JPH0867885A - Cleaner for hydrocarbon fuel - Google Patents

Abstract

PURPOSE: To obtain the subject cleaner useful for diesel engines, containing a specific lipophilic group and a basic nitrogen-containing cyclic group, having excellent cleaning action, capable of reducing an amount of the cleaner added, providing sufficiently water separating performance by the use of only a small amount of a demulsifier because of suppression of affinity for water. CONSTITUTION: A cleaner of the formula R-Ab -(Ch H2h NH)k (Cn H2n )-Y (R is a lipophilic group comprising a 35-720C hydrocarbon group; A is a bonding group of imido, amido, isocyano, ester or ether; Y is a basic nitrogen-containing cyclic group; (b) is 0 or 1; (h) and (n) are 1-5; (k) and (m) are 0-6). Y of the formula, for example, is a group of formula I [R<2> is a 1-40C (phenyl-substituted) alkyl; R<1> is H or R<2> ; B is a 1-10C alkylene; P is 0-10; Q is 0 or 1], a group of formula II or a group of formula III.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention is in the technical field of detergents for hydrocarbon fuel compositions such as gasoline, diesel fuel, jet fuel, heating oil, and hydrocarbon fuel compositions containing detergents. .

[0002]

BACKGROUND OF THE INVENTION Hydrocarbon fuel compositions are prone to deposits in various parts of engines and combustion systems that utilize these fuels, which deposits interfere with the flow of fuel and air mixtures,
It may reduce the efficiency of the engine. Additives, commonly referred to as detergents, are used to reduce or eliminate such deposits. For example, automotive gasoline fuel additives are used in carburetor or fuel injection engines to prevent or eliminate the formation of deposits that contaminate the carburetor and fuel injection ports. In addition, the diesel engine atomizes the high-pressure fuel sent from the fuel injection pump by the nozzle and injects it into the combustion chamber to self-ignite the fuel, and the function of the nozzle is to maximize the performance of the injection pump. At the same time, it is desired to improve the combustion characteristics in the combustion chamber, increase the output of the engine, and exert functions such as keeping exhaust gas clean.

Various types of nozzles such as pintle nozzles and throttle nozzles are known as fuel injection nozzles. In a diesel engine, since the nozzles are arranged in the combustion chamber, they are exposed to a severe environment of high temperature and high pressure accompanying combustion. When exposed, deposits adhered to the injection holes of the nozzles, resulting in abnormal fuel injection. That is, FIG.
FIG. 3 is an enlarged view showing the injection hole portion of the throttle nozzle. The opening area is the distance between the needle valve 1 and the through hole 2 into which the needle valve 1 is inserted, but this injection hole portion is in direct contact with the combustion chamber. Therefore, while the engine is continuously operated, a deposit mainly composed of carbon is generated on the needle valve 1. If the amount of such deposits increases to a certain extent, the area of the open holes will decrease,
As a result, the fuel injection rate changes, which causes various adverse effects such as white smoke, reduced output, and easier knocking.

Hydrocarbon fuel additives, commonly referred to as detergents, are used to reduce or remove deposits, with a chemical structure of molecular weight 100 to 7
Low molecular weight surfactant of about 00 or molecular weight 700-
A compound belonging to a high molecular weight surfactant of about 10,000 is used. The low molecular weight surfactant is usually 10
A low addition amount of 0 ppm or less prevents the formation of deposits in the nozzle, but has little ability to remove deposits. Further, since it has a strong polarity, it may corrode various materials such as seal materials and bearings used for assembling automobile engine parts. High molecular weight surfactants have the ability to prevent and remove nozzle deposit formation, but generally 5
A high addition amount of 00 to 5,000 ppm is required. In particular, when added to gasoline, it was pointed out that the high-molecular-weight surfactant contained in unburned fuel dissolves in engine oil and becomes concentrated, resulting in an increase in engine oil viscosity and a decrease in fuel consumption. Has been done. Furthermore, when a high molecular weight surfactant is dissolved in light oil, the water content in the air is dissolved in the fuel during storage, and when the amount of the high molecular weight surfactant added is low, the light oil becomes cloudy, and when it is high, the emulsion phase It is known that there is a problem in that it causes the clogging of the filter and the corrosion of metal parts.

The use of demulsifiers is a method for solving the deterioration of the water separation performance of fuels. However, since the demulsifier has a low solubility in the fuel, the fuel may become muddy or sediment depending on the conditions of use, which may clog the fuel filter and cause the engine to be unable to start, and may be mixed in the engine oil. It is desirable to limit the addition amount as small as possible because it may cause agglomeration, clogging of the oil filter and seizure of the engine. In order to solve the above-mentioned problems, a high molecular weight surfactant which is excellent in cleaning action even with a small addition amount and which can reduce the addition amount of the demulsifier has been desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a detergent to be added to a hydrocarbon fuel such as a fuel used in a diesel engine, and a sufficient cleaning action can be obtained even if the amount added to the hydrocarbon fuel is small. , High water separation performance,
It is an object of the present invention to provide a detergent for a hydrocarbon fuel which may use a small amount of demulsifier.

[0007]

The present invention is for a hydrocarbon fuel containing a lipophilic group represented by the following general formula (1) and a basic nitrogen-containing cyclic group which may contain a hydrocarbon group as a substituent. It is a cleaning agent. Formula _{(1) R-A b -} (C h H 2h NH) k (C n H 2n) m -Y ( wherein, R is a lipophilic group consisting of a hydrocarbon group having 35 to 720 carbon atoms, b is 0 Or 1, A is a linking group selected from imide, amide, isocyano, ester, and ether groups, h and n are integers from 1 to 5, k and m are integers from 0 to 6, and Y is a basic nitrogen-containing ring. And a basic nitrogen-containing cyclic group is a substituent represented by the following formulas a) to e).

[0008]

Embedded image

(However, R ¹ is hydrogen or 1 to 1 carbon atoms.
An alkyl group which may be substituted with a phenyl group of 40, R ²
Is an alkyl group which may be substituted with a phenyl group having 1 to 40 carbon atoms, P is an integer of 0 to 10, and B is 1 to 1 carbon atoms.
An alkylene group of 0 and Q is 0 or 1. ) Further, it is a hydrocarbon fuel composition containing the above-mentioned detergent for hydrocarbon fuel. Further, it is a method of reducing the formation of deposits on the nozzle of a diesel engine by using the fuel oil containing the above-mentioned hydrocarbon fuel detergent. (However, R ¹ is hydrogen or an alkyl group which may be substituted with a phenyl group having 1 to 40 carbon atoms, R ² is an alkyl group which may be substituted with a phenyl group having 1 to 40 carbon atoms, and P is 0 to 10 represents an integer of 10, B represents an alkylene group having 1 to 10 carbon atoms, and Q represents 0 or 1.) Further, the hydrocarbon fuel composition contains the above-mentioned detergent for hydrocarbon fuel.

That is, the inventors of the present invention have conducted extensive studies and found that many kinds of organic acids are contained in the deposit and are adsorbed on the nozzle metal to bond the carbonaceous substances together. It is considered that the high molecular weight surfactant cleans the nozzle by separating the bond between the metal forming the nozzle and the organic acid by neutralizing the base of its own functional group with the organic acid in the deposit.
Therefore, various surfactants were synthesized based on the assumption that neutralization with an organic acid can be achieved even by adding a small amount by increasing the basicity of the functional group of the high-molecular-weight surfactant, and the performance is evaluated. As a result of changing the functional group of the high molecular weight surfactant to one having at least one basic nitrogen-containing cyclic group, the cleaning action can be remarkably improved as compared with the conventionally used detergents. It has become possible to reduce the addition amount of. The high molecular weight surfactant is composed of a polar functional group and a non-polar hydrocarbon group. The functional group interacts with the polar deposit or the metal layer on the nozzle surface, and the hydrocarbon group dissolves in the fuel to remove the deposit or adsorb the causative compound of the deposit to the metal layer on the nozzle surface. It is believed that a detergent function that interferes with

Further, water is polar and does not mix as it is with a fuel which is a non-polar hydrocarbon, but when a detergent comprising a high molecular weight surfactant is added to the hydrocarbon fuel, water in the hydrocarbon fuel is added. The amount will increase. It is considered that this is because the hydrophilic functional group of the high molecular weight surfactant dissolves water in the fuel. Therefore, the synthesis and performance evaluation were conducted based on the assumption that the interaction with water molecules can be weakened by forming a steric hindrance of the hydrocarbon group in the vicinity of the hydrophilic functional group of the high molecular weight surfactant. When an alkyl group is bonded to the carbon adjacent to the hydrophilic functional group of the high molecular weight surfactant,
The water separation performance of the hydrocarbon fuel is remarkably improved, and the addition amount of the demulsifier can be reduced.

In the detergent for hydrocarbon fuel of the present invention, the lipophilic group is preferably a hydrocarbon group having a carbon number of 35 to 720, and polyisobutene, polypropylene, poly α-olefin, polyalkylene oxide and other hydrocarbons. Polymers can be used. The carbon number is more preferably 40 to 300, and sufficient solubility in hydrocarbon fuel can be obtained by using the lipophilic group having the carbon number in such a range. The linking group between the face-based nitrogen-containing cyclic group and the lipophilic group is preferably an imide group having high thermal stability, and the following groups are particularly preferable.

[0013]

[Chemical 3]

Further, in the following polyamine used during the linking group and a basic nitrogen-containing cyclic _{group, - (C h H 2h NH} ) k (C n H 2n) m h and n is an integer of 1 to 5, k And m are integers from 0 to 6. As the polyamine, ethylenediamine, propylenediamine, 1,4-butanediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like can be used.

Further, the basic nitrogen-containing cyclic group is required to have a property of strongly interacting with a deposit, and a group containing secondary or tertiary nitrogen having a strong degree of basicity is preferable. Examples thereof include those represented by the formulas a) to c). In particular, a) and b) having two basic nitrogens in the basic nitrogen-containing cyclic group have extremely strong basicity and show high cleaning performance. . Further, in a), b) and c), R ² is preferably hydrogen or an alkyl group having a carbon number of 40 or less, and in order to enhance the water separation performance, it is particularly bonded to a carbon atom adjacent to a nitrogen atom. It is preferably an alkyl group having 15 or less carbon atoms. An alkyl group having 15 or more carbon atoms bonded to a carbon atom adjacent to a nitrogen atom has excellent water separation performance, but since the steric hindrance of basic nitrogen becomes too large and lipophilicity increases, the cleaning performance deteriorates. Not preferable.

Further, the detergent for hydrocarbon fuel of the present invention is an additive having both washing action and dispersing action, and the amount of the detergent added to the fuel is 50 to 5,000 pp.
However, the water separation performance becomes worse as the amount of the detergent added increases, and it becomes necessary to add a high-performance demulsifier. In addition, the detergent dissolves in the engine oil during the process of unburned light oil dissolving in the engine oil during vehicle operation,
The viscosity of the engine oil increases and the fuel consumption increases. For the above reasons, the amount of the detergent added to the fuel is preferably as small as possible, and is preferably 50 to 500 ppm. Further, the detergent of the present invention can be applied to a fuel composition composed of hydrocarbons such as gasoline, diesel fuel, jet fuel, and heating oil, and is particularly suitable for use in light oil.

The detergent may be a fuel that dissolves in the preparation of a hydrocarbon fuel and contains the detergent, or the detergent may be used as it is or at the time of refueling a fuel tank of a vehicle or the like, or a mixture of dialkylbenzene or trialkylbenzene. Aromatic naphtha solvent (Shellsol A, S
It is also possible to add and dilute by mixing with a hydrocarbon solvent such as "hellsol AB)". The detergent may be used in combination with various additives that improve fuel performance,
When the fuel is light oil, a cetane number improver, demulsifier, rust preventive, stabilizer, antioxidant, flammability promoter, lubricity improver, low temperature fluidity improver, metal deactivator, deodorant Foam,
It may be used with deodorants, dyes and the like.

[0018]

The detergent for hydrocarbon fuels of the present invention has a small addition of an organic acid having a carbonaceous substance constituting a deposit bound thereto by increasing the basicity of the functional group of the high molecular weight surfactant. Effectively neutralizes even the amount, removes deposits, and because it is composed of polar functional groups and non-polar hydrocarbon groups, it interacts with deposits or the metal layer on the nozzle surface The base dissolves in the fuel to remove deposits,
It interferes with the adsorption of the causative compound of deposits to the metal layer on the nozzle surface, and also causes the steric hindrance of the hydrocarbon group in the vicinity of the hydrophilic functional group to weaken the interaction with water molecules. Since it has suppressed the affinity with, it is possible to obtain sufficient performance by using a small amount of demulsifier, and it is possible to significantly improve the cleaning action compared with the conventional detergents. It has become possible to reduce the amount of agent added.

[0019]

EXAMPLES The present invention will be described in more detail below by showing Examples of the present invention. (Synthesis Example of Compound) Synthesis Example 1 A 2-liter four-necked flask equipped with a mechanical stirrer, a cooler, a thermometer, and a dropping funnel was placed in an average molecular weight of 900
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added and the temperature was raised to 165 ° C. with stirring, and N
40.8 g of-(2-aminoethyl) piperazine was added dropwise over 1 hour. Next, reduce the pressure to 3 mmHg at the same temperature,
The reaction was carried out for 2 hours while removing the produced water to obtain a compound having the following structural formula. The product was identified by infrared spectrophotometry. That is, raw alkenyl anhydride, 1790 cm ^-1 of the infrared spectrum shows a strong absorption at 1870cm ^-1, reacted with an amine, as a result of forming an imide, 17
90cm ^-1, absorption of 1870cm ^-1 disappeared and instead the absorption of imide appeared 1710 cm ^-1, the 1780 cm ^-1. In addition, since the equimolar water is dehydrated during imide formation,
The reaction can be confirmed by collecting the produced water. The analytical properties of this compound were 2.9% by weight of nitrogen and total base number (perchloric acid method) 36, and the product was confirmed by agreement with the theoretical values of the following compounds. The kinematic viscosity (100 ° C.) was 811 cSt.

[0020]

[Chemical 4]

Synthesis Example 2 Average molecular weight of 900 in a 2-liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel.
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 32.6 g of diethylenetriamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, and after reacting for 1 hour while removing generated water, the temperature was cooled to 70 ° C. and returned to normal pressure, 22.8 g of n-butyraldehyde was added dropwise, and after stirring for 30 minutes, 100 ° C. After stirring for 2 hours, the pressure was reduced to 3 mmHg at 120 ° C., and the reaction was performed for 2 hours while removing generated water to obtain a compound having the following structural formula. The infrared spectrum of the starting aldehyde 1725cm ^-1, 2740cm ^-1, strong absorption at 2855cm ^-1 is the reaction results in a ring by the amine and was completed by these spectra are lost. The analytical properties of this compound are:
The product was confirmed by having a weight% and a total base number (perchloric acid method) of 50, which were in agreement with the theoretical values of the following compounds. The kinematic viscosity (100 ° C.) was 1343 cSt.

[0022]

[Chemical 5]

Synthesis Example 3 In a 2 liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel, an average molecular weight of 900
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 59.7 g of tetraethylenepentamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, and after reacting for 1 hour while removing generated water, the temperature was cooled to 70 ° C. and returned to normal pressure, 22.8 g of n-butyraldehyde was added dropwise, and after stirring for 30 minutes, 100 ° C. After stirring for 2 hours, the pressure was reduced to 3 mmHg at 120 ° C., and the reaction was performed for 2 hours while removing generated water to obtain a compound having the following structural formula. The completion of the reaction was confirmed by infrared spectroscopy as in Synthesis Example 2.

The analytical properties of this compound were 4.4% by weight nitrogen and 120 in total base number (perchloric acid method), and the product was confirmed by agreement with the theoretical values of the following compounds. The kinematic viscosity (100 ° C.) was 1317 cSt.

[0025]

[Chemical 6]

Synthesis Example 4 Average molecular weight of 900 in a 2-liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel.
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 26.1 g of diethylenetriamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, the reaction was carried out for 1 hour while removing generated water, the temperature was returned to normal pressure by cooling to 40 ° C., and 14.8 g of n-propionaldehyde was added dropwise 30
After stirring for a minute, and then at 100 ° C for 2 hours, then at 120 ° C for 3
After reducing the pressure to mmHg and reacting for 1 hour while removing the produced water, a compound having the following structural formula was obtained. The completion of the reaction was confirmed by infrared spectroscopy as in Synthesis Example 2. The analytical properties of this compound are as follows: nitrogen 2.4% by weight, total base number (perchloric acid method) 50
And by agreeing with the theoretical value of the following compound,
The product was confirmed. The kinematic viscosity (100 ° C) 14
It was 93 cSt.

[0027]

[Chemical 7]

Synthesis Example 5 Average molecular weight of 900 in a 2-liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel.
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 26.1 g of diethylenetriamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, the reaction was carried out for 1 hour while removing the produced water, the temperature was cooled to 50 ° C. and the pressure was returned to normal pressure, 18.4 g of isobutyraldehyde was added dropwise, and after stirring for 30 minutes, 100 ° C. for 2 hours. After stirring, the pressure was reduced to 3 mmHg at 120 ° C., and the reaction was carried out for 1 hour while removing the produced water to obtain a compound having the following structural formula. The completion of the reaction was confirmed by infrared spectroscopy as in Synthesis Example 2. The analytical properties of this compound were 2.3% by weight nitrogen and total base number (perchloric acid method) of 50, and the product was confirmed by agreement with the theoretical values of the following compounds. Also, kinematic viscosity (100 ° C.) 1490 cSt
Met.

[0029]

Embedded image

Synthesis Example 6 Average molecular weight of 900 in a 2-liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel.
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 26.1 g of diethylenetriamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, and after reacting for 1 hour while purging generated water, the temperature was cooled to 70 ° C. and returned to normal pressure, 32.4 g of 2-ethylhexylaldehyde was added dropwise, and the mixture was stirred for 30 minutes and further 100 minutes. After stirring at ℃ for 2 hours, 120
The pressure was reduced to 3 mmHg at ℃, and after reacting for 1 hour while removing the produced water, a compound of the following structural formula was obtained. The completion of the reaction was confirmed by infrared spectroscopy as in Synthesis Example 2. The analytical properties of this compound were 2.3% by weight nitrogen and total base number (perchloric acid method) of 50, and the product was confirmed by agreement with the theoretical values of the following compounds. The kinematic viscosity (100
C.) 865 cSt.

[0031]

[Chemical 9]

Synthesis Example 7 In a 2 liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel, an average molecular weight of 900
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 26.1 g of diethylenetriamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, and after reacting for 1 hour while removing generated water, the temperature was returned to 70 ° C. and returned to normal pressure, 34.0 g of 2-phenylpropionaldehyde was added dropwise, and after stirring for 30 minutes, 100 After stirring at 2 ° C. for 2 hours, the pressure was reduced to 3 mmHg at 120 ° C., and after reacting for 1 hour while removing generated water, a compound having the following structural formula was obtained. The completion of the reaction was confirmed by infrared spectroscopy as in Synthesis Example 2. The analytical properties of this compound are: nitrogen 2.3% by weight, total base number (perchloric acid method) 5
It was 0, and the product was confirmed by agreement with the theoretical value of the following compound. Also, kinematic viscosity (100 ° C)
It was 1358 cSt.

[0033]

[Chemical 10]

Synthesis Example 8 Average molecular weight of 900 in a 2-liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel.
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, the temperature was raised to 165 ° C. with stirring, and 26.1 g of diethylenetriamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, and after reacting for 1 hour while removing generated water, the mixture was cooled to 70 ° C. and returned to normal pressure, 21.8 g of 3-pentanone was added dropwise, and after stirring for 30 minutes,
After further stirring at 100 ° C. for 2 hours, the pressure was reduced to 3 mmHg at 120 ° C., and the reaction was carried out for 1 hour while removing generated water to obtain a compound having the following structural formula. The completion of the reaction was confirmed by infrared spectroscopy as in Synthesis Example 2. The analytical properties of this compound were 2.4% by weight of nitrogen and total base number (perchloric acid method) of 50, and the product was confirmed by agreement with the theoretical values of the following compounds. Also, kinematic viscosity (100 ° C.) 1536 cSt
Met.

[0035]

[Chemical 11]

Synthesis Example 9 In a 2 liter four-necked flask equipped with a mechanical stirrer, condenser, thermometer, and dropping funnel, an average molecular weight of 900
400 g of alkenyl succinic anhydride having a polyisobutenyl group was added, and the temperature was raised to 100 ° C. with stirring, and 2
-35.6 g of aminomethylpiperidine was added dropwise over 1 hour. Next, after stirring at the same temperature for 1 hour, the temperature was raised to 165 ° C., the pressure was reduced to 3 mmHg, and the reaction was performed for 2 hours while removing generated water to obtain a compound having the following structural formula. The completion of the reaction was confirmed by infrared spectroscopy as in the previous synthesis example. The analytical properties of this compound were 2.0% by weight of nitrogen and total base number (perchloric acid method) 39, and the product was confirmed by agreement with the theoretical values of the following compounds. The kinematic viscosity (100
C.) 790 cSt.

[0037]

[Chemical 12]

Comparative Synthesis Example 1 400 g of an alkenylsuccinic anhydride having a polyisobutenyl group having an average molecular weight of 900 was placed in a 2-liter four-necked flask equipped with a mechanical stirrer, a condenser, a thermometer, and a dropping funnel. The temperature was raised to 165 ° C. with stirring, and diethylenetriamine 32.6 was added.
g was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, the reaction was carried out for 2 hours while removing the produced water, and a compound having the following structural formula was obtained. Completion of the reaction was confirmed by infrared spectroscopy. The analytical properties of this compound were 2.6% by weight nitrogen and a total base number (perchloric acid method) of 50, and the product was confirmed by matching the theoretical values of the following compounds. The kinematic viscosity (100 ° C.) was 1343 cSt.

[0039]

[Chemical 13]

Comparative Synthesis Example 2 400 g of alkenyl succinic anhydride having a polyisobutenyl group having an average molecular weight of 900 was placed in a 2-liter four-necked flask equipped with a mechanical stirrer, a condenser, a thermometer, and a dropping funnel, and stirred. The temperature was raised to 165 ° C., and 59.7 g of tetraethylenepentamine was added dropwise over 1 hour. Next, the pressure was reduced to 3 mmHg at the same temperature, and while removing the generated water, 1
After the reaction for time, a compound having the following structural formula was obtained. Completion of the reaction was confirmed by infrared spectroscopy. The analytical properties of this compound were nitrogen 4.5% by weight and total base number (perchloric acid method) 120, and the product was confirmed by matching the theoretical values of the following compounds. Also, kinematic viscosity (100 ° C) 2233
It was cSt.

[0041]

Embedded image

Comparative Synthesis Example 3 400 g of alkenyl succinic anhydride having a polyisobutenyl group having an average molecular weight of 900 was placed in a 2-liter four-necked flask equipped with a mechanical stirrer, a condenser, a thermometer, and a dropping funnel, and stirred. The temperature was raised to 100 ° C., and 19.0 g of ethylenediamine was added dropwise over 1 hour. Then 1 at the same temperature
After stirring for 1 hour, the temperature was raised to 165 ° C., the pressure was reduced to 3 mmHg, and the reaction was carried out for 2 hours while removing the produced water to obtain the compound of the following structural formula. Completion of the reaction was confirmed by infrared spectroscopy.
The analytical properties of this compound were 2.0% by weight of nitrogen and total base number (perchloric acid method) of 40, and the product was confirmed by matching the theoretical values of the following compounds. The kinematic viscosity (100 ° C.) was 1595 cSt.

[0043]

[Chemical 15]

Example 1 The compounds obtained in the synthesis examples of the compound of the present invention and the comparative compound were mixed with 50 parts by weight of an aromatic naphtha solvent (Shellsol A) at 60 ° C. for easy handling, and homogenized. It was stirred until. Then 600 in light oil
2400 rpm for a diesel engine equipped with a throttle nozzle that dissolves by weight ppm and uses the light oil as fuel.
It was operated for 18 hours at a torque of 12.5 kg · m. After the operation is completed, check the degree of contamination of each throttle nozzle with a needle valve of 0.05 m.
injection hole flow rate ml /
Minutes were measured using 0.5 kg / cm ² of air,
In order to explain the measurement results, plot the needle valve pull-up distance on the vertical axis and the nozzle hole flow rate on the horizontal axis, and plot the graph area from 0.05 mm to 0.50 mm to the graph area of the nozzle before starting the test. Calculated as 100%. That is, if the stain on the nozzle after the test is similar to that before the test, it is 100%, and if it is completely soiled and clogged, it is 0%. The results are shown in Table 1.

[0045]

[Table 1]

Comparative Synthesis Examples 1 to 8 as compared with Comparative Synthesis Examples 1 and 2
Clearly had excellent nozzle cleaning performance, and maintained almost the same cleanliness as before the start of the test. In addition, since Example 9 has only one effective basic nitrogen in the molecule, the cleaning performance is lower than that of Synthesis Examples 1 to 8, but similarly, Comparative Synthesis Example 3 having one effective basic nitrogen in the molecule. It showed better cleaning performance.

Example 2 The cleaning action was examined in the same manner as in Example 1 except that the amount of detergent added was changed, and the results are shown in Table 2.

[0048]

[Table 2]

At each addition amount, the cleaning performance of Synthesis Examples 1 and 3 was superior to that of Comparative Synthesis Example 2, and in particular, the cleaning agent of Synthesis Example 1 showed excellent cleaning performance even at 150 ppm or less.

Example 3 (Water Separation Performance 1) The water separation performance of fuel complies with the water solubility test method defined in JIS K2276, and the performance is quantitatively compared.
The volumes of the aqueous phase, the emulsified phase and the light oil phase after the test were compared in ml. 80 ml of test light oil and 20 ml of distilled water were put into a 100 ml graduated ground-stop graduated cylinder, and the mixture was shaken by hand for 2 minutes and then shaken up and down for 5 minutes. After standing for 5 minutes and after 1 day, the state of water separation was observed. The amount of detergent added was 600 ppm in all cases.
Table 3 shows the obtained results.

[0051]

[Table 3]

Synthetic Examples 2, 4 to 8 have a large volume of aqueous phase and excellent water separation performance as compared with Synthetic Example 1 and Comparative Synthetic Examples 1 and 2. In particular, Synthesis Example 7 showed the best water separation performance.

Example 4 (Water separation performance 2) The improvement effect of the demulsifier was compared by the same test method as in Experimental Example 2 above.

The amount of detergent added was all 600 ppm,
As in Example 3, the respective volumes of the aqueous phase, the emulsified phase and the light oil phase are shown in ml.

[0055]

[Table 4]

Synthetic Examples 2 and 5 have a higher effect of improving the demulsifier as compared with Comparative Synthetic Examples 1 and 2, and the addition amount of each is 1 to 1.
Even at 5 ppm, sufficient water separation performance was exhibited.

[0057]

EFFECTS OF THE INVENTION By enhancing the basicity of the functional group of a detergent for hydrocarbon fuel comprising a high molecular weight surfactant, the organic acid that causes the formation of deposits can be sufficiently neutralized with a small addition amount. By removing the deposit by further, by further forming a steric hindrance of the hydrocarbon group in the vicinity of the hydrophilic functional group, since the interaction with water molecules was weakened and the affinity with water was suppressed, Sufficient water separation performance was obtained by using only a small amount of demulsifier, and a detergent for hydrocarbon fuel was obtained which did not cause the problem due to the large amount of demulsifier used.

[Brief description of drawings]

FIG. 1 is a view showing a nozzle hole portion of a throttle nozzle.

FIG. 2 is a diagram illustrating a measurement result.

[Explanation of symbols]

 1 ... Needle valve, 2 ... Through hole

Claims (4)

[Claims] 1. A detergent for a hydrocarbon fuel comprising a lipophilic group represented by the following general formula (1) and a basic nitrogen-containing cyclic group which may contain a hydrocarbon group as a substituent. .
Formula _{(1) R-A b -} (C h H 2h NH) k (C n H 2n) m -Y ( wherein, R is a lipophilic group consisting of a hydrocarbon group having 35 to 720 carbon atoms, b is 0 Or 1, A is a linking group selected from imide, amide, isocyano, ester, and ether groups, h and n are integers from 1 to 5, k and m are integers from 0 to 6, and Y is a basic nitrogen-containing ring. Indicates a group.) 2. The basic nitrogen-containing cyclic group has the following formulas a) to c).
The detergent according to claim 1, which is a substituent represented by: Embedded image (However, R ¹ is hydrogen or an alkyl group which may be substituted with a phenyl group having 1 to 40 carbon atoms, and R ² is 1 to 1 carbon atoms.
40 is an alkyl group which may be substituted with a phenyl group, P is an integer of 0 to 10, B is an alkylene group having 1 to 10 carbon atoms, and Q is 0 or 1. ) 3. A hydrocarbon fuel composition comprising the detergent according to claim 1 or 2. 4. A method for reducing the formation of deposits on the nozzles of diesel engines, characterized in that a fuel oil containing the detergent according to claim 1 or 2 is used.