JPS60137998A - Fluidity enhancer for fuel oil - Google Patents

Abstract

PURPOSE:To provide titled enhancer for hydrocarbon fuel oil, with low pour point as well as low cold filter plucking point, comprising ethylene/monolefin copolymer and an ester from hydroxyl group-bearing nitrogen-contg. compound and straight-chain saturated fatty acid. CONSTITUTION:The objective enhancer comprising (A) an ester from (i) hydroxyl group-bearing nitrogen-contg. compound [e.g. (di)ethanolamine] and (ii) straight- chain saturated fatty acid (pref. 10-30C fatty acid, e.g. capric acid) and (B) ethylene/monolefin copolymer (pref. with an ethylene content 40-90mol% and number-average molecular weight 1,000-30,000). This enhancer is preferably added to a fuel oil in such an amount as to be 50-1,000ppm.

Description

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

Since the oil crisis, the oil imported into Japan has gradually become heavier, 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, as it is mainly used in the civil and transportation sectors. There is a tendency.

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 and other devices, which obstructs the flow of fuel oil.

Many 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).
No. 4604.453), polyacrylate (U.S. Pat. No. 4604.453)
), polyethylene (U.S. Pat. No. 3.474.157), copolymers of ethylene and vinyl acetate (U.S. Pat. No. 3.
048.479).

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 Blugging Point Test (Co1d) is used to judge the clogging tendency of fuel oil pipe filters at low temperatures.
Filter Plugging Point Te5
t, IF 309), it often has little effect. In particular, there are few effective methods for fuel oil containing a large amount of paraffin.

Pour point tests cannot predict clogging of fuel oil pipe filters due to paraffin crystal particles that occur at temperatures significantly higher than the pour point, but cold filter blogging point (CFPP) tests can detect such phenomena. It is a test method that is currently widely adopted.

As a result of extensive research, the present inventors have discovered that when one specific ester is added to fuel oil, the CFPP is significantly reduced, and when a specific polymer is used in combination, the pour point is also significantly reduced.

That is, the present invention is a fuel oil fluidity improver comprising (B) a nitrogen-containing compound having a hydroxyl group and an ester of a linear saturated fatty acid, and (B) a copolymer of ethylene and monoolefin.

Examples of the nitrogen-containing compound having a hydroxyl group constituting the ester of the present invention include an alkylamine, an alkylolamine epoxide adduct, a furkylamine epoxide adduct,
Examples include polyamine epoxide adducts, fatty acid furkylamides, fatty acid alkylamide epoxide adducts, and the like.

Examples of alkylulamines include ethanolamine, jetanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, dihydrokidipropylamine, bis(
These include dihydroxypropyl)amine and tris(dihydroxypropyl)amine.

The alkylolamine epoxide adduct is the alkylolamine epoxide adduct.
Flukylene 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 epoxide compounds of fulkylamine such as methylamine, butylamine, octylamine, laurylamine, stearylamine, behenylamine, dimethylamine, dibutylamine, dioctylamine, dilaurylamine, distearylamine, dioctylamine, etc. It was added.

Poly7/epoxide adducts include ethylenediamine, propylenediamine, hexamethylenedi7mine, xylylenediamine, diethylenetriamine, triethylenetetramine, tetra'ethylenepentamine, pentaethylenehexamine, polyethyleneimine, and the alkyl7mines mentioned above. Additions of epoxide compounds to polyamines such as ethyleneimine adducts, or polyamines such as acetic acid, purpionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, The epoxide compound is added to a product partially amidated with a fatty acid such as arachidic acid, behenic acid, or lignoceric acid.

Fatty acid alkylol-7mide is a fatty acid such as acetic acid, prupionic acid, butyric acid, capric acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. These include 7midated ethanolamide, jetanol 7mide, Imp 181 Hanolamide, diimpropaturamide, dihydroxypropylamide, bis(dihydroxypropyl)amide, and the like.

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 1fIi of epoxide compounds alone, by mixing two or more epoxide compounds and adding them randomly, or by reacting two or more epoxide compounds in sequence by Xm individually and adding them in a pull-like manner. Do by doing.

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, lauric acid, myristic acid, balmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid, etc., and hydrogenated rapeseed oil fatty acids containing these,
Coconut oil fatty acids, 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 monoolefin constituting the copolymer of the present invention has 3 carbon atoms.
Among the above monoolefins, propylene, 1-butene, 2-butene, isobutyne, hexene, octene, decene, dodecene, etc. can be used.

The ethylene content of the copolymer is 40 to 90 mole, and the number average molecular weight is 1.000 to 30,000, but depending on the target fuel oil and the type of ester used together, the appropriate ethylene content, molecular weight, and monoolefin can be adjusted. It is desirable to select the type of

The copolymer can be easily produced by known methods such as free radical bulk polymerization, emulsion polymerization, and bath liquid polymerization.

The ratio of ester to copolymer in the fluidity improver of the present invention is 1:9 to 9:1 (heavy fk), and outside this range, the CPPP or pour point of the fuel oil may hardly decrease.

The amount of the fluidity improver of the present invention added to fuel oil is 10 to 5. OOOppm, preferably 50-1. OO
If the amount is less than 10 ppm, no sufficient effect can be obtained, and if it exceeds 5,000 ppm, no improvement in the effect is observed, which is economically disadvantageous.

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

When the fluidity improver of the present invention is added to fuel oil, the C of the 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 paraffin and having a relatively high boiling point. Since even high-boiling fractions can be used, the production amount of high-quality fuel oil can be increased.

Next, the present invention will be explained by examples.

Ethylenediamine 120,2 was added to the autoclave of Example 1t.
J' (2 moles) and 10. After adding ti'' potassium hydroxide aqueous solution -4j and dehydrating by heating at 100 to 110°C for 1 hour, ethylene oxide 616.7?
(14 mol) was gradually added to the mixture, and heating was continued at 140"C for 3 hours to complete the addition reaction.

The obtained ethylenediamine ethylene oxide 7 mol adduct 368.57' (1 mol), synthetic fatty acid (carbon number 21
~29, acid value 140, iodine value 2, melting point 63o)
Using t 202 P (3 mol) and 7.9 f of p-toluenesulfonic acid, an esterification reaction was carried out for 15 hours at 140 to 160° C. under a nitrogen stream while removing distilled water to obtain product A1 of the present invention. An ester (WR value 1λ3) was obtained.

By the reaction similar to the above, the present invention products A2 to No. 10 in Table 1 were obtained.
The ester was obtained.

The ethylene/monoolefin copolymer was produced according to the method for producing an ethylene/monoolefin copolymer described in JP-A-57-123205.

In order to evaluate the CPPP and pour point decrease of the products of the present invention, Table 1 shows the CPPP and pour points when the products of the present invention A1=A10 and comparative products All to A15 were added to fuel oil having the following properties.

Test fuel oil properties + 1 + distillation properties Initial boiling point 201°0 10% distillation point 251'Q 50% distillation point 293°C 90% distillation point 333°0 Final point 358°C (2) Pour point -5°C (31CF P P -4°C) From the results in Table 1, it can be seen that the product containing the ester and copolymer of the present invention has a lower pour point than CFPP, indicating that the product of the present invention is excellent as a fluidity improver.

Patent applicant: NOF Corporation

Claims (1)

[Scope of Claims] u+ (Fuel oil fluidity improver comprising an ester of a nitrogen-containing compound having an Al hydroxyl group and a linear saturated fatty acid, and (B) a copolymer of ethylene and monoolefin. (2) The nitrogen-containing compound having a hydroxyl group is an alkyl amine, an alkyl amine epoxide adduct, an alkyl amine epoxide adduct, a polyamine epoxide adduct, a fatty acid furkylamide, or a fatty acid furkyl amide.
The fluidity improver for fuel oil according to claim 1, which is a ruamide epoxide adduct. (3) 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.