JPS612793A - Improver for flow property of fuel oil - Google Patents

Abstract

PURPOSE:An improver for flow properties for providing a fuel having a narrow boiling point range with low-temperature flow properties, containing a specific polyester amide or a polyester (amide)amine salt. CONSTITUTION:The aimed improver for flow properties comprising (A) a polyfunctional carboxylic acid and/or its acid anhydride, (B) a polyhydric alcohol or its partial ester, and (C) a polyester amide, polyesteramine salt or polyester amidoamine salt having about 500-20,000mol.wt. derived from a monoamine. The components A, B, and C are reacted in a molar ratio of preferably 0.05- 20:1:0.5-20.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a fluidity improver for fuel oil, more specifically, a fluidity improver for fuel oil containing a specific polyesteramide, polyesteramine, or polyesteramide amine salt. Regarding.

[Conventional technology]

Petroleum middle distillate fuel oils, such as diesel oil and helium oil, are bad in winter when exposed to low temperatures in cold regions.
Is it possible that the wax-like substance contained in it precipitates and clogs the filter in the engine's fuel piping system, causing problems with starting the engine, or that the fuel oil itself becomes semi-solid or solid and becomes fluid? This causes problems such as loss of oil, oil supply, and total blockage of QIZO. This problem is likely to be exacerbated by the recent trend toward heavier crude oil or the tighter quantity of kerosene, and appropriate countermeasures are desired.

In the past, many studies have been conducted to solve these problems, including ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, ethylene-methacrylate copolymers, branched n$riethelenes, and alkylnaphthalenes. Low-temperature fluidity improvers such as polymers have been reported. These improvers are generally applied to the wax that precipitates when the fuel oil is exposed to low temperatures, or are eutectic with the wax to change the shape and size of the wax crystals. This completely improves the fluidity of fuel oil at discharge temperature.

[Problem that the invention seeks to solve]

However, the composition and properties of petroleum distillate fuel oils, such as wax content and boiling point range, vary depending on the region of oil production, oil field type, distillation, refining, etc., so there is a wide range of types available. No improver has yet been found that allows fuel oil to exhibit good low-temperature fluidity.

[Means for solving problems]

Under these circumstances, the present inventor conducted extensive research and, as a result, discovered a compound that can impart good low-temperature fluidity to a wide range of types of fuel oil, and completed the present invention.

The fuel oil fluidity improver of the present invention has the advantage that it can exhibit good low-temperature fluidity even for fuel oils with a narrow boiling point range, which was not possible with conventional solutions. That is, the present invention provides polyesteramides and polyesteramine salts derived from (→polyhydric carbon lI! also #i/ and its acid anhydride, (t1 polyhydric alcohol or partial ester thereof, and (0) monoamine). Alternatively, there is provided a fluidity improver for fuel oil containing a polyesteramide amine salt.

Polyester amide of the present invention, dispersed ester amine salt, and polyester amide amine salt (hereinafter, in cases where these three are included, they may be referred to as "polyester amide, etc.") (polyvalent of Q) As the carmen powder or acid anhydride, compounds having two or more carboxyl groups or acid anhydrides obtained by dehydration from two or more carboxyl groups, which are generally known in terms of δ, are used. Preferably maleic acid, maleic anhydride, fumaric acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, hepthalic acid, phthalic anhydride, succinic acid, succinic anhydride, ?liisobutenyl succinate Examples include acid anhydride, alkenylsuccinic acid, alkenyl/I/:17 succinic anhydride, azobisuccinic anhydride, and the like.

In addition, as the polyhydric alcohol or partial ester of polyhydric alcohol in φ), all commonly known compounds can be used as long as they are compounds having two or more hydroxyl groups or partial esters of compounds having two or more hydroxyl groups. Preferred examples include ethylene glycol, soropylene glycol, 1,3-7'tanzool, 1,4
-putanzool, 1゜6-hexanediol, 1,4
- cyclohexanediol, glycerin, ridge glycerin, trimethylolethane, trimethylolethane, pentaerythritol, dipentaerythritol, diethylene glycol, nlupitol, sorbitan fatty acid ester, fatty acid ester of broken sigma glycerin, monosaccharides,
Examples include trisaccharides and trisaccharides.

Examples of phantom monoamines include tertiary ditylamine, hezotelamine, octylamine, lavalylamine, myristylamine, stearylamine, oleylamine, tallow amine, eicosylamine, behenylamine,
diethylamine, zoniguethylamine, zorawalylamine, zomystearylamine, dino-9lumitylamine,
Distearylamine, zoeicosylamine, zopehenylamine, zo-hydrogenated tallowamine, dimethyloctylamine,
Dimethyldecylamine, zomethyllahourylamine, dimethylmyristylamine, zomethylnon-9luminal amine,
dimethylstearylamine, dimethyloleylamine,
dimethyleicosylamine, zomethylbehenylamine,
Examples include zolawaryl monomethelamine and trioctylamine.

The thiliester amide etc. of the present invention are compounds (a), (b)
) and tc)t molar ratio from 0.05 to 20:1:0.5
-20, preferably 0.2-8:1:0.5-8 molecular weight 500-20,000, preferably 1000-500o, and its nitrogen content is 0.1-20,000. 10%, preferably 0.5-5% of this thiliester amide, etc.? An amide, amine salt, or amidoamine salt is formed at the carboxyl terminal of the ester carboxylic acid.

Thilesteramide etc. is usually produced by first reacting (a) and (b). Synthesize the ester carmenic acid and add it to (
c) t-Although produced in addition, it can also be produced by reacting (a), (b) and <c>' at the same time.

The reaction of polyhydric carmenic acid and φ) can be carried out by a conventional esterification reaction, for example, at a temperature of 100° C. or higher, preferably in the range of 150 to 220° C., without a catalyst or using a suitable catalyst. The reaction between the polyhydric carboxylic acid anhydride and (b) proceeds satisfactorily at room temperature or higher, preferably from 60 to 150°C, without a catalyst. When carrying out an esterification reaction using a polyhydric alcohol, there may be cases where the raw material polyhydric alcohol is partially esterified, but what is the difference between (a) and the polyhydric alcohol? Permissible as long as it does not interfere with reesterification. Amidation of the thus obtained broken ester cardanic acid with a monoamine can also be carried out by a conventional method. That is, 100°C or higher, preferably 150°C or higher
It can be carried out at a temperature in the range of 220° C. without a catalyst or using a suitable catalyst. 9. What is the amine salt of ester callimenic acid and monoamine? Liester carboxylic acid and monoamine at room temperature or above, preferably 40 to 150
Produced by simply mixing at ℃. Furthermore, (a),
(b) and ←) When reacting at the same time, 100°C
As mentioned above, the reaction can be carried out preferably in the range of 150 to 220° C. without any catalyst or with the use of all suitable catalysts. Although the reaction and mixing of Isn can be carried out without using any solvent, it may also be possible to use all suitable solvents that do not react with the above-mentioned raw materials and intermediates. Suitable catalysts for promoting the entire esterification and/or amidation reaction include, for example, sulfuric acid, phosphoric acid, and radruene sulfone powder. Suitable solvents include, for example, toluene, xynon, ethylbenzene, n-hexane, cyclo-xane, solvent naphtha, kerosene, light oil, and the like.

In this way, depending on the reaction conditions, polyester amide, polyester amine salt, polyester amide amine filler or a mixture thereof can be obtained. All of these have excellent fluidity-improving effects, particularly low-temperature fluidity, and can be used alone or in combination of two or more as the fluidity improver of the present invention.

The fluidity improver may include, if necessary, a compound conventionally known as a fluidity improver for fuel oil.

Examples include ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers, helogonated polyalkylenes, alkyl (meth)acrylate polymers, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids, and fats. Group dicarboxylic acid amides and the like can also be blended. These conventional fluidity modifiers are generally used in the O fluidity modifier of the present invention, preferably about 0 to 98% by weight, preferably θ to 50% by weight.
Weight - Can be blended.

Furthermore, benzoic acid can be added to enhance the fluidity improving effect.

〔Effect of the invention〕

By adding the fuel oil fluidity improver of the present invention to fuel oil, it is possible to impart good low-temperature fluidity to a wide range of rice fuel oils. Although the fluidity improver of the present invention varies depending on the composition, properties, etc. of the fuel oil, the purpose can be achieved by normally blending it into the fuel oil at a concentration of 10 to 10,000 ppm.

〔Example〕

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

Production Example 1 4 moles of an alkenylsuccinic anhydride produced from an isomerized product of an α-olefin having 15 to 20 carbon atoms and maleic anhydride and 1 mole of pentaerythritol were reacted at 120°C for 3 hours using xylene as a solvent. ? Reestercarvone@ was obtained. Add to this 4 moles of hydrogenated beef tallow amine t-80
Mix for 1 hour at ℃ and add amine salt kl! ! I left it behind. Molecular weight: 3
500 Production Example 2 Composition of isomerized α-olefin having 15 to 20 carbon atoms 4 moles of alkenylsuccinic anhydride produced from isomerized α-olefin having 15 to 20 carbon atoms and maleic anhydride and penta What happens when 1 mole of erythritol is reacted with xylene at 120°C for 3 hours? Riester carmenic acid was obtained. This was followed by a reaction of 4 moles of hydrogenated tallow amine at 200° C. for 4 hours while removing all of the produced water to form an amide. Molecular weight: 3420 Production Example 3 3 moles of alkenylsuccinic anhydride produced from an isomerically diluted α-olefin having 15 to 20 carbon atoms and maleic anhydride and trimethylolzolo/971 moles 1
React at 120℃ for 3 hours? diester carmen 1
I got 1. Add to this hydrogenated amine 3 mo#' at 8oC.
After mixing for a period of time, amine salt 11'' was prepared. Molecular weight: 2650
Production Example 4 3 moles of an alkenylsuccinic anhydride produced from an isomeric compound of an α-olefin having 15 to 20 carbon atoms and maleic anhydride were reacted with 1 mole of trimethylol zolo, 9 at t-120°C for 3 hours. hand? A lysestercarline acid association was obtained. This and the water drops, 4 moles of beef tallow amine? 200
The reaction was carried out at °C for 4 hours while removing produced water to obtain an amide. Molecular weight: 2600 Production Example 5 2 moles of azopic acid, 1 mole of 1.4-butanediol, and 2 moles of zobehenylamine were used as total catalysts for Qradruenesulfonic acid and reacted in light oil at 180°C for 5 hours while removing the water produced to form a polyesteramide. Obtained. Molecular weight: Production Example 6 2 moles of azopic acid, 1 mole of sorbitan zooleate, and 2 moles of zo-hydrogenated beef tallow amine were reacted in light oil at 180°C for 5 hours while removing produced water using NO-Qradluenesulfonic acid as a catalyst. Polyesteramide t-obtained. Molecular weight:
Example 1 The fluidity improver of the present invention containing all metals such as &IJ esteramide produced in Production Examples 1 to 6 was blended with the following light oil or TIA heavy oil and tested for low temperature flowability. The test was conducted at the pour point (P) of J Engineering Sx 2269-[80
P) and British standard IP-309 cold filtration clogging point (cy
The measurement of pp) was carried out using a trap. The results are shown in Table 1: Middle East-based initial boiling point 223°C 10% distillation 255°C 30% distillation 281°C 50% distillation 296°C 90% distillation 354°C End point 377°C Light oil B: Middle East system initial boiling point 203°C 10% distillation 246°C 30% distillation 271°C 50% distillation 288°C 90% distillation 340C End point 362°C Light oil C: Kobunda system initial boiling point 236°C 10% distillation 262°C 30% distillation 281C 50 slow distillation 293°C 90 Fengmao 330°C End point 344°C Mu heavy oil: Middle East series initial boiling point 212°C 10% distillation 242°C 30-distillation 270°C 50% distillation 287 ℃ 909! I distillation: 320°C End point: 340°C As is clear from Table 1 below, the fluidity improver of the present invention has the following properties:
It is highly effective against a wide range of fuel oil pressures, especially against narrow fuel oils with a narrow boiling point range, where conventional fluidity improvers were not very effective.

that's all

Claims (1)

[Claims] 1. A polyester amide derived from (a) a polyhydric carboxylic acid or/and its acid anhydride, (b) a polyhydric alcohol or a partial ester thereof, and (c) a monoamine;
A fuel oil fluidity improver characterized by containing a polyester amine salt or a polyester amide amine salt. 2. Polyester amide, polyester amine salt or polyester amide amine salt is (a):(b):(c
) in a molar ratio of 0.05 to 20:1:0.5 to 20 and has a molecular weight of 500 to 20,000. . 3. Ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, halogenated polyalkylene, alkyl (meth)acrylate polymer, condensate of chlorinated paraffin and naphthalene, nitrogen-containing derivative of alkenylsuccinic acid, and aliphatic The fluidity improver for fuel oil according to claim 1 or 2, which contains a compound selected from the group consisting of dicarboxylic acid amides. 4. The fluidity improver for fuel oil according to any one of claims 1 to 3, which contains benzoic acid.