicyliden-1,2-diaminopropane

10-30% xylene

1-5% ethylbenzene

1% phenol

" 1627 ":

n-n'-disecbutil paraphenylenediamine

" 1628 ":

p-phenylenediamine

" 2145 ":

benzotriazole derivative

" 2146 ":

sterically hindered amine (HALS)

" 2149 ":

2-hydroxy-4-n-octyloxy benzophenone

" 2111 ":

Polyisobutylene solvent derivative (45% 5% naphthenic solvent 2-ethylhexan-1-ol)

" 2184 ":

25-50% aromatic solvent

25-50% phenols sterically handicapped

10-25% N, N-Disaliciliden-1,2-diaminopropane

" 2181 ":

Commercial additive for heating diesel, dispersing type, low nitrogen content

" 2119 ":

15-50% petroleum distillate

20% anionic surfactant

22 {226} 10% butyloxytitol

" 141 ":

Manich Base

Stability tests of heating oil

Two trials have been developed that contemplate the stability affecting the factors that most affect diesel of heating of the Spanish market: the presence of copper and the incidence of light. Likewise, the effect that most impacts on the operation of the fuel: the formation of insoluble The amount of copper used and the irradiation have been adapted to the specific experience of the market evaluated.

These stability tests have been performed on different types of diesel, both without additive and using the additives of examples 1 to 20.

The diesel used for the tests have a variable composition; its main components, with Weight percentage intervals are as follows:

Distillation direct 0-100% Naphtha conversion process FCC 0-15% FCC diesel (LCO) 0-5% Middle distillate hydrotreated 0-50% Fraction olefinic heavy 0-5% Middle distillate of process Isomax 0-40% Distilled source of hydrocracking 0-60%

The values of density (measured according to ASTM-D-4052), sulfur content (measured in accordance with ISO-8754) and nitrogen (measured in accordance with ASTM-D-2649) of the diesel used in the tests:

9

Test one

Oxidation stability in the presence of copper

Several samples of 1 kg of the Different types of diesel. The test is always performed on a Sample of the respective diesel without adding the additive, to use as a reference, and on others to which it is added respectively one of the stabilizing compositions according to the invention (Examples 1 to 8, compositions A-H) or one of the additives known in the prior art (Examples 9 to 20), in order to verify the relative and absolute effectiveness of stabilizing compositions according to the present invention. If of the compositions A-H, the amount of components indicated in examples 1-8 is added respectively to 1 kg of the respective diesel. For additives of State of the Art, the doses used vary between 6 and 10,000 mg for each kg of diesel.

The diesel samples are aged following the conditions set out in ISO12205 (350 ml of sample, 16 hours, 95 ° C, with 3L / h oxygen bubbling), in the presence of a 35 cm copper wire. The insoluble produced are determined, as sum of filterable (0.8 microns) and adherent (washed with trisolvent and evaporation at 160 ° C), measured in g / m 3. The Results are reflected in the following table:

10

eleven

12

As you can see, the effectiveness of compositions according to the invention in increasing the stability of the different types of diesel before oxidation of diesel with copper It is very good, and in most cases much better than the effectiveness of the compositions known in the State of Technique.

Test 2

Stability against light

Several samples of the different types are taken of diesel. The test is always performed on a sample of the respective diesel without adding the additive, to use as reference, and on others to which one of the stabilizing compositions according to the invention (Examples 1 to 8, compositions A-H) or the known additives of State of the Art indicated in examples 9-19 in order to verify the relative and absolute effectiveness of the stabilizing compositions according to the present invention. At In the case of compositions A-H, the amount of components indicated in the table of examples 1-8 is the one that would be added respectively to 1 kg of the respective diesel oil. For the additives of the State of the Art the dose used varies from 50-2000 mg per kg of diesel.

A sample of 50 mL of the different is aged diesel at 40 ° C, subjected to constant UV radiation for 48 hours. Insolubles produced similarly to the test 1, adapting the filter, the filtration equipment and the evaporation to the amount of sample used. The results are collected in the following table:

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(Table goes to page next)

13

14

fifteen

As can be seen in the data in the table above, the effectiveness of the compositions according to the present invention is clearly better in virtually all cases (except in the case of CFC2 diesel, a fairly stable diesel per se , in which the effectiveness is identical for both additives).

Claims (11)

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1. Composition of diesel or medium distilled fuel characterized in that it comprises, for each kg of diesel or fuel:

-

from 6 to 50 mg of N, N'-disalicyliden-1,2-diaminopropane;

-

from 0 to 75 mg of poly-isobuten-succinimide;

-

from 0 to 10 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono isomers and triterc-butylphenol;

-

from 0 to 15 mg of N, N'-disecbutyl-paraphenylene diamine;

-

from 0 to 15 mg of 2-hydroxy-n-oxyalkyl benzophenone; Y

-

from 0 to 15 mg of 2- (2'-hydroxyphenyl) benzotriazoles.

2. Composition according to claim 1, characterized in that the weight ratio of poly-isobuten-succinimide with respect to N, N'-disalicylidene-1,2-diaminopropane is from 1: 4 to 1: 8. 3. Composition according to any of claims 1 and 2, characterized in that it consists of 30 to 50 mg of poly-isobuten-succinimide and 10 to 30 mg of N, N'-disalicylidene-1,2-diaminopropane, for each kg of composition or fuel. 4. Composition according to any of claims 1 and 2, characterized in that it consists of 10 to 20 mg of N, N'-disalicylicidene-1,2-diaminopropane, 25 to 45 mg of poly-isobuten-succinimide, from 3 to 6 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and 0 to 25% of mono and triterc-butylphenol isomers, and 6 to 12 mg of N, N'-disecbutyl- paraphenylenediamine, for every kg of composition or fuel. 5. Composition according to any one of claims 1 and 2, characterized in that it consists of 3 to 9 mg of N, N'-disalicylicidene-1,2-diaminopropane, 3 to 12 mg of 2-hydroxy-n-oxyalkyl- benzophenone and 3 to 12 mg of 2- (2'-hydroxyphenyl) benzotriazoles, per kg of composition or fuel. 6. Use of the diesel or fuel composition medium distillate according to any of claims 1 to 5 as heating oil. 7. Procedure for obtaining a medium distilled diesel or fuel composition, characterized in that it comprises adding, for each kg of medium distilled diesel or fuel composition, the following components:

-

from 6 to 50 mg of N, N'-disalicyliden-1,2-diaminopropane;

-

from 0 to 75 mg of poly-isobuten-succinimide;

-

from 0 to 10 mg of a mixture comprising 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono isomers and triterc-butylphenol;

-

from 0 to 15 mg of N, N'-disecbutyl-paraphenylene diamine;

-

from 0 to 15 mg of 2-hydroxy-n-oxyalkyl benzophenone; Y

-

from 0 to 15 mg of 2- (2'-hydroxyphenyl) benzotriazoles.

8. Method according to claim 7, characterized in that poly-isobuten-succinimide is added in a ratio between 1: 4 and 1: 8 with respect to N, N'-disalicylicidene-1,2-diaminopropane. 9. Method according to claim 7, characterized in that 30 to 50 mg of poly-isobuten-succinimide and 10 to 30 mg of N, N'-disalicylicidene-1,2-diaminopropane are added per kg of composition or fuel. 10. Method according to claim 7, characterized in that 10 to 20 mg of N, N'-disalicylicide-1,2-diaminopropane, 25 to 45 mg of poly-isobuten-succinimide, of 3 to 6 mg of a mixture comprising from 75 to 100% of 2,6-diterc-butyl-phenol and from 0 to 25% of mono and triterc-butylphenol isomers, and from 6 to 12 mg of N, N'-disecbutyl-paraphenylene diamine by each kg of composition or fuel. Method according to claim 7, characterized in that 3 to 9 mg of N, N'-disalicylicidene-1,2-diaminopropane, 3 to 12 mg of 2-hydroxy-n-oxyalkyl benzophenone and 3 to 12 mg of 2- (2'-hydroxyphenyl) benzotriazoles per kg of composition or fuel.