JPH10251675A - Fuel oil additive and fuel oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive which is inexplosive, has excellent safety, can improve the igintability and combustion efficiency of a fuel oil and can markedly improve the cetane number of a diesel fuel oil when added thereto by selecting a compound prepared by ozonizing a compound prepared by esterifying an alkenediol as a starting material. SOLUTION: This additive contains a compound obtained by ozonizing at least one member selected among compounds represented by the formula: X-OR<1> O-Y [wherein X and Y are each R<2> CO(AO)n - or H(AO)m -; R1 is a 4-8C alkenylene; R<2> is a 1-21C fatty acid residue; n is an integer of 0-100; m is an integer of 1-100; and AO is oxyethylene and/or oxypropylene]. This is used in an amount of 0.01-30wt.%, desirably 0.1-20wt.%, more desirably 0.3-10wt.% based on the fuel composition. This additive may contain other known fuel additives in addition to the compound of ozonization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having improved ignitability of light oil and heavy oil having a low cetane number, and more particularly to a fuel oil composition capable of satisfactorily operating a diesel engine without knocking.

[0002] The present invention also relates to a fuel oil additive and a fuel oil composition containing the same. More particularly, the present invention relates to a fuel oil composition in which a specific oxygen-containing compound is added to light oil or heavy oil so that exhaust gas is emitted when the engine is driven. The present invention relates to a fuel oil composition for reducing contained air pollutants such as black smoke.

[0003]

2. Description of the Related Art Direct diesel oil (Direct Distil)
(Lation Gas Oil, DGO) or gas oil is originally a middle distillate obtained between a light distillate and a heavy resid in distillation under normal pressure during crude oil refining. Due to its composition and various properties, DGO is a visbreaking gas oil obtained by vacuum distillation of the above heavy residue and a catalytic cracking gas oil (Light Cycle) obtained by catalytic cracking in the presence of a catalyst.
Oil, LCO).

The normal pressure distillation range of DGO is usually 150 ° C.,
The temperature ranges from 200 ° C to 350 ° C and 450 ° C. DGO
Must have a sufficiently high compression ignitability, wherein the compression ignitability is determined by the cetane number (Cetane Num) of the light oil.
ber), and the cetane number of DGO usually has about 45 to 60 without special treatment. On the other hand, LCO
Since the amount of aromatic hydrocarbons and unsaturated hydrocarbons is large, the cetane number is excessively lowered, and is not preferable as it is as a diesel fuel. That is, if the cetane number of LCO can be improved, it can be mixed with DGO or the like and can be used as a diesel fuel, so that the use of these LCOs is expanded.

[0005] The cetane number is determined by the ignition delay (Ignition Delay) after the fuel is injected into the combustion chamber.
s). If the ignition delay is too long, the amount of fuel in the combustion chamber increases, and when ignited, the operation of the engine becomes rough and smoke increases. On the other hand, the shorter the ignition delay, the smoother the operation of the engine and the less smoke.

Heretofore, many types of additives have been used to improve the cetane number of diesel fuel. These include peroxides (Peroxides), nitrites (Nitrites), nitrites (Nitrat).
es). Commercially, alkyl nitrates such as amyl nitrate, hexyl nitrate and mixed octyl nitrate are used. However, since these alkyl nitrates are expensive and have explosive properties, they are classified as Class 5 self-reactive substances of the dangerous substances of the Fire Services Act, and it is difficult to handle them safely. Therefore, as disclosed in JP-A-1-115997, attempts have been made to add a nitrate stabilizer, for example.
It is not essentially an improvement in the safety of the compound and is not a fundamental solution.

[0007] Further, from a diesel engine using a fuel oil, particularly a diesel fuel oil, hydrocarbon (HC), carbon monoxide (CO) and nitrogen oxide (NO) are contained in the exhaust gas.
x), exhaust gas containing air pollutants such as black smoke containing particulates (particulate matter) is released, and reduction of these is urgently required from the viewpoint of global environmental problems, environmental pollution, and the like.

At present, as a measure to reduce black smoke containing particulates, a method of collecting and burning by providing a filter in the middle of an exhaust pipe has been proposed, but it is difficult to control combustion and the like. Further, a method of adding an oxygen-containing compound such as alcohol or acetal to fuel oil has been studied (SA).
E 932734, 1993), these compounds have problems such as low solubility in light oil, emulsification by mixing with water to reduce flammability, and lowering cetane number to deteriorate flammability.

Further, the alkyl nitrate is 0.3
JIS K 2204 when the addition amount is increased to more than
Therefore, there is a problem that the regulation exceeds the "regulation of residual carbon content of 10% residual oil" specified in the above, and does not lead to reduction of pollutants in exhaust gas.

[0010]

DISCLOSURE OF THE INVENTION The present invention is excellent in safety such as no explosiveness, can improve the ignitability and combustion efficiency of fuel oil, and has a cetane number when added to diesel fuel oil. It is an object of the present invention to provide a fuel oil additive capable of remarkably improving the oil content and a fuel oil composition containing the same.

Another object of the present invention is to stably supply a fuel oil additive capable of reducing pollutants in exhaust gas and to provide a fuel oil composition containing the same.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above situation, and as a result, have found that a compound obtained by esterifying alkenediol as a raw material, a compound obtained by adding an alkylene oxide to alkenediol, and an alkenediol It has been found that the above problem can be solved by using a compound obtained by esterifying a compound to which an alkylene oxide has been added and then adding an alkylene oxide with an ozone-containing gas, thereby completing the present invention.

That is, the present invention provides a fuel oil additive containing a compound obtained by ozonating at least one selected from compounds represented by the following general formula (I). During ^{X-OR 1 O-Y (} I) ( ^{wherein, X, Y: R 2 CO} (AO) n - or ^{_{H (AO) m - R 1}} : an alkenylene group having 4-8 carbon atoms R ^2: 1 carbon atoms To 21 fatty acid residues n: an integer of 0 to 100 m: an integer of 1 to 100 AO: represents an oxyethylene group and / or an oxypropylene group.)

[0014] The present invention also provides a fuel oil composition containing the above fuel oil additive in an amount of 0.01 to 30% by weight.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for synthesizing a compound obtained by ozonating at least one compound selected from the compounds represented by the above general formula (I) used in the present invention will be described.

(1) Synthesis of the compound represented by the general formula (I) The compound represented by the above general formula (I) used in the present invention is a compound derived from an alkenediol and is used as a raw material. Examples of the alkene diol include 2-butene-1,4 diol, 3-butene-1,2 diol, hexene diol, peptene diol, octene diol, and the like. Among these, 2-butene-1,4 diol is preferred.

First, examples of the compound derived from the above alkenediol include an esterified product represented by the following general formula (II). R ³ COOR ¹ OOCR ⁴ (II) (wherein, R ¹ is the same as described above, R ³ and R ⁴ represent a fatty acid residue having ^{1 to} 21 carbon atoms, and the carbon chain length of R ³ and R ⁴ is They may be the same or different.

The esterified product represented by the above general formula (II) can be obtained by esterifying an alkenediol with a saturated or unsaturated fatty acid having 2 to 22 carbon atoms. As the fatty acid having 2 to 22 carbon atoms used in this reaction, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Examples include behenic acid, oleic acid, elaidic acid, octadecenoic acid, linoleic acid, linolenic acid, palmitoleic acid, isooleic acid, branched octadecenoic acid, branched hexadecenoic acid, icosenoic acid, docosenoic acid, and undecylenic acid.

In order to synthesize the esterified product represented by the general formula (II), a generally known esterification reaction is performed. That is, 1. to the -OH group of the diol.
0 to 5.0 equivalents, preferably 1.01 to 2.0 equivalents of a saturated or unsaturated fatty acid having a carboxyl group, or a mixture thereof or an ester thereof, in an amount of 0.01 to 10% by weight based on the fatty acid %, Preferably 0.1 to 5% by weight of an acid catalyst, an alkali catalyst or a solid catalyst. The reaction temperature is not particularly limited, but is usually 50 to 250 ° C., and the pressure is reduced to 10 a.
tm. Excess saturated fatty acids or unsaturated fatty acids are removed by an operation such as distillation.

As the esterification catalyst, sulfuric acid, hydrogen fluoride, boron trifluoride, p-toluenesulfonic acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate,
Examples include sodium methoxide.

Next, as the compound derived from the alkenediol, the following general formula (III) or (IV)
In the alkylene oxide adduct represented ^{_{H (AO) m1 OR 1 O}} (AO) m2 H (III) R 3 CO (AO) n1 OR 1 O (AO) n2 OCR 4 (IV) ( wherein, R ¹ , R ³ and R ⁴ are the same as above, and m1, m
2, n1 and n2 are integers from 1 to 100. )

The alkylene oxide adduct represented by the above general formula (III) can be obtained by using a diol as a raw material and conducting a conventionally known alkylene oxide addition reaction. The alkylene oxide adduct represented by the general formula (IV) is obtained by performing a conventionally known alkylene oxide addition reaction using an esterified compound represented by the general formula (II) as a raw material. Can be As the alkylene oxide used in the present invention, ethylene oxide having 2 to 3 carbon atoms and propylene oxide are preferable.

The alkylene oxide addition moles m1, m2, n1 and n2 of the alkylene oxide adducts represented by the above general formulas (III) and (IV) used in the present invention are from 1 to 1
00 mol, preferably 3 to 80 mol. The method of adding the alkylene oxide may be a single product or a mixture of ethylene oxide alone, propylene oxide alone, propylene oxide added after ethylene oxide addition, ethylene oxide added after propylene oxide addition, and the like.

As a method for producing the alkylene oxide adduct represented by the above general formula (III), for example, boron trifluoride, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are conventionally known. It can be produced by adding 0.01 to 5% by weight of a catalyst to a diol and introducing an alkylene oxide. In addition, the alkylene oxide adduct represented by the general formula (IV) is a catalyst in which aluminum-magnesium hydroxide represented by the following general formula (V) is activated as an Al-Mg composite oxide by firing as a catalyst. It is produced by introducing an alkylene oxide using an esterified product represented by the general formula (II) as a raw material. aMgO.Al ₂ O ₃ .bH ₂ O (V) (where a and b are positive numbers)

In the aluminum magnesium magnesium represented by the above general formula (V), a and b are positive numbers and are not particularly limited, but a is preferably a positive number of 1 to 3, particularly preferably 2. 5 is preferred. The firing temperature is 200-1000 ° C,
More preferably, it is 300 to 800 ° C. The reaction using the above aluminum hydroxide / magnesium hydroxide can be easily carried out under ordinary operating procedures and reaction conditions. That is,
The reaction temperature is 80-250 ° C, preferably 120-2.
00 ° C. The reaction pressure depends on the reaction temperature.
20 atm, preferably 2 to 8 atm. The amount of the catalyst used depends on the molar ratio of the alkylene oxide to be used for the reaction and the esterified compound represented by the general formula (II). 01
-20% by weight, preferably 0.1-5% by weight.

(2) Synthesis of a compound obtained by ozonating at least one compound selected from the compounds represented by the general formula (I) 1 selected from the compounds represented by the general formula (I) The method of ozonizing a seed or more can be performed as follows. First, when the compound represented by the general formula (I) has fluidity, it is used as it is, and when the fluidity is insufficient, carbon tetrachloride, methylene chloride, chloroform, dichloroethane, methyl acetate, ethyl acetate inert to ozone gas are used. , A saturated hydrocarbon or the like as a solvent. Next, an ozonation reaction is carried out according to a conventionally known method (Japanese Patent Publication No. 36-4747, Japanese Patent Publication No. 43-9206, German Patent No. 2713863, Japanese Patent Application Laid-Open No. Hei 3-232839).
No., JP-A-4-124311 and WO 93/0299.
No. 1).

Among the above-mentioned methods, the above-mentioned general formula (I)
The method of preferably performing the ozonation reaction of the compound represented by, while flowing the raw material as it is or dissolved in a solvent inert to ozone gas and flowing down the inner wall surface of the reactor as a thin film flow,
In this method, an ozone-containing gas is brought into contact with the thin film flow (WO 93/02991). In this case, the thickness of the thin film flow is in the range of 0.05 to 3 mm. The reaction temperature is
The temperature is 10 to 50C, preferably 20 to 45C. Also,
The ozonation reaction can be performed by using a batch-type reaction vessel in addition to the thin film flow method. In this method, the raw material itself or the raw material is dissolved in a solvent inert to ozone gas, and the ozone-containing gas is circulated as fine bubbles. Regardless of which of the distribution method and the batch method is used, the ozone-containing gas is a gas in which ozone is contained in a gas such as oxygen, air, or carbon dioxide, and the ozone content is 0.01 to 1
0 vol%, preferably 0.1 to 7 vol%, more preferably 0.3 to 5 vol%. In addition, ozone is distributed in 0.9 to 3.0 equivalents, preferably 0.95 to 2.0 equivalents, and more preferably 1.0 to 1.5 equivalents to the double bond contained in the raw material molecules. .

According to such an ozonation reaction, usually,
A high yield of 90 mol% or more in the ozonation reaction rate can be obtained. The obtained ozonized product contains a 1,2,4-trioxolane compound represented by the following general formula (VI). Its content is not constant depending on the raw material to be ozonized and the reaction conditions, but usually 10% by weight in the ozonized material.
Or more, preferably 30% by weight or more, more preferably 5% by weight.
0% by weight or more is contained.

[0029]

Embedded image (In the formula, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group.)

The compound of the present invention obtained by ozonizing the compound represented by the general formula (I) with an ozone-containing gas may contain a compound by-produced in the ozonation reaction. Such compounds include, for example, aldehydes and carboxylic acids formed by ring cleavage of the 1,2,4-trioxolane compound represented by the above general formula (V).

The fuel oil additive of the present invention is present in the fuel oil composition in an amount of 0.01 to 30% by weight, preferably 0.1 to 2% by weight.
0% by weight, more preferably 0.3 to 10% by weight. When the addition amount is less than 0.01% by weight, the effect of improving the cetane number is hardly observed, and the effect of reducing the air pollutants in the exhaust gas is hardly observed. On the other hand, if the content exceeds 30% by weight, the effect of improving the cetane number is small, but the effect of reducing air pollutants in the exhaust gas is small, and the production cost of the fuel oil composition is significantly increased. Not economic. As the fuel oil to be added, gas oil or heavy oil A, and catalytic cracking gas oil (LCO) are preferable.

In the fuel oil additive of the present invention, in addition to the compound obtained by ozonating the compound represented by the general formula (I), other cetane number improvers, oxygen-containing compounds, antioxidants, metals Known fuel oil additives such as a deactivator and a corrosion inhibitor may be contained in the fuel oil composition in an amount of 0.0001 to 30% by weight.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In addition, "%" shown below is "% by weight" unless otherwise specified.

Example 1 A dilauryl ester of 2-butene-1,4-diol was synthesized as follows. A 5-liter five-necked flask was equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser. 300 g of 2-butene-1,4-diol (manufactured by Kanto Chemical Co., Ltd.) and 2920 of methyl laurate (pastel M-12 manufactured by Lion Oreo Chemical Co., Ltd.)
g, 5.45 g of a 28% ethanol solution of sodium ethoxide as a catalyst was added to the flask, and after purging with nitrogen, the temperature was raised under reduced pressure of about 20 mmHg, and the reaction temperature was 100
While maintaining at 4 ° C. for 4 hours, by-product methanol was removed. After completion of the reaction, the reaction product was recrystallized at room temperature using an equal amount of methanol, and 700 g of 2-butene-1,4-
Diol dilaurate (BDL) was obtained. When the esterification rate of the obtained compound was measured by ¹ H-NMR,
The esterification rate was 99%.

The 2-butene-1,4-diol diacetate (BDA) was synthesized according to the above method using methyl acetate (manufactured by Kanto Chemical Co., Ltd.) as a fatty acid ester instead of methyl laurate.

2-butene-1,4-dioldiolate (BDO) was synthesized according to the above method using methyl oleate as a fatty acid ester instead of methyl laurate.

Example 2 An ethylene oxide adduct of dilauryl ester of 2-butene-1,4 diol was synthesized as follows. In a 1 liter autoclave, stirrer, thermometer,
An ethylene oxide introduction tube was attached. 317 g of 2-butene-1,4-diol dilaurate (BDL) synthesized in Example 1 and calcined hydrotalcite (5
4.75 g (00 ° C., 1 hour) was introduced into the autoclave, and the temperature was raised while the pressure was reduced after dehydration with nitrogen replacement. 11
At 0 ° C., disconnect from the vacuum line and set the reaction temperature (1
While maintaining the gauge pressure at 2 kg / cm ² G at 80 ° C. (substantially 3 kg), ethylene oxide was introduced to a predetermined amount (10 moles: 308 g). After 30 minutes of aging at the same temperature, the mixture was filtered at 80 ° C and filtered to give 1,4-polyoxyethylene (1
0) -2-Butene diether dilaurate (POE
(10) BDE-DL (590 g) was obtained.

1,4-polyoxyethylene (10) -2
-Diacetate of butene diether (POE (10)
BDE-DA), 1,4-polyoxyethylene (60)
-2-butene diether diacetate (POE (6
0) BDE-DA) was synthesized according to the above method using 2-butene-1,4-diol diacetate (BDA) as a raw material.

1,4-polyoxyethylene (10) -2
-Butyl diether dioleate (POE (10) B
DE-DO) was synthesized based on the above method using 2-butene-1,4-dioldiolate (BDO) as a raw material.

1,4-polyoxyethylene (10) -2
-Butene diether (POE (10) BDE), 1,
4-Polyoxyethylene (60) -2-butene diether (POE (60) BDE) was synthesized according to the above method using 2-butene-1,4-diol as a raw material.

1,4-polyoxypropylene (10)-
2-butene diether (POP (10) BDE),
1,4-polyoxypropylene (60) -2-butene
Diether (POP (60) BDE) is 2-
It was synthesized according to the above method using butene-1,4-diol and using propylene oxide instead of ethylene oxide.

Example 3 An ozonated dilauryl ester of 2-butene-1,4 diol was synthesized as follows. A stirrer, a thermometer, and an ozone gas introduction tube were attached to a three-necked flask having a content of 1 liter. 2-butene-1,4 synthesized in Example 1
100 g of the dilauryl ester of the diol is dissolved in 300 g of dichloroethane, and the outside of the three-necked flask is cooled so that the reaction temperature can be kept at 30 ° C. or lower. Ozone gas is passed through an ozonizer using pure oxygen and passed through 20 mg /
It is generated in liter (0.93 vol%) and introduced into the reaction system through an ozone gas introduction pipe. The reaction temperature is 30
While keeping the temperature at a temperature of not more than 0 ° C., 1.1 equivalents of ozone (11.6 g) relative to the double bond of the raw material were introduced. After completion of the reaction, dichloroethane as a solvent was removed under reduced pressure (5 torr) for 30 minutes.
At 110 ° C. to give the obtained compound (110 g, BDL-O
When the ozonation ratio of Z) was measured by ¹ H-NMR, the ozonation ratio was 98%. The other compounds synthesized in Examples 1 and 2 were also synthesized as ozonated compounds according to the above method.

Examples 4 to 9 1% of ozonized compounds shown in Table 2 were added to light oil (Table 1) containing DCO and LCO to prepare light oil compositions. The cetane number of the obtained various light oil compositions was determined by JI using a CFR engine.
It was measured according to the method specified in SK2280-1986. Table 3 shows the results.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

As described above, the cetane number can be improved by adding an ozonide to light oil.

Examples 10 to 14 To the light oil containing LCO in DGO used in Examples 4 to 9 was added 5% of an ozonide shown in Evaluation Samples (Table 4) synthesized according to Examples 1 to 3. A light oil composition was prepared. Using the various light oil compositions obtained, using a naturally-aspirated diesel engine with an in-line 4-cylinder vortex chamber with a displacement of 2 liters and observing the state of black smoke under engine operating conditions, it was found that the gas oil without addition of the sample for evaluation was added. Black smoke was reduced compared to when used.

[0049]

[Table 4]

[0050]

By adding the fuel oil additive of the present invention, air pollutants such as black smoke can be reduced, and the cetane number can be significantly improved. In addition, since the oxygen content in the fuel oil can be increased, the ignitability and combustibility of the fuel oil can be improved, and furthermore, the hydrocarbon (HC) and carbon monoxide (CO) in the exhaust gas can be improved. ), Air pollutants such as nitrogen oxide (NOx) can be reduced.

 ──────────────────────────────────────────────────の Continuation of the front page (72) Inventor Takeo Inagaki 1-7-3 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (2)

[Claims] 1. A fuel oil additive comprising a compound obtained by ozonating at least one selected from compounds represented by the following general formula (I). During ^{X-OR 1 O-Y (} I) ( ^{wherein, X, Y: R 2 CO} (AO) n - or ^{_{H (AO) m - R 1}} : an alkenylene group having 4-8 carbon atoms R ^2: 1 carbon atoms To 21 fatty acid residues n: an integer of 0 to 100 m: an integer of 1 to 100 AO: represents an oxyethylene group and / or an oxypropylene group.) 2. The fuel oil additive according to claim 1, wherein
A fuel oil composition containing up to 30% by weight.