JPS62109893A - Fluidity improving agent for fuel oil - Google Patents

Abstract

PURPOSE:To provide the titled improving agent composed of an ester compound having polyether bond and nitrogen in a molecule, imparting excellent low- temperature fluidity even to a fuel oil having wide boiling point range and capable of uniformly dispersing wax crystals in fuel oil. CONSTITUTION:The objective improving agent is composed of a compound of formula [R1 is 1-30C hydrocarbon residue; A and B are 2-4C alkylene; R2 and R3 are H or hydrocarbon residue, at least one of R2 and R3 is 14-30C alkyl; m and n are 1-40) (e.g. diester of polyoxyalkylene glycol, ester of ethylene oxide adduct of polyamine, etc.). EFFECT:Effective to prevent the clogging of filter of a fuel piping and the clogging of oil pipe, etc.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a fluidity improver for fuel oil, which improves the flowability of fuel oil by improving the flowability of fuel oil, which can effectively disperse wax crystals present in the fuel oil. Regarding sex improvers.

[Conventional technology]

When petroleum middle distillate oils, such as diesel oil and heavy fuel oil, are exposed to low temperatures in winter or in cold regions, the wax-like substances contained therein precipitate out, causing damage to the filters in the fuel piping system of diesel engines. This can cause problems such as clogging and hindering engine starting, or the fuel oil itself becoming semi-solid or solid and losing its fluidity, clogging the oil pipe. This problem tends to increase further due to the recent trend toward heavier crude oil or 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-(meth)acrylate copolymers, polyethylene, halogenated polyalkylenes, and alkyl meth)acrylates. Polymers, metal condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids, and aliphatic dicarboxylic acid amides have been reported. These modifiers generally improve the quality of fuel oil at low temperatures by adsorbing on or eutecticizing wax that precipitates when fuel oil is exposed to low temperatures, changing the shape and size of wax crystals. It improves liquidity.

[Problem that the invention seeks to solve]

However, in recent years, there have been changes in the demand for fuel oil, and with regard to diesel oil in particular, during times of strong demand for kerosene, etc., the proportion of low boiling point parts in diesel oil is decreasing, and the boiling point range is becoming narrower. There are situations where it is not possible. For gas oils with such narrow boiling point ranges, even if various fluidity-improving additives are added, including the conventionally used ethylene-vinyl acetate (EVA) copolymer, it is difficult to maintain good low-temperature properties. Since it is difficult to exhibit fluidity, it has been desired to develop an additive that is effective for a wide range of types of fuel oils with various boiling point ranges.

In addition, when fuel oil with conventional fluidity improvers added is slowly cooled in a storage tank or drum pipe, there is a drawback that the precipitated wax is not dispersed in the oil and often settles to the bottom. is desired.

[Means for solving problems]

Under these circumstances, the present inventor has conducted extensive 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 is dispersed in the oil. The present invention was completed by discovering a compound that can reduce sedimentation.

That is, the present invention provides a fuel oil fluidity improver comprising a compound represented by the following general formula.

(In the formula, R1 is a hydrocarbon group having 1 to 30 carbon atoms, A and B are alkylene groups having 2 to 4 carbon atoms, R2 and R1 are hydrogen or a hydrocarbon group, and at least one of R2 and R3 is a carbon It is an alkyl group of number 14 to 30.

m and n are 1-40. ) The compound represented by the above general formula (1) is, for example, an alkylene oxide adduct of a compound represented by the following general formula % formula % ( ) (RI is an alkyl group having 1 to 30 carbon atoms) and 30
It is obtained by reacting and esterifying a saturated fatty acid and, if necessary, other carboxylic acids. The compound represented by the general formula (11) is derived from an alcohol having the structure R1-OH and acrylonitrile.

The alcohol that can be used at this time has 1 to 1 carbon atoms.
Any monohydric alcohol having a molecular weight of 30 may be used, and it may be saturated, branched, or unsaturated. For example, methanol, ethanol, n-propyl alcohol, n-7'tanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, valmityl alcohol, stearyl alcohol, eicosyl Alcohol, behenyl alcohol, linear monohydric alcohols having 11 to 30 carbon atoms such as higher alcohols obtained by Ziegler method, branched alcohols having 7.8 or 9.18 carbon atoms obtained by oxo reaction, 16 obtained by Guerbet reaction To gels such as .18, 20, and 24, carbon number 7 such as alcohol, oleyl alcohol, etc.
Examples include monohydric alcohols having ~30 branched alkyl groups or unsaturated hydrocarbon groups.

Examples of the alkylene oxide used when adding an alkylene oxide to the compound represented by formula (II) include ethylene oxide, propylene oxide, and butylene oxide. When adding these to the compound represented by formula (n), one type of alkylene oxide may be added, or two or more types of alkylene oxide may be added randomly or/and in a block form. . Preferred among alkylene oxides are ethylene oxide and/or propylene oxide, and the number of moles added is preferably 1 to 40.

A compound having 14 to 30 carbon atoms used when reacting and esterifying an alkylene oxide adduct of the compound represented by formula (II) with a saturated fatty acid having an alkyl group having 14 to 30 carbon atoms and, if necessary, other carboxylic acid. Examples of saturated fatty acids having an alkyl group include myristic acid, valmitic acid, stearic acid, arachidic acid, behenic acid,
Examples include lignoceric acid, cerotic acid, montanic acid, melisic acid, and among these, preferred are valmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. These may be used alone or in combination of two or more. For example, a mixed fatty acid obtained by hydrogenating a fatty acid obtained by hydrolyzing natural fats and oils such as beef tallow can also be used as is.

In general formula (1), at least one of R2 and R1 must have an alkyl group having 14 to 30 carbon atoms. Otherwise, CFPP (cold filtration clogging point I
P306), PP (Pour point JIS K 2269
) is less effective in reducing As the alkyl group, a straight chain alkyl group is preferable.

The above-mentioned "other carboxylic acids" have 1 to 30 carbon atoms.
Carboxylic acids, such as straight chain saturated fatty acids with 1 to 13 carbon atoms, such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, lauric acid, etc.), unsaturated fatty acids with 3 to 30 carbon atoms (oleic acid, linoleic acid, lycylic acid, etc.), oxyacids with 2 to 30 carbon atoms (glycolic acid, lycylic acid, etc.), branched fatty acids with 4 to 30 carbon atoms (2-
(ethylhexanoic acid, isostearic acid, etc.), aromatic carboxylic acids (benzoic acid, naphthalene carboxylic acid, etc.), and mixtures of two or more thereof. Among these, preferred are the above straight chain saturated fatty acids and unsaturated fatty acids.

An example of the method for producing the compound represented by the general formula (1) will be explained in more detail.

First step fl, -01 ((R+ is a hydrocarbon group having 1 to 30 carbon atoms) is heated and dissolved, a catalyst such as caustic alkali is added, and acrylonitrile is added and reacted with stirring while heating (cyanoethylation). The product is then hydrogenated using a catalyst such as Raney nickel to give J OCH2Cl12CH2N
A compound represented by l+□ is obtained.

Second step: The compound obtained in the first step is dissolved using an appropriate solvent if necessary, a catalyst such as caustic alkali is added, and alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, etc.) in liquid or gaseous form and react. Random addition polymerization in which two or more types of alkylene oxides are mixed and reacted together, or block addition polymerization in which one type of alkylene oxide is sequentially added first may be performed.

3rd stage Obtained in the 2nd stage, R+ OCHzCHzCHzN
The Hz polyoxyalkylene ether is used as it is, or after being purified to remove unreacted substances and catalysts, it is usually esterified with a carboxylic acid by adding a catalyst such as para-toluenesulfonic acid and heating. The progress of the esterification reaction can be confirmed by monitoring the acid value, hydroxyl value, saponification value, etc.

When the esterified product 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, these esters can be used as they are, or two or more of them can be used as a mixture.

The fluidity improver of the present invention may optionally include compounds known as conventional fuel oil fluidity improvers, such as ethylene-vinyl acetate copolymer, engineered ethylene-(meth)acrylate copolymer, and branched polyethylene. , halogenated polyalkylenes, alkyl (meth)acrylate polymers, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids, aliphatic dicarboxylic acid amides, and the like can also be blended. These conventional flow improvers are
In the fluidity improver of the present invention, 0 to 98%, preferably O to
50% can be blended.

Furthermore, it is also possible to use it in combination with other general fuel oil additives, such as antioxidants, corrosion inhibitors, etc.

Although the fluidity improver of the present invention varies depending on the composition, properties, etc. of the fuel oil, it usually contains 10 to 11,000 in the fuel oil.
The purpose can be achieved by blending so that the amount is 0 pp.

The fuel oil flow improver of the present invention can be used alone for fuel oils with a very narrow boiling point range in which none of the conventional fuel oil flow improvers can reduce CFPP, and for fuel oils with a high low paraffin content. It shows excellent CFPP lowering ability and pp lowering ability against fuel oils with a wide boiling point range. Moreover, the fluidity improver of the present invention further has a function of effectively dispersing wax components in fuel oil precipitated at low temperatures into the oil. The fuel oil river fluidity improver of the present invention can be used in combination with conventional fuel oil river fluidity improvers if necessary, and exhibits excellent effects.

The compound represented by formula (1), which is the fuel oil fluidity improver of the present invention, is an ester compound having a polyether bond and nitrogen in the molecule.

Diesters of polyoxyalkylene glycols, which are compounds containing polyether bonds or nitrogen in the molecule, and esters of ethylene oxide adducts of polyamines are used as fluidity improvers for fuel oil spills. However, these compounds exhibit some degree of PPP lowering ability for distillate fuel oils with a narrow boiling point range, but are inferior in terms of CFPP lowering ability for fuel oils with a wide boiling point range. In addition, the ability to disperse wax components in fuel oil that precipitates during slow cooling was poor.

[Effect]

Although the details of the reason why the fuel oil flow improver of the present invention can impart good low temperature flow properties and good wax dispersibility to a wide range of types of fuel oils are not known,
This is thought to be due to the following characteristics. That is, the ester compound according to the present invention contains a saturated alkyl group that is thought to have the property of adsorbing or eutectic to wax precipitated from fuel oil, and -O-(CI+□)! N+(80)-rc-R)2
(No. 40 is alkylene oxide, n represents the number of moles added.) The alkylene oxide addition structure of the ether amine, represented by the formula, suppresses the growth of wax crystals, resulting in the wax component being dispersed appropriately in the oil. It is presumed that the effect of the present invention is achieved.

〔Example〕

The present invention will be specifically explained below with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited only to these Examples.

Production Example 1 558 g (3.0 mol) of dodecanol having 12 carbon atoms was added to 1
1 was placed in a flask, and under a nitrogen atmosphere, 191.0 g of acrylonitrile was heated and stirred at a temperature of 50°C using 0.50 g (0,009 mol) of caustic potassium as a catalyst.
(3.6 mol) was added dropwise over 3 hours, and after the dropwise addition, the reaction was carried out at a temperature of 50°C for 2 hours. Then, the caustic potash was neutralized with acetic acid, and the excess acrylonitrile was removed under reduced pressure to obtain a cyanoethylated product. Ta.

478.1 g (2.0 mol) of this cyanoethylated product was added to I
The mixture was placed in an autoclave, 0.956 g (0.2% by weight) of Raney nickel was added thereto, and hydrogenation was carried out by applying a hydrogen pressure of about 20 Kg/cm2 to obtain a product (referred to as ether amine).

Next, 486.1 g (2.0 mol) of the obtained ether amine was placed in a No. 11 autoclave, and the atmosphere was replaced with nitrogen.
176.2 g (4.0 mol) of ethylene oxide is heated to a temperature of 140-160°C and heated at this temperature for 1 hour.
and then add 1.1 g of potassium hydroxide (0,0
2 mol) was added thereto, and dehydrated by heating and reducing pressure at 110° C. and 170 mC17O for 1 hour. After that, 140-160
Ethylene oxide was reacted and added for 3 hours at °C. The number of moles of ethylene oxide added was 8.0.

Next, 297.7 g (0
,5 mol), 340 g (1,0 mol) of behenic acid and 3.2 g (0,5% by weight) of para-toluenesulfonic acid t-
The mixture was placed in a No. 11 four-bottle flask and heated and stirred at 140 to 160° C. for 3 hours while removing generated water under a nitrogen stream to obtain an esterified product. The acid value of this ester is 3.
It was 7.

Production Example 2 Ethylene oxide adduct 2 of ether amine of Production Example 1
97.7 g (0.5 mol) and 284 g (1 mol) of stearic acid.
, 0 mol) and 2.9 g of hibaradruenesulfonic acid (0,
5% by weight), an esterified product was obtained in the same manner as in Production Example 1. The acid value of this ester was 4.1.

Production Example 3 The operation was carried out according to Production Example 1 to obtain an esterified product of 4 moles of ethylene oxide and 4 moles of propylene oxide adduct of ether amine derived from stearyl alcohol having 18 carbon atoms and hebenic acid.

Production Example 4 An operation was carried out according to Production Example 1 to obtain an esterified product of 4 moles of ethylene oxide and 4 moles of propylene oxide adduct of an ether amine derived from stearyl alcohol having 18 carbon atoms and stearic acid.

Production Example 5 The operation was carried out according to Production Example 1 to obtain an esterified product of 10 moles of ethylene oxide adduct of ether amine derived from behenyl alcohol having 22 carbon atoms and hardened rapeseed fatty acid.

Production Example 6 The operation was carried out according to Production Example 1 to obtain an esterified product of 4 moles of propylene oxide adduct of ether amine derived from octyl alcohol having 8 carbon atoms and behenic acid.

Production Example 7 The operation was carried out according to Production Example 1, and 1 mole of an adduct of 10 moles of ethylene oxide of ether amine prepared from behenyl alcohol having 22 carbon atoms was reacted with 1 mole of oleic acid and 1 mole of hehenic acid to obtain an esterified product. I got it.

Production Example 8 The operation was carried out according to Production Example 1 to obtain an esterified product of 15 moles of ethylene oxide adduct of ether amine subjected to mR from oleic alcohol and hehenic acid.

Example 1 The esters prepared in Preparation Examples 1 to 8 were diluted with an aromatic solvent and used for testing as a 50% concentrate. The flowability and dispersibility of the fluidity improvers of the present invention containing these concentrates were blended with light oils or heavy oils shown in Table 1, and their fluidity and dispersibility were tested. The results are shown in Table 2.

In addition, the fluidity test is a low temperature clogging test (CFPP, British Standard IP-309) and a pour point test (PP, JIS
K-2269).

In addition, for the dispersibility test, 100ml of the test oil was placed in a 100ml measuring cylinder, and the test oil was heated from room temperature to the final point (CP, JIS) in a low temperature bath with a programmable temperature controller.
K-2269) up to 10°C higher than 1'c/min.
After cooling rapidly at a rate of
I observed the condition. Judgment was made based on the ratio of the wax-dispersed layer of the test oil produced by wax precipitation to the transparent layer of the upper supernatant.

Is the dispersibility of wax the same as this wax? The higher the ratio of 1, the better; if the ratio is 70% or more, ○, and if the ratio is 50% or more, 7
Less than 0% was rated △, and less than 50% was rated ×.

Comparative Example The following three types of additives were used as conventionally known additives.

Comparative Example 1 Ethylene-vinyl acetate copolymer (number average molecular weight 3300
/vinyl acetate content 32x4%) Comparative Example 2 Polyethylene glycol dibehenate Comparative Example 3 Tetrahhenate, an adduct of 4 moles of ethylene oxide of ethylene diamine Table 1 [Effects of the invention] As specifically shown in the examples In addition, the fuel oil fluidity improver of the present invention can exhibit excellent low-temperature fluidity not only for fuel oils with a narrow boiling point range but also for fuel oils with a wide boiling point range, and furthermore, The wax that precipitates when the fuel oil is gradually cooled can be well dispersed in the fuel oil. This can prevent clogging of filters in the fuel piping system, clogging of oil pipes, etc.

Claims (1)

[Claims] 1. A fluidity improver for fuel oil consisting of a compound represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (wherein R_1 is a compound having 1 to 30 carbon atoms) Hydrocarbon group, A, B
is an alkylene group having 2 to 4 carbon atoms, R_2 and R_3 are hydrogen or hydrocarbon groups, and at least one of R_2 and R_3 is an alkyl group having 14 to 30 carbon atoms. m, n
is 1-40. )