JPH0475954B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a fluidity improver, and more particularly to a fluidity improver that is used in petroleum products such as liquid fuels to improve their flow characteristics at low temperatures. BACKGROUND ART In recent years, as crude oil has become heavier and the amount of middle distillates in petroleum products has increased, the use of high boiling point oils has become an issue. Since oils with a high boiling point fraction have poor fluidity at low temperatures, efforts have been made to remove wax (dewaxing), which greatly affects fluidity at low temperatures, and to use fluidity improvers. While dewaxing requires large equipment and is economically disadvantageous, fluidity improvers do not require special equipment.
This is an economically advantageous method, and various methods have been proposed heretofore. Conventionally, as a fluidity improver, ethylene-vinyl acetate copolymer (Japanese Patent Publication No. 39-20069, Japanese Patent Publication No. 43-16153, Japanese Patent Publication No. 43-16755, Japanese Patent Publication No. 48-23165, JP-A-55-137193), a blend system of ethylene-vinyl acetate copolymer and other compounds (JP-A-53-124515, JP-A-Sho
56-93796) and alkenylsuccinic acid amides (Japanese Patent Application Laid-open No. 49-63702, JP-A No. 56-43391), but these do not yet have sufficient performance, especially in narrow spaces. Significantly less effective on distillate range fuel oils. In order to compensate for this drawback and improve the fluidity of narrow-boiling oils, JP-A-57-
No. 177092 proposes a fluidity improver containing a specific polyoxyalkylene ester or ether or ester ether. However, this compound has a problem in that it is less effective against oils with a wide distillation range. OBJECTS OF THE INVENTION An object of the present invention is to provide a fluidity improver that exhibits a fluidity improving effect on both wide-boiling and narrow-boiling oils. Structure of the invention The fluidity improver of the present invention has the following general formula ()
It is characterized by containing a polyester derivative compound represented by: R ¹ COO(AO) _l {COYCOO(AO) _n } _o COR ²
() (In the formula, R ¹ , R ² , A, Y, l, m and n represent the following. R ¹ : C _9-29 alkyl group R ² : C _9-29 alkyl group A: C _2-4 alkylene group Y: alkylene group, alkenylene group or aromatic residue l: 1-25 m: 1-25 n: 1-10) In general formula (), R ¹ and R ² are linear alkyl are preferred, and these are straight chain fatty acid residues (R ¹
CO−, R ² CO−).
Examples of fatty acids include n-decanoic acid, n-dodecanoic acid (lauric acid), n-pentadecanoic acid, n-heptadecanoic acid, n-hexadecanoic acid (palmitic acid),
n-octadecanoic acid (stearic acid), n-eicoic acid, n-behenic acid, n-pentaeicoic acid, n-
Saturated straight chain fatty acids such as heptaeicoic acid, n-hexaeicoic acid, n-octaeicoic acid, and n-triacontanoic acid are mentioned, and these can be used alone or in combination. Furthermore, mixed fatty acids derived from natural products such as fish oil fatty acids, beef tallow fatty acids, and coconut fatty acids can also be used, and these hydrogenated fatty acids are preferably used. A in the general formula () is an ethylene group, a propylene group, a tetramethylene group, etc., and is introduced from ethylene oxide, propylene oxide, tetrahydrofuran, etc. Y in the general formula () represents an aromatic residue such as an alkylene group, an alkenylene group, or a phenylene group, and these are dicarboxylic acid residues (-CO-Y-CO
−) can be introduced as Examples of dicarboxylic acids include oxalic acid (when Y is a C ₀ alkylene group, that is, when CO and CO are directly bonded);
malonic acid, succinic acid, glutaric acid, adipic acid,
Examples include pimelic acid, phthalic acid, terephthalic acid, fumaric acid, naphthalic acid, and anhydrides thereof. l and m indicate the number of moles of oxyalkylene groups (A ¹ O) and (A ² O) added, respectively, and 1
-25, preferably 1-10. For example, (A ¹ O) _l can be introduced by adding a single alkylene oxide such as ethylene oxide, or by sequentially adding ethylene oxide and propylene oxide, or by adding a mixture of these alkylene oxides. It can also be introduced in the form of block addition, random addition, etc. n represents a number from 1 to 10, preferably from 1 to 5. The polyester derivative compound used in the present invention can be prepared by, for example, first adding an alkylene oxide to a fatty acid, then adding a dibasic acid, and then adding an alkylene oxide, and if necessary, performing an addition step of the dibasic acid and the alkylene oxide. It can be produced repeatedly and finally by crosslinking the obtained alkylene oxide adduct with a dibasic acid. In addition, there is a method in which a polyoxyalkylene glycol and a dibasic acid are reacted in advance to obtain a polyester polyol having a hydroxyl group at the end, and then the terminal hydroxyl group is ester-blocked with a fatty acid. to produce an ester polyether with hydroxyl groups,
Any method can be employed, such as a method of crosslinking this with a dibasic acid. The fluidity improver of the present invention has a polyester derivative compound represented by the general formula () as an essential component, but may optionally contain known fluidity improvers such as ethylene-vinyl acetate copolymer, chlorinated wax, and naphthalene. copolymer with polyacrylate,
It can be used in combination with alkenyl succinic acid amide, maleated oleic acid amide (JP-A-57-229357), and the like. It is appropriate to use these known fluidity improvers in an amount of 0.2 to 10 parts by weight per 1 part by weight of the polyester derivative compound of the present invention. When used in combination with these known fluidity improvers, a complementary fluidity improvement effect is exhibited,
In particular, it has a remarkable effect on lowering the pour point. The fluidity improver of the present invention can be used without a solvent, or can be diluted with a suitable solvent such as petroleum fuel oil, aromatic solvent, aliphatic solvent, etc. The fluidity improver of the present invention is used in petroleum products including liquid fuels, and is suitable for middle distillates such as jet fuel, light oil, and A-heavy oil. The amount of the fluidity improver of the present invention added to fuel oil is:
Appropriately 10 to 5000ppm by weight, preferably 50ppm
~1000ppm. If the amount added is less than 10 ppm, a sufficient effect will not be obtained, while if it exceeds 5000 ppm, the added effect will be saturated and no significant effect will be obtained. Effects of the invention By adding the fluidity improver of the present invention,
For both narrow-boiling and wide-boiling distilled oils, it is possible to improve filter passage and prevent filter clogging in diesel engines, etc., and to transport high-boiling point oils containing wax at low temperatures or in diesel engines. Easy to use in institutions. As a result, it is possible to expand the usage limit for fuel oil and increase production volume. Synthesis example 1 Potassium acetate 0.5% by weight based on 341 parts by weight of behenic acid
was charged into an autoclave, dissolved, nitrogen-substituted, degassed, and subjected to an addition reaction with 200 parts by weight of ethylene oxide at 150 to 190°C to form polyoxyethylene behenate (average number of added moles of ethylene oxide: 4.5,
A monoester polyether with a hydroxyl value of 107 and an acid value of 2.9) was obtained. To this monoester polyether, succinic anhydride in an amount equivalent to its hydroxyl value (acid value basis) was charged into a flask, 0.5% by weight of para-toluenesulfonic acid was added, and a dehydration reaction was carried out at 140 to 160°C while flowing nitrogen. Succinic acid di(polyoxyethylene behenate) ester (esterification reaction rate 93%)
of polyester ether was obtained. Here, the esterification reaction was expressed as a reduction rate with respect to the acid value at the time of reaction preparation. Hereinafter, synthesis was carried out in the same manner except that the reagents shown in Table 1 were used to obtain Synthesis Examples 2 to 7. Table 1 shows the results.
Shown below.

[Table] Synthesis example 8 Polyethylene glycol (average molecular weight 200) 200
50 parts by weight of succinic anhydride (mole ratio:
PEG/succinic anhydride = 2/1) was dehydrated in the presence of 0.5% by weight of para-toluenesulfonic acid at 140 to 160°C under nitrogen flow to produce polyester polyether (hydroxyl value 246, average degree of polymerization 0.95).
I got it. Furthermore, for this polyester polyale,
Using behenic acid in an amount equivalent to the hydroxyl value (acid value basis), 0.5% by weight of paratoluenesulfone was added, and an esterification reaction was carried out at 140 to 160°C while nitrogen was flowing. %) was obtained. Here, the reaction rate is expressed as the rate of decrease with respect to the acid value at the time of charging. The following synthesis was carried out in the same manner to obtain Synthesis Examples 9 to 12.
The results are shown in Table 2.

[Table] Same as below.
Synthesis Example 13 341 parts by weight of behenic acid was dehydrated with 150 parts by weight of triethylene glycol in the presence of 0.5% by weight of para-toluenesulfonic acid at 140 to 160°C under flowing nitrogen to form triethylene glycol monobehenate. (hydroxyl value 123, acid value 2.8) was obtained. Furthermore, for this triethylene glycol monobehenate, using phthalic anhydride in an amount equivalent to its hydroxyl value (based on acid value), while flowing nitrogen in the presence of 0.5% by weight of para-toluenesulfonic acid at a temperature of 140 to 160°C. A dehydration esterification reaction was performed to obtain phthalic acid di(triethylene glycol monobehenate) ester (reaction rate 96%). Here, the reaction rate is expressed as the rate of decrease with respect to the acid value at the time of charging. The following synthesis was carried out in the same manner to obtain Synthesis Examples 14 to 17.
The results are shown in Table 3.

[Table] Example The polyester derivative compound of the present invention obtained in the above synthesis example was added to light oil having the following properties, and CFPP and pour point were measured. A gas oil (narrow boiling oil) B gas oil (broad boiling oil) Initial boiling point 211℃ 198℃ 10vol% distillation temperature 256℃ 243℃ 50vol% distillation temperature 290℃ 294℃ 90vol% distillation temperature 328℃ 347℃ Dry point 348℃ 369℃ PP* ⁵ -7.5℃ -7.5℃ CFPP※ ⁶ -6℃ -2℃ *5) PP: pour point, JIS
Measured by K2269/1980. *6) CFPP: Cold Filter Plugging Point
(low temperature clogging temperature), measured by IP309/80. Indicates standards for filter passability at low temperatures.

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[Table] Next, a combination system with a known fluidity improver was evaluated. The results are shown in Table 5.

【table】

【table】

Claims (1)

[Claims] 1 General formula () R ¹ COO(AO) _l {COYCOO(AO) _n } _o COR ²
() (In the formula, R ¹ , R ² , A, Y, l, m and n represent the following. R ¹ : C _9-29 alkyl group R ² : C _9-29 alkyl group A: A fluid characterized by containing a polyester derivative compound represented by _C2-4 alkylene group Y: alkylene group, alkenylene group or aromatic residue l: 1-25 m: 1-25 n: 1-10) Sex enhancer.