JPS61281198A - Fluidity improver for fuel oil - Google Patents

Abstract

PURPOSE:A fluidity improver having improved solubility in hydrocarbon fuel oils and improved low-temperature filtering characteristics, consisting of an ester of a specific alcoholic hydroxyl group-containing nitrogen compound and a specified carboxylic acid mixture. CONSTITUTION:The aimed fluidity improver consisting of an ester of (A) an alcoholic hydroxyl group-conaining nitrogen compound [e.g., alkylamine(epoxide compound), alkylamine epoxide compound, etc.] and (B) a carboxylic acid mixture containing 20-90mol% (preferably 30-80mol%) >=18C (preferably 18-30C) straight-chain saturated fatty acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a low temperature fluidity improver for hydrocarbon fuel oil.

[Conventional technology]

As a low-temperature fluidity improver for hydrocarbon fuel oil, a copolymer of ethylene and vinyl acetate (U.S. Pat. No. 3
．． No. 048.479 Specification 11:) etc. have been disclosed and used.

However, all of these were developed in Europe and the United States, and are often ineffective against fuel oil in Japan, which has a different compositional property from that in Europe and the United States.

Distillation temperature I of fuel oil, especially middle distillate fuel oil such as light oil and A heavy oil used for transportation where low-temperature fluidity is important!
ill! The range is considerably narrower in Japan than in Europe and the United States. This is inevitable due to Japan's unique fuel oil supply and demand structure, in which kerosene is consumed in large quantities for home heating, and middle distillates with low distillation temperatures are used for kerosene.

In addition to these conventional circumstances, there are also factors such as the increasing weight of imported crude oil, a decrease in demand for heavy fuel oil as oil becomes the dominant oil for energy-intensive industries, and an increase in demand for automobile fuel oils such as gasoline and diesel oil. Due to changes in the supply and demand structure, the distillation temperature range of middle distillate fuel oil tends to become narrower.

The low temperature fluidity of fuel oil is due to the relatively high molecular weight n-
Since the paraffin content is reduced by crystallization, a trap for improving low-temperature fluidity must control the shape and size of this precipitated crystal. In fuel oils with a wide distillation temperature range, the proportion of n-paraffin precipitated each time the temperature drops below the cloud point is small, and the shape and size of precipitated crystals can be controlled by a low-temperature fluidity improver. The amount of n-paraffin that must be removed is quite small. Therefore, it is possible to improve the low-temperature fluidity relatively easily. On the other hand, in the case of fuel oils with a narrow distillation temperature range, the ratio of the amount of n-paraffin precipitated every time the temperature drops by IC is extremely large, and conventional low-temperature fluidity improvers do not have the same shape as the precipitated culture crystals. It is difficult to control the size and no improvement in cold fluidity is observed.

As a low-temperature fluidity improver for fuel oil having a narrow distillation temperature range, JP-A-57-170,993 and JP-A-58-138,791 disclose nitrogen-containing compounds having hydroxyl groups and linear saturated Although esters with fatty acids have been disclosed,
The drawback is that it has a high melting point and is difficult to dissolve in fuel oil.

In order to improve these shortcomings, Japanese Patent Application Laid-Open No. 59-14998
No. 8 discloses an ester of an adduct of a compound represented by a specific structural formula of fullkylene oxide, styrene oxide, or glycidol and a linear saturated fat.

Although this has significantly improved solubility, etc., it is still not sufficient.

[Problem that the invention seeks to solve]

However, it is not satisfactory because it has poor solubility in fuel oil and has insufficient solubility in fuel oil.

・OII・- is intended as a mobility improver.

[Means for solving problems]

As a result of intensive research, the present inventors have found that a specific ester has excellent solubility in fuel oil and has increased low-temperature filterability (
The present invention was completed based on the discovery that the pour point can be significantly lowered when used in combination with a specific compound.

That is, the present invention provides a fuel oil comprising an ester of (1) a nitrogen-containing compound having two or more alcohol hydroxyl groups and (2) a carboxylic acid mixture containing 20 to 90 moles of a linear heavy-phase fatty acid having 18 or more carbon atoms. A fluidity improver, and (b) a polymer of the above ester and one or more monomers selected from (a) olefin, ethylenically unsaturated carboxylic acid furkyl, and saturated fat/vinyl;・・・
This fluidity improver for fuel oil is used in combination with a compound selected from the group consisting of logenated polyolefin, a condensation compound of paraffin and naphthalene, and a nitrogen-containing derivative of μ)alkenylco-phosphoric acid.

Examples of nitrogen-containing compounds having two or more alcohol hydroxide groups constituting the ester of the present invention include alkylolamines, alkylolamine epoxide adducts, alkylamine epoxide adducts, polyamine epoxide adducts,
Examples include fatty acid alkylolamides and fatty acid alkylolamides epoxide adducts.

Examples of alkylolamines include ethanolamine, triethanolamine, diyne7'O/<nol7mine, triisopropanolamine, dihydrobutibylamine, bis(dihydroxypropyl)amine, tris(dihydroxypropyl)amine, etc. There is.

Alkylol 7mine eboxide adducts are obtained by adding epoxide compounds such as alkylene oxide, styrene oxide, glycidol, etc. to monohydroxyalkylamines such as ethanolamine and isopropanolamine, and the above-mentioned alkylolamines. Examples of the alkylene oxide used here include ethylene oxide, propylene oxide, and butylene oxide.

Furkylamine epoxide adducts include epoxide compounds added to monoalkylamines such as methylamine, ethylamine, butylamine, octylamine, laurylamine, stearylamine, and behenylamine, and dimethylamine, diethylamine, butylamine, and dioctylamine. , dilaurylamine, distearylamine, nbehenylamine, and other dialkylamines with glycidol added.

Polyamine epoxide adducts include ethylene diamino, propylene diamine, hexamethylene diamine, xylylene diamine, diethylene triamine, triethylene tetramine, tetraethyl V/pentami/, pentaethylene hexamine, polyethyne imine, and ethylene imine addition of the above mono- and dialkyl amines. The above-mentioned epoxide compounds are added to polyamines, such as polyamines, or polyamines are added to acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargon 1mugi, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid. ,
The epoxide compound is added to a product partially amidated with a fatty acid such as behenic acid or lignoceric acid.

Fatty acid alkyl p-ramide is a fatty acid such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc. Amidated jetanol 7mide, diimpropanolamide, dihydrokidipurpyramide, bis(
dihydroxypropyl)amide, etc.

Fatty acid alkylolamide epoxide adducts include those obtained by adding the above-mentioned epoxide compound to the above-mentioned fatty acid alkylolamide, and those obtained by adding glycidol to monohydroxyalkylamides such as ethanolamide and isopropanolamide amidated with the above-described fatty acid. It is.

Adducts of epoxide compounds can be produced by adding one type of epoxide compound alone, by randomly adding a mixture of two or more types of epoxide compounds, or by reacting two or more types of epoxide compounds one by one. Obtained by applying a pull-like pressure.

The number of moles of the epoxide compound added is 1 to 100 moles, preferably 1 to 30 moles, per mole of the nitrogen-containing compound having a hydroxyl group. If more than 100 moles are added, the degree of improvement in low-temperature filtration properties will be too small to be practical.

The content of straight chain saturated fatty acids having 18 or more carbon atoms in the carb/acid mixture constituting the ester of the present invention is 20 to 9
0 mol, preferably 30 to 80 mol. If the amount exceeds 90 moles, the solubility of the ester in the fuel oil will be poor, and if it is less than 20 moles, the effect of the ester in improving the low-temperature resistance of the fuel oil will be weakened.

As a straight chain saturated fatty acid with carbon number 18 or more, carbon number 18
-30 straight chain saturated fatty acids are preferred, such as stearic acid, arachidic acid, behennodrate, lignoceric acid, cerotic acid, montanic acid, melisic acid, etc., including hydrogenated beef tallow fatty acids, hydrogenated palm oil fatty acids, hydrogenated Rapeseed oil fatty acids, hydrogenated fish oil fatty acids, fatty acids obtained by distilling and fractionating these, synthetic fatty acids derived from α-onfin, etc. can be used.

Carboxylic acids to be used with straight chain saturated fatty acids having 18 or more carbon atoms include straight chain consonant fatty acids having 17 or less carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, octanoic acid, and decanoic acid; oleic acid, linoleic acid , arachidonic acid, erucic acid, etc.; branched fatty acids such as imbutyric acid, neopentanoic acid, 2-ethylbutyric acid, 2-ethylhexa/acid, isonona/acid, indoridecanoic acid, impalmitic acid, isostearic acid; hexahydro Alicyclic monocarboxylic acids such as benzoic acid, cyclohexyl acetic acid, cyclohexyl caffeic acid, naphthenic acid; benzoic acid, methylbenzoic acid, t-butylbenzoic acid, phenylacetic acid, phenylcapric acid, phenylstearic acid, human Aromatic monocarboxylic acids such as carpinic acid; oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, methylsuccinic acid, azelaic acid, toluenedicarboxylic acid, benzenetetracarboxylic acid, furkyl or alkenylsuccinic acid, These include polybasic carboxylic acids such as oleic acid dimer; oxyacids such as hydroxypropionic acid, HF7xystearic acid, epoxystearic acid, and digetostearic acid; and various substituents on these carboxylic acids. It is also possible to use carboxylic acids into which .

The ester of the present invention is produced by combining (1) a nitrogen-containing compound having two or more alcoholic hydroxyl groups and (2) a carboxylic acid mixture containing a linear saturated fatty acid having 18 or more carbon atoms in the presence of an esterification catalyst or without a catalyst. , obtained by dehydration condensation by heating under normal pressure or reduced pressure. During this reaction, a solvent that is azeotropic with water may be used to promote the reaction. It is desirable to appropriately select the type and ratio of the nitrogen-containing compound and carboxylic acid mixture so that the ester thus obtained exhibits an excellent effect in improving fluidity.

In the present invention, the olefin constituting the polymer of one or more monomers selected from olefin, ethylenically unsaturated carboxylic acid furkyl, and saturated fatty acid vinyl used together with the ester has 2 to 30 carbon atoms. onfines, and α-onfines are particularly preferred; ethylene, propylene, zute/-1, isobutyne, pente/
-1, hexene-1, heptene-1, octene-1, diisozutene, dodecene-1, octadecene-1, icosene-1, tetracosenate, triaconteso-1, and the like.

The ethylenically unsaturated carboxylic acid furkyl constituting the polymer U) includes acrylic acid, methacrylic acid, itaconic acid, and phosphoric acid.
It is an ester of a monocarbo/acid or dicarboxylic acid having an ethylenic double bond, such as tonic acid, maleic acid, or sodium fumarate, and a saturated alcohol having 1 to 30 carbon atoms.

In addition, the saturated fatty acid vinyl constituting the polymer (a) is an ester of a saturated fatty acid having 1 to 30 carbon atoms and vinyl alcohol, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, and vinyl octanoate. vinyl,
Vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl arachinate, vinyl behenate, lig/vinyl serate,
Examples include vinyl melysinate.

The polymer (-r) used in the present invention is one of the above monomers.
Polymerization of a species or a mixture of two or more species by a conventional method, graft polymerization of another monomer after polymerization, transesterification of the ester moiety after polymerization in the case of ester type monomers, ethylenic monomers, etc. Some of them are commercially available as fuel oil additives, which are obtained by esterifying a saturated carboxylic acid with an alcohol after polymerization, or chemically or physically modifying it after polymerization. The number average molecular weight of the polymer (a) is preferably 500 to so, ooo.

In the present invention, the halogenated polyone fin used together with the ester (-J) is a halide of a polymer of omfin, which is a component of the polymer (a), and has a halogen content of 5 to 50% by weight and a molecular weight of 500. ~20.000
, halogens include chlorine, bromine, fluorine, etc., and preferably have a molecular weight of 1,000 to 5. OOO1 is chlorinated polyethylene with a chlorine content of 10 to 30% by weight.

(c) The condensate of chlorinated paraffin and phthalene used in the present invention is a 7 Liedl-Crafts condensation product of a chlorinated paraffin having 10 to 50 carbon atoms (containing chlorine [5 to 25% by weight)] and naphthane. with a molecular weight of 1,000
There are ~10,000 examples.

Examples of nitrogen-containing derivatives of alkenylcohelic acid used in the present invention include alkenylsuccinic acid having an alkenyl group having 10 to 30 carbon atoms or its anhydride, mono- or dialkylamine, polyalkylenepolyamine, polyethyleneimine, alkylpolyamine. Among them, the reaction product of realkenylsuccinic acid or its anhydride which also has an alkenyl group having 12 to 24 carbon atoms and dialkylamine having 2iVA alkyl group having 12 to 24 carbon atoms. Preferably.

The ester of the present invention can be used alone as a fluidity improver to improve low-temperature filterability, or can be used in combination with the above-mentioned compounds to significantly improve low-temperature filterability and pour point. When used together, the ratio of both is 1:9 to 9:
1 (weight is preferred.

The amount of the fluidity improver of the present invention added to fuel oil is 10 to 5. OOOppm, preferably 2° to 1,000
ppm, and if it is less than 10 ppm, sufficient effects cannot be obtained; 5. Even if the amount exceeds OOOppm, no improvement in effectiveness is observed, which is economically disadvantageous.

The flowability improver of the present invention can be added to general fuel oil.
It can also be used in combination with antioxidants, corrosion inhibitors, cetane number improvers, other flow ratio improvers, etc.

[For production]

Although the action of the fluidity improver of the present invention has not been fully elucidated at present, it can be considered as follows.

When the fuel oil is gradually cooled and the n-paraffin content present in the fuel oil begins to precipitate, the ester of the present invention becomes a crystal nucleus of the precipitated n-paraffin, significantly increasing the number of n-paraffin crystals. As a result, the n-paraffin crystals become finer, the low-temperature filterability is significantly improved, and the low-temperature flowability is improved.

In addition, the compound used in combination has the effect of controlling the shape of the fine n-paraffin crystals, and as a result of making the crystals granular,
It is believed that the distance between the crystals is kept as large as possible to improve the flow of fuel oil.

〔Effect of the invention〕

The fluidity improver of the present invention has excellent solubility in fuel oil and can greatly improve the low temperature pie and pour point of fuel oil, so it can be used even when storing fuel oil with a narrow distillation temperature range. This makes it possible to solve various problems related to low-temperature fluidity during transportation. Furthermore, by using the fluidity improver of the present invention, even fractions with a narrow distillation temperature range can be used as fuel oil without any problems, which is a major advantage in that the yield rate and degree of freedom in formulation design of each petroleum product can be dramatically increased. There are advantages.

〔Example〕

Next, the present invention will be explained by examples.

Example 1 An ester of the present invention was synthesized using the starting materials listed in Table 1. The synthesis method was carried out according to the method described in JP-A-59-149988. The composition of the comparative product is also shown in Table 1.

The products of the present invention and comparative products were added to gas oil distillate fuel oil to evaluate low temperature solubility and low temperature filterability.

Low-temperature solubility means that while stirring fuel oil cooled to 5C,
A 10% xylene solution of the inventive product and a comparative product was added to this in a predetermined amount, and the dissolution state was observed.
Those that dissolve in less than 10 seconds are rated as having good solubility (○), 10~
Those that dissolve in 60 seconds have slightly poor solubility (Δ), and those that remain insoluble even after 60 seconds have poor dissolution (×)
It was evaluated as follows.

Cold filterability was evaluated by the cold filter blacking point (CFPP) method specified in IP309.

The properties of the gas oil fraction fuel oil used are as follows.

Properties of gas oil fraction fuel oil (boiling point range Initial boiling point 203C 10% distillation point 253C 50C distillation point 295C 90 Mooring point 335C End point 355C (2) Pour point -5C (31CF)
Table 2 shows the test results of P P -4C low temperature solubility and low temperature filterability. From the results in Table 2, it can be seen that the fluidity improver of the present invention has good solubility even at low temperatures and significantly reduces CFPP.

Table 2 Example 2 Pour point and low-temperature filterability were evaluated when the ester of the present invention and the compound were used together.

Compounds used in Examples will be explained.

Compound 1 is a copolymer of ethylene and t9 vinyl acetate,
The solvent (approximately 50% by weight) was removed (10
(I', 30 ambient Hg, 20 hours).

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

Lauryl alcohol 451. Paratoluenesulfonic acid 0
．． After esterifying a mixture of 2y and xylene Loop for 10 hours while refluxing xylene and distilling off water under a nitrogen stream, the mixture was gradually poured into a large excess of methanol to remove the precipitate. It was separated and dried.

Compound 3 is an α-olefin 339y having 20 to 28 carbon atoms.
(1,0 mol), maleic anhydride 98y (1,0 mol)
A mixture of 500 y of xylene and 4 y of di-t-butyl peroxide was gradually added to the mixture under a nitrogen stream while heating it so that the xylene refluxed, and then a solution of 4 y of di-t-butyl peroxide dissolved in 50 y of xylene was continued under this condition for 10 hours. Tayu,
2-ethylhexyl alcohol 273y (2.1 mol)
Yohibara toluenesulfonic acid 2y was added to carry out an esterification reaction for 10 hours, and then xylene was distilled off.

Compound 4 is a branched polyethylene ACP-1702 (
Manufactured by Allied Chemical Co., USA, number average molecular weight 1100, softening point 85C).

Compound 5 is a polyalkyl methacrylate, Acryloid 152 (manufactured by P-Mand... USA, polyalkyl methacrylate number average molecular weight 17,000, alkyl group having 12 to 20 carbon atoms).

Compound 6 was an ethylene propylene copolymer (containing ethyl 1 and z7!7) synthesized continuously using a 4-ton autoclave.
9 molti, number average molecular t4800). That is, from the top of the reactor, hexane/2t/hour, a hexane solution of vanadyl trichloride (4 mmol/1) 1t/hour, a hexane solution of sesquiethylaluminum sesquichloride (32 mmIJ)
Each of them was continuously fed into the reactor at a rate of mol/l) I L/hour, while the reaction solution was quickly drawn out from the bottom of the reactor so that the amount of reaction solution in the reactor was always 2 tons. At the same time, a mixed gas of ethylene, propylene and hydrogen (ethylene 140t/hour, propylene 40t/hour) was pumped from the top of the reactor.
12,017 hours) of hydrogen were supplied, and the reaction was carried out continuously at 35C. A small amount of methanol was added to the reaction solution taken out to stop the reaction, and then washed with water three times, and hexane was distilled off to obtain an ethylene propylene copolymer.

Compound 7 is chlorinated polyethylene, Tolad35
(manufactured by Petrolite, USA, number average molecule of chlorinated polyethylene [2000, chlorine content 23% by weight)]
! It was obtained by removing the solvent (approximately 50% by weight) in the same manner as IJ1.

Compound 8 is Lubra/AD (manufactured by Toho Chemical Industry Co., Ltd.), which is a Friedel-Crafts reaction condensate of chlorinated paraffin and naphthalene.

Compound 9 is an amidation product of algenyl co-carbon and dialkylamine, and has 15 carbon atoms in the alkenyl group of the amidide.
~21, alkyl group having 16 to 18 carbon atoms), compound proboscis 1
It was obtained by removing the solvent (approximately 40% by weight) in the same manner as above.

Table 3 shows the pour point and CFPP of the gas oil distillate fuel oil used in Example 1, in which the ester and compound used in the present invention were used in combination as a fluidity improver.

Pour point (pp) is used as a macroscopic evaluation method for flowability.
It was measured according to the method specified in IS K 2269.

From the results in Table 3, it can be seen that the fluidity improvers of the present invention, esters and compounds used in combination (A24 to &32) are PP and C
It can be seen that both have low FPP and are excellent as flowability improvers.

Table 3

Claims (1)

[Scope of Claims] 1 Consists of an ester of (1) a nitrogen-containing compound having two or more alcoholic hydroxyl groups and (2) a carboxylic acid mixture containing 20 to 90 mol% of straight chain saturated fatty acids having 18 or more carbon atoms. Fluidity improver for fuel oil. 2. The nitrogen-containing compound having two or more alcoholic hydroxyl groups is an alkylolamine, an alkylolamine epoxide adduct, an alkylamine epoxide adduct, a polyamine epoxide adduct, a fatty acid alkylolamide, or a fatty acid alkylolamide epoxide adduct. A fluidity improver for fuel oil according to claim 1. 3 (A) (1) An ester of a nitrogen-containing compound having two or more alcoholic hydroxyl groups and (2) a carboxylic acid mixture containing 20 to 90 mol% of a straight chain saturated fatty acid having 18 or more carbon atoms, and (B) (a) a polymer of one or more monomers selected from olefins, ethylenically unsaturated alkyl carboxylates, and saturated fatty acid vinyl; (b) halogenated polyolefins; (c) chlorinated paraffins and naphthalene; A fluidity improver for fuel oil comprising a compound selected from the group consisting of a condensate of (2) and a nitrogen-containing derivative of (d)alkenylsuccinic acid. 4. The nitrogen-containing compound having two or more alcoholic hydroxyl groups is an alkylolamine, an alkylolamine epoxide adduct, an alkylamine epoxide adduct, a polyamine epoxide adduct, a fatty acid alkylolamide, or a fatty acid alkylolamide epoxide adduct. A fluidity improver for fuel oil according to claim 3.