JPS60101194A - Fluidity improver - Google Patents

Abstract

PURPOSE:To provide a fluidity improver for liquid petroleum fuel, consisting of an oil-soluble polar compd. (salt) obtained by interaction of a specified succinic acid deriv. and an active hydrogen compd. and exhibiting high fluidity at a low temp. without lowering of fluidity with time. CONSTITUTION:A succinic acid deriv. (A) is prepd. by reacting (a) 11-60C unsatd. compd. having at least one C=C unsatd. bond and one amide or ester bond in the molecule with (b) 4-6C alpha,beta-unsatd. dibasic acid (anhydride) (e.g. maleic anhydride). The fluidity improver consisting of an oil-soluble polar compd. (salt) is obtained by reacting 1mol (A) with 0.4-2.2mol (B) at least one active hydrogen compd. selected from among 8-40C long-chain aliphatic alcohols and long-chain aliphatic amines having at least one 8-40C aliphatic group. The fluidity improver is added to liquid petroleum fuel such as jet engine fuel in an amt. of 50-10,000ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a fluidity improver for improving the fluidity of petroleum-based liquid fuel containing wax, particularly the fluidity at low temperatures and stability over time.

(Prior art) In recent years, due to changes in the demand structure for petroleum-based liquid fuels and improved profit margins for value-added products during petroleum refining,
For example, the proportion of high-boiling fractions in various middle distillates such as jet fuel, kerosene, light oil, and A-heavy oil tends to increase. Increasing the content of high boiling point fractions in petroleum-based fuels,
Inevitably, the amount of wax with a high molecular weight and high crystallization temperature increases, resulting in a problem of decreased fluidity at low temperatures, which limits its use in winter or in cold regions. The cause of this decrease in fluidity is that the wax forms large crystals as the temperature decreases, and petroleum-based liquid fuels that are expected to be used in winter or in cold regions require dewaxing treatment to remove wax. Alternatively, fluidity at low temperatures can be maintained by a method of suppressing wax crystal growth and causing all fine crystals to precipitate. The former method of dewaxing requires large equipment, which is rarely used throughout its life, and also poses problems such as a reduction in fuel equivalent to the reduction in wax flow.

On the other hand, the latter method of adding fluidity improvers requires only addition and mixing when necessary, does not require special equipment, and does not cause a decrease in fuel consumption, making it more economical. I'm here.

Conventional! Also called flow improver and motion point depressant. ), it is known that ethylene-vinyl acetate copolymer exhibits good performance, but in recent years the proportion of high boiling point fractions in petroleum-based liquid fuels has increased, and the proportion of waxes with high crystallization temperatures has increased. There is a tendency for this to increase, so there is a desire for a more effective fluidity improver. In order to obtain such fluidity improvers, various methods have been proposed in which multiple fluidity improvers are used in combination. For example, JP-A-51-1232
No. 03 discloses a fluidity improver in which an ethylene-vinyl acetate copolymer and a polyacrylic acid ester are used in combination. Further, JP-A-53-12.4515 discloses a fluidity improver using a combination of an ethylene-vinyl acetate copolymer and an oil-soluble succinamic acid or an amine salt thereof. However, although the performance of these #L dynamic properties has not been improved compared to when the constituent components are used alone, their fluidity at low temperatures is still insufficient, and they are unstable and deteriorate over time. The retention of fluidity is also insufficient, and it is desired to develop a fluidity improver with even higher performance.

(Objective) The object of the present invention is to provide a fluidity improver that can produce petroleum-based liquid fuel F4 that has good fluidity at low temperatures and does not deteriorate in fluidity over time. .

(Structure) The fluidity improver for petroleum-based liquid fuel of the present invention has a total carbon number of ii to 60 and has at least one carbon-carbon unsaturated bond and one amide bond or ester bond in the molecule. A succinic acid derivative obtained by reaction with an unsaturated compound and an α,β-unsaturated dibasic acid or its anhydride, a long-chain aliphatic alcohol having 8 to 4 carbon atoms, and at least one carbon atom. It is characterized by containing an oil-soluble polar compound or a salt thereof obtained by reaction with at least one active hydrogen compound selected from the group consisting of long-chain aliphatic amines having 8 to 40 aliphatic groups. . The fluidity improver of the present invention preferably contains (A) the oil-soluble polar compound or its salt, and (B) an oil-soluble ethylene polymer or alkylnaphthalene compound having a polar group. Since the oil-soluble polar compound or its salt, which is an essential component of the present invention, is considered to have a high ability to control paraffin crystal formation, the hydrocarbon group of this oil-soluble polar compound or its salt may be linear or branched. It may be chain-like or either, but the shorter the number of carbon atoms or the fewer τ branched chains, the better.
It is preferable that the number of carbon atoms in the linear portion is 8 or more.

The unsaturated compound having a total of 11 to 60 carbon atoms used in the production of the succinic acid derivative in the present invention is a saturated or unsaturated aliphatic basic acid having 2 to 40 carbon atoms and a saturated or unsaturated compound having 1 to 40 carbon atoms. A structure corresponding to a reaction product with a saturated aliphatic alcohol, ammonia or a primary or secondary aliphatic amine having at least one saturated or unsaturated aliphatic group having 1 to 40 carbon atoms. It is a compound having a lipophilic group having 8 or more carbon atoms. The unsaturated bond may be present in any hydrocarbon group such as an aliphatic-basic acid, an aliphatic-hydric alcohol, or an aliphatic amine, but the number of carbon atoms in the unsaturated hydrocarbon group must be 4 or more. be.

The aliphatic basic acid is a saturated or unsaturated carboxylic acid having 2 to 40 carbon atoms, and particularly preferably a saturated monocarboxylic acid having 2 to 30 carbon atoms or an unsaturated monocarboxylic acid having 4 to 30 carbon atoms. Specific examples of such aliphatic-basic acids include acetic acid, propionic acid, acetic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Saturated carboxylic acids such as stearic acid, alagic acid, behenic acid, lignoceric acid, montanic acid, crotonic acid, hexenoic acid, dodecenoic acid, tetradecenoic acid, palmitoleic acid, oleic acid, petroselic acid, elaidic acid, eicosenoic acid, erucic acid, Examples include unsaturated carboxylic acids such as tetradecenoic acid, linoleic acid, linuric acid, and arachito/acid. These aliphatic-basic acids may be used alone or in a mixture of two or more, such as oil/oil fatty acids, beef tallow fatty acids,
Tall oil fatty acids can also be used. When a saturated compound is used as the aliphatic alcohol or aliphatic amine, an aliphatic basic acid containing an unsaturated carboxylic acid as a main component is used.

The aliphatic alcohol is a saturated or unsaturated secondary or secondary alcohol having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, and may be an alcohol derived from a natural product or a synthetic alcohol. In particular, primary alcohols having 1 to 30 carbon atoms or secondary alcohols having 3 to 30 carbon atoms are preferred.

A specific example of such an aliphatic alcohol is methanol.

Ethanol, propatool, butanol, 2-ethylhexanol, ur) IJ alcohol, mi') still alcohol, cetyl alcohol, stearyl alcohol,
Examples include saturated alcohols such as eicosanol, coconut oil alcohol and hydrogenated tallow alcohol, unsaturated alcohols such as allyl alcohol, futhynyl alcohol, hexenol, hexadecenol, oftadecenol (oleyl alcohol), eicosanol, lylyl alcohol and hylyllinyl alcohol. Examples of synthetic alcohols include primary and secondary alcohols produced by methods such as hydroformylation, Garbett reactions, and n-paraffin oxidation reactions. However, a mixture of two or more types may be used. Also, a mixture of saturated alcohol and unsaturated alcohol may be used, and for example, beef tallow alcohol can be used.

In addition, there are no particular restrictions on these alcohols when the aliphatic-basic acid is an unsaturated carboxylic acid, but in the case of a saturated carboxylic acid, an aliphatic-hydric alcohol containing at least an unsaturated alcohol as a main component must be used. .

The aliphatic amine is suitably a primary or secondary amine having 1 to 2 saturated or unsaturated aliphatic groups having 1 to 40 carbon atoms. Specific examples of such aliphatic amines include methylamine, ethylamine, propylamine, butylamine, octylamine%denylamine, dodenylamine, tetradecylamine, hexadecylamine, octadecylamine/, eicosylamine, tocodylamine,
Tetratria; saturated primary amines such as butylamine, hexatriacontylamine and hardened tallow alkylamine, dimethylamine, diethylamine, dibutylamine, didodecylamine, ditetradefluamine, dioctadecylamine, dioctadecylamine and dihardened tallow Saturated secondary amines such as alkylamines, allylamines,
Unsaturated primary amines such as methallylamine, butylamine, hexadecenylamine and octadecenylamine and unsaturated secondary amines such as dioctadecenylamine are mentioned. These aliphatic amines may be used alone or in a mixture of two or more. Further, a mixture of a saturated amine and an unsaturated amine may be used, and for example, tallow alkylamine, di-tallow alkylamine, etc. can also be used. These amines are not particularly limited when the aliphatic-basic acid is an unsaturated carboxylic acid, but when the aliphatic-basic acid is a saturated carboxylic acid, an aliphatic amine containing at least an unsaturated amine as a main component must be used.

In the present invention, the unsaturated compound having a total of 11 to 6 carbon atoms contains the aliphatic basic acid and the aliphatic alcohol, ammonia, or an aliphatic amine in at least one of them. It can be easily produced by carrying out a conventional reverse reaction using a compound having a saturated hydrocarbon group.

The succinic acid derivative used in the production of the oil-soluble polar compound used in the present invention is composed of the above-mentioned unsaturated compound and α, β.
- It can be easily obtained by reverse reaction with an unsaturated dibasic acid or its anhydride by a conventional method. The α,β-unsaturated dibasic acids suitable for the present invention have 4 to 6 carbon atoms, and include, for example, maleic acid, fumar M1 itaconic acid, and the like.

The oil-soluble polar compound used as an essential component in the fluidity improver of the present invention is produced by reacting the above-mentioned succinic acid derivative with an active hydrogen compound. The active hydrogen compound is a long chain aliphatic alcohol having 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms, and a long chain aliphatic alcohol having 1 or 2 aliphatic groups having 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms. selected from the group amines. The long chain aliphatic alcohols are saturated or unsaturated, primary or secondary, natural or synthetic alcohols. Synthetic alcohols can be produced by hydroformylation reactions, gerbenot reactions, n-paraffin oxidation reactions, and the like. Examples of these longer chain aliphatic alcohols include octatool, decanol, undecanol, dotecanol, tridecanol, tetradecanol, pentadecamer, hexadecanol, octadecanol, icozanol, docosanol, hexadecanol, Oftadecenol (oleyl alcohol fz
g), -r-icosenol, rilyl alcohol, rilyu/L-alcohol, etc., which may be used alone or as a mixture of two or more. Examples of mixed aliphatic alcohols include oil/oil alcohol, tallow alcohol, and the like.

Long chain aliphatic amines are saturated or unsaturated primary or secondary amines, specific examples of which include octylamine,
Decylamine, undecylamine, dodecylamine, tridecylamine, tetrazonolamine, pentadecylamine, hexadecalamine, octatoolamine, eikonruamine, tocodylamine, tetratriacontylamine, hexa) l) By acontylamine and Garbesoto reaction Primary amines such as amines and secondary amines such as didecylamine, didecylamine, didecylamine, ditetrathenylamine, dioctadecylamine, hexadecyloctadecylamine, dioctadecylamine and didecylamine are obtained by amination of the resulting β-branched alcohol. These can be used alone or as a mixture of two or more. Examples of mixed aliphatic amines include coconut oil alkylamine, hydrogenated tallow alkylamine, tallow alkylamine, shirt oil alkylamine, di-hardened tallow alkylamine, and di-tallow alkylamine.

The oil-soluble polar compound, which is an essential component of the fluidity improver of the present invention, can be easily produced by reacting the succinic acid derivative and an active hydrogen compound using a conventional method. This oil-soluble dust compound must have at least one lipophilic group derived from an active hydrogen compound. On the other hand, unreacted succinic acid derivatives may be included in the oil-soluble polar compound since they do not reduce the performance of the fluidity improver. In this case, the proportion of the oil-soluble polar compound may be 40% by weight or more, preferably 50% by weight or more, and therefore the active hydrogen compound should be about 0.0% by weight per mole of the succinic acid derivative.
4 to 2.2 moles are used. If the succinic acid derivative does not completely react, the carboxyl group remaining in the oil-soluble polar compound may be left as is (acid or amine salt), or may be neutralized using an appropriate base.

The fluidity improver of the present invention contains the above-mentioned oil-soluble polar compound as an essential component, or optionally contains a conventionally known fluidity improver such as an oil-soluble ethylene polymer having a polar group or an alkylnaphthalene compound. Especially, ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) or alkylnaphthalene compound is preferred. FiVA suitable for the present invention has a number average molecular weight of 800 to 40,000 and a vinyl acetate unit content of 10 to 50 mm%.
It is within the range of . Particularly preferred EVA has a number average molecular weight in the range of 1,000 to 30,000, and a vinyl acetate unit content of 1,000 to 30,000.
5 to 405 to 40 parts by weight. The 1-alkylnaphthalene compound is suitably one having a molecular weight in the range of 800 to 20,000, which is produced by the reaction of naphthalene and chlorinated paraffin. When all such known fluidity improvers are used in combination, 0.2 parts per part of the fluidity improver lii of the present invention.
A range of 10 parts by weight is appropriate; outside this range, no benefits can be obtained from the combined use.

The fluidity improver of the present invention may be used without a medium or as a solution dissolved in a suitable solvent. Examples of the solvent include petroleum fuel oil, aromatic solvents, and aliphatic solvents.

The fluidity improver of the present invention can be used, for example, in jet fuel, kerosene,
It can be used for various liquid fuels that are petroleum middle distillates such as light oil and A heavy oil, and the amount used is such that the total amount of fluidity ratio improver is 50 to 10,000 ppm, preferably 100 ppm.
The amount is within the range of ~5,000 ppm.

(Effect) The fluidity improver of the present invention has an excellent fluidity improving effect, especially when used in combination with a known fluidity improver such as an oil-soluble ethylene polymer having a polar group or an alkylnaphthalene compound. Liquid fuel that does not deteriorate in performance over time can be produced.

(Example) The present invention will be explained in further detail by showing examples below. The fluidity was evaluated according to the pour point method and CFPP method shown below. In addition, in the overall evaluation, ◯ indicates good, △ indicates somewhat good, and X indicates poor.

pour point method It was conducted according to JIS K-2269.

CFPP (Cold Filter Plugin)
g Po1nt) method - Cool the sample in a 34"C bath, and measure the temperature of the sample at which 20 ml of the sample cannot pass through a 350 mesh (44μ) stainless steel screen in 60 seconds. The CFPP value was determined.

Production example (manufacture of oil-soluble polar compound) React at a reaction temperature of 140-160°C for 4 hours at a ratio of 1 chemical equivalent of hydrogenated beef tallow alcohol (hydroxyl value 205) to 1 chemical equivalent of oleic acid with an oxidation rate of 196 and an iodine value of 87. As a result, oleic acid hardened beef tallow alcohol ester (unsaturated compound) was obtained with a reaction rate of 96.2%.

Next, a reaction temperature of 1.3 chemical equivalents of maleic anhydride was added to 1 chemical equivalent of this oleic acid hardened beef tallow alcohol ester (iodine value 44) (based on the iodine value).
After stirring the addition reaction at 90 to 210°C for 6 hours, unreacted maleic anhydride was distilled off under reduced pressure to obtain maleated oleic acid hardened beef tallow alcohol ester (Kono) containing unreacted oleic acid hardened beef tallow alcohol ester. - phosphoric acid derivative) was obtained. The acid value of this succinic acid derivative after hydrolysis is 149
Met.

Furthermore, based on the acid value, 1 chemical equivalent of di-cured tallow alkylamine (an active hydrogen compound) having an amine value of 111 was added to 1 chemical equivalent of this phosphoric acid derivative at a reaction temperature of 140 to 160°C. The reaction product (A-1)f obtained was directly extracted as an oil-soluble polar compound.
Used as a fluidity improver.

This reaction product has an amidation rate of 54% calculated from the acid value.
The content of the di-cured tallow alkylamide amine salt in the maleated oleic acid-cured tallow alcohol ester is 9.
It was 3.6% by weight.

Various oil-soluble polar compounds were synthesized in the same manner.

These oil-soluble polar compounds are shown in Table 1.

Incidentally, the reaction rate of the co-phosphoric acid derivative in Table 1 indicates the reaction rate of the co-phosphoric acid derivative and the active hydrogen compound, and the reaction rate of 50 molar means that one of the two carboxyl groups on average This means that the carboxyl group of

Table 1 (Unit: % by weight) 5 parts by weight of the reaction product (component A) containing the oil-soluble polar compound listed in Table 1 as the main component was dissolved in 95 parts by weight of light oil to give a concentration of 5% by weight. A fluidity improver solution was prepared. Similarly, oil-soluble ethylene polymer or polyalkylnaphthalene compound (B component) listed in Table 2, or di-hardened beef tallow alkylamide amine salt of octadecenyl succinic acid (A component: A-o) s weight A fluidity improver solution having a concentration of 5% by weight was prepared by dissolving 1 part in 955 parts by weight of light oil.

Samples were prepared by adding a predetermined amount of a previously prepared solution of a fluidity improver in light oil to light oil or heavy oil and shaking the mixture to make it homogeneous.

The obtained sample was tested for fluidity using two methods: pour point method and CFPP method. The results are shown in Tables 3 and 4 along with the type and amount of fluidity improver added.

In addition, the distillation temperature of light oil is 267℃ at 10% and 3℃ at 50%.
00°C, 331°C at 90% and 340°C at 95%, pour point was 15°C, (!PPP was 11°C.A
The heavy oil had a specific gravity d2o of 0.82, a flash point of 80°C, a viscosity of 2.66 cst, and a pour point of 0°C.

Table 2 Note) VAc indicates vinyl acetate.

Table 3 (light oil) Table 4 (A heavy oil)

Claims (1)

[Claims] 1 (a) An unsaturated compound having a total of 11 to 6 carbon atoms and having at least one carbon-carbon unsaturated bond and one amide bond or ester bond in the molecule, and an α,β-unsaturated dibasic acid or A succinic acid derivative obtained by reaction with the anhydride; ←) a long-chain aliphatic alcohol having 8 to 40 carbon atoms; and a long-chain aliphatic amine having at least one aliphatic group having 8 to 4 carbon atoms. 1. A fluidity improver for liquid fuel characterized by containing at least one oil-soluble polar compound or a salt thereof obtained by reaction with an active hydrogen compound selected from the group consisting of: