JPH0987644A - Low-temperature fluid fuel oil composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a fuel oil composition having a narrow boiling point range and a wide boiling point range, which has improved fluidity at low temperatures. [Structure] Alcantriore or Alcantrio
It is essential to include two components, an ester of polyoxyalkylene ether and a fatty acid, and a sulfur-containing compound having a hydroxyl group or an ester of a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and a fatty acid. Fuel oil composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for improving the fluidity of a fuel oil prepared from a heavy fraction of petroleum and a low temperature fluidity improver. As is well known, among the fractions obtained by distilling crude oil, the middle and heavy fractions with a boiling point of 150 to 450 ° C are used in large quantities as various fuel oil sources such as kerosene, light oil, and heavy oil A. To be done. Above all, light oil and heavy oil A may precipitate a wax contained in the oil at a low temperature, so that the fluidity may be significantly deteriorated and a serious problem may occur.
For example, in cold weather, the wax content in light oil may precipitate, and the light oil itself may become semi-solid or gel and may block the oil feed pipe, or may disable the supply of fuel to the internal combustion engine. Heavy oil A is also used for engine driving of fishing boats, warmers for greenhouse heating cultivation, and building heating. However, this may also cause combustion failure due to wax deposited under cold weather.

[Prior art]

As a method for improving the low temperature fluidity of fuel oil, a method of adding a low temperature fluidity improver is known. The action of the low-temperature fluidity improver affects the precipitation of the wax from the fuel oil, hinders the huge growth of the wax, and stabilizes it with fine crystals. Various chemical synthetic products have been proposed for the low temperature fluidity improver, but the effect varies extremely depending on the target fuel oil properties, and there was an urgent need to grasp the fuel oil properties for stable quality control. It is extremely difficult due to factors such as the crude oil type and complicated operating conditions of the distillation apparatus.

Several studies have been conducted on the properties of the target fuel oil in order to effectively bring out the effect of addition by the low temperature fluidity improver. For example, there is a method of improving low-temperature fluidity by adding 0.2 to 1.5 parts by weight of an ethylene copolymer and n-paraffin having 26 to 27 carbon atoms to 100 parts by weight of middle distillate fuel oil. However, in this method, it is necessary to add both ethylene copolymer and n-paraffin to the fuel, which not only complicates the equipment and operation, but also causes n- which is a main cause of deterioration of low temperature fluidity due to wax precipitation.
The amount of wax deposited increases due to the addition of paraffin. As a result, the fluidity improver often fails to function effectively. When used as a diesel fuel, which is a typical application, a strainer is provided in the middle of the fuel supply line. However, a large amount of wax deposits shortens the wax saturation time in the strainer. , Will cause an early blockage.

Further, studies have been conducted on a fuel oil composition in which a fluidity improver is used in light oil in which the amount of paraffin wax precipitated at −20 ° C. is adjusted to a specific amount. However, even for light oils with a specified amount of paraffin wax that precipitates at -20 ° C, the addition of a fluidity improver can reduce the CFP content.
In some cases, P (low temperature filtration plugging temperature) does not decrease at all, or only in a specific type of fluidity improver.

Further, in recent years, fuel oils, especially light oils, have been forced to narrow the boiling point range by decreasing the proportion of low boiling point portions to meet the strong demand for kerosene. By narrowing the boiling point range in this way, n
-The carbon chain distribution of paraffin is narrowed, and the ethylene-vinyl acetate type fluidity improver conventionally used for such fuel oil can no longer exert its effect.

Accordingly, in recent years, a fluidity improver effective for fuel oil having a narrow boiling range has been developed. Typical examples thereof include esterification reaction products or salts thereof synthesized from a nitrogen-containing compound having a hydroxyl group and saturated fatty acids, esterification reaction products synthesized from polyhydric alcohols and saturated fatty acids, and polyoxyethylene. Examples thereof include an esterification reaction product synthesized from an alkylene glycol and a saturated fatty acid, and an esterification reaction product synthesized from an ethylene oxide adduct of a polyhydric alcohol or a partial ester thereof and a saturated fatty acid.

When these fluidity improvers are used alone, for example, an ester synthesized from polyalkylene glycol and a saturated fatty acid cannot obtain the CFPP lowering ability unless a relatively large amount is added. As a result, the oil permeability of the fuel oil containing the fluidity improver may deteriorate. Further, depending on the properties of the fuel oil, the CFPP lowering ability tends to decrease as the addition amount increases, which is not satisfactory.

[0008]

As described above, the current state of the art is that the specific additive exerts its effect only on the fuel oil having the specific property. The problem to be solved by the present invention is the inhibition of oil permeability by the addition of a high concentration of a fluidity improver,
It is in the property of fuel oil and the selectivity of the fluidity improvement effect.

[0009]

The inventors of the present invention have reached the present invention as a result of extensive studies to solve such problems. That is, the present invention relates to a fuel oil having a narrow boiling point range or a wide boiling point range, which is an esterification reaction product of two components (alkane triol or polyoxyalkylene ether of alcantholol and straight chain saturated fatty acid). By containing a small amount of a reaction product and a sulfur-containing compound having a hydroxyl group or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and a linear saturated fatty acid, oil permeability and low temperature fluidity can be obtained. It is based on the finding that a fuel oil composition having excellent properties can be obtained.

The alkanol used in the present invention includes glycerin, trimethylolpropane, trimethylolethane, trimethylolbutane and the like.
As the straight chain saturated fatty acid, mistyric acid, baltimic acid,
Examples thereof include stearic arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid and melissic acid, with preference given to baltimic acid, stearic acid, behenic acid, arachidic acid and eicosic acid.

The method for obtaining the product of the present invention is not particularly limited. For example, an alkane triol or a polyoxyalkylene ether of an alkantriol and a linear saturated fatty acid, a sulfur-containing compound having a hydroxyl group or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and a linear saturated fatty acid may be used. Each is a known method, for example, a method in which esterification is performed using paratoluenesulfonic acid as a catalyst, and the mixture is separately mixed with fuel oil, or an anthanol or an alkanthol polyoxyalkylene ether and a sulfur-containing compound having a hydroxyl group Alternatively, a method of esterifying a mixture of a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and a straight-chain saturated fatty acid by a known method, and mixing with a fuel oil, or an alkantriol or an alkantriol polyoxyalkylene Esterification of ether and excess linear saturated fatty acid by known methods, After that, an excess amount of a sulfur-containing compound having a hydroxyl group equal to or more than the equivalent amount of the linear saturated fatty acid or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group is added and esterified by a known method and mixed with fuel oil. Conversely, a sulfur-containing compound having a hydroxyl group or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and an excess of a linear saturated fatty acid are esterified by a known method, and then an equivalent amount of the excess linear saturated fatty acid or A method in which an equivalent amount or more of alkantriol or polyoxyalkylene ether of alkantriol is added and esterified by a known method and mixed with fuel oil can be considered.

The improved effect of the fuel oil thus obtained can be confirmed by observing the state of precipitation of paraffin wax crystals at low temperature under slow cooling. For example, when an ester of polyoxyalkylene glycol and a straight chain saturated fatty acid is added to a fuel oil having a narrow boiling point range, the paraffin wax will not be fine unless the addition amount is 0.05% by weight or more. It is hard to become.
On the other hand, the fuel oil composition of the present invention can be so fine as to pass through the wire mesh for CFPP measurement even when the amount of the esterification reaction product mixture added is about 0.01% by weight. Even if the absolute values of CFPP are compared, the fuel oil composition of the present invention shows that if the addition amount of the esterification reaction product mixture described in the claims is made the same amount, the fuel oil composition of alkanetriol or alkantriol can be obtained. Polyoxyalkylene
An esterification reaction product of a ter with a linear saturated fatty acid, or an esterification reaction product of a sulfur-containing compound having a hydroxyl group or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group with a linear saturated fatty acid It tends to show a better value than that used in, and is excellent in terms of performance and economy.

In the fuel oil composition of the present invention, if necessary, a compound known as a conventional fluidity improver, such as an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylate copolymer, Branched polyethylene, halogenated polyalkylene, alkyl- (meth) acrylate copolymer, condensate of chlorinated paraffin and naphthalene, nitrogen-containing derivative of alkenylsuccinic acid, and aliphatic dicarboxylic acid amide can be contained. . These conventional flow improvers can be contained in the fuel oil composition of the present invention in an amount of usually 0 to 1% by weight, preferably 0 to 0.5% by weight.

[0014]

EXAMPLES The present invention will be described in more detail with reference to specific examples and comparative examples, but the present invention is not limited to these examples.

Example 1 Trimethylolpropane (PO) ₉ (EO) ₉ having an average molecular weight of 1052 and a hydroxylation of 160 [9 mol of propylene oxide and 9 mol of ethylene oxide added to trimethylolpropane] 105.2 Parts (0.1 mol) and average molecular weight 530, hydroxylated 2
00 thiodiglycol (PO) ₄ (EO) ₄ [4 mol ethylene oxide added to propylene oxide 4 mol addition product of thiodiglycol] 53 parts (0.1 mol) and behenic acid 85.3 parts (0.25 mol)
And 71 parts (0.25 mol) of stearic acid and 2 parts of paratoluenesulfonic acid as a catalyst were stirred at 140 ° C. for 4 hours while stirring while blowing nitrogen to produce an esterification reaction product in fuel oil of 50 ppm. And 15
A fuel oil composition of the present invention was prepared by adding 0 ppm and 50 ppm of tetradecyl methacrylate polymer, respectively.

Example 2 Glycerin (PO) ₆ (EO) ₆ having an average molecular weight of 704 and hydroxylated 239 [6 mol of propylene oxide adduct of glycerin with 6 mol of ethylene oxide further added] 70.4 parts (0. 1 mol) and average molecular weight 1
035, hydroxylated 163 thioglycerol (3
-Mercapto-1,2-propanediol) (PO) ₉
(EO) ₉ [addition product of 9 mol of propylene oxide to thioglycerol and 9 mol of ethylene oxide] 105 parts (0.1 mol), behenic acid 102 parts (0.3 mol) and stearic acid 85. The esterification reaction product produced by reacting 2 parts (0.3 mol) in the same manner as in Example 1 was added to fuel oil at 50 ppm and 15
A fuel oil composition of the present invention was prepared by adding 0 ppm and 50 ppm of tetradecyl methacrylate polymer, respectively.

Example 3 Trimethylolpropane (PO) ₆ (EO) ₆ having an average molecular weight of 746 and hydroxylated 226 [6 mol of propylene oxide adduct of trimethylolpropane with 6 mol of ethylene oxide added] 74.6 Parts (0.1 mol) and average molecular weight 734, hydroxylated 1
53. thiodiglycol (PO) ₆ (EO) ₆ [6 mol of propylene oxide adduct of thiodiglycol with 6 mol of ethylene oxide further added] 73.4 parts (0.1 mol) and behenic acid 85. 3 parts (0.25 mol)
And 71 parts (0.25 mol) of stearic acid were reacted in the same manner as in Example 1 to add 50 ppm and 150 ppm of an esterification reaction product and 50 ppm of tetradecyl methacrylate polymer to fuel oil, respectively. The composition was used as the fuel oil composition of the present invention.

Comparative Example 1 Thiodiglycol (PO) ₄ (EO) ₄ having an average molecular weight of 530 and a hydroxylation of 212 [4 mol of propylene oxide adduct of thiodiglycol with 4 mol of ethylene oxide added] 106 parts ( 0.2 mol), behenic acid 68.2 parts (0.2 mol) and stearic acid 56.
The esterification reaction product produced by reacting 8 parts (0.2 mol) in the same manner as in Example 1 was added to fuel oil at 50 p.
A fuel oil composition for comparison was prepared by adding 50 ppm each of pm and 150 ppm and tetradecyl methacrylate polymer.

Comparative Example 2 Thioglycerol (PO) ₆ (EO) ₆ having an average molecular weight of 720 and hydroxylation of 234 [6 mol of propylene oxide adduct of thioglycerol with 6 mol of ethylene oxide added] 144 parts ( 0.2 mol), behenic acid 102.3 parts (0.3 mol) and stearic acid 8
The esterification reaction product produced by reacting 5.2 parts (0.3 mol) in the same manner as in Example 1 was used as fuel oil.
Fuel oil compositions for comparison were prepared by adding 0 ppm and 150 ppm of tetradecyl methacrylate polymer and 50 ppm of tetradecyl methacrylate polymer, respectively.

Comparative Example 3 Trimethylolpropane (PO) ₆ (EO) ₆ having an average molecular weight of 746 and hydroxylation of 226 [6 mol of propylene oxide adduct of trimethylolpropane with 6 mol of ethylene oxide added] 149.2 Parts (0.2 mol) and behenic acid 102.3 parts (0.3 mol)
And stearic acid (85.2 parts, 0.3 mol) were reacted in the same manner as in Example 1 to produce an esterification reaction product in fuel oil at 50 ppm and 150 ppm and tetradecyl methacrylate polymer at 50 ppm, respectively. The added one was used as a fuel oil composition for comparison. The results are shown in Table-1 and Table-2.

[0021]

[0022]

[0023]

EFFECTS OF THE INVENTION As is clear from Tables 1 and 2, the alkantriol or alkantriol according to the present invention is used.
Fuel oil composition containing an esterification reaction product mixture of a polyoxyalkylene ether / sulfur-containing compound having a hydroxyl group or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and a linear saturated fatty acid is distilled. Irrespective of the properties, the fuel oil composition containing the esterification product of the comparative example (an esterification reaction product of an alkantriol or a polyoxyalkylene ether of an alkantriol and a linear saturated fatty acid, or a hydroxyl group Low-temperature fluidity superior to that of a fuel oil composition containing only the esterification reaction product of a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group or a sulfur-containing compound having a hydroxyl group with a linear saturated fatty acid That is clear.

Claims (6)

[Claims] 1. An esterification reaction product of (A) an alkanthol or a polyoxyalkylene ether of an alkanthol and one or more kinds of linear saturated fatty acids, and (B) a hydroxyl group. A fuel oil composition containing two components of an esterification reaction product of a sulfur-containing compound or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and one or more linear saturated fatty acids. 2. The polyoxyalkylene ether of the alkanthol of (A) has an alkylene group having 1 to 4 carbon atoms, a molecular weight of 200 to 3000, and a linear saturated fatty acid of 1
In the case of two kinds, it is a mixed fatty acid containing 20 mol% or more of a straight chain saturated fatty acid having 14 to 30 carbon atoms and in the case of two or more kinds, it has a hydroxyl group of (B). The alkylene group of the polyoxyalkylene ether of the sulfur-containing compound has 1 to 4 carbon atoms and is directly esterified with the sulfur-containing compound having a hydroxyl group or the polyoxyalkylene ether of the sulfur-containing compound having a hydroxyl group. When the chain saturated fatty acid is one type, it has 14 to 30 carbon atoms, and when it is two or more types, it has 14 to 30 carbon atoms.
2. The fuel oil composition according to claim 1, which is a mixed fatty acid containing 20 mol% or more of the straight chain saturated fatty acid. 3. The fuel oil composition according to claim 1 or 2, wherein the ester of the polyoxyalkylene ether of the alkanthol of (B) and the linear saturated fatty acid is a partial ester. Stuff. 4. The weight ratio of (A) and (B) is 10:90.
To 90:10, the fuel oil composition according to claim 1 to claim 3. 5. From 0.0001% by weight to 0.5% by weight of the esterification reaction mixture of "claim 1" to "claim 4"
Fuel oil composition containing. 6. An ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylate copolymer, a branched polyethylene, a halogenated polyalkylene, an alkyl (meth) acrylate polymer, a chlorinated paraffin and naphthalene, if necessary. The fuel oil according to any one of claims 1 to 5, which contains one or more compounds selected from the group consisting of a condensate with the above, a nitrogen-containing derivative of alkenylsuccinic acid, and an aliphatic dicarboxylic acid amide. Composition.