JPH0987643A - 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] It is essential to include two components, an ester of polyoxyalkylene glycol 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, and an esterification reaction product of two components (an esterification reaction product of a polyoxyalkylene glycol and a linear saturated fatty acid) and a sulfur-containing sulfur-containing hydroxyl group. By adding a small amount of a compound or a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and a linear saturated fatty acid, a fuel oil composition having excellent oil permeability and low temperature fluidity can be obtained. It is based on the discovery that it can be done.

The alkylene group of the polyoxyalkylene glycol used in the present invention has 1 to 4 carbon atoms, preferably polyethylene glycol or propylene glycol. Examples of the linear saturated fatty acid include mistyric acid, baltimic acid, stearic arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, etc., but preferably baltimic acid, stearic acid,
Behenic acid, arachidic acid and eicosic acid.

Two types of esterification compounds synthesized to obtain the fuel oil composition of the present invention, specifically, an esterification reaction product of polyoxyalkylene glycol and a linear saturated fatty acid, and a hydroxyl group The esterification reaction product of a polyoxyalkylene ether of a sulfur-containing compound having a sulfur-containing compound or a sulfur-containing compound having a hydroxyl group with a linear saturated fatty acid may be a complete ester or a partial ester.

The method for obtaining the product of the present invention is not particularly limited. For example, polyoxyalkylene glycol and straight-chain saturated fatty acid, sulfur-containing compound having hydroxyl group or polyoxyalkylene ether of sulfur-containing compound having hydroxyl group and straight-chain saturated fatty acid can be prepared by known methods, for example, paratoluenesulfonic acid. As a catalyst and separately mixing with fuel oil, or a mixture of polyoxyalkylene glycol and a sulfur-containing compound having a hydroxyl group, or a mixture of a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group and linear saturation A method of esterifying a fatty acid by a known method and mixing it with fuel oil,
Further, a polyoxyalkylene glycol and an excess of a linear saturated fatty acid are esterified by a well-known method, and then a sulfur-containing compound having a hydroxyl group or a sulfur-containing compound having a hydroxyl group of an equivalent amount or an equivalent amount or more of the excess linear saturated fatty acid. Is added to the fuel oil by esterification by a well-known method, and the sulfur-containing compound having a hydroxyl group or the sulfur-containing compound having a hydroxyl group is directly added to the polyoxyalkylene ether in excess of the known method. A method in which a chain saturated fatty acid is esterified by a well-known method, and then an excess amount of a linear saturated fatty acid equivalent or an equivalent amount or more of polyoxyalkylene glycol is added and esterified by a well-known method and mixed with fuel oil, etc. Conceivable.

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 when compared in terms of the absolute value of CFPP, the fuel oil composition of the present invention shows that when the addition amount of the esterification reaction product mixture described in the claims is the same, polyoxyalkylene glycol and straight chain saturated are obtained. Better than using the esterification reaction product of a fatty acid or 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 alone It tends to show values 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, for example, 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.

[0015]

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 40 parts (0.1 mol) of polyethylene glycol having an average molecular weight of 400 and hydroxylated 281 and an average molecular weight of 53
0, hydroxylated 200 thiodiglycol (PO)
₄ (EO) ₄ [4 mol ethylene oxide added to propylene oxide 4 mol addition product of thiodiglycol] 53 parts (0.1 mol), behenic acid 68.2 parts (0.2 mol) and stearin Acid 56.8 parts (0.2 mol) was used as a catalyst with 2 parts of paratoluenesulfonic acid as a catalyst
The esterification reaction product produced by reacting for 4 hours with stirring while blowing nitrogen at 5 ° C into fuel oil
The fuel oil composition of the present invention was prepared by adding 0 ppm and 150 ppm of tetradecyl methacrylate polymer and 50 ppm of tetradecyl methacrylate polymer, respectively.

Example 2 30 parts (0.1 mol) of polyethylene glycol having an average molecular weight of 300 and hydroxylated 374 and an average molecular weight of 103
5, hydroxylated 163 thioglycerol (3-mercapto-1,2-propanediol) (PO) ₉ (E
O) ₉ [Addition of 9 mol of ethylene oxide to 9 mol of propylene oxide of thioglycerol] 105 parts (0.1 mol), 85.3 parts of behenic acid (0.25 mol) and 71 stearic acid. Of the esterification reaction product prepared by reacting 1 part (0.25 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 60 parts (0.2 mol) of polyethylene glycol having an average molecular weight of 300 and hydroxylated 374 and an average molecular weight of 73
4, hydroxylated 153 thiodiglycol (PO)
₆ (EO) ₆ [6 mol of propylene oxide adduct of thiodiglycol with 6 mol of ethylene oxide added] 73.4 parts (0.1 mol) and behenic acid 11
An esterification reaction product produced by reacting 9.4 parts (0.35 mol) with 85.2 parts (0.35 mol) of stearic acid in the same manner as in Example 1 was added to fuel oil at 50 pp.
The fuel oil composition of the present invention was prepared by adding 50 ppm of each of m and 150 ppm and tetradecyl methacrylate polymer.

Comparative Example 1 60 parts (0.2 mol) of polyethylene glycol having an average molecular weight of 300 and hydroxylation of 374 and behenic acid of 68.2.
(0.2 mol) of stearic acid and 56.8 parts (0.2 mol) of stearic acid were reacted in the same manner as in Example 1 to produce an esterification reaction product in fuel oil at 50 ppm and 15
A fuel oil composition for comparison was prepared by adding 0 ppm and 50 ppm of each of 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 Thiodiglycol (PO) ₄ (EO) ₄ having an average molecular weight of 530 and hydroxylation 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. The results of the above Examples and Comparative Examples are shown in Tables 1 and 2.

[0022]

[0023]

[0024]

As is apparent from Tables 1 and 2, the polyoxyalkylene glycol / sulfur-containing compound having a hydroxyl group or the sulfur-containing compound having a hydroxyl group in the present invention is directly combined with the polyoxyalkylene ether. The fuel oil composition containing the esterification reaction product mixture with the chain saturated fatty acid was the fuel oil composition containing the esterification product of the comparative example (polyoxyalkylene glycol and linear saturated fatty acid) regardless of the distillation property. A fuel oil composition containing, alone, 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, and a linear saturated fatty acid ) It is clear that it has better cold flow properties.

Claims (5)

[Claims] 1. A sulfur-containing compound having a hydroxyl group, (A) an esterification reaction product of (A) polyoxyalkylene glycol and one or more linear saturated fatty acids.
Alternatively, a fuel oil composition containing two components of an esterification reaction product of a polyoxyalkylene ether, which is a sulfur-containing compound having a hydroxyl group, and one or more linear saturated fatty acids. 2. A polyoxyalkylene glyco-of (A)
The alkylene group has 1 to 4 carbon atoms and a molecular weight of 200
To 3,000, the number of straight-chain saturated fatty acids is one, and the number of carbon atoms is 14 to 30; A sulfur-containing compound having a hydroxyl group, wherein the sulfur-containing compound having a hydroxyl group of (B) has 1 to 4 carbon atoms in the alkylene group of the polyoxyalkylene ether;
Alternatively, the linear saturated fatty acid to be esterified with a polyoxyalkylene ether of a sulfur-containing compound having a hydroxyl group is 1
The carbon number is 14 to 30 in the case of type, and the mixed fatty acid containing 20 mol% or more of the straight chain saturated fatty acid having 14 to 30 in the case of 2 or more types. Fuel oil composition. 3. The weight ratio of (A) and (B) is 10:90.
To 90:10, the fuel oil composition according to claim 1 or claim 2. 4. From 0.0001% by weight to 0.5% by weight of the esterification reaction mixture of "claim 1" to "claim 3".
Fuel oil composition containing. 5. 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 4, containing one or more compounds selected from the group consisting of a condensate of alkenyl succinic acid, a nitrogen-containing derivative of alkenylsuccinic acid, and an aliphatic dicarboxylic acid amide. Composition.