WO2021000317A1

WO2021000317A1 - Fuel additive, method of using fuel additive, and fuel mixture

Info

Publication number: WO2021000317A1
Application number: PCT/CN2019/094698
Authority: WO
Inventors: Xin Huo; Weifeng Wang; Jinrong Zhang; Sibian MA; Mengling LI; Zhiyu Shi; Yinfang Yao
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2019-07-04
Filing date: 2019-07-04
Publication date: 2021-01-07
Anticipated expiration: 2022-01-04
Also published as: CN114341319B; CN114341319A

Abstract

Provided is a fuel additive, a method of using the same, and a fuel mixture. Specifically, the fuel additive comprises: 70 to 95% by weight of a nonylphenol polyetheramine and 5 to 30% by weight of an aromatic amine, based on the total weight of the fuel additive. When only a small amount (e.g. less than 400 ppm of the total amount of a fuel) of the fuel additive is added to the fuel, it can significantly reduce deposits on the components such as a fuel injector, an intake valve or the like in a vehicle.

Description

FUEL ADDITIVE, METHOD OF USING THE SAME, AND FUEL MIXTURE

TECHNICAL FIELD

The present invention relates to the technical field of fuel additives, and in particular to a fuel additive, a method of using the same and a fuel mixture.

BACKGROUND

It is well known to those skilled in the art that during the operation of an engine, deposits are formed on the surfaces of engine components (such as carburetor ports, throttle bodies, fuel injectors, intake ports, and intake valves) , due to the oxidation and polymerization of a hydrocarbon fuel. Deposits are also formed in the combustion chamber of an internal combustion engine due to the incomplete combustion of a mixture comprising air, fuel and oil. These deposits, even when present in relatively minor amounts, often cause noticeable driving problems, such as stalling and poor acceleration. Moreover, the engine deposits can significantly increase the automobile’s fuel consumption and the production of exhaust pollutants. Specifically, when the gasoline used in a given engine is of a constant octane number, the power output decreases when deposits are formed. In order to maintain the power output at a predetermined desired level, it then becomes necessary to increase the octane number of the fuel over the course of time. This Octane Requirement Increase (ORI) is undesirable. Therefore, the development of effective fuel detergents or deposit control additives to prevent or control such deposits is of considerable importance, and numerous such materials are known in the art.

In addition, currently, the automobiles that control fuel supply through an electronic device have gradually replaced the automobiles that are fueled by a carburetor. In a vehicle that controls fuel supply by an electronic device, the fuel injector in the engine has a small aperture, a high operating temperature, and poor fuel lubricity, so that the fuel injector is easily blocked by carbon deposits, thereby causing the problems such as poor atomization, poor oil supply, oil consumption, and polluted emissions. After long-term use, carbon deposits are easily formed on the sealing surface of the intake valve of the engine so that the seal of the cylinder is not tight, resulting in reduced engine power and non-combustion. This seriously reduces the economy of the fuel, the power output of the engine, and the quality of the exhaust gas, which degrades the performance of the engine.

In order to solve the problem of carbon deposition, the currently widely used method is to add a fuel additive to the fuel. There are currently two main types of fuel additives commercially available.

One type of fuel additive comprises a hydrocarbyl-substituted amine, such as those prepared by reacting an olefin and an olefin polymer with an amine, including a polyamine. A typical example of the hydrocarbyl-substituted amine is a polyisobutene amine. The polyisobutene amine fuel additive has a cleaning effect on the fuel injector and the intake valve in the gasoline engine, and can effectively suppress and clean the deposits on these components in the gasoline engine. However, this type of fuel additive will bring the deposits washed from the fuel intake system into the combustion chamber, resulting in a significant increase in the deposits in the combustion chamber. When the total amount of deposits in the combustion chamber of the gasoline engine is significantly increased, the compression ratio of the engine is increased, and the generated heat is not easily dissipated, resulting in an increase in the temperature of the gas at the end of the compression in the combustion chamber. In severe cases, this increases the mechanical interference between the top of the piston and the cylinder head, which ultimately increases the fuel consumption of the engine and deteriorates the quality of the exhaust gas. In addition, the polyisobutylene amines are believed to produce more combustion chamber deposits than a fuel alone.

Another type of fuel additive comprises a polyetheramine. Typically, the polyetheramine is a “single molecule” additive in which there are an amine functional group and a polyether functional group in the same molecule. A typical example of a polyetheramine-based fuel additive is a urethane product comprising a repeating butylene oxide unit. The polyetheramine is easily decomposed at high temperature so that it does not form new carbon deposits in the combustion chamber, which somewhat reduces the increase of carbon deposits in the combustion chamber. It is generally recognized in the art that the polyetheramine-based fuel additive is preferable because the oxygenation from the polyether functionality is thought to reduce the particulate matter and nitrogen oxide (NO _x) emissions and combustion chamber deposits. However, the polyetheramine-based fuel additive must be used in a fuel at a relatively high concentration (above 400 ppm) so as to achieve the desired cleaning results.

Besides the cleaning performance, a more important function for the fuel additive is to avoid the forming of the deposit in the fuel injectors or intake valves. For this target, polyisobutene amine is effective in low concentration, on the order of 300-500 ppm in the gasoline. However, for the polyether amine, it does not work well when the concentration is lower than 400ppm in the gasoline. Additionally, people always want to spend less money to achieve the same or better effect. Thus, it is important to develop a fuel additive capable of producing a good deposit function at a low concentration in the gasoline.

SUMMARY OF THE INVENTION

In view of the technical problem set forth above, an object of the present invention is to provide a fuel additive capable of significantly reducing deposits on the components such as a fuel injector, an intake valve or the like in a vehicle when only a small amount (e.g. less than 400 ppm of the fuel) of the fuel additive is added to the fuel.

The present inventors have completed the present invention through intensive research.

According one embodiment, the present disclosure provides a fuel additive comprising:

70 to 95%by weight of a nonylphenol polyetheramine; and

5 to 30%by weight of an aromatic amine, based on the total weight of the fuel additive.

In some embodiments, the nonylphenol polyetheramine is represented by the following general formula (I) :

wherein x is an integer from 9 to 15.

In some embodiments, the nonylphenol polyetheramine has a weight average molecular weight in the range of 800 to 1200.

In some embodiments, the nonylphenol polyetheramine is present in an amount from 85%by weight to 90%by weight in terms of the total weight of the fuel additive.

In some embodiments, the aromatic amine is represented by the following general formula (II) :

wherein R ₁, R ₂ and R ₃ are each independently selected from an alkyl group having 1 to 8 carbon atoms, and X is O or N.

In some embodiments, the aromatic amine has a molecular weight in the range of 100 g/mol to 500 g/mol.

In some embodiments, the aromatic amine is present in an amount from 10%by weight to 15%by weight in terms of the total weight of the fuel additive.

In some embodiments, the fuel additive further comprises a corrosion inhibitor.

In some embodiments, the fuel additive further comprises a diluent.

In some embodiments, the diluent is present in an amount from more than 0 %by weight to 25 %by weight in terms of the total weight of the fuel additive.

In some embodiments, there provides a method of using a fuel additive as described above, comprising a step of adding the fuel additive to a fuel.

In another embodiment, the present disclosure provides a fuel mixture including a fuel and a fuel additive, according to any one of the fuel additive in the above embodiments of the present disclosure.

In some embodiments, the fuel additive is present in the fuel mixture in an amount less than 400 ppm, based on the total weight of the fuel mixture.

In some embodiments, the fuel additive is present in the fuel mixture in an amount less than 200 ppm, based on the total weight of the fuel mixture.

The advantages of the present invention over the prior art in the field are the following: the fuel additive is capable of significantly reducing deposits on the components such as a fuel injector, an intake valve or the like in a vehicle when only a small amount (e.g. less than 400 ppm of the fuel) of the fuel additive is added to the fuel.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be further described in detail below in conjunction with the drawings and specific embodiments. It will be appreciated that other embodiments may be practiced without departing from the scope or spirit of the invention. Therefore, the following detailed description is non-limiting.

All numbers indicating the sizes, quantities, and physicochemical properties of a feature used in the specification and claims, unless otherwise indicated, are understood to be modified in all instances by the term “about” . Accordingly, the numerical parameters set forth in the above description and the appended claims are approximations unless otherwise indicated, and those skilled in the field are able to use the teachings disclosed herein. The range of values defined by endpoints includes all numbers in the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, or the like.

According to the technical solution of the present invention, there provides a fuel additive capable of significantly reducing deposits on the components such as a fuel injector, an intake valve or the like in a vehicle when only a small amount (e.g. less than 400 ppm of the fuel) of the fuel additive is added to the fuel.

Specifically, the present disclosure provides a fuel additive comprising:

70 to 95%by weight of a nonylphenol polyetheramine; and

The fuel additive according to the present disclosure comprises a nonylphenol polyetheramine as a main cleaning component. Nonylphenol polyetheramine has excellent deposit control capabilities, which can significantly reduce the deposit buildup on the fuel injector, the intake valve and other components in a vehicle.

wherein x is an integer from 9 to 15.

In some embodiments, the nonylphenol polyetheramine has a weight average molecular weight in the range of 800 to 1200. When the weight average molecular weight is lower than 800 or higher than 1200, the deposit control performance will be reduced. In some embodiments, the nonylphenol polyetheramine is present in an amount from 85%by weight to 90%by weight based on the total weight of the fuel additive. When the amount of polyetheramine is lower than 85%or higher than 90%by weight, the deposit control performance may be decreased. Specific examples of the commercially available products of nonylphenol polyetheramine which can be used in the fuel additive according to the present disclosure include: a nonylphenol polyetheramine produced by Univar Trade Co., Ltd. under the product name of PEA-1000 (it has a structure represented by the general formula (I) , wherein x is 12 and the weight average molecular weight thereof is about 1000) ; a nonylphenol polyetheramine produced by Univar Trading Co., Ltd. under the product name of PEA-800 (it has a structure represented by the general formula (I) , wherein x is 9 and the weight average molecular weight thereof is about 800) ; and a nonylphenol polyetheramine produced by Univar Trading Co., Ltd. under the product name of PEA-1200 (it has a structure represented by the general formula (I) wherein x is 15 and the weight average molecular weight thereof is about 1200) .

In order to reduce the amount of nonylphenol polyetheramine added for cleaning, the fuel additive according to the present disclosure comprises an aromatic amine. The inventors of the present invention have found that the aromatic amine has an unexpected promoting effect on the cleaning behavior of nonylphenol polyetheramine. Without wishing to be bound by theory, it is believed that the aromatic amine can be effectively adsorbed on a surface of a metal because it comprises an amine group having polarity, thereby preventing or delaying the carbon deposits on the components such as a fuel injector, an intake valve or the like in a vehicle; on the other hand, the aromatic amine also has an aromatic ring structure similar to that of the nonylphenol polyetheramine, thereby helping the nonylphenol polyether amine to be dispersed on the surfaces of the components, such as a fuel injector, an intake valve or the like in a vehicle so as to achieve a better cleaning effect.

wherein R ₁, R ₂ and R ₃ are each independently selected from an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, or the like) , and X is O or N. In some embodiments, the aromatic amine has a molecular weight in the range of 100 to 500 g/mol, preferably 1.50 to 450 g/mol, more preferably, 200 to 400 g/mol, and even more preferably, 250 to 350 g/mol. In some embodiments, the aromatic amine is present in an amount from 10%by weight to 15%by weight based on the total weight of the fuel additive. Specific examples of the commercially available products of aromatic amines that can be used in the fuel additive according to the present invention include: an aromatic amine having a molecular weight of about 177 g/mol manufactured by Qingyuanxing Chemical Technology Co., Ltd. under the name of AO-177; an aromatic amine having a molecular weight of about 149 g/mol produced by Qingyuanxing Chemical Technology Co., Ltd. under the name of AO-149; and an aromatic amine having a molecular weight of about 445 g/mol produced by Qingyuanxing Chemical Technology Co., Ltd. under the name ofAO-445.

In addition to the above-mentioned nonylphenol polyetheramines and aromatic amines, the fuel additive according to the present invention may further comprise other components to provide additional desirable properties to the fuel additive. In particular, the fuel additive according to the present invention may further comprise a corrosion inhibitor to mitigate the corrosive effect of the fuel on the engine components. There is no particular limitation on the specific type of corrosion inhibitor that can be added to the fuel additive according to the present invention, and it can be selected from any corrosion inhibitor which is usually added to the ordinary commercial gasoline as long as the corrosion inhibitor does not affect the respective functions of the nonylphenol polyetheramine and the aromatic amine.

Further, the fuel additive according to the present invention may further comprise a diluent to dilute the fuel additive to an appropriate concentration for the sake of storage, transportation and use. The specific type of the diluent which can be added to the fuel additive according to the present invention is not particularly limited as long as the diluent does not affect the respective effects of the nonylphenol polyetheramine and the aromatic amine. Preferably, the diluent is selected from one or more of a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, and a saturated cycloalkane. Specific examples of the saturated aliphatic hydrocarbon that can be used in the fuel additive of the present invention include D60 produced by Mobil Company as well as D100 produced by Mobil Company. Specific examples of the aromatic hydrocarbon that can be used in the fuel additive of the present invention include S 150 produced by Mobil Company as well as S200 produced by Mobil Company. The diluent may be appropriately selected within the range of the products described above. In some embodiments, the flash point of the diluent is in the range of 60 to 100 ℃. In order to achieve the better dilution effect, the diluent is present in an amount from equal or more than 0 %by weight to 25 %by weight based on the total weight of the fuel additive. When the diluent amount is more than 25 %by weight, the deposit control performance may be reduced.

The preparation method of the fuel additive according to the present invention is not particularly limited, and for example, the components of the fuel additive may be mixed by a conventional mixing method in the field. Specifically, the components for preparing the fuel additive may be mixed in a stainless steel container at a normal temperature (about 25 ℃) and under a normal pressure (about 1 atm) to obtain a fuel additive. In the mixing process, the addition order of the raw materials is not particularly limited.

According to another aspect of the present disclosure, there provides a fuel mixture comprising a fuel and a fuel additive, which may be used as a fuel for a variety of vehicles or machines that require a fuel. There is no particular limitation on the specific type of the fuel that can be employed in the present disclosure, and it can be selected from various grades of fuel currently on sale, such as National Standard 92#gasoline, National Standard 95#gasoline, or the like. In order to achieve the technical effects of the present disclosure, the fuel additive is present in the fuel mixture in an amount less than 400 ppm, based on the total weight of the fuel mixture. Preferably, the fuel additive is present in the fuel mixture in an amount less than 200 ppm, based on the total weight of the fuel mixture.

The invention will be described in greater detail with reference to the embodiments. It is to be understood that the description and examples are intended to be illustrative, and not restrictive. The scope of the invention is defined by the appended claims.

Examples

In the present invention, unless otherwise indicated, the reagents employed were all commercially available and used directly without further purification. Further, the mentioned “%” is “%by weight” , and the mentioned “part” is “part by weight” .

The raw materials used in the examples and comparative examples according to the present invention are as shown in Table 1 below. Unless otherwise indicated, the raw materials were used directly without additional purification.

Table 1 List of raw materials used in the examples and comparative examples

Tests for Performances

The samples prepared in the respective examples and comparative examples described in detail below were tested for the deposit control property according to the specific methods listed below. The test results are shown in Table 2 below.

Deposit Control Property

The process of carbon deposition in an intake valve was simulated and the deposit control level was evaluated according to a method described in detail in Chinese Standard GB 19592-2004.

Specifically, a sample prepared in the following respective examples and comparative examples was added at a ratio of 1: 5000 (200 ppm) at normal temperature (about 25 ℃) and under normal pressure (about 1 atm) into a National Standard 92#gasoline so as to prepare a fuel mixture to which a fuel additive was added.

A test plate was soaked in alcohol for 60 minutes to clean the surfaces thereof. The test plate was then placed in an oven at 100 ℃ for 15 minutes. The test plate was then removed from the oven and placed in a desiccator at room temperature. The exact weight (m0) of the test plate was recorded.

300 mL of the fuel mixture prepared above was added to a volumetric flask. The volumetric flask was then put into an intake system deposit simulation tester with a model of L-2 whose supplier is Lanzhou Weike Petrochemical Instrument Co. Limited. The test plate was then also placed into the L-2 intake system deposit simulation tester. The simulation tester was then turned on to rise the temperature to 170 ℃. The fuel mixture to which the fuel additive was added was sprayed onto the test plate in 70 minutes. Subsequently, the test plate was taken out and washed with heptane and petroleum ether, respectively. Subsequently, the test plate was dried and weighed. The exact weight (m1) of the test plate was recorded.

According to the technical solution of the present disclosure, an amount m (mg) of the deposit on the simulated intake valve was calculated by the following formula:

m = m0 -m1

wherein m is the amount m (mg) of the deposit on the simulated intake valve; m1 is the weight (mg) of the test plate after gasoline spraying; m0 is the weight (mg) of the test plate before gasoline spraying.

Further, according to the present invention, the amount (mg) of the deposit on the simulated intake valve is rated to evaluate the deposit control performance, wherein: when the amount (mg) of the deposit on the simulated intake valve is less than 1.0, the deposit control level is “Very Good” ; when the amount (mg) of the deposit on the simulated intake valve is greater than or equal to 1.0 and less than 2.0, the deposit control level is “Good” ; when the amount (mg) of the deposit on the simulated intake valve is greater than or equal to 2.0 and less than 3.0, the deposit control level is “Normal” ; and when the amount (mg) of the deposit on the simulated intake valve is greater than or equal to 3.0, the deposit control level is “Poor” .

Example E 1

The nonylphenol polyetheramine PEA-1000 and the aromatic amine AO-177 were mixed in a stainless steel container at normal temperature (about 25 ℃) and under normal pressure (about 1 atmosphere) to obtain a Fuel Additive 1, wherein the nonylphenol polyetheramine PEA-1000 accounted for 70%by weight and the aromatic amine AO-177 accounted for 30%by weight based on the total weight of the Fuel Additive 1.

Examples E2-E10 and Comparative Examples C1-C4

Examples E2-E10 and Comparative Examples C1-C4 were carried out in the same manner as that in Example E1 to obtain Fuel Additives 2-10 and Comparative Fuel Additives 1-4, except that the specific types and contents of respective components were changed as shown in Table 2.

Comparative Example C5

In Comparative Example C5, PN7029 produced by 3M China Ltd. was used as a Comparative Fuel Additive 5.

Comparative Example C6

Comparative Example C6 was carried out in the same manner as that in Example E1 to obtain a Comparative Fuel Additive 6, except that 70%by weight of PEA-1000 was replaced with 70%by weight of N-phenyl-2-naphthylamine.

Comparative Example C7

Comparative Example C6 was National Standard 92#gasoline without adding a fuel additive.

Examples 1-10 and Comparative Examples C1-C7 were tested for the deposit control performance according to the methods listed above. The results of Examples E1-E10 and Comparative Examples C1-C4 are shown in Table 2 below, and the results of Comparative Examples C5-C7 are shown in Table 3 below.

Table 3 Details for the Compositions in Comparative Examples C5-C7 and the testing results for performance thereof

Obviously, various modifications and variations may be made to this disclosure by the person skilled in the art without deviating from the spirit and the scope of this disclosure. Thus, if these modifications and variations of this disclosure are within the scope of the claims of this invention and equivalent techniques thereof, this disclosure also intends to encompass these modifications and variations.

Claims

A fuel additive comprising:

70 to 95%by weight of a nonylphenol polyetheramine; and

5 to 30%by weight of an aromatic amine, based on the total weight of the fuel additive.
The fuel additive according to claim 1, wherein the nonylphenol polyetheramine is represented by the following general formula (I) :

wherein x is an integer from 9 to 15.
The fuel additive according to claim 1, wherein the nonylphenol polyetheramine has a weight average molecular weight in the range of 800 to 1200.
The fuel additive according to claim 1, wherein the nonylphenol polyetheramine is present in an amount from 85%by weight to 90%by weight in terms of the total weight of the fuel additive.
The fuel additive according to claim 1, wherein the aromatic amine is represented by the following general formula (II) :

wherein R1, R2 and R3 are each independently selected from an alkyl group having 1 to 8 carbon atoms, and X is O or N.
The fuel additive according to claim 1, wherein the aromatic amine has a molecular weight in the range of 100 g/mol to 500 g/mol.
The fuel additive according to claim 1, wherein the aromatic amine is present in an amount from 10%by weight to 15%by weight in terms of the total weight of the fuel additive.
The fuel additive according to claim 1, wherein the fuel additive further comprises a corrosion inhibitor.
The fuel additive according to claim 1, wherein the fuel additive further comprises a diluent.
The fuel additive according to claim 9, wherein the diluent is present in an amount from more than 0 %by weight to 25 %by weight in terms of the total weight of the fuel additive.
A method of using a fuel additive according to any one of claims 1 to 10, comprising a step of adding the fuel additive to a fuel.
A fuel mixture, comprising a fuel and a fuel additive according to any one of claims 1 to 10.
The fuel mixture according claim 12, wherein the fuel additive is present in the fuel mixture in an amount less than 400 ppm, based on the total weight of the fuel mixture.
The fuel mixture according claim 12, wherein the fuel additive is present in the fuel mixture in an amount less than 200 ppm, based on the total weight of the fuel mixture.