An alcohol-based environmentally friendly clean fuel additive and its preparation method and application

Abstract

The present invention relates to an alcohol-based environmentally friendly clean fuel additive and a preparation method and application thereof, and relates to the technical field of fuel additives. The alcohol-based environmentally friendly clean fuel additive comprises the following components by weight: 45 to 60 parts of a monoester compound and 8 to 15 parts of isooctyl nitrate; the monoester compound is obtained by esterification reaction of any C9 to C11 saturated straight-chain alkanedioic acid and tert-butyl alcohol. The present invention uses a monoester compound and isooctyl nitrate, which are connected by an alkyl chain of suitable length and have a tert-butyl ester group and a carboxyl group as end groups at both ends, respectively, and further controls the dosage ratio of the two, thereby significantly improving the cleaning performance and metal corrosion resistance of the alcohol-based fuel under low-dose addition, improving the shortcomings of the existing alcohol-based fuel, and having excellent environmental protection performance.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel additives, and in particular to an alcohol-based environmentally friendly clean fuel additive and a preparation method and application thereof. Background Art

[0002] For a long time, the fuels used in various civilian heating stoves, catering stoves, kilns and boilers, automobiles, etc. have been mainly traditional energy sources such as coal, natural gas, and oil. The use of the above raw materials has led to high carbon emissions, making air pollution, water pollution, soil pollution and other environmental pollution increasingly serious, causing great harm to humans and global organisms and the increasing shortage of global energy.

[0003] Alcohol-based fuel is a liquid fuel mainly composed of methanol, mixed with polyols such as ethanol and propanol, and alkanes, and is also named "methyl fuel". Alcohol-based fuel has a wide range of raw materials and is a cheap, environmentally friendly clean energy source, providing a feasible way to solve the contemporary energy crisis. However, due to the high methanol content in alcohol-based fuels and the defects of methanol itself, such as easy corrosion and wear of the engine, alcohol-based fuels have problems such as poor metal corrosion resistance and poor cleaning performance during use, which limits their widespread application. Summary of the invention

[0004] In order to solve the above problems, the present invention provides an alcohol-based environmentally friendly clean fuel additive and a preparation method and application thereof.

[0005] In a first aspect, the present invention provides an alcohol-based environmentally friendly clean fuel additive, which comprises the following components in parts by weight:

[0006] 45-60 parts of monoester compound and 8-15 parts of isooctyl nitrate;

[0007] The monoester compound is obtained by esterification reaction of any C9-C11 saturated straight-chain alkanedioic acid and tert-butyl alcohol.

[0008] Furthermore, the weight ratio of the monoester compound to the isooctyl nitrate is (4-5):1, preferably 4.5:1.

[0009] Furthermore, the alcohol-based environmentally friendly clean fuel additive comprises the following components in parts by weight:

[0010] 54 parts of monoester compound and 12 parts of isooctyl nitrate.

[0011] Further, the monoester compound includes at least two of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate.

[0012] Furthermore, the monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl sebacate in a weight ratio of (20-30):(3-7).

[0013] Furthermore, the monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl undecanediolate in a weight ratio of (20-30):(13-16).

[0014] Furthermore, the monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:15.

[0015] In a second aspect, the present invention provides a method for preparing the alcohol-based environmentally friendly clean fuel additive according to any one of the first aspects, the preparation method comprising the following steps:

[0016] The monoester compound and isooctyl nitrate are mixed to obtain a mixture;

[0017] The mixed material is subjected to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive.

[0018] In a third aspect, the present invention provides use of the alcohol-based environmentally friendly clean fuel additive described in any one of the first aspect and the second aspect in the preparation of alcohol-based fuel.

[0019] In a fourth aspect, the present invention provides an alcohol-based fuel, comprising methanol and an additive; the additive is the use of the alcohol-based environmentally friendly clean fuel additive described in any one of the first aspect and the second aspect in the preparation of the alcohol-based fuel.

[0020] The above technical solution provided by the present invention has at least the following advantages compared with the prior art:

[0021] The invention provides an alcohol-based environmentally friendly clean fuel additive. The invention uses a monoester compound and isooctyl nitrate, which have tert-butyl ester group and carboxyl group as end groups at both ends respectively and are connected by an alkyl chain of suitable length, and further controls the usage ratio of the two, thereby achieving significantly improving the cleaning performance and metal corrosion resistance of the alcohol-based fuel under the condition of low-dose addition, improving the shortcomings of the existing alcohol-based fuel, and having excellent environmental protection performance. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described in combination with the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0024] In a first aspect, the present invention provides an alcohol-based environmentally friendly clean fuel additive, which comprises the following components in parts by weight:

[0025] 45-60 parts of monoester compound and 8-15 parts of isooctyl nitrate;

[0026] The monoester compound is obtained by esterification reaction of any C9-C11 saturated straight-chain alkanedioic acid and tert-butyl alcohol.

[0027] The invention provides an alcohol-based environmentally friendly clean fuel additive. The invention uses a monoester compound and isooctyl nitrate, which have tert-butyl ester group and carboxyl group as end groups at both ends respectively and are connected by an alkyl chain of suitable length, and further controls the usage ratio of the two, thereby achieving significantly improving the cleaning performance and metal corrosion resistance of the alcohol-based fuel under the condition of low-dose addition, improving the shortcomings of the existing alcohol-based fuel, and having excellent environmental protection performance.

[0028] In some specific embodiments, the C9-C11 saturated straight-chain alkanedioic acid can be selected from azelaic acid, sebacic acid and undecanedioic acid.

[0029] In some specific embodiments, the alcohol-based environmentally friendly clean fuel additive may consist of only a monoester compound and isooctyl nitrate.

[0030] In some specific embodiments, the weight ratio of the monoester compound to the isooctyl nitrate is (4-5):1, preferably 4.5:1.

[0031] In some specific embodiments, the alcohol-based environmentally friendly clean fuel additive includes the following components in parts by weight:

[0032] 54 parts of monoester compound and 12 parts of isooctyl nitrate.

[0033] In some specific embodiments, the monoester compound includes at least two of mono-tert-butyl azelate, mono-tert-butyl sebacate, and mono-tert-butyl undecanediolate.

[0034] In the present invention, mono-tert-butyl azelate (CAS No.: 1290540-34-9), mono-tert-butyl sebacate (CAS No.: 34081-96-0), and mono-tert-butyl undecane dioate (CAS No.: 1789702-17-5) can be directly purchased from the market or prepared in-house according to the preparation method disclosed in the prior art. Taking mono-tert-butyl azelate as an example, the preparation method of mono-tert-butyl azelate generally involves an esterification reaction, in which azelaic acid and tert-butyl alcohol undergo an esterification reaction under the action of a catalyst. The following is an overview of a typical preparation method:

[0035] Raw material preparation: Azelaic acid, as the acid source for the esterification reaction; tert-butanol, as the alcohol source for the esterification reaction; Catalyst: inorganic or organic acids such as sulfuric acid and p-toluenesulfonic acid, used to promote the esterification reaction.

[0036] Esterification reaction: Azelaic acid and tert-butyl alcohol are mixed in a certain proportion, a catalyst is added, and the esterification reaction is carried out at an appropriate temperature (such as reflux temperature) and under stirring conditions; water may be generated during the reaction, so the generated water can be removed through a water separator or a desiccant to promote the reaction in the direction of esterification.

[0037] Post-treatment: After the reaction is completed, the mono-tert-butyl azelate is separated by distillation, extraction and other methods. If the catalyst is an inorganic acid, neutralization, washing and other operations can be performed to remove the catalyst residue. Finally, the pure mono-tert-butyl azelate product is obtained by drying, filtering and other steps.

[0038] In some specific embodiments, the monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl sebacate in a weight ratio of (20-30):(3-7).

[0039] In some specific embodiments, the monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl undecanediolate in a weight ratio of (20-30):(13-16).

[0040] In some specific embodiments, the monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:15.

[0041] In a second aspect, based on the same inventive concept, the present invention provides a method for preparing the alcohol-based environmentally friendly clean fuel additive according to any one of the first aspects, the preparation method comprising the following steps:

[0042] The monoester compound and isooctyl nitrate are mixed to obtain a mixture;

[0043] The mixed material is subjected to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive.

[0044] The preparation method of the alcohol-based environmentally friendly clean fuel additive provided by the present invention is simple to operate, does not require additional specific equipment, and is suitable for batch industrial production.

[0045] In some specific embodiments, the working condition parameters of the ultrasonic treatment include: ultrasonic power of 500-700W, and ultrasonic time of 15-30 minutes.

[0046] In a third aspect, based on the same inventive concept, the present invention provides the use of the alcohol-based environmentally friendly clean fuel additive described in any one of the first aspect and the second aspect in the preparation of alcohol-based fuel.

[0047] In a fourth aspect, based on the same inventive concept, the present invention provides an alcohol-based fuel, which includes methanol and an additive; the additive is the use of the alcohol-based environmentally friendly clean fuel additive described in any one of the first aspect and the second aspect in the preparation of the alcohol-based fuel.

[0048] It should be noted that, for the alcohol-based environmentally friendly clean fuel additive and the preparation method thereof provided by the present invention, the components and raw materials involved, unless otherwise specified or explained, each component can directly use commercially available products; the operation steps involved, unless otherwise specified or explained, can be carried out in accordance with the operation methods disclosed in the prior art or using existing equipment according to its usage method.

[0049] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually measured according to national standards. If there is no corresponding national standard, then the conditions recommended by the manufacturer are followed.

[0050] Example 1

[0051] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0052] 54 parts of monoester compound and 12 parts of isooctyl nitrate;

[0053] The monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:15.

[0054] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0055] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0056] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0057] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0058] Example 2

[0059] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0060] 45 parts of monoester compound and 15 parts of isooctyl nitrate;

[0061] The monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:15.

[0062] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0063] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0064] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0065] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0066] Example 3

[0067] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0068] 60 parts of monoester compound and 8 parts of isooctyl nitrate;

[0069] The monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:15.

[0070] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0071] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0072] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0073] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0074] Example 4

[0075] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0076] 54 parts of monoester compound and 12 parts of isooctyl nitrate;

[0077] The monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl sebacate in a weight ratio of 24:5.

[0078] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0079] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0080] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0081] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0082] Example 5

[0083] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0084] 54 parts of monoester compound and 12 parts of isooctyl nitrate;

[0085] The monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl undecanediolate in a weight ratio of 28:15.

[0086] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0087] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0088] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0089] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0090] Comparative Example 1

[0091] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0092] 54 parts of monoester compound and 12 parts of isooctyl nitrate;

[0093] The monoester compound is 1,5-pentanedioic acid mono-tert-butyl ester.

[0094] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0095] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0096] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0097] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0098] Comparative Example 2

[0099] This example provides an alcohol-based environmentally friendly clean fuel additive, which includes the following components in parts by weight:

[0100] 54 parts of a monoester compound and 12 parts of ethyl nitrate;

[0101] The monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:15.

[0102] The preparation of the alcohol-based environmentally friendly clean fuel additive comprises the following steps:

[0103] Step (1): mixing the monoester compound and isooctyl nitrate to obtain a mixture;

[0104] Step (2): subjecting the mixture obtained in step (1) to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive;

[0105] The working condition parameters of the ultrasonic treatment include: ultrasonic power of 600W and ultrasonic time of 20 minutes.

[0106] Test Case

[0107] In this example, the alcohol-based environmentally friendly clean fuel additives obtained in the above examples and comparative examples were subjected to performance tests.

[0108] 1) Cleanliness performance test: The cleanliness test was conducted according to the method in GB / T 37322-2019 standard "Gasoline Detergent Evaluation Gasoline Engine Intake Valve Deposits Simulation Test Method", with specific parameters including: the oil sample to be tested is 300mL M15 methanol gasoline, the sediment collector temperature is 180°C, and the amount of alcohol-based environmentally friendly clean fuel additive added is 400mg / L. The test results are shown in Table 1.

[0109] 2) Metal corrosion resistance test: According to ASTM G31-72 "Recommended Specifications for Metal Laboratory Immersion Corrosion Tests" and national standard GB378-64 "Engine Fuel Copper Strip Corrosion Test Method", the metal corrosion performance test was carried out. The specific process includes: the treated H65 brass samples of the same size were immersed in M30 methanol gasoline and M30+ alcohol-based environmentally friendly clean fuel additives (the amount of alcohol-based environmentally friendly clean fuel additives added was 400 mg / L), sealed with rubber stoppers, and connected to the atmosphere with an external condenser. Each group of parallel samples has 2 to 3, and the test temperature is controlled at (25±1)℃ for 10 days. The test results are shown in Table 2.

[0110] Table 1 Cleaning performance test results

[0111]

[0112] Table 2 Test results of metal corrosion resistance

[0113] Test samples Metal corrosion rate (%) M30 Methanol Gasoline 1.220 M30 methanol gasoline + Example 1 0.015 M30 methanol gasoline + Example 2 0.042 M30 methanol gasoline + Example 3 0.037 M30 methanol gasoline + Example 4 0.021 M30 methanol gasoline + Example 5 0.026 M30 methanol gasoline + comparative example 1 0.957 M30 methanol gasoline + comparative example 2 0.619

[0114] It can be seen from Table 1 and Table 2 that, compared with the comparative example, the alcohol-based environmentally friendly clean fuel additive provided by the embodiment of the present invention can significantly improve the cleaning performance and metal corrosion resistance of the alcohol-based fuel when added in a low dose, improve the shortcomings of the existing alcohol-based fuel, and has a wide range of practical application value.

[0115] In summary, the embodiments of the present invention provide an alcohol-based environmentally friendly clean fuel additive, and a preparation method and application thereof. The present invention uses a monoester compound and isooctyl nitrate, which have tert-butyl ester and carboxyl groups as end groups at both ends respectively and are connected by an alkyl chain of appropriate length, and further controls the usage ratio of the two. This achieves significant improvement in the cleaning performance and metal corrosion resistance of the alcohol-based fuel when added in low doses, improves the shortcomings of existing alcohol-based fuels, and has excellent environmental protection performance.

[0116] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0117] The foregoing is merely a specific embodiment of the present invention, which enables those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features claimed herein.

Claims

1. An alcohol-based environmentally friendly clean fuel additive, characterized in that: The alcohol-based environmentally friendly clean fuel additive includes the following components in parts by weight: 45-60 parts of monoester compound and 8-15 parts of isooctyl nitrate; The monoester compound is obtained by esterification reaction of any C9-C11 saturated straight-chain alkanedioic acid and tert-butyl alcohol.

2. The alcohol-based environmentally friendly clean fuel additive according to claim 1, characterized in that: The weight ratio of the monoester compound to the isooctyl nitrate is (4-5):

1.

3. The alcohol-based environmentally friendly clean fuel additive according to claim 1, characterized in that: The alcohol-based environmentally friendly clean fuel additive includes the following components in parts by weight: 54 parts of monoester compound and 12 parts of isooctyl nitrate.

4. The alcohol-based environmentally friendly clean fuel additive according to claim 1, characterized in that: The monoester compound includes at least two of mono-tert-butyl azelate, mono-tert-butyl sebacate, and mono-tert-butyl undecanedioate.

5. The alcohol-based environmentally friendly clean fuel additive according to claim 1, characterized in that: The monoester compound is composed of mono-tert-butyl azelate and mono-tert-butyl sebacate in a weight ratio of (20-30):(3-7).

6. The alcohol-based environmentally friendly clean fuel additive according to claim 1, characterized in that: The monoester compound is composed of azelaic acid mono-tert-butyl ester and undecane dioic acid mono-tert-butyl ester in a weight ratio of (20-30):(13-16).

7. The alcohol-based environmentally friendly clean fuel additive according to claim 1, characterized in that: The monoester compound is composed of mono-tert-butyl azelate, mono-tert-butyl sebacate and mono-tert-butyl undecanediolate in a weight ratio of 27:4:

15.

8. A method for preparing the alcohol-based environmentally friendly clean fuel additive according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The monoester compound and isooctyl nitrate are mixed to obtain a mixture; The mixed material is subjected to ultrasonic treatment to obtain the alcohol-based environmentally friendly clean fuel additive.

9. Use of the alcohol-based environmentally friendly clean fuel additive according to any one of claims 1 to 8 in the preparation of alcohol-based fuel.

10. An alcohol-based fuel, characterized in that: The alcohol-based fuel comprises methanol and an additive; the additive is the alcohol-based environmentally friendly clean fuel additive according to any one of claims 1 to 8.

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