JP5545684B2 - Washing soap - Google Patents

Description

  The present invention relates to a cleaning agent used by adding to a fuel in order to clean and remove deposits attached to a fuel injection system.

  A diesel engine mounted on a truck, a construction machine, a fishing boat, a generator, or the like includes a piston that reciprocates and a cylinder that covers and surrounds the piston, and combustion formed by the piston and the cylinder. Air is supplied into a chamber (a chamber in which fuel is combusted), the air is compressed by a piston, and fuel is injected into the compressed and heated air to self-ignite.

  In a diesel engine, an injection pump is indispensable for injecting fuel into a combustion chamber at a high pressure. The types of injection pumps include a row type injection pump, a distribution type injection pump, and an independent type injection pump. The fuel injection method includes a method of injecting fuel using these mechanical injection pumps. In recent years, many unit injector types and common rail types that perform electronically controlled injection have been adopted in place of these types of mechanical injection pumps, and the common rail type has become the mainstream.

  The unit injector type is a fuel injection system that integrates a fuel injection nozzle called an injector and a plunger that pressurizes the fuel. Since there is no fuel supply pipe between the plunger and the nozzle, high-pressure fuel injection is realized by the plunger. it can. The common rail type is a fuel injection method in which high-pressure fuel is stored in a long and narrow pipe called a common rail and is uniformly supplied to each injector connected to the pipe. In this common rail type, fuel is pressurized by a supply pump and reliably injected into the combustion chamber using an injector. The injection control is performed by the control unit.

  In the supply pump, the fuel is compressed. However, when air is mixed in the fuel for some reason, the air is adiabatically compressed, and the surrounding air becomes locally hot (local high temperature), which tends to generate unburned carbon. As a result, various additives are deposited and deposited and deposited inside the injector. In addition, the fuel contains foreign substances such as iron-based compounds, organic acids and salts thereof, and dust, and these foreign substances adhere and accumulate. These are called deposits, and if they adhere and accumulate in large quantities, they cause engine performance degradation and non-uniform injection.

  This deposit / deposition is considered to be precipitated by a low-temperature fluidity improver, a lubricity improver, and the like, which are added to the fuel in the winter, and their degradation products. The fuel to which these are added, for example, when a common rail system is used to inject from the fuel supply pump into the injector under high pressure conditions, while air bubbles generated by the supply pump and air that has entered from the outside are locally heated in the supply pump. In connection with this, it has become clear that various additives in the fuel are also thermally decomposed by raising the temperature to generate new deposits (see, for example, Patent Document 1).

  This deposit can be completely removed by disassembling and cleaning the injector, but this takes time and effort. Therefore, a cleaning agent to be added to the fuel tank is commercially available, and the cleaning agent can be added to the fuel and cleaned and removed during the running operation. Polybuteneamine, polyetheramine, N-alkyl-pyrrolidone and the like are known and currently used as components of a cleaning agent effective in cleaning and removing deposits.

  In addition, aromatic solvent 5 to 50% by weight, glycol ether and / or glycol ether acetate solvent 5 to 25% by weight, fatty acid 5 to 25% by weight, nonionic surfactant 5 to 25% by weight, aqueous ammonia and / or Alternatively, a diesel engine intake system cleaning aerosol product containing 1 to 15% by weight of amine and 10 to 40% by weight of water has been proposed (see Patent Document 2). Examples of the aromatic solvent include ethylbenzene, amylbenzene, 1-methylnaphthalene and the like. As the amine, polyoxyethylene alkylamine is mentioned.

  Further, a metal member comprising 10 to 40% by weight of a water-soluble amine compound, 10 to 30% by weight of benzyl alcohol, 20 to 60% by weight of a water-soluble organic solvent having an aliphatic alcohol residue, and 10 to 40% by weight of a weak alkaline aqueous solution. A cleaning agent for cleaning has also been proposed (see Patent Document 3). Examples of the water-soluble amine compound include diethylamine and monoethanolamine.

  50-80% by weight polyoxyalkylene alkylamine, 5-20% by weight glycol monoalkyl ether, 5-15% by weight glycol dialkyl ether, 5-15% by weight heterocyclic compound, 1-5% by weight water There has also been proposed a diesel fuel additive composition comprising (see Patent Document 4).

JP 2006-257934 A JP 2002-129198 A JP 2006-193653 A JP 2010-106173 A

  Conventionally used polybuteneamines and polyalkenyl succinimides are polymer components, have good heat resistance, and have a problem of depositing themselves. Polyetheramine and N-alkyl-pyrrolidone have detergency but not so high detergency. For this reason, in order to clean until no deposit can be visually confirmed, as described in Patent Document 1, a large amount such as several tens of weight% with respect to the fuel must be added. Such a large amount of addition has a problem in running performance, and since both of these are amines and contain nitrogen, there is a problem that NOx in the combustion exhaust gas increases.

  In the cleaning agents of Patent Documents 2 to 4, the amines and ethers mentioned are not high in cleaning properties by themselves, and a large amount is required for cleaning until no deposits can be visually confirmed. It is necessary to add to or wash for a long time. Therefore, it is currently used in consideration of the fact that some deposits remain. As a result, deposits gradually accumulate, resulting in engine performance degradation and non-uniform injection.

  In addition, as fuel injection system components, rubber O-rings and resin products are used for supply pumps, injectors, and fuel filters. For this reason, the cleaning agent added to the fuel comes into contact with the O-ring and the resin product. Polybuteneamine, polyetheramine, N-alkyl-pyrrolidone and the like that have been used as cleaning agents so far swell these O-rings. Furthermore, ethers such as diethylene glycol monomethyl ether and ethylene glycol monobutyl ether also swell these O-rings.

  O-ring swelling is preferable in that it fills the gaps between parts to a certain extent and improves the sealing force. However, swelling above a certain level will cause cracks and increased hardness in the rubber, which will cause protrusions from the seal site. In contrast, the sealing force is reduced. Such deformation of the rubber causes fuel leakage, and the leaked liquid has a risk of ignition. Since the above-described conventional cleaning agents swell to a certain level or more, there is a possibility that the sealing force is reduced and liquid leakage occurs.

  Therefore, it is desirable to provide a cleaning agent that can be used by adding to fuel, which can remove deposits deposited and deposited on the fuel injection system, and in addition, can suppress swelling of the O-ring and the like. It was rare.

  As a result of intensive investigations, the inventors of the present invention have at least one component selected from diethylbenzylamine, tribenzylamine, diethylenetriamine, and 1-phenylpiperazine, and thus have good detergency and swelling such as an O-ring. I found that there was almost no. This invention is made | formed by discovering this, The said subject can be solved by providing the cleaning agent of this invention.

  That is, according to the present invention, there is provided a cleaning agent added to the fuel in order to remove deposits adhering in the fuel injection system from the fuel supply means for supplying the fuel to the nozzle for injecting the fuel. A cleaning agent containing at least one component selected from diethylbenzylamine, tribenzylamine, diethylenetriamine, and 1-phenylpiperazine is provided.

  The cleaning agent is added in an amount of 0.1 to 30% by volume with respect to the fuel. One or more of the above components contained in the cleaning agent is contained in an amount of at least 70% by volume of the cleaning component (cleaning component) contained in the cleaning agent in order to suppress swelling such as an O-ring. In addition, as washing | cleaning components other than the said component, conventionally used, for example, alkylene glycol alkyl ether, N-alkyl-pyrrolidone, etc. can be contained.

  By providing the cleaning agent of the present invention, deposits deposited and deposited on the fuel injection system can be removed well, and in addition, swelling of a rubber O-ring or the like can be suppressed. As a result, there is no decrease in engine performance or non-uniform injection, no rubber cracking, no hardness increase, no overhang from the seal portion, and no reduction in sealing force or liquid leakage. Moreover, since it can be used by adding to the fuel, it is not necessary to remove the fuel injection system, disassemble the parts into parts, and wash each part, and it can be easily washed.

The figure which showed the structural example of the fuel-injection system. The figure which showed the injector before washing | cleaning and the injector after washing | cleaning. The figure which showed the detergency evaluation result when the injector which the deposit adhered to the cleaning agent of this invention was immersed and wash | cleaned. The figure which showed the degree of swelling when the rubber-made O-ring was immersed in the cleaning agent of the present invention. The figure which showed the washing | cleaning evaluation result and the swelling degree of an O-ring when what mixed the diethyl benzylamine and NMP was used as the washing | cleaning agent and it added to the light oil.

  The cleaning agent of the present invention is a cleaning agent added to the fuel in order to remove deposits adhering in the fuel injection system from the fuel supply means for supplying the fuel to the nozzle for injecting the fuel. This cleaning agent is preferably used in a vehicle, more preferably in a vehicle equipped with a diesel engine. In addition to vehicles, this cleaning agent can also be used in construction machines, fishing boats, power generators, heating furnaces and boilers that heat fluid by burning fuel. Hereinafter, the case where it uses for the vehicle carrying a diesel engine is demonstrated.

  Diesel engines use light oil as fuel. For this reason, the cleaning agent of the present invention is added to the light oil at a predetermined ratio. First, a fuel injection system for a vehicle equipped with a diesel engine will be briefly described with reference to FIG. The fuel injection system is a system through which fuel passes from a supply pump 10 as a fuel supply means to an injector 11 as a nozzle for injecting fuel, and includes a fuel supply pipe 12 and a common rail 13. For this reason, the fuel supply system shown in FIG. 1 is a common rail system.

  A pressure sensor 14 is attached to the common rail 13, and a return line 16 a is connected via a pressure control valve 15. The return line 16 c is connected to the supply pump 10, the return line 16 b, and the injector 11. Here, although it demonstrates as a common rail type | system | group, the cleaning agent of this invention is applicable also to the fuel injection system using said unit injector type, a row | line | column type injection pump, a distribution type injection pump, and an independent type injection pump. .

  FIG. 1 also shows a fuel tank 17 and a fuel filter 18 other than the fuel injection system. Although not shown, the fuel tank 17 may include a prefilter. Further, in FIG. 1, a control unit 19 for receiving a signal from a pressure sensor 14 for detecting the pressure in the common rail 13 through a signal line indicated by a one-dot broken line, instructing the injector 11 and controlling the fuel injection amount. Is also shown.

  Light oil as fuel is put in the fuel tank 17 and sucked through the fuel filter 18 by the supply pump 10 that is started when the diesel engine is started. The supply pump 10 is pressurized to a predetermined pressure and then supplied to the common rail 13 through the fuel supply pipe 12. The injector 11 has a needle-like tip portion and includes a needle and a solenoid set at a position closing the fuel injection hole. By adjusting the lift time of the needle by the solenoid, fuel is injected into the combustion chamber through the injection hole. Spray. Until the fuel injection from the injector 11 is started, the fuel from the supply pump 10 is returned to the fuel tank 17 via the return line 16b.

  The fuel filter 18 separates and removes foreign substances having a size that can be captured, such as iron compounds, organic acids and salts thereof, and dust contained in the fuel. The supply pump 10 sucks the fuel in the fuel tank 17, raises the pressure to 200 MPa, for example, and discharges it to the fuel supply pipe 12. The supply pump 10, the injector 11, and the fuel filter 18 are provided with rubber O-rings and resin products. This rubber O-ring prevents fuel leakage.

  The fuel supplied to the common rail 13 is accumulated until it is injected from the injector 11, but the pressure in the common rail 13 is detected by the pressure sensor 14, and the fuel discharge amount of the supply pump 10 is controlled by an instruction from the control unit 19. To do. Thereby, the pressure in the common rail 13 is controlled. The injector 11 injects fuel into the fuel chamber in the form of a mist and causes it to self-ignite.

  As described above, in the supply pump 10, air is mixed from the outside for some reason, the air is compressed and becomes a local high temperature, unburned carbon is generated as the temperature rises, and adheres to the inside of the injector 11. accumulate. Various additives such as the low-temperature fluidity improver and the lubricity improver described above are added to the fuel. Various additives are deposited by the fuel etc. which became high temperature, and also thermally decompose and adhere and deposit inside the injector 11. Further, iron-based compounds and the like in the fuel adhere and deposit. These become deposits, hindering the movement of the needle and hindering proper fuel injection of the injector 11. Thereby, engine performance falls.

  The fuel is atomized by spraying from the injector 11 at high pressure, and self-ignition is enabled by the atomization. For this reason, it is necessary to raise the pressure by the supply pump 10, and the fuel becomes high temperature as the pressure is increased. Therefore, the generation of deposits cannot be avoided, and it is necessary to remove the generated deposits.

  The deposit gradually adheres and accumulates, and is oxidized and hardened by air. In order to remove this, it is desirable to remove the supply pump 10, the common rail 13, etc., disassemble them into parts, and immerse each part in a cleaning agent. However, removing them and disassembling them into parts is laborious and must be assembled and attached after cleaning. Therefore, the present invention provides a cleaning agent that is used by adding to such a troublesome fuel. A cleaning agent used by adding to a conventional fuel cannot obtain a sufficient cleaning effect unless it is added by several tens of weight% with respect to the fuel. Since it has an effect, the above-described running performance due to the addition of a large amount is hindered, and the problem that NOx in the combustion exhaust gas increases does not occur.

The novel cleaning agent of the present invention has, as main components, diethylbenzylamine (C ₁₁ H ₁₇ N), tribenzylamine (C ₂₁ H ₂₁ N), diethylenetriamine (C ₄ H ₁₃ ) in order to impart high detergency. N ₃ ) and 1 or more components selected from 1-phenylpiperazine (C ₁₀ H ₁₄ N ₂ ). These components have high detergency as well as high flash point, so they are relatively easy to handle, and are not applicable to the Chemical Management Promotion Act and the Poisonous and Deleterious Substances Control Law, which are problematic in sales. This is a desirable component. The chemical formulas are shown in order in the following formulas 1 to 4.

  Incidentally, the flash point is 77 ° C for diethylbenzylamine represented by the above formula 1, 122 ° C for tribenzylamine represented by the above formula 2, 102 ° C for diethylenetriamine represented by the above formula 3, and 1 represented by the above formula 4. -Phenylpiperazine is 140 ° C, which is a relatively high temperature.

  This cleaning agent can be added in an amount of 0.1 to 30% by volume with respect to the fuel. Although it may be 30% by volume or more, the above range is sufficient in consideration of the price and the cleaning effect. Thus, since it has a sufficient cleaning effect with a small amount, it does not hinder the running performance and can solve the problem of increasing NOx in the exhaust gas. One or more said components contained in a cleaning agent are contained at least 70 volume% among the cleaning components contained in the cleaning agent. This is to suppress swelling above a certain level, such as a rubber O-ring.

  In the cleaning agent of the present invention, all of the cleaning components can be one or more components selected from the above-mentioned diethylbenzylamine, tribenzylamine, diethylenetriamine, and 1-phenylpiperazine, but contain other cleaning components For example, alkylene glycol alkyl ether, N-alkyl-pyrrolidone, etc. which are conventionally used can be contained. Examples of other cleaning components include diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone (NMP), and the like. Since this is an example, it is possible to use other cleaning components.

  This cleaning agent includes additive components not generally related to cleaning, such as a lubricity improver, a low-temperature fluidity improver, an antifoaming agent, a cetane number improver, a clean dispersion. The component contained in the agent may be contained within a range that does not affect the cleaning properties. These components include long-chain fatty acid monoesters, long-chain dibasic acids, fatty acid amides, etc. for improving lubricity, ethylene-vinyl acetate copolymers, polyhydric alcohols and higher grades for improving low-temperature fluidity. Examples include esters of fatty acids. In addition, alkyl nitrates for improving the cetane number and the like, polyisobutenes for cleaning and dispersing action, and the like can be mentioned. The cleaning agent of the present invention is not limited to these additive components, and may contain other additive components.

  The cleaning agent of the present invention is placed in a bottle having a predetermined capacity calculated from the amount of fuel when the fuel tank 17 is full so that the volume% is within the above range with respect to the fuel. Sometimes it can be added to the fuel tank 17 from its bottle. In one example, 400 cc of detergent can be added to 100 liters of fuel.

  In order to evaluate the detergency of the novel detergent of the present invention and to evaluate the degree of swelling of the rubber O-ring, the following tests were conducted. In order to evaluate the cleaning performance, the injector 11 with the black deposit removed from the 4t truck that has traveled more than 100,000 km is placed in the ultrasonic cleaning device (UT-105S) manufactured by Sharp Manufacturing System Co., Ltd. The sample was immersed in the cleaning agent, irradiated with ultrasonic waves for 30 minutes, and the appearance of the deposit adhered to the injector 11 was visually evaluated.

  In order to evaluate the degree of swelling, a fluororubber O-ring having heat resistance, oil resistance, and chemical resistance and widely used mainly in automobile applications was used as the rubber O-ring. The O-ring was immersed in a cleaning solution, and the change in weight after 1 day and 5 days elapsed was measured. The swelling degree was calculated by dividing the weight after swelling by the weight before swelling.

  In general, the degree of swelling up to 1.5 is taken into consideration in the design, filling the gap and improving the sealing force, but the degree of swelling exceeding it causes cracks and increases the hardness and causes fuel leakage from the sealing part. Arise. The degree of swelling decreases as the number of days elapses, and when the number of days elapses, it does not increase so much after 5 days. Therefore, the degree of swelling is evaluated by whether the degree of swelling is 1.5 or less even after 5 days. Went.

  In Example 1, diethylbenzylamine selected as a cleaning component to be contained in the cleaning agent of the present invention was used as the cleaning agent. In Example 2, tribenzylamine selected as a cleaning component to be contained in the cleaning agent of the present invention was used as the cleaning agent. Since tribenzylamine is solid at normal temperature, light oil was used as a solvent, and 0.5 g of tribenzylamine dissolved in 5 ml of light oil was used. In Example 3, diethylenetriamine selected as a cleaning component to be contained in the cleaning agent of the present invention was used as the cleaning agent. In Example 4, 1-phenylpiperazine selected as a cleaning component to be contained in the cleaning agent of the present invention was used as the cleaning agent.

  In Example 5, a mixture of 90% by volume of diethylbenzylamine and 10% by volume of NMP was used as the cleaning agent. In Example 6, a mixture of 70% by volume of diethylbenzylamine and 30% by volume of NMP was used as a cleaning agent.

  In order to compare the cleaning property with the cleaning agent of the present invention, the same test was performed using the following as a cleaning agent. In Comparative Example 1, light oil was used instead of the cleaning agent. This is to confirm that light oil has no cleaning effect. In Comparative Example 2, NMP as a cleaning component conventionally used was used as the cleaning agent. In Comparative Example 3, diethylene glycol monomethyl ether as a cleaning component conventionally used was used. In Comparative Example 4, a detergent mixed with 50% by volume of diethylbenzylamine and 50% by volume of NMP was used. This is for the purpose of confirming the influence of the detergency and swelling degree depending on the content of the diethylbenzylamine solution selected as a cleaning component to be contained in the cleaning agent of the present invention.

  The photograph which image | photographed the injector 11 before washing | cleaning and the injector 11 after washing | cleaning is shown in FIG. FIG. 2A is a photograph of the injector 11 before cleaning. Since it is before washing | cleaning, the black deposit adheres entirely. FIG. 2B is a photograph of the injector 11 taken after washing with diethylene glycol monomethyl ether of Comparative Example 3 above. Deposits remain overall, and in particular, a lot of deposits remain at the tip.

  FIG. 2C is a photograph of the injector 11 taken after cleaning with the NMP of Comparative Example 2 described above. Most of the deposit has been removed, but the deposit still remains at the tip. FIG. 2 (d) is a photograph of the injector 11 taken after washing with diethylbenzylamine of Example 1 above. The deposits of the entire injector 11 are completely removed, making it look like a new one.

  The results of visual evaluation of the cleaning properties are shown in FIG. As shown in FIG. 2 (d), the black deposit has been completely removed, indicated by a double circle, and as shown in FIG. 2 (c), approximately 80% or more can be removed by a circle. As shown in FIG. 2B, those that can be removed by about 20% or more and less than about 80% are indicated by triangles, and those that are less than about 20% and hardly removed are indicated by crosses. Each of Examples 1 to 6 was indicated by a double circle, and it was confirmed that good detergency was exhibited.

  On the other hand, the light oil which is not the cleaning agent of Comparative Example 1 is indicated by a cross and it was confirmed that it was not removed at all. Further, it was confirmed that Comparative Examples 2 and 3 showed a certain degree of detergency as indicated by circles and triangles, respectively, but the detergency was not sufficient. In addition, since Comparative Example 4 contained 50% by volume of diethylbenzylamine which is the main component of the cleaning agent of the present invention, it was confirmed that the cleaning property was good as indicated by double circles.

  The result of the degree of swelling is shown in FIG. Examples 1 to 6 were found to have almost no effect on the rubber O-ring because it was 1.5 or less after 5 days and almost 1.0. In the case of the light oil of Comparative Example 1, no swelling occurs and there is no effect on the O-ring, but in the case of Comparative Examples 2 and 3, the degree of swelling exceeds 1.5, which may affect the O-ring. It was found. Therefore, a cleaning component such as diethylbenzylamine selected as a component to be contained in the cleaning agent of the present invention has a good cleaning property and has no influence of swelling on the O-ring and is added to the fuel. It was found to be suitable as At the same time, as shown in Comparative Example 4, since only 50% by volume of diethylbenzylamine affects the O-ring, the cleaning component selected as a component to be included in the cleaning agent of the present invention is: It has been found that it is necessary to contain at least 70% by volume of the cleaning components contained in the cleaning agent.

  FIG. 5 shows the results of the cleaning performance of the injector 11 and the swelling degree of the O-ring using the cleaning agent actually added to the fuel. The test was performed in the same manner as described above, using light oil as the fuel, 90% by volume of light oil, 10% by volume of the cleaning agent, and changing the ratio of diethylbenzylamine and NMP among the components of the cleaning agent. It was found that the volume ratio of diethylbenzylamine / NMP was 9/1, 7/3, and 5/5 with good detergency. Although the washing component was diluted by mixing with light oil, it was found that the deposit could be sufficiently removed by the good washability of diethylbenzylamine.

  On the other hand, the influence on the O-ring was 9/1, 7/3, even after 5 days, the degree of swelling was 1.5 or less, but in the case of 5/5, 1 Already exceeded 1.5 after the day. From this, it was found that diethylbenzylamine should be 70% by volume or more of the total washing components. Similar results were obtained when diethylene glycol monomethyl ether was used instead of NMP.

  The results of the detergency and the degree of swelling are shown in FIG. 5 only when the ratio of the light oil to the detergent is 9/1 as described above, but in the range of 99.9 / 0.1 to 7/3, that is, Even when 0.1 to 30% by volume of the detergent was added to the light oil, good detergency and a degree of swelling of 1.5 or less were obtained. And in order to make swelling degree 1.5 or less, it was necessary to make diethylbenzylamine etc. which should be contained in the cleaning agent of this invention into 70 volume% or more of all the washing | cleaning components.

  Although the cleaning agent of the present invention has been described in detail so far, the present invention is not limited to the above-described embodiments, and those skilled in the art will conceive other embodiments, additions, modifications, deletions, and the like. It can be changed within the range that can be achieved, and any aspect is included in the scope of the present invention as long as the effects and effects of the present invention are exhibited. Therefore, the object to swell is not limited to rubber O-rings, but may be sealing materials such as rubber packings. In addition to light oil and gasoline, it is added to naphtha, kerosene, biofuel, etc. It is also possible to use it.

DESCRIPTION OF SYMBOLS 10 ... Supply pump, 11 ... Injector, 12 ... Fuel supply pipe, 13 ... Common rail, 14 ... Pressure sensor, 15 ... Pressure control valve, 16a, 16b, 16c ... Return line, 17 ... Fuel tank, 18 ... Fuel filter, 19 …control unit

Claims (3)

A cleaning agent added to the fuel in order to remove deposits adhering in the fuel injection system from the fuel supply means for supplying the fuel to the nozzle for injecting the fuel,
A cleaning agent comprising at least one component selected from diethylbenzylamine , tribenzylamine , and 1-phenylpiperazine.   The cleaning agent according to claim 1, wherein 0.1 to 30% by volume is added to the fuel.   The cleaning agent according to claim 1 or 2, wherein at least 70% by volume of the one or more components contained in the cleaning agent is contained among the components having cleaning properties contained in the cleaning agent.