Antirust agent composition for methanol fuel

Abstract

The invention relates to a methanol fuel antirust agent composition. The composition comprises boric acid ester, benzotriazole, an imidazoline derivative, a dinonyl naphthalene sulfonic acid derivative and base oil, the structure of the imidazoline derivative is shown in the specification, and the structure of the dinonyl naphthalene sulfonic acid derivative is shown in the specification. The corrosion inhibitor has an excellent corrosion inhibition effect on copper, aluminum, zinc, tin, steel and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of rust preventive, and particularly relates to a methanol fuel rust preventive composition. BACKGROUND

[0002] The alternative use of renewable and environmentally friendly fuels can reduce dependence on oil.

[0003] Among many liquid alternative fuels, methanol fuel is concerned and valued. The production of methanol from raw coal not only has low cost, but also does not cause serious harm to the environment.

[0004] However, methanol also has some disadvantages when used as an internal combustion engine fuel, and strong corrosion is one of the most important disadvantages. Methanol will have some acidic substances in the production process, and will absorb a small amount of moisture during storage, and will produce organic acids through air oxidation. Therefore, it has corrosion to some non-ferrous metals such as copper, aluminum, etc.

[0005] In addition, methanol will produce incomplete combustion products formaldehyde and formic acid in the combustion process, which will corrode some parts in the engine fuel supply system and the intake system after mixing with water vapor in the air, causing nozzle blockage and affecting the normal work of the engine. Therefore, rust and corrosion inhibitors need to be added to methanol fuel to improve the performance of methanol. The commonly used rust and corrosion inhibitors for methanol fuel include benzotriazole, methyl benzotriazole, etc., but this type of rust and corrosion inhibitor is mainly aimed at the rust and corrosion prevention of copper and other non-ferrous metals, and has poor rust and corrosion prevention ability for ferrous metals. Oil-soluble additives such as sulfonates, organic carboxylic acids, and imidazoline derivatives for rust and corrosion prevention of ferrous metals cannot be dissolved in methanol, so that methanol fuel cannot simultaneously satisfy the rust and corrosion prevention of copper, steel, aluminum, zinc, tin and other metals.

[0006] Chinese patent application CN113430021A discloses a methanol fuel additive and a preparation method thereof. The components of the methanol fuel additive include rust and corrosion inhibitors, detergent dispersants, etc. The rust and corrosion inhibitors include benzotriazole, methyl benzotriazole and ammonium benzoate. Since the rust and corrosion prevention components for copper are used in the patent, it is difficult to effectively protect ferrous metals such as steel. SUMMARY

[0007] In view of the deficiencies in the prior art, the application provides a methanol fuel rust preventive composition.

[0008] In order to achieve the purpose of the application, the technical scheme adopted is as follows:

[0009] The raw materials of the composition include borate, benzotriazole, imidazoline derivative, dinonylnaphthalene sulfonic acid derivative and base oil.

[0010] Preferably, the composition comprises the following components by weight percentage:

[0011]

[0012]

[0013] Preferably, the composition comprises the following components by weight percentage:

[0014]

[0015] Preferably, the borate is selected from one or more of monoethanolamine borate, diethanolamine borate, and triethanolamine borate by weight parts.

[0016] Preferably, the base oil is one or more of API I, II, and III lubricating oil base oils.

[0017] Preferably, the imidazoline derivative has the following structure:

[0018]

[0019] In the formula, R1 is a phenyl group; R2 is a C8-C12 aliphatic hydrocarbon group, and n is 7-20.

[0020] Preferably, the method for preparing the imidazoline derivative comprises:

[0021] (1) adding an aromatic carboxylic acid and a polyene polyamine in a reactor to obtain an imidazoline derivative intermediate;

[0022] (2) adding an alcohol ether carboxylic acid to the imidazoline intermediate, reacting, and distilling under reduced pressure to obtain the imidazoline derivative.

[0023] Preferably, the reaction in step (1) is carried out by heating to 140-160°C for 1-3 hours, and then heating to 200-240°C for 4-8 hours.

[0024] Preferably, the reaction in step (2) is carried out by cooling the imidazoline intermediate to 130-150°C, adding an alcohol ether carboxylic acid, and reacting for 3-5 hours.

[0025] Preferably, the method for preparing the imidazoline derivative comprises:

[0026] (1) adding an aromatic carboxylic acid and a polyene polyamine in a reactor, heating to 140-160°C for 1-3 hours, and then heating to 200-240°C for 4-8 hours to obtain an imidazoline derivative intermediate;

[0027] (2) After the imidazoline intermediate is cooled to 130-150°C, the alcohol ether carboxylic acid is added, and the reaction is carried out for 3-5 hours. After the reaction is completed, the imidazoline derivative is obtained by distillation under reduced pressure.

[0028] The structure of the dinonyl naphthalene sulfonic acid derivative is shown in the following formula:

[0029]

[0030] In the formula, R3 is a C8-C12 aliphatic hydrocarbon group, and m is 7-20.

[0031] Preferably, the preparation method of the dinonyl naphthalene sulfonic acid derivative comprises:

[0032] (1) The hydrocarbon-substituted aromatic sulfonic acid is mixed with phosphorus oxychloride, and the reaction is carried out to generate arylsulfonyl chloride.

[0033] (2) Pyridine is added, stirring is carried out, the reaction temperature is kept at 5-10°C, the fatty alcohol polyoxyethylene ether is added in 3 batches within 30 minutes, the reaction is carried out for 2-6 hours, and then concentrated hydrochloric acid is added to continue stirring for 1-3 hours.

[0034] (3) Dichloromethane and water are added to the reaction product of step (2), the layers are separated, the dichloromethane layer is washed with water until neutral, and then dichloromethane is removed by distillation under reduced pressure to obtain the product.

[0035] Preferably, the reaction in step (1) is carried out by heating to 170-190°C for 2-5 hours.

[0036] Preferably, in step (2), after pyridine is added and stirring is carried out, the reaction temperature is kept at 5-10°C, the fatty alcohol polyoxyethylene ether is added in 3 batches within 30 minutes, and the reaction is carried out for 2-6 hours.

[0037] Preferably, the preparation method of the dinonyl naphthalene sulfonic acid derivative comprises:

[0038] (1) The hydrocarbon-substituted aromatic sulfonic acid is mixed with phosphorus oxychloride, and the reaction is carried out by heating to 170-190°C for 2-5 hours to generate arylsulfonyl chloride.

[0039] (2) Pyridine is added, stirring is carried out, the reaction temperature is kept at 5-10°C, the fatty alcohol polyoxyethylene ether is added in 3 batches within 30 minutes, the reaction is carried out for 2-6 hours, and then concentrated hydrochloric acid is added to continue stirring for 1-3 hours.

[0040] (3) Dichloromethane and water are added to the reaction product of step (2), the layers are separated, the dichloromethane layer is washed with water until neutral, and then dichloromethane is removed by distillation under reduced pressure to obtain the product.

[0041] Another object of the present application is to provide a preparation method of the above-mentioned composition, which comprises mixing and stirring the borate ester, the benzotriazole, the imidazoline derivative, the dinonyl naphthalene sulfonic acid derivative, and the base oil to obtain the product.

[0042] Preferably, the temperature of the stirring is 60-120℃, and the time of the stirring is 1-3 hours.

[0043] It is another object of the present application to provide the use of the above composition in preparing a methanol fuel rust inhibitor.

[0044] Compared with the prior art, the present application has the following advantages:

[0045] The methanol fuel rust inhibitor composition of the present application is easily soluble in methanol fuel, and has excellent rust and corrosion prevention performance, and excellent corrosion inhibition effect on copper, aluminum, zinc, tin, steel and the like. DETAILED DESCRIPTION

[0046] The present application will be further described below in conjunction with specific embodiments.

[0047] Example 1

[0048] A methanol fuel rust inhibitor composition, the content of its component agents being shown in Table 1, the structural formulae of the imidazoline derivative and the dinonyl naphthalene sulfonic acid derivative being shown in formula (3) and formula (4) respectively. The preparation method is to mix borate ester, benzotriazole, imidazoline derivative, dinonyl naphthalene sulfonic acid derivative and base oil and stir to obtain; the stirring temperature is 60℃, and the stirring time is 3 hours.

[0049] Table 1 Composition table of the rust inhibitor

[0050]

[0051] The preparation method of formula (3) is as follows:

[0052] (1) 97g of benzoic acid and 103g of diethylenetriamine are added into a reactor, heated to 140℃ and reacted for 3 hours, then heated to 200℃ and reacted for 8 hours to obtain an imidazoline derivative intermediate.

[0053] (2) The imidazoline derivative intermediate is cooled to 130℃, then 552g of dodecanol polyoxyethylene ether carboxylic acid (7EO) is added, and kept at 130℃ for 5 hours. After the reaction is completed, it is distilled under reduced pressure to obtain.

[0054] The preparation method of formula (4) is as follows:

[0055] Step 1, 460g of dinonyl naphthalene sulfonic acid is added into a reactor, and 73g of phosphorus oxychloride is added, heated to 190℃ and reacted for 5h to generate aryl sulfonic acid chloride.

[0056] Step 2, add 1526 g of pyridine into the reactor, start mechanical stirring to make the arylsulfonyl chloride generated in step 1 completely dissolved. Keep the reaction temperature at 10°C, add 1066 g of dodecanol polyoxyethylene ether (20EO) in 3 batches within 30 minutes, after adding, react for 6 hours, then add 432 g of concentrated hydrochloric acid and continue stirring for 3 hours.

[0057] Step 3, add 508 g of dichloromethane and 508 g of water into the reactant of step 2, after layering, transfer the dichloromethane layer to a water washing kettle, wash to neutral. Finally transfer to a distillation kettle, remove dichloromethane under reduced pressure to obtain a dinonyl naphthalene sulfonic acid derivative.

[0058] Example 2

[0059] A methanol fuel rust inhibitor composition, the component content of which is shown in Table 2, taking the total weight as 100%, the imidazoline derivative and dinonyl naphthalene sulfonic acid derivative are shown in formula (5) and formula (6) respectively. The preparation method is to mix borate, benzotriazole, imidazoline derivative, dinonyl naphthalene sulfonic acid derivative and base oil and stir to obtain; the stirring temperature is 90°C, and the stirring time is 2 hours.

[0060] Table 2 Rust inhibitor composition ingredient table

[0061]

[0062] The preparation method of formula (5) is as follows:

[0063] (1) Add 97 g of benzoic acid and 103 g of diethylenetriamine into the reactor, heat to 140°C and react for 3 hours, then heat to 200°C and react for 8 hours to obtain an imidazoline derivative intermediate.

[0064] (2) After cooling the imidazoline derivative intermediate to 130°C, add 533 g of dodecanol polyoxyethylene ether carboxylic acid (9EO), keep the temperature at 130°C and react for 5 hours, after the reaction is completed, distill under reduced pressure to obtain a rust inhibitor for methanol fuel.

[0065] The preparation method of formula (6) is as follows:

[0066] Step 1, add 460 g of dinonyl naphthalene sulfonic acid into the reactor, and add 73 g of phosphorus oxychloride, heat to 190°C and react for 5 hours to generate arylsulfonyl chloride.

[0067] Step 2, add 1147 g of pyridine into the reactor, start mechanical stirring to make the arylsulfonyl chloride generated in step 1 completely dissolved. Keep the reaction temperature at 10°C, add 687 g of decanol polyoxyethylene ether (12EO) in 3 batches within 30 minutes. After adding, react for 6 hours, then add 432 g of concentrated hydrochloric acid and continue stirring for 3 hours.

[0068] Step 3, add 382 g dichloromethane and 382 g water to the reactant of step 2, after layering, transfer the dichloromethane layer to the water washing kettle, wash to neutral. Finally transfer to the distillation kettle, remove dichloromethane by distillation under reduced pressure to obtain dinonyl naphthalene sulfonic acid derivative.

[0069] Example 3

[0070] A methanol fuel rust inhibitor composition, the component content of which is shown in Table 3, based on 100% of the total weight, the structural formula of imidazoline derivative and dinonyl naphthalene sulfonic acid derivative are shown in formula (7) and formula (8) respectively. The preparation method is to mix borate, benzotriazole, imidazoline derivative, dinonyl naphthalene sulfonic acid derivative and base oil and stir to obtain; the stirring temperature is 120℃, and the stirring time is 1 hour.

[0071] Table 3 Rust inhibitor composition ingredient table

[0072]

[0073]

[0074] The preparation method of formula (7) is as follows:

[0075] (1) Add 97 g benzoic acid and 103 g diethylenetriamine to the reactor, heat to 140℃ and react for 3 hours, then heat to 200℃ and react for 8 hours to obtain imidazoline derivative intermediate.

[0076] (2) After the imidazoline derivative intermediate is cooled to 130℃, 572 g octanol polyoxyethylene ether carboxylic acid (10EO) is added, and the reaction is maintained at 130℃ for 5 hours. After the reaction is completed, distillation under reduced pressure is performed to obtain the rust inhibitor for methanol fuel.

[0077] The preparation method of formula (8) is as follows:

[0078] Step 1, add 460 g dinonyl naphthalene sulfonic acid to the reactor, and add 73 g phosphorus oxychloride, heat to 190℃ and react for 5h to generate arylsulfonyl chloride.

[0079] Step 2, add 411 g pyridine to the reactor, start mechanical stirring to make the arylsulfonyl chloride generated in step 1 completely dissolved. Keep the reaction temperature at 10℃, and add 898 g octanol polyoxyethylene ether (7EO) in 3 batches within 30 minutes. After adding, react for 6h, then add 432 g concentrated hydrochloric acid and continue stirring for 3h.

[0080] Step 3, add 300 g dichloromethane and 300 g water to the reactant of step 2, after layering, transfer the dichloromethane layer to the water washing kettle, wash to neutral. Finally transfer to the distillation kettle, remove dichloromethane by distillation under reduced pressure to obtain dinonyl naphthalene sulfonic acid derivative.

[0081] Comparative Example 1

[0082] Comparative Example 1 was compared with Example 3, without adding the rust inhibitor, as a blank group, to investigate the effect of adding the corrosion inhibitor on the rust and corrosion resistance of the methanol fuel.

[0083] Comparative Example 2

[0084] A benzotriazole commonly used in methanol fuel was used as the rust inhibitor, wherein the benzotriazole was 90%, and the remaining components were methanol.

[0085] Comparative Example 3

[0086] To compare the solubility of the rust inhibitor composition of the present application in methanol, a traditional oil-soluble imidazoline derivative and dinonyl naphthalene sulfonic acid derivative were used, i.e., a methanol fuel rust inhibitor composition was prepared with boric acid monoethanolamine ester, benzotriazole, heptadecenyl aminoethyl imidazoline, neutral dinonyl naphthalene sulfonic acid barium, and MVI150 base oil. The component content was 100% of the total weight, as shown in Table 4.

[0087] Table 4 Rust Inhibitor Composition Ingredient Table

[0088] composition content monoethanolamine borate 10％ benzotriazole 40％ heptadecenyl aminoethyl imidazoline 30％ neutral barium dinonylnaphthalene sulfonate 10％ mvi150 base oil 10％

[0089] Performance evaluation: the rust inhibitors prepared in Comparative Examples 2, 3 and Examples 1-3 were added to methanol at 0.3% (mass fraction), and first the solubility was observed, and then a variety of test pieces were subjected to rust test according to GB / T 34548-2017 "Automobile Methanol Gasoline Additives" Appendix A (Metal Corrosion Test Glassware Method), the smaller the change value of the test piece, the better the rust resistance.

[0090] Table 5 Solubility and Rust Resistance

[0091]

[0092] From table 5, it can be seen that when no rust and corrosion inhibitor is used in the comparative example 1, the test pieces of red copper, steel, zinc, tin and brass are severely rusted, and the change value of the test pieces is far beyond the index requirement of GB / T 34548-2017 “Automobile methanol gasoline additive”. After adding commonly used benzotriazole as a rust and corrosion inhibitor in the comparative example 2, the corrosion resistance of each type of test piece is improved to a certain extent, but the change value of the test pieces of steel, zinc and tin is still unqualified. In the comparative example 3, water-soluble rust inhibitor boric acid monoethanolamine ester, oil-soluble rust inhibitor heptadecenyl aminoethyl imidazoline and neutral barium dinonylnaphthalene sulfonate are added on the basis of the comparative example 2, and the change value of the test pieces of red copper, steel, zinc, tin and brass is unqualified, which indicates that the addition of oil-soluble rust inhibitor cannot enhance the rust and corrosion resistance of methanol fuel, but has certain negative influence. Compared with the above comparative examples, the addition of the rust inhibitor composition prepared in the examples 1-3 of the present application greatly improves the rust and corrosion resistance of methanol fuel, and the change value of the test pieces of red copper, steel, zinc, tin and brass meets the index requirement.

Claims

1. A methanol fuel rust inhibitor composition, characterized in that, The raw materials for the composition include borate esters, benzotriazole, imidazoline derivatives, dinonylnaphthalenesulfonic acid derivatives, and base oils.

2. The composition according to claim 1, characterized in that, The composition comprises the following components by weight percentage:

3. The composition according to claim 1, characterized in that, The composition comprises the following components by weight percentage:

4. The composition according to claim 1, characterized in that, Based on parts by weight, the borate ester is selected from one or more of monoethanolamine borate, diethanolamine borate, and triethanolamine borate.

5. The composition according to claim 1, characterized in that, The base oil is one or more of API Group I, II, and III lubricating oil base oils.

6. The composition according to claim 1, characterized in that, The structure of the imidazoline derivative is shown in formula (1): In formula (1), R1 is phenyl; R2 is an aliphatic hydrocarbon group of C8 to C12, where n is 7-20.

7. The composition according to claim 1, characterized in that, The preparation method of the imidazoline derivative includes: (1) Add aromatic carboxylic acid and polyene polyamine to a reactor and react to obtain an imidazoline derivative intermediate; (2) Add alcohol ether carboxylic acid to the imidazoline intermediate, react, and distill under reduced pressure to obtain the imidazoline derivative.

8. The composition according to claim 7, characterized in that, The reaction described in step (1) is to heat to 140℃~160℃ and react for 1~3 hours, and then heat to 200℃~240℃ and react for 4~8 hours.

9. The composition according to claim 7, characterized in that, The reaction described in step (2) involves cooling the imidazoline intermediate to 130℃~150℃, adding an alcohol ether carboxylic acid, and reacting for 3~5 hours.

10. The composition according to claim 1, characterized in that, The structure of the dinonylnaphthalenesulfonic acid derivative is shown in formula (2) below: In formula (2), R3 is an aliphatic hydrocarbon group of C8 to C12, where m is 7 to 20.

11. The composition according to claim 10, characterized in that, The preparation method of the dinonylnaphthalenesulfonic acid derivative includes: (1) Mix hydrocarbon-substituted aromatic sulfonic acid with phosphorus oxychloride and react to generate aromatic sulfonyl chloride; (2) Add pyridine, stir, and keep the reaction temperature at 5-10℃. Add fatty alcohol polyoxyethylene ether, react for 2-6 hours, and then add concentrated hydrochloric acid and continue stirring for 1-3 hours. (3) Add dichloromethane and water to the reactants in step (2), separate the layers, wash the dichloromethane layer with water until neutral, and remove the dichloromethane by vacuum distillation to obtain the product.

12. The composition according to claim 11, characterized in that, The reaction described in step (1) involves heating to 170℃-190℃ and reacting for 2-5 hours.

13. The composition according to claim 11, characterized in that, In step (2), add pyridine, stir, and keep the reaction temperature at 5-10℃. Add fatty alcohol polyoxyethylene ether in 3 batches within 30 minutes and react for 2-6 hours.

14. A method for preparing the composition according to any one of claims 1-13, characterized in that, The product is obtained by mixing and stirring borate ester, benzotriazole, imidazoline derivative, dinonylnaphthalenesulfonic acid derivative and base oil.

15. The preparation method according to claim 14, characterized in that, The stirring temperature is 60–120°C, and the stirring time is 1–3 hours.

16. Use of the composition according to any one of claims 1-13 in the preparation of a methanol fuel rust inhibitor.

Images