JPS60166389A - Fluidity improver for fuel oil - Google Patents

Abstract

PURPOSE:A fluidity improver for hydrocarbon based fuel oil, consisting of a polymer of an ester of a hydroxyl group- and nitrogen-containing compound with a specific fatty acid with a monomer, e.g. an olefin, and an oil-soluble surfactant, and capable of reducing greatly cold filter plugging point and pour point. CONSTITUTION:A fluidity improver for hydrocarbon based fuel oil consisting of a polymer of (A) an ester of a hydroxyl group- and nitrogen-containing compound, e.g. an alkylolamine, with (ii) a 10-30C straight chain saturated fatty acid with (B) one or more monomers selected from olefins, alkyl esters of ethylenically unsaturated carboxylic acids and vinyl esters of saturated fatty acids and (C) an oil-soluble surfactant, preferably having one or more elements such as acids, amines, acid amine salts, acid ammonium salts, hydroxy groups and ether groups. The amount of the improver to be added is preferably 50-1,000ppm based on the fuel oil.

Description

[Detailed description of the invention] The present invention relates to a fluidity improver for hydrocarbon fuel oil.

Since the oil shock, the oil imported into Japan's I8 has become increasingly heavy, and this trend is expected to intensify in the future.

On the other hand, demand for heavy fuel oil is decreasing due to the shift away from petroleum, such as thermal power generation, which uses a large amount of energy.On the other hand, demand for medium to light fuel oil is increasing because it is mainly used in the civil and transportation sectors. There is a tendency to

In order to respond to this supply and demand situation, there is a movement to use some of the heavy distillates as medium or light fuel oils, and in particular, middle distillate products such as light oil and A heavy oil are becoming heavier. .

Such heavy fuel oil contains a large amount of paraffin with a large molecular weight compared to conventional fuel oil, and paraffin tends to precipitate at low temperatures, and loses fluidity at relatively high temperatures. In addition, large paraffin crystal particles are generated even at temperatures that maintain fluidity, resulting in clogging of filters and pipes in fuel oil pipes in diesel engines, etc., and obstructing the flow of fuel oil.

A number of fluidity improvers have been disclosed to solve these problems, including a condensation product of chlorinated paraffin and naphthalene (U.S. Pat. No. 1.815.022).
), polyacrylate (U.S. Pat. No. 2,604,45)
No. 3), polyethylene (U.S. Pat. No. 3.474.157)
), copolymer of ethylene and propylene (French Painting Patent No. 1)
．． 438.656) and a copolymer of ethylene and vinyl acetate (US Pat. No. 4048.479).

These fluidity improvers are tested according to the pour point test (JISK 226
9) shows a good pour point lowering effect, but the cold filter plugging point test (Co1 d
Filter Plugging Point Te5
t, IP 309) There are many cases where there is no VC effect. In particular, there are few effective methods for fuel oil pressure containing a large amount of high molecular weight paraffin.In pour point tests, it is possible to predict clogging of fuel oil pipe filters due to paraffin crystal particles generated at temperatures much higher than the pour point. However, the cold filter plugging point (hereinafter abbreviated as CFPP) test is a test method that is currently widely used to predict such a phenomenon. As a result of repeated research to solve problems related to low-temperature fluidity of oils, we found that (1) CFPP is (2) When a specific polymer is used alone or when a specific polymer and an oil-soluble surfactant are used together, the pour point decreases in both cases. ,
He discovered that CFPP does not decrease at all, and (3) that when a specific ester and a specific polymer are used together, both CFPP and pour point decrease, and he filed a series of applications including Japanese Patent Application No. 57-1'8974.

Finally, when a specific ester, a specific polymer, and the king of oil-soluble surfactants were used in combination, both the CFPP1 pour point and the conventional fluidity improver were lower than those of the conventional fluidity improver. The present invention was completed based on the discovery that this method shows excellent effects even on types of fuel oil for which the effects were small.

That is, the present invention provides one or more monomers selected from (4) esters of nitrogen-containing compounds having hydroxyl groups and linear saturated fatty acids, olefins, ethylenically unsaturated alkyl carboxylates, and saturated fatty acid vinyl body polymers,
It is a fluidity improver for fuel oil consisting of (Q) and an oil-soluble surfactant.

Examples of the nitrogen-containing compound having a hydroxyl group constituting the ester of the present invention include alkylolamine, alkylolamine epoxide adduct, alkylamine epoxide adduct,
Examples include polyamine epoxide adducts, fatty acid alkylolamides, and fatty acid alkylolamido epoxide adducts.

Examples of alkylolamines include ethanolamine, jetanolamine, triethanolamine, isopropanolamine, cynopropanolamine, triinpropanolamine, dihydroxyglobilamine, bis(
These include dihydroxyglobil)amine and tris(dihydroxyglopyru)amine.

The alkylolamine epoxide adduct is an alkylene oxide, styrene oxide,
It is added with an epoxide compound such as glycidol. Examples of the alkylene oxide used here include ethylene oxide, propylene oxide, and butylene oxide.

Alkylamine epoxide adducts are suitable for alkylamines such as methylamine, ethylamine, butylamine, octylamine, laurylamine, stearylamine, behenylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine, dilaurylamine, distearylamine, diethylamine, etc. The above epoxide compound is added to the epoxide compound.

Polyamine epoxide adducts include ethylene diamine, propylene diamine, hexamethylene diamine, xylylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, polyethylene imine, and ethylene imine adducts of the above alkyl amines. Addition of the above epoxide compound or polyamine with acetic acid,
The above epoxides are partially amidated with fatty acids such as propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. It is an addition of a compound.

Fatty acid alkylolamides are amides with fatty acids such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, capric acid, myristic acid, valmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, etc. These include ethanolamide, jetanolamide, ingropanolamide, diimpropaturamide, dihydroxyglopyramide, and bis(dihydroxyglobil)amide.

The fatty acid alkylolamide epoxide adduct is obtained by adding the epoxide compound to the fatty acid alkylolamide.

Addition of epoxide compounds can be carried out by adding a 1'm epoxide compound alone, by mixing two or more epoxide compounds and adding them randomly, or by reacting two or more epoxide compounds one by one in sequence. This is done by adding the following.

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 deterioration of CFPP will become small and this is not practical.

The linear saturated fatty acids that make up the ester have 10 to 3 carbon atoms.
0 fatty acids such as capric acid, capric acid, myristic acid, valmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisonic acid, etc. Palm oil fatty acid, hydrogenated rapeseed oil fatty acid, coconut oil fatty acid,
Hydrogenated fish oil fatty acids, fatty acids obtained by distilling and fractionating these fatty acids, or synthetic fatty acids derived from α-olefins can also be used.

The ester used in the present invention can be obtained by esterifying the nitrogen-containing compound having a hydroxyl group with the fatty acid in a conventional manner.

The olefins constituting the polymer are olefins having 2 to 30 carbon atoms, and (Kα-olefin polymer tL, -1, diisobutene, dodecene-1, octadecene-1, icosene-1, tetracosene-1, and triacontin-1.

The ethylenically unsaturated alkyl carboxylate constituting the polymer is a monocarboxylic acid or dicarboxylic acid having an ethylenic double bond such as acrylic acid, methacrylic acid, iconic acid, crotonic acid, maleic acid, or fumaric acid and a carbon number of 1. ~
It is an ester with 30 saturated alcohols.

The saturated fatty acid vinyl constituting the polymer has 1 to 30 carbon atoms.
Esters of saturated fatty acids and vinyl alcohol, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, stearin. Examples include vinyl acid, vinyl arachinate, vinyl behenate, vinyl lignocerate, and vinyl melisinate. .

The polymer used in the present invention is an ester type monomer, which is obtained by polymerizing a mixture of 111 or 211 or more of the above monomers by a conventional method, or by graft polymerizing another monomer after polymerization. can be obtained by methods such as transesterification of ester moieties after polymerization, esterification of ethylenically unsaturated carboxylic acids with alcohols after polymerization, porological or physical modification after polymerization, etc. Some are commercially available as oil additives. The number average molecular weight of the polymer is SOO
-5oooo is suitable.

Oil-soluble surfactants include anionic, cationic,
Among zwitterionic and nonionic surfactants, it is possible to use a moderate amount of surfactant that dissolves in fuel oil and exhibits surface activity in fuel oil even at low temperatures where improvement of fluidity is required. However, since it is added to fuel oil, it is preferable to use a surfactant that does not contain elements that may cause problems in practical use. Most preferred are surfactants that are composed only of elements that are present in large amounts.

Preferred oil-soluble surfactants are those having at least one element such as an acid, an amine, an acid amine salt, an acid ammonium salt, a hydroxyl group, or an ether group in one molecule.

Preferred acids include carboxylic acids, sulfonic acids, sulfuric acid esters, and carbolic acids having a hydrocarbon group of 6 or more carbon atoms, including caprylic acid, lauric acid, oleic acid, isostearic acid, naphthenic acid, benzoic acid, alkyl or alkenyl succinic acid. acid, petroleum sulfonic acid, olefin sulfonic acid,
Examples include polyolefin sulfonic acid, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyl sulfate, and alkyl phenol.

As the amine, primary amines, 27ζ amines, and tertiary amines having one or more swelling hydrogen groups with a total number of carbon atoms of 6 or more are preferable, including octylamine, dibutylamine salt dimethylamine, and di(2-ethylhexyl)amine. , dodecylisobutylamine, tallow alkylamine, chassis oil alkylamine, tallow alkyldimethylamine, and oleylbenzylamine.

The amine salts and acid ammonium salts include (1) amine salts or ammonium salts of organic acids such as carboxylic acids, sulfonic acids, sulfuric acid esters, and carbonic acids having a hydrocarbon group having 8 or more carbon atoms, and (2) total Preferably, carboxylates, sulfonates, carbonates or sulfates of primary, secondary, or tertiary amines having at least one hydrocarbon group having 8 or more carbon atoms are used, and myristic acid dodecyl Amine salt, didecylaionic acid naanthenate, dioctadecylamine benzoate, tallow alkylamine salt of dodecylbenzenesulfonic acid, 2-ethylhexylnaphthalenesulfonic acid ammonium salt, polybutene (number average molecular weight 36θ) sulfone salt Ethylenediamine salt, petroleum sulfonic acid (number average molecular weight 400) dibutylamine salt, oleyl sal 7ate triptylamine salt, 2-ethylhexylphenol chastis oil alkylamine salt, 015-2
1 Alkenyl succinic acid di-hardened beef tallow alkylamide di-hardened beef tallow algylamine salt, laurylbrayate dodecylamine salt, dioctadecylamine propionate, behenylamine carbonate, chassis oil alkylamine hexanoate, beef tallow alkylaminoinopropyfluamine olein Examples include acid salts, octadecyl imidacillin acetate, rapeseed oil alkylamine sulfate, and di-tallow alkylaminoacetic acid %E droxyethyl gyoho alkylamine lacrate.

Examples of those having a hydroxyl group and an ether group include alcohols having a hydrocarbon group having 6 or more carbon atoms;
Partial esterification products of alcohols with hydroxyl groups of 8 or more and carboxylic acids, sulfonic acids, sulfuric esters or carbolic acids with hydrocarbon groups of 8 or more carbon atoms, fatty acid amines and amides with hydrocarbon groups of 8 or more carbon atoms ,alcohol,
2 selected from acids or esters of ethylene oxide, carboxylic acids with globylene oxy groups, sulfonic acids, sulfuric esters or condensates of carbolic acid and alkylolamines, epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidol, etc. Copolymers of at least one epoxide compound are preferred, including oleyl alcohol, dioctylamine droxystearate, sorbitan trilaurate,
Glycerin chassis oil fatty acid ester, 4 moles of ethylene oxide adduct of di-tallow alkylamine, 1 mole of glycidol adduct of phenylaminoinglobilamine, 1 mole of propylene oxide adduct of laurin jetanolamide, polyethylene glycol (number average molecular weight 150
) Nisdel monofatty acid, norbitane trioleate adduct with 2 moles of ethylene oxide, beef tallow fatty acid jetanolamide, and copolymers of 20 moles of ethylene oxide and 50 moles of propylene oxide.

The present invention provides one or more esters of a nitrogen-containing compound having a captive hydroxyl group and a linear saturated fatty acid as described above, (6) an olefin, an ethylenically unsaturated alkyl carboxylate, and a vinyl saturated fatty acid. This is a fluidity improver for fuel oil consisting of a polymer of monomers (Q) and an oil-soluble surfactant (Q).
Each of these components (1) and (Q) must be contained in an amount of 1% by weight or more, preferably 10% by weight or more, and if it is less than 1% by weight, the effect is insufficient.

The amount of the fluidity improver of the present invention added to fuel oil is IQ ~ 5. OOOp p m s tL<is 50
~1. OOOp p m, and if it is less than 10 ppm, a sufficient effect cannot be obtained, and even if it exceeds 5,0θOPPm, no improvement in the effect is observed, which is economically disadvantageous.

The fluidity improver of the present invention can also be used in combination with antioxidants, corrosion inhibitors, and other fluidity improvers added to common fuel oils.

When the fluidity improver of the present invention is added hydraulically to fuel, the C of fuel oil increases.
Since PPP and pour point can be significantly lowered,
It becomes possible to solve various problems related to low-temperature fluidity during storage and transportation of distillate fuel oil containing paratwins and having a relatively high boiling point. Since even high boiling point fractions can be utilized, the production of high quality fuel oil can be increased.

The present invention will now be explained in more detail by way of examples.

Ethylenediamine 12o, z was added to the autoclave of Example 1t.
P (2 mo/I/) and a 10-weight striped potassium oxide aqueous solution 24/ were added and dehydrated by heating at 100 to 110°C for 1 hour, and then ethylene oxide 61a7/(1
4-E#) was gradually added, and heating was continued at 140°C for 3 hours to complete the addition reaction.

The obtained ethylenediamine ethylene oxide 7 mol adduct 36&5/(1 mol), synthetic fatty acid (carbon number 21-2
9, acid value 140, iodine value 2, melting point 63°0) 1202
7' (3 mol) and no(radluenesulfonic acid 7.9
1, the esterification reaction was carried out for 15 hours at 140 to 160°C under a nitrogen stream while removing the distilled water, and the ester of /I61 used in the present invention shown in Table 1 /l/(acid value IL3 ) was obtained.

The esters No. 2 to No. 11 shown in Table 1 used in the present invention were obtained by the reaction similar to the above.

The polymers shown in Table 2 used in the present invention will now be explained.

Polymer 1 is a copolymer of ethylene and vinyl acetate, A
ynoco-547p (manufactured by Amoco Chemical Company, USA)
Number average molecular weight 2600, proportion of vinyl acetate 43% by weight, solvent content (approximately 50% by weight)! Removal (100°C130
(adjusted Hg for 20 hours).

Polymer 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) 47/.

Lauryl alcohol 45F, paratoluenesulfonic acid 0
．． The mixture of No. 21 and xylene to o go was distilled off in a water tube by flowing xylene tm under a nitrogen stream and allowed to undergo an esterification reaction for 10 hours, and then gradually poured into a large excess of methanol to remove the precipitate. It was dried after p separation.

Polymer 3 is α-olefin 3397 having 20 to 2B carbon atoms.
' (1°0 mol), maleic anhydride 98/(1.0 mol) and xylene 500/ were heated under a nitrogen stream so that the xylene refluxed, and di-t-butyl peroxide 4 Jlr xylene 50F was heated. 2-ethylhexyl alcohol 273F (21 mol) and p-toluenesulfonic acid 21 were added and the polymerization reaction was continued in this state for 10 hours.
An esterification reaction is carried out, and then xylene is distilled off.

Polymer 4 is branch polyethylene ACP-1702 (
Manufactured by Ando Chemical Company, USA, number average molecule-Biooo,
The softening point is 85°C).

Polymer 5 is Acryloid 152 (manufactured by Rohm and Haas, USA, number average molecule: 117,000, carbon number of alkyl group: 12 to 20), which is a polyalkyl methacrylate.

Polymer 6 is an ethylene propylene copolymer (ethylene content: 79 molar coefficient, number average molecular weight: 4,800) synthesized continuously using a 4-t autoclave. That is, from the top of the reactor, they were reacted at a rate of 2 t/hour of hexane, 1 t/hour of a hexane solution of vanadyl trichloride (4 mmol/l), and 1 t/hour of a hexane solution of sesquiethylaluminum sesquichloride (32 mmol/1). A mixed gas of ethylene, propylene, and hydrogen ( Ethylene 140t/hour, propylene 40t/hour,
Hydrogen (12,017 hours) was supplied, and the reaction was carried out continuously at 35°C. A small amount of methanol was added to the extracted reaction solution to stop the reaction, and then washed with water three times, and hexane was distilled off to obtain an ethylene propylene copolymer.

Further, Table 3 shows oil-soluble surfactants used in the present invention.

The performance of the fluidity improver of the present invention comprising the ester shown in Table 1, the polymer shown in Table 2, and the oil-soluble surfactant shown in Table 3 was evaluated using light oil having the following properties.

Properties of the test gas oil (1) Distillation properties Initial boiling point 212'C 10' distillation point 266'C 50' distilling point 304°C 90' distilling point 339'0 Final point 354'C (2) Pour point -6 °C (3) CF P P -2'C The results of the pour point test (measured according to JIS K 2269-1980) and the CFPP test (measured according to IP 309776) are shown in Table 4.

From the evaluation results in Table 4, the fluidity improver comprising the ester, polymer, and oil-soluble surfactant of the present invention lowers the pour point and CFPP more than when only the ester and polymer are used together. It turns out that it is effective.

Patent applicant: NOF Corporation

Claims (1)

[Scope of Claims] (1) One type selected from (A) an ester of a nitrogen-containing compound having a hydroxyl group and a linear saturated fatty acid, and (6) an olefin, an ethylenically unsaturated alkyl carboxylate, and a saturated fatty acid vinyl. In addition, a fluidity improver for fuel oil consisting of a polymer of monomers of 1112 m or more and (Q oil-soluble surfactant). The fluidity improver for fuel oil according to claim 1, which is an alkylamine epoxide adduct, a polyamine epoxide adduct, a fatty acid alkylolamide, or a fatty acid alkylolamine epoxide adduct. (3) Straight chain The fluidity improver for fuel oil according to claim 1, wherein the linear saturated fatty acid is a linear saturated fatty acid having 10 to 30 carbon atoms.(4) The fluidity improver for fuel oil according to claim 1, wherein the olefin is an olefin having 2 to 30 carbon atoms. The fluidity improver for fuel oil according to claim 1. (6) The fluidity improver for fuel oil according to claim 1, wherein the ethylenically unsaturated alkyl carboxylate is an ester. ) The fluidity improver for fuel oil according to claim 1, wherein the vinyl saturated fatty acid is an ester of a saturated fatty acid having 1 to 30 carbon atoms and vinyl alcohol. (7) The oil-soluble surfactant is an acid, The fluidity improver for fuel oil according to claim 1, which is an oil-soluble surfactant having at least one element of an amine, an acid amine salt, an acid ammonium salt, a hydroxyl group, or an ether group in one molecule.