Environment-friendly high-performance bio-new energy fuel and preparation method thereof

Abstract

The application discloses an environment-friendly high-performance biological new energy fuel and a preparation method thereof, and relates to the technical field of biological fuels.The application aims at the corrosion and swelling problems of methanol gasoline to rubber and metal of a fuel system, and a modified sulfonic acid-based benzotriazole is prepared through a specific process to be used as a metal corrosion inhibitor, and swelling inhibitors and other components are compounded.The formula utilizes sulfonic acid groups and carboxyl groups to enhance adsorption, forms a protective film to prevent corrosion, blocks a swelling path through an amphiphilic structure, optimizes the proportion of components to improve compatibility, effectively solves the material compatibility problem, and promotes the popularization of methanol gasoline.

Description

Technical Field

[0001] This invention relates to the field of biofuel technology, specifically to an environmentally friendly, high-performance biofuel and its preparation method. Background Technology

[0002] With the rapid development of the global transportation industry, the increasing depletion of oil resources has become a key bottleneck restricting the sustainable development of the industry, driving the research and application of alternative fuels. Against this backdrop, methanol gasoline, with its significant advantages such as being clean and environmentally friendly, low-cost, highly efficient, and having a wide range of raw material sources, is widely recognized as one of the most promising alternative fuels for automobiles. Countries around the world are investing heavily in related research, aiming to alleviate dependence on oil resources, reduce carbon emissions, and contribute to the transformation of the energy structure through its large-scale application.

[0003] Despite its numerous advantages as a substitute, methanol gasoline faces significant material compatibility challenges in practical applications. Methanol gasoline can cause corrosion, swelling, stickiness, brittleness, or softening of rubber and plastic components in automotive fuel systems, particularly affecting commonly used sealing materials such as nitrile rubber. Simultaneously, components like fiber gaskets can gradually soften due to prolonged contact, increasing the risk of fuel leaks. These issues not only affect the sealing performance and lifespan of fuel systems but also pose potential safety hazards, severely hindering the widespread adoption of methanol gasoline.

[0004] To address the aforementioned issues, this application constructs a methanol gasoline system that combines corrosion resistance, swelling resistance, and system stability by optimizing the formulation design and modifying functional components. Summary of the Invention

[0005] The purpose of this invention is to provide an environmentally friendly, high-performance biofuel and its preparation method to solve the problems existing in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] An environmentally friendly, high-performance biofuel comprises, by weight percentage: 10-40% methanol, 5-10% vegetable oil, 0.1-0.5% atomizing combustion control agent, 0.1-0.2% metal corrosion inhibitor, 0.1-0.2% swelling inhibitor, and the remainder being solvent oil.

[0008] Preferably, the metal corrosion inhibitor uses fuming sulfuric acid as a sulfonating agent to sulfonate benzotriazole via an electrophilic substitution reaction to obtain sulfonated benzotriazole; then, lauric acid is used to introduce a carboxyl group into the sulfonated benzotriazole to obtain modified sulfonated benzotriazole.

[0009] Preferably, the atomizing combustion control agent is a mixture of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate, wherein the mass ratio of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate is 7-9:1:1.5-2.

[0010] Preferably, the swelling inhibitor is a mixture of fatty alcohol and calcium petroleum sulfonate, wherein the mass ratio of fatty alcohol to calcium petroleum sulfonate is 3 to 3.5:1.

[0011] Preferably, the vegetable oil is a mixture of palm oil and nut oil; the weight ratio of the palm oil to the nut oil is 1 to 2:1.

[0012] Preferably, the sulfur content of the solvent oil is less than 10 mg / kg.

[0013] Preferably, the modified sulfonated benzotriazole comprises the following preparation steps: sulfonated benzotriazole and lauric acid are added to transformer oil in a volume of 12 to 15 times the mass of lauric acid, and the mixture is reacted at a temperature of 155 to 165°C for 7 to 8 hours. After the reaction is complete, the mixture is allowed to stand and separate into layers, and the lower layer product is taken to obtain the modified sulfonated benzotriazole.

[0014] Preferably, the molar ratio between the sulfonylbenzotriazole and lauric acid is 1.1 to 1.3:1.

[0015] Preferably, the sulfonyl benzotriazole comprises the following preparation steps: concentrated sulfuric acid, 50% fuming sulfuric acid, and mercuric sulfate powder are placed in an ice bath and stirred until homogeneous. Then, benzotriazole at a mass of 40-45 times that of the mercuric sulfate powder is gradually added. After the addition is complete, the mixture is stirred for 10-15 minutes and reacted at a temperature of 110-120°C for 1.5-2 hours. After the reaction is complete, the temperature is lowered to 95-100°C, then lowered to 0-5°C and allowed to stand for 4-5 hours. The mixture is filtered and washed 3-5 times with deionized water, recrystallized with deionized water, and the recrystallized product is dried at a temperature of 80-85°C to obtain sulfonyl benzotriazole.

[0016] Preferably, the mass ratio of concentrated sulfuric acid, 50% fuming sulfuric acid and mercuric sulfate powder is 28-32:98-102:1.

[0017] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0018] This application uses modified sulfonic acid benzotriazole as a metal corrosion inhibitor. By introducing the carboxyl group of lauric acid and the sulfonic acid group formed by sulfonation, a conjugated system of benzotriazole with "multiple adsorption centers" is constructed. The N atom provides the basis for chemical adsorption. The polar groups of carboxyl group and sulfonic acid group further enhance the binding force with the metal surface, significantly improve the corrosion inhibition efficiency, and solve the problem of insufficient adsorption capacity of traditional benzotriazole in the oil phase.

[0019] Components containing sulfonic acid polar groups (including modified sulfonic acid benzotriazole and swelling inhibitors) form a strong protective film by means of a structure in which "polar ends are adsorbed on the rubber surface and non-polar ends face the oil phase". This film specifically blocks the swelling path of "gasoline wetting-methanol penetration" and prevents methanol gasoline from corroding nitrile rubber from a mechanistic perspective.

[0020] The lipophilicity of lauric acid and the alcoholophilicity of sulfonic acid groups work synergistically to make the modified product amphiphilic, which enhances the emulsification compatibility of methanol with solvent oil and vegetable oil, avoids stratification, and improves the uniformity of dispersion of each functional component in the system, ensuring that the corrosion inhibition, anti-swelling and other effects are effectively exerted. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0022] Example 1

[0023] S1. Concentrated sulfuric acid, 50% fuming sulfuric acid, and mercuric sulfate powder were mixed in an ice bath at a mass ratio of 28:98:1. Then, benzotriazole powder with a mass ratio of 40 times that of mercuric sulfate powder was gradually added. After the addition was completed, the mixture was stirred for 10 minutes and reacted at 110°C for 1.5 hours. After the reaction was completed, the temperature was lowered to 95°C, then to 0°C and allowed to stand for 4 hours. The mixture was filtered, washed three times with deionized water, recrystallized with deionized water, and dried at 80°C to obtain sulfonated benzotriazole.

[0024] S2. Add sulfonated benzotriazole and lauric acid to transformer oil with a molar ratio of 1.1:1 and 12 times the mass of lauric acid. React at 155℃ for 7 hours. After the reaction is complete, allow the mixture to stand and separate into layers. Take the lower layer product to obtain modified sulfonated benzotriazole.

[0025] S3. Mix the following components in the following proportions: 10% methanol, 5% vegetable oil, 0.1% atomizing combustion control agent, 0.1% metal corrosion inhibitor, 0.1% swelling inhibitor, and the remainder being solvent oil. The atomizing combustion control agent is a mixture of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate, with a mass ratio of 7:1:1.5. The vegetable oil is a mixture of palm oil and nut oil, with a weight ratio of 1:1. The swelling inhibitor is a mixture of fatty alcohol and calcium petroleum sulfonate, with a mass ratio of 3:1.

[0026] Example 2

[0027] S1. Concentrated sulfuric acid, 50% fuming sulfuric acid, and mercuric sulfate powder were mixed in an ice bath at a mass ratio of 30:100:1. Then, benzotriazole powder with a mass ratio of 42.5 times that of mercuric sulfate powder was gradually added. After the addition was completed, the mixture was stirred for 12.5 min and reacted at 115℃ for 1.8 h. After the reaction was completed, the temperature was lowered to 98℃, then to 2℃ and allowed to stand for 4.5 h. The mixture was filtered, washed 4 times with deionized water, recrystallized with deionized water, and dried at 85℃ to obtain sulfonated benzotriazole.

[0028] S2. Add sulfonated benzotriazole and lauric acid to transformer oil at a molar ratio of 1.2:1, in an amount 13.5 times the mass of lauric acid. React at 160℃ for 7.5 hours. After the reaction is complete, allow the mixture to stand and separate into layers. Take the lower layer product to obtain modified sulfonated benzotriazole.

[0029] S3. Mix the following components in the following proportions: 25% methanol, 7.5% vegetable oil, 0.3% atomizing combustion control agent, 0.15% metal corrosion inhibitor, 0.15% swelling inhibitor, and the remainder being solvent oil. The atomizing combustion control agent is a mixture of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate, with a mass ratio of 8:1:1.75. The vegetable oil is a mixture of palm oil and nut oil, with a weight ratio of 1.5:1. The swelling inhibitor is a mixture of fatty alcohol and calcium petroleum sulfonate, with a mass ratio of 3.25:1.

[0030] Example 3

[0031] S1. Concentrated sulfuric acid, 50% fuming sulfuric acid and mercuric sulfate powder were mixed in an ice bath at a mass ratio of 32:102:1. Then, benzotriazole powder with a mass ratio of 45 times that of mercuric sulfate powder was gradually added. After the addition was completed, the mixture was stirred for 15 minutes and reacted at 120°C for 2 hours. After the reaction was completed, the temperature was lowered to 100°C, then to 5°C and allowed to stand for 5 hours. The mixture was filtered and washed 5 times with deionized water. It was recrystallized with deionized water and dried at 85°C to obtain sulfonated benzotriazole.

[0032] S2. Add sulfonated benzotriazole and lauric acid to transformer oil at a molar ratio of 1.3:1, in a volume 15 times the mass of lauric acid. React at 165°C for 8 hours. After the reaction is complete, allow the mixture to stand and separate into layers. Take the lower layer product to obtain the modified sulfonated benzotriazole.

[0033] S3. Mix the following components in the following proportions: 40% methanol, 10% vegetable oil, 0.5% atomizing combustion control agent, 0.2% metal corrosion inhibitor, 0.2% swelling inhibitor, and the remainder being solvent oil. The atomizing combustion control agent is a mixture of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate, with a mass ratio of 9:1:2. The vegetable oil is a mixture of palm oil and nut oil, with a weight ratio of 2:1. The swelling inhibitor is a mixture of fatty alcohol and calcium petroleum sulfonate, with a mass ratio of 3.5:1.

[0034] Example 4

[0035] The difference from Example 2 is that the metal corrosion inhibitor used in this example is benzotriazole;

[0036] Example 5

[0037] The difference from Example 2 is that the metal corrosion inhibitor used in Example 2 is sulfonated benzotriazole;

[0038] Example 6

[0039] The difference from Example 2 is that lauric acid is used as the metal corrosion inhibitor in this example;

[0040] Example 7

[0041] The difference from Example 2 is that the metal corrosion inhibitor in this example is prepared by mixing lauric acid and sulfonated benzotriazole in a molar ratio of 1:1.

[0042] Example 8

[0043] The difference from Example 2 is that the metal corrosion inhibitor in Example 2 is prepared by mixing lauric acid and benzotriazole in a molar ratio of 1:1.

[0044] air permeability test

[0045] The performance evaluation experiments of swelling inhibition of the bio-new energy fuels prepared in Examples 1 to 8 were carried out in accordance with GB / T1690-2006 Test Method for Liquid Resistance of Vulcanized Rubber or Thermoplastic Rubber, mainly examining the mass change rate to measure the swelling inhibition ability.

[0046] The corrosion level of copper strips was tested using GB / T 5096-2017, the test method for copper strip corrosion of petroleum products.

[0047] The test results are shown in Table 1 below;

[0048] Table 1

[0049]

[0050]

[0051] A comparison of the experimental data from Examples 1 to 3 in Table 1 shows that the biofuels prepared by this invention all have good swelling inhibition and low corrosivity.

[0052] As can be seen from Examples 6 and 8, the addition of lauric acid without grafting leads to increased corrosivity, mainly due to the decrease in its adsorption capacity, which in turn leads to a decrease in its adhesion capacity, resulting in its inability to form a protective film on the metal surface.

[0053] The mass change rate in Examples 4 to 8 all showed significant changes, mainly because the structure of polar end adsorbing on the rubber surface and non-polar end facing the oil phase was not formed, which resulted in the metal corrosion inhibitor being unable to block on the rubber surface, or the barrier formed was easily penetrated.

[0054] The saturated vapor pressure test was performed using the Reid method, and the test results are shown in Table 2 below.

[0055] For the water resistance test, 5% water was added to each of the materials prepared in the above examples. The test results are shown in Table 2 below:

[0056] Table 2

[0057]

[0058]

[0059] The test results in Table 2 clearly show that the fuel of this invention exhibits excellent water resistance. When the moisture content is below 5%, the fuel does not show any stratification, demonstrating significant water resistance. Simultaneously, this fuel also possesses good low vapor resistance. It is worth mentioning that, according to the test results, it is less affected by temperature fluctuations, and can provide users with the same convenience in use, storage, and transportation as commercial gasoline.

[0060] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. An environmentally friendly high-performance bio-new energy fuel, characterized in that, By weight percentage, it includes: 10-40% methanol, 5-10% vegetable oil, 0.1-0.5% atomizing combustion control agent, 0.1-0.2% metal corrosion inhibitor, 0.1-0.2% swelling inhibitor, and the remainder is solvent oil; The metal corrosion inhibitor uses fuming sulfuric acid as a sulfonating agent to sulfonate benzotriazole via an electrophilic substitution reaction to obtain sulfonated benzotriazole; then, lauric acid is used to introduce a carboxyl group into the sulfonated benzotriazole to obtain modified sulfonated benzotriazole. The swelling inhibitor is a mixture of fatty alcohol and calcium petroleum sulfonate, wherein the mass ratio of fatty alcohol to calcium petroleum sulfonate is 3~3.5:1; The modified sulfonate benzotriazole includes the following preparation steps: sulfonate benzotriazole and lauric acid are added to transformer oil in a volume of 12 to 15 times the mass of lauric acid, and the reaction is carried out at a temperature of 155 to 165°C for 7 to 8 hours. After the reaction is completed, the mixture is allowed to stand and separate into layers. The lower layer product is then taken to obtain the modified sulfonate benzotriazole. The molar ratio between the sulfonic acid benzotriazole and lauric acid is 1.1~1.3:1; The sulfonated benzotriazole comprises the following preparation steps: concentrated sulfuric acid, 50% fuming sulfuric acid and mercuric sulfate powder are placed in an ice bath and stirred until well mixed. Then, benzotriazole with a mass of 40 to 45 times that of mercuric sulfate powder is gradually added. After the addition is complete, the mixture is stirred for 10 to 15 minutes and reacted at a temperature of 110 to 120°C for 1.5 to 2 hours. After the reaction is complete, the temperature is lowered to 95 to 100°C, then lowered to 0 to 5°C and allowed to stand for 4 to 5 hours. The mixture is filtered and washed 3 to 5 times with deionized water, recrystallized with deionized water, and the recrystallized product is dried at a temperature of 80 to 85°C to obtain sulfonated benzotriazole. The mass ratio of concentrated sulfuric acid, 50% fuming sulfuric acid, and mercuric sulfate powder is 28~32:98~102:

1.

2. The environmentally friendly, high-performance biofuel according to claim 1, characterized in that, The atomizing combustion control agent is a mixture of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate, wherein the mass ratio of polymethyl phenyl ethanol, polymethyl phenyl ether, and diethyl malonate is 7~9:1:1.5~2.

3. The environmentally friendly, high-performance biofuel according to claim 1, characterized in that, The vegetable oil is a mixture of palm oil and nut oil; the weight ratio of the palm oil to the nut oil is 1~2:

1.

4. The environmentally friendly, high-performance biofuel according to claim 1, characterized in that, The sulfur content of the solvent oil is less than 10 mg / kg.

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