JPS61213292A - Modifier for fluidity of fuel oil - Google Patents

Abstract

PURPOSE:A modifier for fluidity capable of dispersing well crystal of wax existing in a fuel oil, comprising an ester of an adduct of a compound with an alkylene oxide, containing a specific alkyl group, etc. CONSTITUTION:The aimed fluidity modifier comprising an ester of (A) an adduct of an active hydrogen-containing compound with an alkylene oxide (AO) and (B) 7-30C monofunctional carboxylic acid, consisting of a compound containing 7-30C branched chain alkyl group and/or unsaturated hydrocarbon group, and 11-30C straight-chain saturated alkyl group in the molecule. Ethylene oxide, propylene oxide, or butylene oxide may be cited as the preferably AO example of the component A, and number of moles of addition of AO is preferably 1-60mols based on 1mol active hydrogen-containing compound. Lauric acid, myristic acid, isostearic acid, 2-ethylhexanoic acid, etc., may be cited as the component B.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is an ester of an alkylene oxide adduct and has a specific alkyl group in the molecule. The present invention relates to a fluidity improver for fuel oil, which is made of a compound and is capable of favorably dispersing wax crystals present in fuel oil.

[Conventional technology]

When petroleum middle distillate oils, such as diesel oil and heavy oil, are exposed to low temperatures in winter or in cold regions, the wax-like substances contained therein precipitate and can clog the filters in the fuel piping system of diesel engines. This causes problems such as impeding engine starting, etc., and the fuel oil itself becomes semi-solid or solid and loses fluidity, causing oil pipes to become clogged. This problem is likely to increase further due to the recent trend toward heavier crude oil and the tighter quantity of kerosene and diesel oil, and appropriate measures to address this problem are desired.

Many studies have been conducted to solve these problems, including ethylene-vinyl acetate copolymers, ethylene-(methanoacrylate copolymers, branched polyethylenes, halogenated polyalkylenes, and alkyl (meth)acrylates). Polymers, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids, and aliphatic dicarboxylic acid amides have been reported.These modifiers are generally used when fuel oil is exposed to low temperatures. This invention completely improves the fluidity of fuel oil at low temperatures by adsorbing on or eutecticizing the wax that precipitates when the wax is deposited and changing the shape and size of wax crystals. However, it is difficult for these fluidity improvers to exhibit good low-temperature fluidity for a wide variety of fuel oils with various boiling point ranges. When added to fuel oil, when the fuel oil in a storage tank or drum is gradually cooled, the precipitated wax does not disperse in the oil and often settles to the bottom, which has the disadvantage that improvements are desired.

[Means for solving problems]

Under these circumstances, the present inventor conducted intensive research and found that it is possible to impart good low-temperature fluidity to a wide range of types of fuel oil, and that when slowly cooled, the precipitated wax can be dispersed in the oil. discovered a compound that can reduce sedimentation.

The present invention has been completed and the present invention is directed to an ester of a purkylene oxide adduct of a compound having at least one active hydrogen and a monohydric carboxylic acid having 7 to 30 carbon atoms, A branched alkyl group or/and an unsaturated hydrocarbon group having 7 to 30 carbon atoms and at least one carbon number 1
The present invention provides a fluidity improver for fuel oil comprising a compound having 1 to 30 linear saturated alkyl groups (hereinafter referred to as an "ester compound").

Specifically, the ester compounds used in the present invention include alcohols, amines, carboxylic acids, acid amides, and mercaptans having a branched alkyl group or unsaturated hydrocarbon group having 7 to 30 carbon atoms. , alkylene oxide adducts such as phenols, and carbon all
Esters of carboxylic acids having ~30 linear saturated alkyl groups; ■ alcohols, amines, carboxylic acids, acid amides, mercaptans having linear saturated alkyl groups having 11 to 30 carbon atoms; Alkylene oxide adducts such as phenols, esters of carboxylic acids having a branched alkyl group having 7 to 30 carbon atoms, or an unsaturated carbon-hydrogen group, and alkylene oxide adducts of compounds having two or more active hydrogens. and the following mixed acid, i.e. carbon number 7-30
An ester of a mixed acid with a carboxylic acid having an unsaturated hydrocarbon group and a carboxylic acid having a linear saturated alkyl group having 11 to 30 carbon atoms;
An alkylene oxide compound of a compound having two or more active hydrogen atoms and a branched alkyl group having 7 to 30 carbon atoms or an unsaturated hydrocarbon group, and an alkylene oxide compound having 11 to 30 carbon atoms.
Examples include esters of carboxylic acids containing a linear saturated alkyl group.

The ester compound used in the present invention is produced from an alkylene oxide adduct of a compound having at least one corresponding active hydrogen and a carboxylic acid by a method known per se. There is no need to be, but a mixture with other compounds t
- Can be used. However, a mixture containing the ester compound t-50% by weight or more (hereinafter referred to as H), preferably 60% or more, more preferably 7096% or more is used.

The alkylene oxide adduct of the compound having at least one active hydrogen used to produce the ester compound according to the present invention can be obtained by a known general method from the compound having the active hydrogen and alkylene oxide. As a compound having at least one active hydrogen.

Alcohols, amines, carboxylic acids, acid amides,
Examples include mercaptans and phenols. Among these, examples of alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol,
Stearyl alcohol, eicosyl alcohol, behenyl alcohol, linear alcohols with 11 to 30 carbon atoms such as higher alcohols by Ziegler method: Branched alcohols with 7.8, 9.18 carbon atoms, etc. obtained by Oquine reaction, Guerbet reaction Carbon number obtained with 16.18.20.24
Monohydric alcohols having branched alkyl groups or unsaturated hydrocarbon groups having 7 to 30 carbon atoms such as Guerbet alcohol and oleyl alcohol; ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1 .5-bentanediol, 1,6-hexanediol, hexylene glycol, 1,4-cyclohexanediol, neopentyl glycol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol.

Examples of amines include polyhydric alcohols such as dipentaerythritol and nrubitol, such as dilaurylamine.

Secondary amines having at least one straight chain alkyl group having 11 to 30 carbon atoms, such as simiristylamine, civalmitylamine, distearylamine, dihardened beef tallow amine, dilaurylamine, dilaurylamine; ammonia, methyl Amine, ethylamine, ingloviramine, butylamine% tert-butylamine, heptylamine,
octylamine, laurylamine, myristylamine,
Branched alkyl groups having 7 to 3 carbon atoms such as stearylamine, oleylamine, tallow amine, hardened tallow amine, eicosylamine, behenylamine, etc., or primary amines such as amines having unsaturated hydrocarbon groups; ethylenediamine,
Propylene diamine, hexamethylene diamine.

Polyamines such as xylylenediamine, diethylenetriamine, triethylenetetramine; 2-alkylaminoethylamine, 2-alkylaminoisopropyl with alkyl groups such as methyl, ethyl, furoyl, methyl, hexyl, octyl, lacryl, myristyl, palmityl, araquinyl, pehel, etc. Amine% 6-alkylaminohexylamine, alkyldi(aminoethyl)amine,
Examples include polyamines such as alkyltri(aminoethyl)amine and alkyltetra(aminoethylamine); polyethyleneimine obtained by polymerizing ethyleneimine, and the like.

(9) Examples of carboxylic acids used as compounds having active hydrogen include linear alkyl groups having 11 to 30 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. t-having m
Carboxylic acids: 7 or more carbon atoms such as instearic acid, 2-ethylhexanoic acid, oleic acid, erucic acid, linoleic acid, etc.
Monovalent carboxylic acids with 30 branched alkyl groups and an unsaturated hydrocarbon base; maleic acid, fumaric acid, heptalic acid, inphthalic acid, terephthalic acid, trimellitic acid, bilomeridutic acid, succinic acid, adipic acid, alkenyl Examples include polycarboxylic acids such as succinic acid and polyisobutynylsuccinic acid.

Examples of acid amides include acid amides obtained from monovalent calga/acid used as the above-mentioned active hydrogen-containing compound, and acids obtained from lower fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, and caproic acid. Amides and the like can be mentioned. As the amine used to produce this acid amide, not only the above-mentioned amines can be used, but also lower amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, Octylamine, nonylamine, decylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine can be used.

Furthermore, examples of mercaptans include those having 11 to 30 carbon atoms, such as lauryl mercaptan, tridecyl mercaptan, myristyl mercaptan, pentadecyl mercaptan, hexadecyl mercaptan, and nutearyl mercaptan.
2-ethylhexyl mercaptan, nonyl mercaptan, dodecyl mercaptan, isostearyl mercaptan, oleyl mercaptan, valmitoleyl mercaptan, etc.; Examples include mercaptans with saturated hydrocarbon funds.

Furthermore, phenols include alkylphenols which are reaction products of phenol and α-olefins having 8 to 30 carbon atoms such as diisobutylene and nonene; Examples include compounds.

The alkylene oxide added to the compound having at least one active hydrogen is preferably ethylene oxide, propylene oxide, or butylene oxide, and the number of moles of alkylene oxide added is 51 to 120 moles per mole of the compound having active hydrogen, Especially 1-60
Moles are preferred.

In the production of the ester compound according to the present invention, carbon number 7 is conveniently used for esterification of alkylene oxide adducts.
~30 monovalent carboxylic acids include, for example, lauric acid,
m carboxylic acids having a linear alkyl group with 11 to 300 carbon atoms such as myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid; isostearic acid, 2-ethylhexanoic acid, oleic acid, erucic acid, linoleic acid Examples of the branched alkyl group t7t having 7 to 30 carbon atoms include a monohydric carboxylic acid having an unsaturated hydrocarbon group.

When the ester compound thus obtained is blended with fuel oil, it has an excellent effect of improving low-temperature fluidity and dispersing precipitated wax. In the fuel oil fluidity improver of the present invention, the esters may be used as they are or in a mixture of two or more.

The flow improver of the present invention may optionally contain compounds known as conventional flow improvers for fuel oil, such as ethylene-vinyl acetate copolymer, ethylene-(methacrylate copolymer, branched It is also possible to blend polyethylene, halogenated polyalkylene, alkyl (meth)acrylate polymers, condensates of chlorinated paraffins and naphthalene, carboxyl derivatives of alkenylsuccinic acids, aliphatic dicarboxylic acid amides, etc. The flow improver is
It can be generally blended in the fluidity improver of the present invention in an amount of 0 to 98%, preferably 0 to 50%.

Yet again. It is also possible to use it in combination with other common fuel oil additives, such as antioxidants, corrosion inhibitors, etc.

[For production]

Although we do not know the details of why the fuel oil flow improver of the present invention is able to impart good low temperature flow properties and good wax dispersibility to a wide range of types of fuel oils, the following useful features It is thought to have originated from That is, the ester compound according to the present invention contains a branched alkyl group and an unsaturated hydrocarbon group, which are thought to improve the solubility of fuel oil.

A linear saturated alkyl group that is thought to have the property of adsorbing or eutectic on WAVX crystals precipitated from fuel oil, and a function of dispersing WAVX crystals into fuel oil after precipitation.
This is thought to be because it has an alkyleneoxy group represented by the general formula →OR← (wherein R is an alkyl group and n represents the number of moles added).

〔Effect of the invention〕

The fluidity improver of the present invention can impart good low-temperature fluidity to a wide range of types of fuel oil by adding it to fuel oil. Although the composition, properties, etc. may vary, the purpose can be achieved by blending it into fuel oil so that it becomes 10~io, oooppm. [Example] Next, production examples and examples are given. The present invention will now be explained.

Production Example I p-octylphenol 206 obtained by reacting phenol with diiso and butylene in an IJ autoclave
f (1.0 mol) was heated and dissolved in 100 t:'. Next, add 0.56) (0.01 mol) of potassium hydroxide, and after purging the autoclave with nitrogen, 110c,
7 g ++ Dehydrated by heating and depressurizing for 1 hour at +aaH%.
o Thereafter, the mixture was reacted with ethylene oxide for 3 hours at 140-t60c for addition. The addition mole of ethylene oxide was 4.0.

mKp-octylphenol ethylene oxide adduct 152.87 (0.4 mol), behenic acid 136 SF
-(0,4 mol) and para-toluenesulfone @1.
41F CO0.5% by weight) Place in a 1-500- four-bottle flask and remove the produced water under the air stream L Nacala 140
The esterified product was obtained by heating and stirring at ~160C' for 3 hours.The acid value of this ester was 4.3 and was 0.Production Example 2 According to Production Example 1, 1 mole of phenol and 20 to 2 carbon atoms were added.
B α-olefin (Dialene 208 manufactured by Mitsubishi Kasei) 1
3.5 moles of ethylene oxide was added to the alkylphenol obtained by reacting 1 mole of the product with 1 mole of behenin to obtain an esterified product. The acid value of this ester is 467.

Production Example 3 According to Production Example 1, an esterified product was obtained from 1 mole of a product obtained by adding 4.6 moles of ethylene oxide to 1 mole of hardened rapeseed alcohol and 1 mole of olein. The acid value of this ester was 5.1 and 7t.

Production Example 4 According to Production Example IK, 6.0 moles of ethylene oxide was added to 1 mole of 2-ethylhexanol to obtain an esterified product from 1 mole of the product and 1 mole of behenic acid. The acid value of this ester was 3.9 and 0. Production Example 5 According to all Preparation Example 1, 7.3 moles of ethylene oxide was added to 1 mole of behenyl alcohol, and the next product was 1 mole and 7111 moles of 2-ethylhexane. Got nine. The acid value of this ester is 5.3, which is 7t.

Production Example 6 According to Production Example 1, 6.0 moles of ethylene oxide was added to 1 mole of di-hardened beef tallow amine, and 1 mole of the product and olein! An esterified product was obtained from 11 moles. The acid value of this ester is 4.1 and 721. .

Production Example 7 According to Production Example 1, 1 mole (2 equivalents) of a product obtained by adding 10.2% ethylene oxide to 1 mole of stearylamine, and 2 moles (1:1) of a mixture of behenic acid and erucic acid.
molar ratio) to obtain the esterified product. The acid value of this ester was 7.0, which was 0. Production Example 8 According to Production Example 1, 5.0 mole of propylene oxide was added to 1 mole of diethylenetriamine, and then 10.3 mole of ethylene oxide was added to produce 1 mole of the product. t5 equivalent) and a mixture of behenic acid and erucic acid (7:3 molar ratio)
The acid value of the ester obtained from 5 moles of ester was 9.6. Example 1 The ester of the alkylene oxide adduct produced in Production Examples 1 to 8 was diluted with an aromatic solvent. It was used in the test as a 50% concentrate. The fluidity improver of the present invention containing these concentrates t-light oil of Table 1 7tl:t'! The fluidity and dispersibility of good products blended with A heavy oil were tested and the results are shown in Table 2.

The fluidity test is performed using the low temperature clogging point test (CRPP, British Standard IP-309) and the flow flashing @ (PP, JI
8 K-2269).

In addition, the dispersibility test was conducted using 100116 test oil'i 100
d into a graduated cylinder and place it in a low-temperature bath with a programmable temperature controller until the cloudiness of the test oil reaches 9 points (CP% JI8) from room temperature.
K-2269) Rapidly cool the yellowtail to a high temperature of 1OC at a rate of IC per minute, then gradually cool it to a low temperature of 5C per hour at a rate of IC per hour, leave it at that temperature for 2 hours, and then
The condition was observed. The dispersibility of wax is determined by the ratio of the wax-dispersed layer of the test oil and the transparent layer of the supernatant, which are formed during wax-free precipitation. ○ more than 50 cm or more but less than 70 cm? 1il-△, less than 50% × binding.

As is clear from Table 2 in the margin below, the fluidity improver of the present invention is
Shows good fluidity and dispersibility for a wide range of fuels.

that's all

Claims (1)

[Claims] 1. An ester of an alkylene oxide adduct of a compound having at least one active hydrogen and a monohydric carboxylic acid having 7 to 30 carbon atoms, which has at least one branched alkyl group having 7 to 30 carbon atoms in the molecule or/ and a compound having an unsaturated hydrocarbon group and at least one linear saturated alkyl group having 11 to 30 carbon atoms.