JPH0710985B2 - Fuel oil stabilizer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a stabilizer for preventing deterioration of fuel oil, particularly during storage, and more specifically to various fuel oils, in particular kerosene obtained from various pyrolysis processes. Petroleum-based fuel oils including oils and light oils, coal liquefied oils, sand oils, shale oils, and mixed oils containing two or more thereof during storage and / or under the action of heat, light, chemicals, etc. The present invention relates to a stabilizer which prevents deterioration and deterioration, forms sludge (precipitate, suspended matter, gum, etc.) and lowers the hue, and improves long-term stability.

B. Conventional technology Fuel oil including kerosene and light oil obtained by various thermal cracking processes (catalytic cracking, thermal cracking, coking process, etc.), coal liquefied oil, sand oil, shale oil, and two or more of them The storage stability of the mixed oil is significantly poorer than that of the conventional crude straight-run fuel oil. Storage stability of fuel oil means decrease in hue during storage, sludge (precipitate, float, gum, etc.)
Is the tendency of generation. Fuel oil with poor stability causes problems in combustion of internal combustion engines and boilers. For example, the strainer may be clogged, sludge may be attached to the nozzle, and irregular combustion may lead to a serious accident. A sludge dispersant is generally used to eliminate such troubles, which suppresses the generation of sludge in fuel oil and prevents clogging of the strainer and clogging of the nozzle. Although various surfactants (anionic, nonionic, cationic, amphoteric surfactants) etc. are effective as sludge dispersants for straight run fuel oils, cracked fuel oils that have undergone the above heat history are petroleum resources. Although there is a tendency for it to increase more and more with the effective use of the oil, it is extremely unstable as compared with straight run fuel oil, and therefore a part of the oil has been mixed to limit its use in order to prevent quality problems. Most of the additives for stabilizing the fuel oil subjected to the heat history are amines such as alkanolamine, N, N-dimethylcyclohexylamine, alkane containing secondary amine, and heterocyclic amine; It was a combination of an antioxidant such as 6-di-t-butyl-4methyl-phenol; a dispersant such as methyl methacrylate and polyaminopolyol; and a metal deactivator such as N, N-disalicylidenediaminopropane. However, even if any kind of additive or a composition combining them is used, the effect is not sufficient, and depending on the additive, even if the sludge generation can be suppressed to some extent, it may even worsen the hue. The situation was far from satisfactory.

C. Object of the Invention The object of the present invention is to eliminate or significantly alleviate the above-mentioned problems, and further improve the effect by adding a small amount than conventional products, easy to handle and not dangerous, for long-term fuel oil. The object is to provide a stabilizer that significantly improves the stability over time.

The present inventor has carried out an experimental study based on the above-mentioned object and found that an alkylbenzyl-substituted amine has a considerable effect in suppressing sludge in fuel oil and preventing hue deterioration, and further reexamined with a conventionally known additive. In addition, a more effective synergistic stabilizer for fuel oil has been found by the combination of a specific one of them with the above-mentioned alkylbenzyl-substituted amine, and a series of the present invention has been achieved. .

D. Structure of the Invention The fuel oil stabilizer of the present invention comprises (a) a dialkylamine having 2 to 10 carbon atoms and 1 carbon atom.
A condensate of an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate I); a condensate of an alkylphenol having 4 to 25 carbon atoms, a diaminoalkane having 4 to 30 carbon atoms, and an aliphatic aldehyde having 1 to 5 carbon atoms (Hereinafter, referred to as condensate II); and at least one reaction product (hereinafter, referred to as alkylbenzyl-substituted amine) is constituted as an active ingredient.

As an example, the alkylbenzyl-substituted amine of the present invention is
Of the dialkylamines (C2-10), the most suitable amine, dibutylamine and aliphatic aldehydes (C1-C1)
5) Formalin (37% wt / wt) of 5) is mixed in a weight ratio of 5: 1 to 25, stirred, heated to 50 ° C. and reacted for several minutes. The resulting reaction product is allowed to stand for about 1 hour, and after separating the two layers, the upper layer oily substance is designated as Condensate I.

The most suitable P-dodecylphenol among P-alkylphenols (4-20 carbon atoms) and the most suitable ethylenediamine among diaminoalkanes (4-16 carbon atoms) in a weight ratio of 15: 1 to 10 are almost the same amount. Mix with the aromatic solvent.
Next, formalin (37% wt / wt) was added to this mixture at a weight ratio of 10:
Add at a rate of 1 to 15. The mixture is stirred and heated to 120 ° C. After holding for about 10 minutes, the pressure is reduced to 50 mmHg to remove water, and a condensate II is obtained.

The condensates I and II are mixed in a weight ratio of 5: 1 to 25, heated to 50 ° C., and then kept under reduced pressure at about 50 mmHg for about 1.5 hours to obtain the obtained product (alkylbenzyl-substituted amine).

(B) At least one dispersant selected from polymethacrylic dispersants and olefin copolymer dispersants is added to the fuel oil stabilizer of the present invention to further increase the sludge formation suppressing effect of the stabilizer. You can The weight ratio of the alkylbenzyl-substituted amine of (a) to the dispersant of (b) is preferably about 1: 1. Also, instead of (b), (b) is added by adding (c) at least one compound selected from the group consisting of N, N-dimethylcyclohexylamine, dicyclohexylamine, N, N-, and disalicylidene-diaminopropane. It is also possible to achieve the same effect as when The weight ratio of (a) to (c) is preferably about 3: 2 to 2: 3.

Furthermore, the fuel oil stabilizer of the present invention further comprises a dispersant (b) and (c)
By adding the compound of (3) as a ternary composition stabilizer and specifying the compounding ratio of each component, it is possible to exert a remarkable synergistic effect on sludge generation suppression and hue stabilization. The preferred blending ratio is (a) 20 to 40% (wt%, the same applies hereinafter), and (b) is based on the total weight of the stabilizer.
40 to 60% and (c) 10 to 30%.

The stabilizer of the present invention is 10 to 1 based on the volume of fuel oil.
It is preferable to add it at an addition rate of 0.00000 ppm by weight, and it is more preferable to add it at about 50 ppm by weight in view of the effect and economy.

The stabilizers of the present invention, with or without (b), (c) and / or conventional stabilizers, are most commonly supplied as pre-compounded formulations in which the solvent Even if other diluents are not used, they can be easily homogenized by adding them to the fuel oil and mixing them.

E ₁ Example The present invention will be described in more detail by way of examples.

Throughout this example, the following light oils were blended and used: The above-mentioned compounded sample (hereinafter referred to as "sample") was prepared by adding no stabilizer to the control, and the sample containing the stabilizer of the present invention was used as an example of the conventional stabilizers other than the present invention. What added was used for the comparative example.

Example-1 200 ml of each sample is put into a 500 ml Pyrex bottle with a screw cap, and 1 piece of polished iron piece 2 × 15 × 30 mm is put as a catalyst. After replacing the inside of the bottle with oxygen, cover the bottle. 100 ° C
After leaving it for a certain period of time in a constant temperature bath adjusted to, leave it in a cool and dark place. After about 2 hours, the sample is filtered with a membrane filter (1 μm). The solution is evaluated for hue according to the method of ASTM D1500. Clean the inside of the bottle and the filter with a cleaning solution (isooctane). Next, the precipitate on the filter is dissolved with a solvent (benzene: acetone: methanol = 1: 1: 1), and the solution is placed in a constant and weighed beaker. The beaker is dried at 105 ° C for 2 hours and then cooled in a desiccator. The weight of the beaker after cooling is measured, and the difference between that value and the constant weight of the beaker is taken as the weight of sludge. The results are shown in Table-1. As is clear from this table, (a) alone is quite effective, and (a) +
(B) or (a) + (c) further increases the sludge generation suppression effect, and (a) + (b) + (c) further increases the sludge suppression effect and hue improvement.

Example-2 Using the same sample as in Example-1, 0.8 l of the sample was put in the steel container of No. 1 and left for a year in the room for a long-term test. During this period, the lid was covered so that foreign matter such as dust could be prevented from entering and the sample could be breathed.

The result is that the control oil is hue, ASTM color
L4.5, sludge amount 4.6mg / 100ml, stabilizer 50p of test No. 21
pm added sample is ASTM color L2.5, sludge amount 0.1mg / 100ml
The storage stability of fuel oil has been dramatically improved and improved as follows.

F. Effects of the Invention According to the fuel oil stabilizer of the present invention, sludge formation and hue decrease during storage of fuel oil are significantly suppressed, the fuel oil is stabilized for a long period of time, and the flammability is improved. The effect on security management is expected to be great.
It is also possible to modify the combination and composition of the stabilizer of the present invention according to the type of fuel oil and the use conditions to adapt it to a wide range of conditions.

Claims (9)

[Claims] 1. (a) A condensate of a dialkylamine having 2 to 10 carbon atoms and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate I); an alkylphenol having 4 to 25 carbon atoms and a carbon number. At least one reaction product (hereinafter, referred to as alkylbenzyl-substituted amine) with a condensate of 4 to 30 diaminoalkane and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate II) as an active ingredient. A stabilizer for fuel oil, characterized by containing. 2. The stabilizer according to claim 1, wherein the dialkylamine is dibutylamine, the aliphatic aldehyde is formaldehyde, the alkylphenol is P-dodecylphenol, and the dialkylamine is ethylenediamine. 3. (a) A condensate of a dialkylamine having 2 to 10 carbon atoms and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate I); an alkylphenol having 4 to 25 carbon atoms and a carbon number. At least one reaction product (hereinafter referred to as alkylbenzyl-substituted amine) with a condensate of a 4 to 30 diaminoalkane and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate II); and (b ) A stabilizer for fuel oil, comprising at least one dispersant selected from polymethacrylic dispersants and olefin copolymer dispersants as an active ingredient. 4. The stabilizer according to claim 3, wherein the dialkylamine is dibutylamine, the aliphatic aldehyde is formaldehyde, the alkylphenol is P-dodecylphenol, and the dialkylamine is ethylenediamine. 5. (a) a condensate of a dialkylamine having 2 to 10 carbon atoms and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate I); an alkylphenol having 4 to 25 carbon atoms and a carbon number At least one reaction product (hereinafter, referred to as alkylbenzyl-substituted amine) with a condensate of 4 to 30 diaminoalkane and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate II), and
(C) A stabilizer for a fuel oil, containing at least one compound selected from the group consisting of N, N-dimethylcyclohexylamine, dicyclohexylamine and N, N-disalicylidene-diaminopropane as an active ingredient. . 6. The stabilizer according to claim 5, wherein the dialkylamine is dibutylamine, the aliphatic aldehyde is formaldehyde, the alkylphenol is P-dodecylphenol, and the dialkylamine is ethylenediamine. 7. (a) A condensate of a dialkylamine having 2 to 10 carbon atoms and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate I); an alkylphenol having 4 to 25 carbon atoms and a carbon number. At least one reaction product (hereinafter referred to as alkylbenzyl-substituted amine) with a condensate of a 4 to 30 diaminoalkane and an aliphatic aldehyde having 1 to 5 carbon atoms (hereinafter referred to as condensate II); (b) At least one dispersant selected from polymethacrylic dispersants and olefin copolymer dispersants, and (c) at least one selected from the group consisting of N, N-dimethylcyclohexylamine, dicyclohexylamine, and N, N-disalicylidene-diaminopropane. A stabilizer for fuel oil, which comprises a compound as an active ingredient. 8. The stabilizer according to claim 7, wherein the dialkylamine is dibutylamine, the aliphatic aldehyde is formaldehyde, the alkylphenol is P-dodecylphenol, and the dialkylamine is ethylenediamine. 9. (a) relative to the total weight of the active ingredients of the stabilizer.
20-40% by weight of alkylbenzyl-substituted amine of
The stabilizer according to claim 7, wherein the dispersant (b) is contained in an amount of 40 to 60% by weight and the compound (c) is included in an amount of 10 to 30% by weight.