JPS59189192A - Fluidity improver for fuel oil - Google Patents

Abstract

PURPOSE:To provide a fluidity improver consisting of an ester of an epoxide adduct of a specified compd. having at least two nitrogen atoms and a straight- chain saturated fatty acid, which has a low freezing point and a low crystallization temperature when dissolved in fuel oil and exhibits excellent performance. CONSTITUTION:The fluidity improver consists of an ester of a compd. of formula I [where X is a group of formula II (l is 1-30) or a group of formula III; R5 is a 1-30C aliphatic hydrcarbon group; R0, 1, 2, 3, 4 are shown by formula IV(m is 0-25), V (n is 0-25), VI VII or VIII. At least one of them is of formula VI, VIIor VIII] (e.g. 4mol ethylene oxide adduct of polyethyleneimine) or alkylene oxide (e.g. ethylene oxide), styrene oxide or glycidol adduct of polyethyleneimine, and a straight-chain saturated fatty acid (e.g. palmitic acid). It has a low freezing point and a low crystalliation temperature when dissolved in fuel oil and exhibits excellent fluidity improving performance.

Description

[Detailed description of the invention] The present invention relates to a fluidity improver for hydrocarbon fuel oil.

Since the oil crisis, it is expected that Japan's imported crude oil will become even heavier in the future due to diversification of sources and a decline in the proportion of light crude oil production.

On the other hand, in conjunction with regulations on sulfur oxide emissions, the proportion of distilled fuel oils such as kerosene and diesel oil, as well as A-heavy oil, is increasing. Therefore, in order to obtain as much fuel oil as possible from heavy crude oil containing many paraffins with large molecular weights by distillation fractionation, it is necessary to extract only one or more high-boiling point fractions.

As a result, the content of paraffin with a large molecular weight increases in the fuel oil.

Paraffin crystals are more likely to precipitate and grow in such fuel oils at low temperatures than in conventional fuel oils.

You will lose liquidity. It also results in the generation of large paraffin crystal particles even when heated, which retains fluidity.

Filters and piping inside fuel oil pipes in diesel engines etc. become clogged and prevent the flow of fuel oil.

Many fluidity improvers have been disclosed to solve these problems, such as a condensation product of chlorinated paraffin and naphthazine (US Pat. No. 1,815,022).
, polyacrylate (US Pat. No. 2,604,453),
Polyethylene (U.S. Pat. No. 4,434,74157), copolymer of ethylene and propylene (French patent 'H'g143)
No. 8656).

Copolymer of ethylene and vinyl acetate (US Pat. No. 3+1.
No. 18479).

These flow improvers are tested by pour point test (J I 5K22
69) shows a good pour point lowering effect, but cold filter plugging boiler/tochist (Co
1d Filter Plugging Point T
e5t) has almost no effect in many cases.

In particular, there are few effective methods for fuel oil containing a large amount of paraffin.

Although the pour point test cannot predict clogging of fuel oil pipe filters due to paraffin crystal particles that occur at temperatures significantly higher than the pour point, the cold filter blugging point (CFPP) test can detect this phenomenon. It is a test method that is currently widely used for prediction purposes.

JP-A-57-170993 describes CFPP for fuel oil.
An ester of a nitrogen-containing compound having a hydroxyl group and a linear saturated fatty acid has been disclosed as a fluidity improver that can effectively reduce li, but this fluidity improver has a slightly high melting point and is difficult to use in fuel oil It has the disadvantage of being difficult to dissolve.

As a result of extensive research in search of a fluidity improver that does not have these drawbacks, the present inventors found that esters of epoxide adducts of compounds having two or more specific nitrogen atoms and linear saturated fatty acids have a freezing point. 9. It is an ester that has a low crystallization temperature when dissolved in fuel oil and exhibits an excellent effect as a fluidity improver.9. It has been found that when such a specific ester is added to fuel oil, CFPP is greatly reduced, and when the ester and a specific polymer are used together, the pour point is also significantly reduced along with CFPP.

That is, the present invention is a fluidity improver for fuel oil comprising a compound represented by the general formula (1) or an adduct of polyethyleneimine with alkylene oxide, styrene oxide, or glycidol and a linear saturated fatty acid; This is a fluidity improver for fuel oil that uses the above ester in combination with a polymer of one or more monomers selected from olefins, ethylenically unsaturated alkyl carboxylates, and saturated vinyl fatty acids.

The compound of formula (1) constituting the ester is an adduct of ethylene oxide with 4 moles of ethylene diamine.

4 mole propylene oxide adduct of ethylenediamine 9
Adduct of 2 moles of ethylene oxide and 2 moles of propylene oxide of ethylene diamine, 4 mole of ethylene oxide adduct of propylene diamine, 4 mole of propylene oxide adduct of propylene diamine, 3 mole of ethylene oxide and 1 mole of propylene oxide adduct of propylene diamine, adduct of hexamethylene diamine Ethylene oxide 4 mole addition, hexamethylene diamine propylene oxide 4
Molar adduct, 2 mole ethylene oxide/2 mole propylene oxide adduct of hexamethylene diamine, 4 mole ethylene oxide adduct of xylylene diamine, 4 mole propylene oxide adduct of xylylene diamine 1 2 mole ethylene oxide-propylene oxide of xylylene diamine 2 mole adduct, 5 mole ethylene oxide adduct of diethylene triamine, 5 mole propylene oxide adduct of diethylene triamine, 3 mole ethylene oxide/2 mole propylene oxide adduct of diethylene triamine, 6 mole ethylene oxide adduct of triethylenetetramine, triethylenetetraminenopropylene 6 moles of oxide adduct, 3 moles of ethylene oxide and 3 moles of propylene oxide adduct of triethylenetetramine, or methyl, ethyl, propyl, butyl, hexyl.

Octyl, lauryl, myristyl, noklumicyl.

Alkyl &' such as stearyl, alaxyl, and behenyl
Alkyl polyvalent amines such as 2-alkylaminoethylamine, 2-alkylaminoisopropylamine, 6-alkylaminohexylamine, alkyldi(aminoethyl)amine, alkyltri(aminoethylamine), alkyltetra(aminoethyl)amine, etc. , and further acetic acid 9-propionic acid, butyric acid, hexanoic acid, octanoic acid,
Fatty acids such as nonanoic acid, decanoic acid, lauric acid, myristic acid, norlumitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid and ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, xyl/lylenediamine, etc. Examples include amidation reaction products with polyvalent amines.

Polyethyleneimine constituting the ester (obtained by polymerizing ethyleneimine, 1st, 2nd, 3rd)
It contains a class amine group and has a branched structure. The polyethyleneimine used in the present invention has an average molecular weight of 20
0 to 30,000 is suitable.

Furthermore, alkylene oxides to be added to the compound of formula (1) or polyethyleneimine include ethylene oxide, propylene oxide, butylene oxide, and the like. The number of moles of styrene oxide or glycidol added to the compound of formula (1) or polyethyleneimine is 1 of the alkylene oxide added to the compound of formula (1) or polyethyleneimine.
1 to 100 moles, preferably 1 to 3 moles
Chill at 0 mole.

If more than 100 moles are added, the degree of deterioration of CFPP will be small, which is not practical.

The linear saturated fatty acids that make up the ester have 12 to 3 carbon atoms.
0 fatty acids, including valmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid.

Acid such as melisic acid, hydrogenated beef tallow fatty acids, hydrogenated rapeseed oil fatty acids, hydrogenated fish oil fatty acids, etc. containing these fatty acids can also be used.

The ester used in the present invention can be obtained by esterifying the compound of formula (1) or an epoxide compound of polyethyleneimine with the above-mentioned fatty acid by a conventional method.

The olefin constituting the polymer is a olefin having 2 to 30 carbon atoms, and α-olefin is particularly preferred.
Ethylene, propylene, butene-1, isobutyne, pentene-1, hexene-1, heptene-1, octene-1
, diimbutene, dodecene-1, octadecene-1, icosene-1. Tetracosene-1, triacontin-1
etc. are scattered.

The ethylenically unsaturated alkyl carboxylate constituting the polymer is an ester of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid and a saturated alcohol having 1 to 30 carbon atoms. be. Examples of saturated alcohols used here are methyl alcohol, ethyl alcohol, phthyl alcohol, and amyl alcohol.

hexyl alcohol, 2-ethylhexyl alcohol,
Octyl alcohol, lauryl alcohol.

Cetyl alcohol, behenyl alcohol, alcohol, oxo alcohol.

The saturated fatty acid vinyl constituting the polymer has 1 to 30 carbon atoms.
Saturated fatty acid vinyl esters of vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, behenic acid Vinyl, vinyl heptaphosphate.

Examples include vinyl melysinate.

The polymer used in the present invention can be obtained by combining one or more of the above monomers in a conventional manner, or when using a polymer of ethylenically unsaturated carboxylic acid as a raw material. Some are obtained by esterification reaction with alcohol and are commercially available as additives for fuel oil. The number average molecular weight of the polymer is 500 to 50,000. Preferably 1000 to 20000 is suitable.

The ratio of ester to polymer in the fluidity improver of the present invention is 1:9 to 9:1 (by weight), and outside this range, the cFppb or pour point of the fuel oil may hardly be lowered.

The amount of the fluidity improver of the present invention added to fuel oil is 10 to 5000 ppm by weight, preferably 50 to 11000 ppm.
If p is less than 10 ppm, sufficient effect cannot be obtained,
Even if it exceeds 5000 ppm, no improvement in effectiveness is observed, which is economically disadvantageous.

The fluidity improver of the present invention can also be used in combination with antioxidants, corrosion inhibitors, other fluidity improvers, etc. that are added to common fuel oils.

When the fluidity improver of the present invention is added to fuel oil, the C of the fuel oil increases.
Since PPP and pour point can be significantly lowered,
It has been found that it is possible to solve various problems related to cold fluidity during storage and transportation of relatively boiling point distillate fuel oil containing paraffin. Since it can be used in high-boiling distillate trenches, it is possible to increase the production amount of high-quality fuel oil.

Next, the present invention will be explained with reference to examples.

Example 1 4 mol adduct of ethylenediamine with propylene oxide (PO) 292j (1.0 mol) was placed in a 1 ton autoclave.
And Kaseika 98.8? Enter (0.3 weight width),
After heating and dehydrating at 100 to 110°C for 1 hour,
Addition reaction of ethylene oxide (EO) was carried out at °C for 3 hours. The amount of EO added was 78 moles.

Next, ethylenediamine PO (4.0 mol) EQ
(7,8 mol) adduct 171.6/(0,5 mol).

Behenic acid (acid value 162.6) 690j' (2.0 mol)
The present invention was carried out using paratoluenesulfonic acid (4.31 < o, 5 weight ratio) at 140 to 160 °C under a nitrogen stream while removing distilled water at 10 o'clock. Ethylenediamine PO of Product 1 (Table 1)
(4,0 mol EO (7,8 mol/I/) adduct Tet7
Behenic acid ester was obtained. The obtained product A1 of the present invention had an acid value of 135. The hydroxyl value was 19.2.

The invention products/f62-16 in Table 1 were obtained by the reaction according to the above.
14 Ihii X7.

In order to evaluate the CF″PP lowering ability of the product of the present invention, the product of the present invention A91 was added to a gas oil fraction with the following properties obtained from Middle Eastern crude oil.
e when adding ~1614 and comparison products 1615~17
f” I) I) is shown in Table 1.

From the results in Table 1, the fluidity improver of the present invention is CFP Pf.
, c can be seen to be significantly reduced.

Raw state of gas oil fraction (1) υμ point range Initial boiling point 225'C20
% distillation point 280°0 90% distillation point 352°C End point 373°C (2) Pour point -5°C (3)
CFPP Example 2 CFPP was evaluated when the ester of the present invention and the polymer were used together.

The polymers used in Examples will be explained.

Polymer 1 is an AC made of a copolymer of ethylene and vinyl acetate.
P-430 (manufactured by Allied Chemical Company, USA).

Number average molecular weight 3500. (proportion of vinyl acetate 29% by weight)
It is.

Polymer 2 is AC made from a copolymer of ethylene and acrylic acid.
P-5120 (manufactured by Allied Chemical Co., USA, number average molecular weight 3500. acid value 120) 47/.

Lauryl alcohol 4st, paratoluenesulfonic acid 0
．． 2,? and xylene 100. A mixture of P.

Water is distilled off by refluxing xylene under a nitrogen stream, and 1
After esterification reaction for 0 hours, the mixture was gradually poured into a large excess of methanol, and the precipitate was separated and dried.

Polymer 3 is an α-olefin having 20 to 28 carbon atoms 339/
' (1,0 mol), a mixture of maleic anhydride 98IP410 mol) and xylene 5001.

While heating the xylene to reflux under a nitrogen stream, a solution of di-t-butyl peroxide 4P dissolved in xylene soy was gradually added, and then the polymerization reaction was continued in this state for 10 hours, and then 2-ethylhexyl alcohol was added. 273
．． P (11 mol) and para-toluenesulfonic acid 2tk
In addition, an esterification reaction was carried out for 10 hours, and then xylene was distilled off.

Polymer 4 is branched polyethylene ACP-1702 (
Manufactured by Allied Chemical Co., USA, number average molecular weight 1100. The specific gravity is 088).

Polymer 5 is polyalkyl methacrylate Acryloid 152 (manufactured by Rohm Antonos, USA, number average molecular weight 1700 (1, carbon number of alkyl group 12 to 20).

The pour point and C of a gas oil fraction obtained from Middle Eastern crude oil with a slightly high boiling point and a narrow boiling point range, and in which the ester and polymer used in the present invention are used in combination as a fluidity improver.
FPP is shown in Table 2.

Properties of gas oil fraction (1) Boiling point range Initial boiling point 227'c20°C Distillation point 290°C 90% distillation point 343'C End point 360'C (2) Pour point -25°C (3) CFPP
, °C From the results in Table 2, 1. Flow properties of the present invention: The two-component mixture of ester and polymer (A18~/+626) has a low pour point as well as CFPP, and is excellent as a fluidity improver. I understand that.

Claims (1)

[Scope of Claims] 1. A fuel oil fluidity improver comprising an ester of a compound of general formula (1) or an adduct of polyethyleneimine with alkylene oxide, styrene oxide or glycidol and a linear saturated fatty acid. However, X is R6N (R3)'), 6 Ct=
1-30) R5 is an aliphatic hydrocarbon group having 1-30 carbon atoms. Ro, R,, R2, R3, R4 are CH, 3(
cJ(2)m-(m-o-25), (m, (CL(
2) n■-(n=0~25), -CH2Cl(2
0 to -(Jl(CT(3) CH20H, -C'H2C
H(OH)CH□OHt7) Ej' Reka,
(1) R8+ R, R2゜R31R in one molecule of the formula compound
At least one of 4 is -CH2CH20H. -C) I(CH3) CI(,20H or -CI(2
CH(0H)CH20H. λ (a) an ester of the compound of general formula (1) or an adduct of polyethyleneimine with alkylene oxide, styrene oxide or glycidol and a linear saturated fatty acid; and (b) an olefin, an ethylenically unsaturated alkyl carboxylate and a saturated fatty acid. A fluidity improver for fuel oil comprising vinyl-fcIA or a polymer of two or more monomers. However, X also applies to s −N (R3) ')) − (L
= 1 to 30) or -CR2i>R2-N (R4)
- Deoshi. R5 is an aliphatic hydrocarbon group having 1 to 30 carbon atoms. RO, R11R21R31R4 is CH3(CH2)m
−(m=0~2s>, C)13(CLi2) n
Co-(n=o~2s), -CH2Cl(20H
. -CI((C1(3)CH20a -CH2Cl((0
1()CH20I ((7), and at least one of R8, R,, R2゜R,3,R, in one molecule of the compound of formula (1) is -CH2CH20H. -CH(C, +13 )C1120I-I or -CH2
CH(OH)CH20H.