Nonmetal gasoline antiknock agent and preparation method thereof

Abstract

The invention provides a non-metal gasoline antiknock agent and a preparation method thereof, and belongs to the technical field of antiknock agents, the non-metal gasoline antiknock agent comprises a compound shown as a formula I and a compound shown as a formula II, and the mass ratio of the compound shown as the formula I to the compound shown as the formula II is (7-10): (3-5). The effect of the prepared antiknock agent is obviously improved, furan structures possibly substituted at different positions can provide different combustion paths in the combustion process, and the synergistic interaction effect is achieved, so that the antiknock effect is obviously achieved, and the octane number of gasoline is obviously increased. The formula I of the imgabs 0 # is shown in the specification, and the formula II of the imgabs 1 # is shown in the specification.

Description

Technical Field

[0001] The invention relates to the technical field of antiknock agents, and in particular to a non-metallic gasoline antiknock agent and a preparation method thereof. Background Art

[0002] The knock phenomenon that occurs during the use of gasoline engines is mainly related to the composition and properties of gasoline. If gasoline is easily oxidized, the peroxide formed during the compression process of the gasoline engine is not easy to decompose, causing the gasoline's auto-ignition point to drop. It will burn in advance before the spark plug ignites, causing incomplete combustion of gasoline, strong vibrations in the engine, and knock. Therefore, the anti-knock property of gasoline is an important quality indicator for measuring gasoline quality. The higher the octane number, the better the anti-knock property of gasoline.

[0003] There are usually two ways to increase the octane number of gasoline. One is to produce gasoline with a high octane number through petroleum refining methods such as catalytic cracking, catalytic reforming, alkylation, etc., and then blend gasoline with different octane numbers to obtain suitable anti-knock gasoline for automobiles; the other is to add gasoline anti-knock agents to gasoline to increase the anti-knock agent of gasoline. The research and development history of gasoline anti-knock agents has experienced ash-containing metal additives such as lead, iron, manganese and alkali metals since the beginning of the 20th century. Such additives are prohibited from use due to their own toxicity, and because they are easy to produce sediments to block pipelines, affect the life of spark plugs, and easily cause the deactivation of three-way catalysts.

[0004] The main problems currently existing in gasoline non-metallic antiknock agents are: (1) Low efficiency. Large amounts are added to gasoline. For example, the amount of methyl tert-butyl ether commonly used in refineries is generally 10%.

[0005] (2) It has an adverse effect on gasoline. The addition of aniline gasoline antiknock agents will reduce the combustion rate of gasoline. At the same time, it will have a great impact on the induction period of gasoline and the sealing performance of some pipelines in the car.

[0006] Therefore, it is of great significance to develop a low-cost, high-efficiency non-metallic gasoline antiknock agent that has no adverse effects on gasoline.

[0007] Chinese patent publication CN 108587705 A discloses a non-metallic gasoline antiknock agent, wherein the effective ingredients and their weight proportions meet the requirements: 15-40 parts of ester octane improver, 10-20 parts of amine octane improver, 15-30 parts of ether octane improver, 10-20 parts of amide octane improver, 15-30 parts of organic phenol octane improver, 3-8 parts of alcohol octane improver, 3-8 parts of detergent dispersant, and 3-8 parts of cosolvent.

[0008] The Chinese patent authorization version CN 104711049 B discloses a new type of non-metallic gasoline antiknock agent, which is composed of oxygen-containing aromatic amine compounds, ester compounds and phenol compounds, and does not contain metal components; by weight, the oxygen-containing aromatic amine compounds are 20-50 parts, the ester compounds are 50-80 parts, and the phenol compounds are 0.01-1 parts.

[0009] However, the non-metallic gasoline antiknock agent prepared above does not significantly improve the octane number after being added to gasoline, which limits its application. Summary of the invention

[0010] The purpose of the present invention is to provide a non-metallic gasoline antiknock agent and a preparation method thereof, which has the characteristics of simple synthesis, good oil solubility, low corrosiveness, excellent antiknock, etc., reduces the occurrence of knock, has a synergistic effect, thereby significantly playing an antiknock effect, and significantly improves the octane number of gasoline.

[0011] The technical solution of the present invention is achieved in this way: The present invention provides a non-metallic gasoline antiknock agent having a structure as shown in Formula I and / or Formula II: Formula I; Formula II; When the non-metallic gasoline antiknock agent is the compound represented by Formula I and the compound represented by Formula II, the mass ratio thereof is 7-10:3-5.

[0012] The present invention further protects a method for preparing the above-mentioned non-metallic gasoline antiknock agent, comprising the following steps: S1. Mix o-methylphenol and dimethylamine, add formaldehyde, heat to reflux reaction, add sodium chloride, and continue the reaction to obtain intermediate 1, the structure of which is as follows: ; S2. Intermediate 1 and salicylic acid are mixed, a catalyst is added, and the mixture is heated under reflux to react to obtain intermediate 2, the structure of which is as follows: ; S3. The intermediate 2 and 3-chloromethylfuran or 2-chloromethylfuran are mixed, a base is added, and the mixture is heated and stirred for reaction to obtain the compound represented by formula I and the compound represented by formula II.

[0013] As a further improvement of the present invention, the mass ratio of o-cresol, dimethylamine, formaldehyde and sodium chloride in step S1 is 20-22:20-22:13-15:30-35.

[0014] As a further improvement of the present invention, the heating reflux reaction time in step S1 is 1-3 hours, and the continued reaction time is 15-25 minutes.

[0015] As a further improvement of the present invention, the molar ratio of the intermediate 1 to salicylic acid in step S2 is 1:1-1.1, and the added amount of the catalyst is 5-10 wt % of the mass of salicylic acid.

[0016] As a further improvement of the present invention, the catalyst in step S2 is concentrated sulfuric acid or p-toluenesulfonic acid.

[0017] As a further improvement of the present invention, the molar ratio of the intermediate 2, 3-chloromethylfuran or 2-chloromethylfuran in step S3 is 1:1-1.1.

[0018] As a further improvement of the present invention, the base in step S3 is selected from at least one of triethylamine, diethylamine, NaOH, KOH, and sodium carbonate.

[0019] As a further improvement of the present invention, the temperature of the heating and stirring reaction in step S3 is 50-60° C. and the time is 3-5 h.

[0020] The present invention has the following beneficial effects: The invention combines phenols, nitrides, substituted furans, esters, ethers and other groups together, thereby giving full play to the advantages of phenols, furans, esters, ethers and amine compounds, and has the characteristics of simple synthesis, good oil solubility, low corrosiveness, excellent anti-knock and the like. The hydroxyl group in the phenolic compound can provide hydrogen atoms to react with free radicals, thereby interrupting the oxidation reaction chain and playing an antioxidant role, which helps to improve the stability of the fuel. It can react with peroxides to decompose peroxides, reduce the influence of peroxides on fuel combustion, reduce the possibility of knocking, and also improve the octane number of gasoline. The substituted furan can improve the anti-knock of gasoline by preventing gasoline from spontaneous combustion. Explosion performance, added together with ester anti-knock agents into gasoline, can significantly increase the octane number of gasoline. Ester compounds contain oxygen atoms, which can provide additional oxygen during the combustion process, promote the combustion of fuel, and improve combustion efficiency. They have higher octane numbers and lower vapor pressures, which can improve the combustion performance of fuel and reduce engine wear. Ether compounds have higher octane numbers and can effectively improve the anti-knock performance of gasoline. The nitrogen atoms in amine compounds can provide lone pairs of electrons, react with free radicals, and generate inactive molecules, thereby inhibiting free radical chain reactions and reducing the occurrence of knock. They can effectively increase the octane number of gasoline and enhance the anti-knock performance of gasoline.

[0021] The present invention prepares two different compounds of formula I and formula II by substituted furans at different positions. After the two compounds are combined, the effect of the prepared antiknock agent is significantly improved. The furan structures substituted at different positions may provide different combustion paths during the combustion process, thereby adjusting the combustion speed and combustion stability of the fuel. The compound of formula I promotes the complete combustion of the fuel, and the compound of formula II can inhibit unstable combustion reactions, thereby reducing the occurrence of knock. It has a synergistic effect, thereby significantly playing an antiknock role and significantly improving the octane number of gasoline. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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. Example 1

[0023] This embodiment provides a method for preparing a non-metallic gasoline antiknock agent, a compound shown in Formula I.

[0024] The synthetic route is as follows: ; The following steps are involved: S1. Under nitrogen protection, 20 g of o-methylphenol and 62 g of a 33 wt% aqueous solution of dimethylamine were mixed, stirred at 30°C for 1 h, 37 g of a 37 wt% formaldehyde solution was added dropwise, heated to reflux for 1 h, 30 g of sodium chloride was added, and the reflux reaction was continued for 15 min. The organic phase was separated, washed, dried, and filtered. The filtrate was distilled under reduced pressure at 2.5 kPa to remove water, formaldehyde, and dimethylamine to obtain the product intermediate 1 with a yield of 94.2%; ESI-MS calculated value: C 13 H 23 N 2 O(M+H) + 223.17, measured value: 223.2.

[0025] NMR results: 1 H NMR (300 MHz, CDCl 3 )δ6.59 (s, 2H), 5.0 (br, 1H), 3.72 (s, 4H), 2.39 (s, 3H), 2.21 (s, 12H).

[0026] S2. 0.1 mol of intermediate 1 and 0.1 mol of salicylic acid were mixed and added to 200 mL of toluene, and concentrated sulfuric acid was added in an amount of 5 wt% of the mass of salicylic acid. The mixture was heated under reflux for 8 h, and the product was washed with NaOH solution until neutral. The organic phase was collected and dried, and the solvent was removed by vacuum distillation. The mixture was separated by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 75.3%; ESI-MS calculated value: C 20 H 27 N 2 O 3 (M+H) + 343.19, measured value: 343.2.

[0027] NMR results: 1 H NMR (300 MHz, CDCl 3 )δ7.82(d, J =5.6Hz, 1H), 7.39 (m, 1H), 6.87 (m, 1H), 6.75 (s, 2H), 6.80 (d, J =6.4Hz, 1H), 5.1 (br, 1H), 3.72 (s, 4H), 2.39 (s, 3H), 2.22 (s, 12H).

[0028] S3. 0.1 mol of intermediate 2 and 0.1 mol of 3-chloromethylfuran were mixed and added to 250 mL of acetonitrile, and 0.3 mol of triethylamine was added. The mixture was heated to 50°C and stirred for 3 h. The mixture was washed with water, and the organic phase was separated. The solvent was removed by vacuum distillation and separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound of formula I with a yield of 91.5%. ESI-MS calculated value: C 25 H 31 N 2 O 4 (M+H) + 423.22, measured value: 423.2.

[0029] NMR results: 1 H NMR (300 MHz, CDCl 3 )δ8.10(d, J =6.5Hz, 1H), 7.32 (m, 1H), 7.25 (d, J =5.1Hz, 1H), 7.15 (s, 1H), 6.85-6.92 (m, 2H), 6.68 (s, 2H), 6.22 (d, J =5.0Hz, 1H), 5.2 (s, 2H), 3.58 (s, 4H), 2.32 (s, 3H), 2.21 (s, 12H). Example 2

[0030] This embodiment provides a method for preparing a non-metallic gasoline antiknock agent, a compound shown in Formula I, comprising the following steps: S1. Under nitrogen protection, 22 g of o-methylphenol and 64 g of a 33 wt % aqueous solution of dimethylamine were mixed, stirred at a constant temperature of 30 ° C for 1 h, 39 g of a 37 wt % formaldehyde solution was added dropwise, heated to reflux for 3 h, 35 g of sodium chloride was added, and the reflux reaction was continued for 25 min. The organic phase was separated, washed, dried, and filtered. The filtrate was distilled under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde and dimethylamine to obtain the product intermediate 1 with a yield of 95.5%; S2. 0.1 mol of intermediate 1 and 0.11 mol of salicylic acid were mixed and added to 200 mL of toluene, and p-toluenesulfonic acid was added, wherein the amount of p-toluenesulfonic acid added was 10 wt % of the mass of salicylic acid, and the mixture was heated under reflux for 8 h. The product was washed with a NaOH solution until neutral, and the organic phase was collected and dried. The solvent was removed by distillation under reduced pressure, and the mixture was separated by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 76.9%; S3. 0.1 mol of intermediate 2 and 0.11 mol of 3-chloromethylfuran were mixed and added to 250 mL of acetonitrile, and 0.3 mol of diethylamine was added. The mixture was heated to 60°C and stirred for 5 h. The mixture was washed with water, and the organic phase was separated. The solvent was removed by distillation under reduced pressure, and the mixture was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound of formula I with a yield of 92.1%. Example 3

[0031] This embodiment provides a method for preparing a non-metallic gasoline antiknock agent, a compound shown in Formula II.

[0032] The synthetic route is as follows: ; The following steps are involved: S1. Under nitrogen protection, 21 g of o-methylphenol and 63 g of a 33 wt% aqueous solution of dimethylamine were mixed, stirred at a constant temperature of 30 ° C for 1 h, 38 g of a 37 wt% formaldehyde solution was added dropwise, heated to reflux for 2 h, 32 g of sodium chloride was added, and the reflux reaction was continued for 20 min. The organic phase was separated, washed, dried, and filtered. The filtrate was distilled under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde and dimethylamine to obtain the product intermediate 1 with a yield of 95.8%; S2. 0.1 mol of intermediate 1 and 0.105 mol of salicylic acid were mixed and added to 200 mL of toluene, and concentrated sulfuric acid was added in an amount of 7 wt % of the mass of salicylic acid. The mixture was heated under reflux for 8 h, and the product was washed with NaOH solution until neutral. The organic phase was collected and dried, and the solvent was removed by vacuum distillation. The mixture was separated by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 76.5%; S3. 0.1 mol of intermediate 2 and 0.105 mol of 2-chloromethylfuran were mixed and added to 250 mL of acetonitrile, and 0.3 mol of triethylamine was added. The mixture was heated to 55°C and stirred for 4 h. The mixture was washed with water, and the organic phase was separated. The solvent was removed by vacuum distillation and separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound of formula II with a yield of 92.0%. ESI-MS calculated value: C 25 H 31 N 2 O 4 (M+H) + 423.22, measured value: 423.2.

[0033] NMR results: 1 H NMR (300 MHz, CDCl 3 )δ8.13(d, J =6.5Hz, 1H), 7.40 (m, 1H), 7.32 (d, J =5.2Hz, 1H), 7.15 (s, 1H), 6.90-6.98 (m, 2H), 6.68 (s, 2H), 6.19 (d, J =4.8Hz, 1H), 5.22 (s, 2H), 3.57 (s, 4H), 2.34 (s, 3H), 2.25 (s, 12H). Example 4

[0034] This embodiment provides a method for preparing a non-metallic gasoline antiknock agent, a compound shown in Formula II, comprising the following steps: S1. Under nitrogen protection, 21 g of o-methylphenol and 63 g of a 33 wt% aqueous solution of dimethylamine were mixed, stirred at a constant temperature of 30 ° C for 1 h, 38 g of a 37 wt% formaldehyde solution was added dropwise, heated to reflux for 2 h, 32 g of sodium chloride was added, and the reflux reaction was continued for 20 min. The organic phase was separated, washed, dried, and filtered. The filtrate was distilled under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde and dimethylamine to obtain the product intermediate 1 with a yield of 95.7%; S2. 0.1 mol of intermediate 1 and 0.105 mol of salicylic acid were mixed and added to 200 mL of toluene, and p-toluenesulfonic acid was added. The amount of p-toluenesulfonic acid added was 8 wt % of the mass of salicylic acid. The mixture was heated under reflux for 8 h. The product was washed with NaOH solution until neutral. The organic phase was collected and dried. The solvent was removed by distillation under reduced pressure. The mixture was separated by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 75.9%; S3. 0.1 mol of intermediate 2 and 0.105 mol of 2-chloromethylfuran were mixed and added to 250 mL of acetonitrile, and 0.3 mol of NaOH was added. The mixture was heated to 55°C and stirred for 4 h. The mixture was washed with water, and the organic phase was separated. The solvent was removed by distillation under reduced pressure, and the mixture was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound of formula II with a yield of 92.2%. Example 5

[0035] A non-metallic gasoline antiknock agent comprises a compound represented by formula I and a compound represented by formula II in a mass ratio of 7:3. Example 6

[0036] A non-metallic gasoline antiknock agent comprises a compound represented by formula I and a compound represented by formula II in a mass ratio of 10:5. Example 7

[0037] A non-metallic gasoline antiknock agent comprises a compound represented by formula I and a compound represented by formula II in a mass ratio of 8:4.

[0038] Comparative Example 1 A non-metallic gasoline antiknock agent comprises a compound represented by formula I and a compound represented by formula II in a mass ratio of 10:1.

[0039] Comparative Example 2 A non-metallic gasoline antiknock agent comprises a compound represented by formula I and a compound represented by formula II in a mass ratio of 1:10.

[0040] Test Example 1 Using 75# aviation gasoline and 70# motor gasoline as base oils, at a temperature of 27°C, the non-metallic gasoline antiknock agents prepared in Examples 1, 3, 5-7 and Comparative Examples 1-2 were added to the base oils in an amount of 5wt% to observe the dissolution. The results are shown in Table 1.

[0041] Table 1 ; It can be seen from the above table that the non-metallic gasoline antiknock agent prepared in the present invention has good solubility in both 75# aviation gasoline and 70# motor gasoline.

[0042] Test Example 2 Using 75# aviation gasoline as the base oil, according to the method of GB / T 5096-85, a copper sheet with a purity of >99.5% was suspended and immersed in a base oil containing 5wt% of the non-metallic gasoline antiknock agent prepared in Examples 1, 3, 5-7 and Comparative Examples 1-2 and commercially available methylcyclopentadienyl tricarbonyl manganese for 2 hours. The results are shown in Table 2.

[0043] Table 2 ; Note: "Petroleum Products Copper Strip Corrosion Test Method" is graded according to the corrosion standard color plate, 1a, 1b means: Level 1 is a slight discoloration, a is light orange, almost the same as a newly polished copper strip; b is dark orange.

[0044] It can be seen from the above table that the non-metallic gasoline antiknock agent prepared by the present invention has no obvious corrosiveness.

[0045] Test Example 3 The effect on the anti-knock performance of gasoline was tested according to the gasoline octane number determination method of GB / T 5032-1995.

[0046] Test objects: non-metallic gasoline antiknock agents prepared in Examples 1, 3, 5-7 and Comparative Examples 1-2, and commercially available methylcyclopentadienyl manganese tricarbonyl.

[0047] Addition amount: 1wt%.

[0048] The octane number of 1# base gasoline (straight-run gasoline) is 67; the octane number of 2# base gasoline (a mixture of straight-run gasoline and 93# commercial gasoline in a volume ratio of 2:3) is 85; the octane number of 3# base gasoline (commercially available 90# gasoline) is 90.4.

[0049] Experimental conditions: room temperature 15℃, humidity 29%. Pressure 10215kPa, calculation correction value 5, lubricating oil pressure 193105kPa, lubricating oil temperature 135℃, intake temperature 40-50℃, mixture temperature 150℃, coolant temperature 100℃, amplification value 180, widening value 174, engine speed 600r / min, anti-knock effect measured on octane number tester.

[0050] The results are shown in Table 3.

[0051] Table 3 ; It can be seen from the above table that the non-metallic gasoline antiknock agents prepared in Examples 5-7 of the present invention can significantly increase the octane number of gasoline.

[0052] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A non-metallic gasoline antiknock agent, characterized in that: Having the structure shown in Formula I and / or Formula II: Formula I; Formula II; When the non-metallic gasoline antiknock agent is the compound represented by Formula I and the compound represented by Formula II, the mass ratio thereof is 7-10:3-5.

2. A method for preparing the non-metallic gasoline antiknock agent as claimed in claim 1, characterized in that: The following steps are involved: S1. Mix o-methylphenol and dimethylamine, add formaldehyde, heat to reflux reaction, add sodium chloride, and continue the reaction to obtain intermediate 1, the structure of which is as follows: ; S2. Intermediate 1 and salicylic acid are mixed, a catalyst is added, and the mixture is heated under reflux to react to obtain intermediate 2, the structure of which is as follows: ; S3. The intermediate 2 and 3-chloromethylfuran or 2-chloromethylfuran are mixed, a base is added, and the mixture is heated and stirred for reaction to obtain the compound represented by formula I and the compound represented by formula II.

3. The preparation method according to claim 2, characterized in that: The mass ratio of o-cresol, dimethylamine, formaldehyde and sodium chloride in step S1 is 20-22:20-22:13-15:30-35.

4. The preparation method according to claim 2, characterized in that: The heating reflux reaction time in step S1 is 1-3 hours, and the continued reaction time is 15-25 minutes.

5. The preparation method according to claim 2, characterized in that: In step S2, the molar ratio of the intermediate 1 to salicylic acid is 1:1-1.1, and the amount of the catalyst added is 5-10wt% of the mass of salicylic acid.

6. The preparation method according to claim 2, characterized in that: The catalyst in step S2 is concentrated sulfuric acid or p-toluenesulfonic acid.

7. The preparation method according to claim 2, characterized in that: The molar ratio of the intermediate 2, 3-chloromethylfuran or 2-chloromethylfuran in step S3 is 1:1-1.

1.

8. The preparation method according to claim 2, characterized in that: The base in step S3 is selected from at least one of triethylamine, diethylamine, NaOH, KOH and sodium carbonate.

9. The preparation method according to claim 2, characterized in that: The temperature of the heating and stirring reaction in step S3 is 50-60° C. and the time is 3-5 h.

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