Amine hydrate carbon dioxide carbonylation antiknock agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of fuel additives, in particular to an amine hydrate carbon dioxide carbonylation antiknock agent and a preparation method and application thereof.The antiknock agent is obtained by mixing and reacting an amine mixture, a hydrated electron base solution and carbon dioxide, and the mass ratio of the amine mixture to the hydrated electron base solution to the carbon dioxide is (6.0-9.0): (0.8-1.2): (7.0-11.0); the problem of environmental pollution of a traditional antiknock agent and the technical problem of CO2 resource utilization are solved, and collaborative development of greenhouse gas emission reduction and efficient antiknock agent preparation is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fuel additives, in particular to a hydrated amine carbon dioxide carbonylation anti-knock agent, a preparation method and application thereof. BACKGROUND

[0002] With the continuous improvement of global environmental protection requirements and the continuous increase of carbon emission reduction pressure, the traditional anti-knock agent technology is facing unprecedented challenges. Although metal anti-knock agents such as MMT (methylcyclopentadienyl manganese tricarbonyl) have significant effects on improving octane value (0.20-0.25 ON / ppm), they are strictly limited due to the problems of engine deposits and environmental pollution caused by metal residues. The traditional oxygen-containing anti-knock agent MTBE has been banned in many countries due to groundwater pollution.

[0003] Although the existing non-metal anti-knock agents are environmentally friendly, their octane value contribution efficiency is generally low, such as the ONCE value of MTBE is only 0.03-0.04 ON / ppm, which cannot achieve ideal anti-knock effect while considering environmental protection. More importantly, the existing technical path has not effectively solved the problem of CO2 resource utilization and anti-knock agent preparation.

[0004] Traditional CO2 conversion technology often requires harsh reaction conditions (high temperature 120-180℃, high pressure 8-15MPa) or expensive noble metal catalysts (such as rhodium, palladium, etc.), which seriously restricts its industrial application prospects. In particular, in the electrochemical reduction of CO2, the conventional method has problems such as catalyst poisoning, difficulty in controlling selectivity, high energy consumption, etc., making it difficult to achieve efficient conversion of CO2 to high-value-added chemicals.

[0005] Hydrated electron-based liquid as a new strong reducing carrier has super strong electron-donating ability (oxidation-reduction potential up to-800mV) and excellent stability in strong alkaline environment, but its application in the preparation of anti-knock agents by CO2 carbonylation has not been reported. The existing technology lacks an effective technical path to combine CO2 resource utilization with green anti-knock agent preparation. SUMMARY

[0006] The purpose of the present application is to provide a hydrated amine carbon dioxide carbonylation anti-knock agent, a preparation method and application thereof, which solves the environmental pollution problem of traditional anti-knock agents and the technical problem of CO2 resource utilization, and realizes the coordinated development of greenhouse gas emission reduction and efficient anti-knock agent preparation.

[0007] The application adopts the technical scheme of a hydrated amine carbon dioxide carbonylation anti-knock agent, which is obtained by mixing reaction of an amine mixture, a hydrated electron-based liquid and carbon dioxide, and the mass ratio of the three is in the range of 6.0-9.0:0.8-1.2:7.0-11.0; the amine mixture contains one or more of n-decylamine, tetradecylamine, 4-isopropyl aniline and tri(2-ethylhexyl)amine; the hydrated electron-based liquid has a pH value of greater than or equal to 14 and an oxidation-reduction potential of-350 mV to-1.8 V; and the reaction product is a mixture of formamide compounds and carbamic acid salts. The hydrated electron-based liquid used in the application is an electromagnetic-based liquid prepared in the US11691906B1 patent, which has a strong alkaline environment with a pH value of 14 + and an oxidation-reduction potential window of-350 mV to-1.8 V, and can efficiently activate CO2 molecules under mild conditions.

[0008] Preferably, the amine mixture contains, by mass percentage, n-decylamine: 30-40%, tetradecylamine: 45-55%, 4-isopropyl aniline: 5-15% and tri(2-ethylhexyl)amine: 3-8%. The four amines are mixed in a specific ratio for the preparation of the CO2 carbonylation anti-knock agent, which has the following technical advantages: 1. complementary molecular structure, adjustment of polarity and solubility: n-decylamine and tetradecylamine are long-chain aliphatic amines, and the N-formylate generated in the reaction has a relatively long alkyl chain, which is beneficial to dispersion and dissolution in hydrophobic gasoline phase; and the medium and short-chain 4-isopropyl aniline and tri(2-ethylhexyl)amine are used to adjust the overall polarity and viscosity of the mixture. 2. balance of reaction activity and conversion rate: the nucleophilicity and basicity of different amines are different, the reaction rate of n-decylamine with CO2 is moderate, and a higher yield of N-formylate can be obtained; the more active tri(2-ethylhexyl)amine can quickly form carbamic acid salt, which is then efficiently converted into formamide by hydrogenation. 3. optimization of physical properties: tetradecylamine has the largest molecular weight, so that the viscosity of the mixture is moderate at room temperature and is not easy to volatilize; the N-formylate generated by n-decylamine and tri(2-ethylhexyl)amine forms a more uniform free radical capture layer in the engine combustion chamber.

[0009] Preferably, the amine mixture contains, by mass percentage, n-decylamine: 30-40%, tetradecylamine: 45-55%, 4-isopropyl aniline: 5-15% and tri(2-ethylhexyl)amine: 3-8%. The four amines are mixed in a specific ratio for the preparation of the CO2 carbonylation anti-knock agent, which has the following technical advantages: 1. complementary molecular structure, adjustment of polarity and solubility: n-decylamine and tetradecylamine are long-chain aliphatic amines, and the N-formylate generated in the reaction has a relatively long alkyl chain, which is beneficial to dispersion and dissolution in hydrophobic gasoline phase; and the medium and short-chain 4-isopropyl aniline and tri(2-ethylhexyl)amine are used to adjust the overall polarity and viscosity of the mixture. 2. balance of reaction activity and conversion rate: the nucleophilicity and basicity of different amines are different, the reaction rate of n-decylamine with CO2 is moderate, and a higher yield of N-formylate can be obtained; the more active tri(2-ethylhexyl)amine can quickly form carbamic acid salt, which is then efficiently converted into formamide by hydrogenation. 3. optimization of physical properties: tetradecylamine has the largest molecular weight, so that the viscosity of the mixture is moderate at room temperature and is not easy to volatilize; the N-formylate generated by n-decylamine and tri(2-ethylhexyl)amine forms a more uniform free radical capture layer in the engine combustion chamber.

[0010] The application discloses a preparation method of a hydrated amine carbon dioxide carbonylation anti-knock agent, and comprises the following steps: step one, preparing a hydrated electron base solution with a pH value of 14.0 and an oxidation-reduction potential of -350 mV to -1.8 V under the protection of inert gas; step two, performing oxygen removal treatment on a reaction kettle so that the oxygen content in the reaction kettle is less than 5 ppm; step three, adding an amine mixture and the hydrated electron base solution into the reaction kettle at a time under the protection of inert gas, sealing the reaction kettle, and then adding CO2; the mass ratio of the amine mixture, the hydrated electron base solution and CO2 ranges from 6.0 to 9.0:0.8 to 1.2:7.0 to 11.0; step four, stirring the mixture, wherein the stirring speed is 400 rpm to 500 rpm, the stirring temperature is 34.8 DEG C to 50 DEG C, the stirring pressure is 35 kg to 45 kg, and the stirring time is 4 hours to 6 hours; and step five, keeping the stirring pressure and the stirring temperature unchanged, and standing for 10 hours to 13 hours to obtain a liquid.

[0011] Further, the application further comprises step six, which comprises the following steps: first-stage countercurrent extraction: mixing the liquid and ethyl acetate according to a volume ratio of 1:2, stirring at a stirring speed of 300 rpm for 30 minutes at a temperature of 25 DEG C + / - 2 DEG C to obtain organic phase and aqueous phase, filtering the organic phase to obtain first-stage aqueous phase; second-stage countercurrent extraction: adding ethyl acetate into the first-stage aqueous phase, the amount of the added ethyl acetate being the same as that of the liquid in the first-stage extraction, stirring at a stirring speed of 300 rpm for 30 minutes at a temperature of 25 DEG C + / - 2 DEG C to obtain organic phase and aqueous phase, filtering the organic phase to obtain second-stage aqueous phase; third-stage countercurrent extraction: adding ethyl acetate into the second-stage aqueous phase, the amount of the added ethyl acetate being the same as that of the liquid in the first-stage extraction, stirring at a stirring speed of 300 rpm for 30 minutes at a temperature of 25 DEG C + / - 2 DEG C to obtain organic phase and aqueous phase, filtering the organic phase to obtain third-stage aqueous phase; and combining the organic phases obtained in the third-stage countercurrent extraction to obtain an ethyl acetate solution containing formamide compounds.

[0012] Further, the application further comprises step seven: mixing the third-stage aqueous phase obtained in step six and n-butanol according to a volume ratio of 1:1.5, performing secondary extraction at a temperature of 30 DEG C, and obtaining carbamate salt; performing hydrogenation conversion of the carbamate salt under the action of a 5% Pd / C catalyst, wherein the amount of the catalyst is 5% of the mass of the carbamate salt, hydrogen is introduced, the reaction temperature is 80 DEG C + / - 5 DEG C, the reaction pressure is 2.0 MPa, the reaction time is 4 hours, and the stirring speed is 800 rpm, to obtain formamide. The carbamate compound is a product directly chemically absorbed by the amine and CO2, and can be further converted into a formamide compound through catalytic hydrogenation, so that the yield of the anti-knock agent is improved.

[0013] Furthermore, the method further includes step eight: using a distillation tower to distill and purify the feed liquid obtained in step five and the organic phase obtained in step six, wherein the top temperature of the distillation tower is 145-155°C, the bottom temperature is 180-190°C, the reflux ratio is 3:1, and the vacuum degree is -0.08MPa to obtain a formamide anti-explosion agent.

[0014] Preferably, in step three, CO2 is added in a semi-continuous feeding manner, and CO2 is added three times, with the same amount added each time and the interval time being 2 hours.

[0015] The application of hydrated amine carbonylation antiknock agent in gasoline, with the addition concentration of the antiknock agent ranging from 100-500ppm, has the following effects on different gasoline grades: 92 gasoline: adding 100ppm can increase the octane number by 0.8-1.5; 95 gasoline: adding 300ppm can increase the octane number by 2.4-4.5; 98 gasoline: adding 500ppm can increase the octane number by 4.0-7.5.

[0016] The advantages of the present invention are: the present invention achieves efficient conversion of CO2 without the need for high temperature, high pressure, or precious metal catalysts, with a carbonylation degree of 45.5% and a total CO2 utilization rate of 63.5%, far exceeding the conversion efficiency of traditional methods, and a CO2 fixation rate of 63.5%, of which 37% forms stable chemical bonds; the present invention achieves multiple environmental benefits: it not only uses CO2 as a reaction raw material, reducing the problem of greenhouse gas emissions, but also ultimately obtains a PPM-level antiknock agent that can better process gasoline. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the basic flow chart of the present invention. Figure 2 It is a schematic diagram of the molecular configuration and electron cloud distribution of the anti-explosion agent of the present invention. DETAILED DESCRIPTION

[0018] In order to better understand the technical content of the present invention, the present invention is further described below with reference to the accompanying drawings.

[0019] Example 1: Carbonylation of n-decylamine Raw material feeding: 60g of n-decylamine, 8g of hydrated electronic base liquid (pH≈16, ORP≈-500mV), 70g of CO2; a total of 138g The hydrated electronic base liquid is prepared by using the method patented in US11691906B1.

[0020] A 1 L steel autoclave was selected, the autoclave was deoxygenated to make the oxygen content <5 ppm, under nitrogen protection, n-decylamine and hydrated electron base liquid were added into the autoclave, after sealing, CO2 was slowly introduced, and the pressure was increased to about 38-40 kg; the reaction temperature was controlled at 48-50°C, the stirring speed was 400-500 rpm, the reaction was carried out for 4-6 h, then the pressure was kept for 10-12 h, the yield of the liquid was 60 g+8 g+21 g=89 g, and the liquid mainly contained N-formyl n-decylamine and n-decylamine carbamate.

[0021] After standing for 10 hours, the degree of formylation in the liquid was about 40%; After standing for 11 hours, the degree of formylation in the liquid was about 46%; After standing for 12 hours, the degree of formylation in the liquid was about 50%; In this embodiment, the chemical utilization rate of CO2 was about 30%.

[0022] Example 2: Carbonylation of 4-isopropylaniline Raw material feeding: 4-isopropylaniline 60 g, hydrated electron base liquid 8 g (pH≈16, ORP≈-800 mV), CO2 70 g.

[0023] Reaction conditions: The same equipment as in Example 1 was used.

[0024] Due to the slightly lower activity of aromatic amines, the stirring stage can be appropriately extended to 6 h, the temperature is kept at 50°C, the pressure is about 40 kg, and the other parameters are the same as in Example 1. Finally, the yield of the liquid is 60 g+8 g+17.5 g=85.5 g.

[0025] The obtained mixture contains N-formyl 4-isopropylaniline and its carbonate salt.

[0026] After standing for 10 hours, the degree of formylation in the liquid was about 35%; After standing for 11 hours, the degree of formylation in the liquid was about 37%; After standing for 12 hours, the degree of formylation in the liquid was about 40%; In this embodiment, the chemical utilization rate of CO2 was about 25%.

[0027] Example 3: Co-carbonylation of tri(2-ethylhexyl)amine and tetradecylamine Raw material feeding: Amine mixture 110 g+hydrated electron base liquid 15 g+CO2 120 g=245 g Reaction conditions: The same operation in the oxygen removal autoclave. After the amine was added once, CO2 was introduced to increase the pressure to about 40 kg, the reaction was carried out for 5 h, and was left for 11 h, and finally the yield of the feed liquid was 110 g+15 g+54 g=179 g.

[0028] The chemical utilization rate of CO2 was about 45%.

[0029] The feed liquid obtained in this example contains N-formyl tri(2-ethylhexyl) amine, N-formyl tetradecylamine and corresponding carbamate compounds, and the degree of carbonylation can reach 45%. The solubility of the carbonylation products of the two amines in gasoline is complementary, so it can be seen that the performance of the antiknock agent can be optimized by adjusting the ratio of different amines.

[0030] The above three examples show that different amines can generate corresponding N-formyl amides and carbamate compounds under the conditions of hydrated electrons and CO2.

[0031] Example 4: Preparation of antiknock agent by carbonylation of mixed amine with n-decylamine as the main component, Raw material preparation: Ammonia mixture 300 g (n-decylamine 106 g, tetradecylamine 149 g, 4-isopropyl aniline 30 g, tri(2-ethylhexyl) amine 15 g) Hydrated electron base liquid 40 g (pH=16.0, ORP -500 mV, density 1.20 g / mL), CO2 (industrial grade, ≥99.9%) 350 g; Reaction equipment: 1000 ml steel autoclave; As Figure 1 shown, the preparation method of the application is as follows: Step 1: Reactor pretreatment The 1000 ml steel autoclave was subjected to systematic oxygen removal treatment. First, vacuum to 0.1 kPa, then fill high-purity nitrogen (99.999%) to normal pressure, repeat this process 3 times, ensure that the oxygen content in the reactor is <5 ppm. The reactor is equipped with a precision temperature control system (±1℃), a pressure monitoring system and a high-efficiency mechanical stirrer; Step 2: Establishing the reaction system Under the protection of nitrogen, 300 g of amine mixture and 40 g of hydrated electron base liquid were added into the reactor at one time. After sealing the reactor, 350 g of CO2 was accurately introduced by mass flow controller to establish the initial pressure. At this time, the reaction system showed a characteristic deep blue color, indicating that the hydrated electron base liquid was in an active state; Step 3: Intensive stirring reaction phase Start mechanical stirrer, set speed at 400 rpm. Control reaction temperature to gradually increase from initial 34.8 °C to 50 °C, pressure stabilizes at 38 kg. Intensive stirring for 6 h under this condition. During the reaction, the color of the system gradually changes from dark blue to red, and finally presents orange-brown, which intuitively reflects the degree of chemical reaction; Step 4: Equilibrium reaction phase Stop mechanical stirring, stand for 13 h at 38 kg constant pressure and 50 °C temperature; Step 5: Product collection and preliminary analysis After the reaction is completed, slowly release the pressure and collect the reaction product. 335 g of orange-brown uniform product is obtained, no stratification phenomenon, no odor volatilization. Through material balance calculation, it is determined that: CO2 consumption is 224 g (64% utilization rate), of which 56 g (16%) is consumed in carbonylation reaction, and 155 g of formamide compound mixture is formed.

[0032] As Figure 2 shown, the reaction mechanism and chemical equation of the present application are as follows: The mechanism of the hydrated electron-based liquid promoting CO2 carbonylation reaction is as follows: CO2 molecules in the hydrated electron-based liquid first form CO2• - radical anions through electron transfer: CO2 + e - (aq) → CO2• - The CO2 activation mechanism may include: Direct electron transfer: CO2 + e - (aq) → CO2• - Base-catalyzed activation: CO2 + OH - → HCO3 - Synergistic mechanism: amine-CO2 - formation of hydrated electron ternary complex Activated CO2• - radical anions and amine molecules undergo carbonylation reaction: For aliphatic amines (taking n-decylamine as an example): C 10 H 21 NH2 + CO2• - → C 10 H 21 NH-COO - + H• C 10 H 21 NH-COO - + H• → C 10 H 21NH-CHO (N-formyl n-decylamine) For aromatic amines (e.g. 4-isopropylaniline): (CH3)2CH-C6H4-NH2 + CO2• - → (CH3)2CH-C6H4-NH-COO - + H• (CH3)2CH-C6H4-NH-COO - + H• → (CH3)2CH-C6H4-NH-CHO Some amines directly react with CO2 to form carbamates: 2RNH2 + CO2 → RNH3 + + RNHCOO - (carbamate) Catalytic hydrogenation of carbamates: RNHCOO - + H2 -> [Pd / C] -> RNH-CHO + H2O This reaction pathway produces carbonyl amine products with unique electronic structure and spatial configuration: 1. The high electron density of the formyl group makes it an excellent radical acceptor; 2. The lone pair of electrons on the N atom enhances the nucleophilicity of the molecule, helping to capture active radicals in combustion; 3. The long-chain alkyl group (n-decylamine, tetradecylamine, etc.) provides good oil solubility, ensuring uniform dispersion in gasoline; 4. The overall configuration of the molecule is conducive to the formation of a protective film in the combustion chamber, inhibiting the knock chain reaction.

[0033] Therefore, the unique molecular configuration and electron cloud distribution of the formamide anti-knock agent produced by the invention are the molecular basis for its excellent anti-knock performance. Compared with traditional synthesis methods, this pathway has higher selectivity (45.5%) and atomic economy.

[0034] Product composition analysis: N-formyl n-decylamine (C 10 H 21 NH-CHO): 55g, N-formyl tetradecylamine (C 14 H 29 NH-CHO): 70g, N-formyl-4-isopropylaniline ((CH3)2CH-C6H4-NH-CHO): 18g, N-formyl tris(2-ethylhexyl)amine: 12g, Corresponding carbamate mixture: 168g, Other ingredients: 12 g, Example results: Total amount of reaction product: 335 g, Formamide compound content: 155 g (46.3%), Carbamate content: 268 g (80.0%), Degree of carbonylation: 46%, Total CO2 utilization rate: 64%, Application effect: In 92# gasoline, add 100 ppm, and the octane number is increased from 92 to 93.2 (1.2 increase), In 95# gasoline, add 300 ppm, and the octane number is increased from 95 to 98.6 (3.6 increase), In 98# gasoline, add 500 ppm, and the octane number is increased from 98 to 104 (6.0 increase).

[0035] Example 5: Preparation of antiknock agent by carbonylation of mixed amine with tetradecylamine as the main component Raw material preparation: Amine mixture 315 g (n-decylamine 95 g, tetradecylamine 173 g, 4-isopropyl aniline 28 g, tri (2-ethylhexyl) amine 19 g) Hydrated electron-based liquid 42 g (pH 15.5, ORP-800 mV) CO2 (industrial grade, ≥99.9%) 378 g Reaction equipment: 1000 ml steel high-pressure reaction kettle Preparation method: Step 1-2 is the same as Example 4.

[0036] Step 3: Strong stirring reaction stage Start the mechanical stirrer, set the speed to 450 rpm. Control the reaction temperature to gradually increase from the initial 34.8°C to 48°C, and the pressure is stable at 40 kg. Strong stirring for 5 h under this condition.

[0037] Step 4: Equilibrium reaction stage Stop the mechanical stirring, and stand for 12 h at 40 kg constant pressure and 48°C temperature.

[0038] Step 5: Product collection and preliminary analysis After the reaction is completed, 342 g of orange-brown product is obtained.

[0039] Product composition: N-formyl n-decylamine: 46 g, N-formyl tetradecylamine: 88 g, N-formyl-4-isopropyl aniline: 17 g, N-formyl tri (2-ethylhexyl) amine: 11 g, Carbamate mixture: 275g, Example results: Total reaction product: 342g, Formamide mixture: 162g (47.4%), Carbamate mixture: 275g (80.4%), Degree of carbonylation: 47%, Total CO2 utilization: 65%, Application results: Add 150ppm to No. 92 gasoline, octane value increased by 1.5, Add 350ppm to No. 95 gasoline, octane value increased by 4.2, Add 450ppm to No. 98 gasoline, octane value increased by 5.4.

[0040] Example 6: Preparation of antiknock agent by carbonylation of mixed amines enhanced by aromatic amine, Raw material preparation: Amine mixture 320g (n-decylamine 96g, tetradecylamine 144g, 4-isopropyl aniline 48g, tris (2-ethylhexyl) amine 32g), Hydrated electron-based liquid 45g (pH 16.0, ORP -1.2V), CO2 (industrial grade, ≥99.9%) 385g; Preparation method: Step 1-2 same as example 4; Step 3: Strong stirring reaction stage, the π electron system of aromatic hydrocarbon (take 4-isopropyl aniline as an example) can further stabilize the captured free radicals; due to the high content of aromatic amine, the stirring time is extended to 6 hours, the speed is 500 rpm, the temperature is 50℃, and the pressure is 40kg; Step 4: Equilibrium reaction stage standing for 11h; Step 5: Product collection and preliminary analysis obtained 348g product; Step 6: Extraction separation process uses ethyl acetate as extractant, 348ml of feed liquid is mixed with 696ml of ethyl acetate (volume ratio 1:2) to carry out three-stage countercurrent extraction: First stage: 348ml of feed liquid + 696ml of ethyl acetate, Second stage: water phase of the first stage + 348ml of fresh ethyl acetate, Third stage: water phase of the second stage + 348ml of fresh ethyl acetate, Combine the organic phases of the three stages to obtain about 920ml of ethyl acetate solution containing formamide compounds, the extraction rate is 88%; Step 7: Carbamate recovery and conversion, the water phase after tertiary extraction was extracted with n-butanol (volume ratio 1:1.5), to recover carbamate 112g, under the action of 5% Pd / C catalyst (5.6g), hydrogenation conversion was carried out by passing H2: Reaction conditions: 80±5℃, 2.0MPa H2, 4h, 800rpm stirring; Conversion rate: 75%, additional formamide 84g was obtained, Step 8: rectification purification, the formamide product was purified by rectification column with theoretical plate number≥10: Operation conditions: top 145-155℃, bottom 180-190℃, reflux ratio 3:1, vacuum degree-0.08MPa, Collecting 150-165℃ fraction, Final product composition: High purity N-formyl n-decylamine: 58g, High purity N-formyl tetradecylamine: 124g, High purity N-formyl-4-isopropyl aniline: 68g, High purity N-formyl tris (2-ethylhexyl) amine: 55g, Example results: Total amount of high purity formamide antiknock agent: 305g, Purity: ≥98% (GC analysis), Total yield: 90% (based on theoretical yield), Application effect: Add 200ppm in 92# gasoline, octane number increases by 1.8, Add 400ppm in 95# gasoline, octane number increases by 4.8, Add 500ppm in 98# gasoline, octane number increases by 6.5.

[0041] Example 7: preparation of high purity antiknock agent by optimized process, This example adds steps 6-8 based on example 5; Step six: tertiary countercurrent extraction was carried out using ethyl acetate as the extractant, feed liquid: extractant volume ratio 1:2. Each extraction time was 30 minutes, temperature 25±2℃, mechanical stirring 300rpm. After extraction, the organic phase and water phase were separated after standing for 15 minutes; First stage extraction: 170ml feed liquid + 340ml ethyl acetate, formamide compounds were extracted; Second stage extraction: first stage water phase + 170ml fresh ethyl acetate, to improve extraction completeness; Third stage extraction: second stage water phase + 170ml fresh ethyl acetate, to ensure maximum recovery rate.

[0042] The third organic phase was combined to obtain about 600 ml of ethyl acetate solution containing formamide compounds, with an extraction rate of 88%; Step seven: Carbamate recovery: The aqueous phase after the third extraction was extracted with n-butanol, with an extraction ratio of 1:1.5 (v / v), secondary extraction, 25 minutes per level, temperature 30°C; 92 g of carbamate was recovered, with a recovery rate of 82%; Catalytic conversion process: 92 g of recovered carbamate was subjected to hydrogenation conversion under the action of 5% Pd / C catalyst (4.6 g) by passing in H2: Reaction conditions: 80±5°C, 2.0 MPa, 4 hours, 800 rpm stirring; Reaction mechanism: R2NH-COO - +H2→R2N-CHO+H2O; Conversion rate: 75%, 69 g of additional formamide was obtained; Step eight: rectification purification: The formamide product was purified by rectification column (theoretical tray number≥10): Operating conditions: top temperature 145-155°C, bottom temperature 180-190°C; Reflux ratio: 3:1, vacuum degree: -0.08 MPa; Collect target fraction: formamide compounds (boiling point 150-165°C); Example results: High-purity formamide antiknock agent: 304 g; Purity: ≥98% (GC analysis); Total yield: 90% (based on theoretical yield); ONCE value: 0.08-0.12 ON / ppm; Treatable gasoline: 608 L (500 ppm addition concentration, increase 98# gasoline octane value by 6 units).

[0043] 338 g of reaction product needs to be purified by a systematic extraction purification process to obtain an antiknock agent product that meets the application standard. Based on the chemical composition and physical properties of the product, a multi-stage extraction separation process was designed. First, ethyl acetate was used as an extractant to separate formamide compounds by selective dissolution, with an expected recovery rate of more than 90%. Second, n-butanol was used to extract carbamate, with a recovery rate of about 85%; The conversion of carbamates is a crucial step in improving the overall octane booster yield. Through a catalytic hydrogenation process (using a 5% Pd / C catalyst, at 80°C, 2.0 MPa H2, for 4 hours), carbamates can be efficiently converted into formamidines, with a conversion rate expected to exceed 75%. This conversion process not only increases the overall yield of octane boosters but also enables further CO2 fixation and utilization; Considering the extraction recovery rate and conversion efficiency, approximately 304g of high-purity formamidine octane boosters can be obtained from 338g of reaction products. This yield level is quite outstanding in the fine chemical industry, providing a solid foundation for the industrial application of the technology. The use of steel reactors also provides an important reference for the design of subsequent industrial equipment.

[0044] The 304g of formamidine octane boosters exhibit excellent performance potential in practical applications. According to the typical addition concentration of gasoline octane boosters, at a standard addition level of 500ppm, approximately 608L of gasoline can be treated; at a lower addition level of 300ppm, approximately 1013L of gasoline can be treated. This treatment capacity is already quite substantial for a single experimental output.

[0045] The working mechanism of formamidine octane boosters is mainly based on their free radical capture effect in the combustion process. In the combustion reaction of gasoline, formamidine compounds can effectively capture free radicals that cause detonation, thereby improving the anti-knock performance of gasoline. Compared with traditional oxygen-containing octane boosters, formamidine compounds do not cause groundwater pollution; compared with metal-containing octane boosters, their combustion products are cleaner and do not form harmful deposits in the engine.

[0046] From an environmental perspective, the use of formamidine octane boosters will significantly improve the environmental impact of gasoline combustion. Their combustion products are mainly CO2, H2O, and N2, without heavy metals or toxic organic substances. This clean combustion characteristic meets the increasingly stringent environmental protection requirements and makes an important contribution to the development of green fuel technology.

[0047] The most important environmental significance of this technology is the efficient resource utilization of CO2. Each batch consumes 378 grams of CO2, equivalent to reducing 0.378 kg of greenhouse gas emissions. Although the emission reduction of a single batch is relatively limited, the scalable nature of the technology makes it have significant cumulative emission reduction potential. According to a scale of 1000 tons of octane boosters per year, approximately 1250 tons of CO2 can be consumed annually, with an emission reduction effect equivalent to planting about 60,000 mature trees.

[0048] More importantly, this emission reduction is achieved by converting CO2 into valuable chemicals, rather than simple sequestration or disposal. This resource utilization mode not only solves the problem of greenhouse gas emission reduction, but also creates actual economic value, embodying the benign combination of environmental protection and economic development. With the establishment and improvement of global carbon pricing mechanism, this double value will further highlight.

[0049] The life cycle environmental impact analysis of the technology shows that the environmental load is mainly concentrated in the production of amine raw materials in the whole process from raw material mining to product application. However, considering the recyclable characteristics of amine raw materials and the resource utilization benefits of CO2, the carbon footprint of the whole technology route is significantly lower than that of the traditional petroleum chemical route. Especially in the background of the increasing proportion of renewable energy power, the environmental friendliness of the technology will be further improved.

[0050] Advantages: Compared with the prior art, the present application has the following obvious advantages: 1. Technological innovation breakthrough: for the first time, the CO2 carbonylation reaction promoted by hydrated electron-based liquid is realized, which efficiently activates CO2 molecules under mild conditions (50℃, 40kg pressure) to form a CO2• - radical anion intermediate. This activation method is fundamentally different from traditional catalytic activation methods, which do not rely on noble metal catalysts and do not require high temperature and high pressure conditions (traditional methods require 120-180℃, 8-15MPa);

[0051] 2. Outstanding environmental benefits: each batch consumes 378g of CO2, and the annual production of 1000 tons of antiknock agent can consume about 1250 tons of CO2, which is equivalent to planting about 60,000 adult trees. The combustion products of the product are clean (mainly CO2, H2O, N2), do not contain heavy metals or toxic organic matter, and meet strict environmental protection requirements;

[0052] 3. Excellent antiknock performance: the prepared formamide antiknock agent shows excellent octane number improvement effect in the addition concentration range of 100-500ppm. For 92# gasoline, every 100ppm can improve 0.8-1.5 octane number; for 95# gasoline, every 100ppm can improve 0.8-1.3 octane number; for 98# gasoline, every 100ppm can improve 0.8-1.5 octane number. This linear relationship facilitates accurate adjustment of the addition amount according to the needs of different specifications of gasoline;

[0053] 4. Reasonable process economy: the reaction conditions are mild, the equipment requirements are relatively simple, and the steel reactor technology is mature and reliable. The raw material cost is reasonable, the product has high added value, and it has good economic feasibility. The process has strong scalability and is suitable for industrial production;

[0054] 5. Good product stability: excellent thermal stability (loss ≤8% at 150℃ / 24h), long storage stability (≥12 months), good compatibility with gasoline, no engine deposits or groundwater pollution;

[0055] 6. Resource utilization value: CO2 waste is converted into high-value anti-knock agent, embodying the concept of circular economy. CO2 utilization rate is 63.5%, of which 37% forms stable chemical bonds, providing a new way for CO2 resource utilization;

[0056] 7. Raw material ratio optimization: through scientific proportioning of four kinds of amines, perfect combination of molecular structure complementation, reaction activity balance and physical property optimization is realized, and the comprehensive performance of the product is maximized.

Claims

1. A hydrated amine carbonylation antiknock agent, characterized in that: The anti-knock agent is obtained by a mixed reaction of an amine mixture, a hydrated electronic base liquid and carbon dioxide, with the mass ratio of the three ranging from 6.0-9.0:0.8-1.2:7.0-11.0; the amine mixture contains one or more of n-decylamine, tetradecylamine, 4-isopropylaniline and tri(2-ethylhexyl)amine; the hydrated electronic base liquid has a pH value of ≥14 and an oxidation-reduction potential of -350mV to -1.8V; and the reaction product is a mixture of formamide compounds and carbamates.

2. The hydrated amine carbonylation antiknock agent according to claim 1, characterized in that: The amine mixture comprises, by mass percentage, 30-40% of n-decylamine, 45-55% of tetradecylamine, 5-15% of 4-isopropylaniline, and 3-8% of tri(2-ethylhexyl)amine.

3. The hydrated amine carbonylation antiknock agent according to claim 2, characterized in that: The amine mixture comprises, by mass percentage, 35.4% of n-decylamine, 49.5% of tetradecylamine, 10.0% of 4-isopropylaniline, and 5.1% of tri(2-ethylhexyl)amine.

4. The method for preparing the antiknock agent of any one of claims 1 to 3, characterized in that: The method comprises the following steps: Step 1: Under the protection of an inert gas, preparing a hydrated electronic base liquid with a pH value of ≥14 and an oxidation-reduction potential of -350 mV to -1.8 V; Step 2: Deoxygenate the reactor to reduce the oxygen content in the reactor to less than 5 ppm; Step 3: Under the protection of inert gas, add the amine mixture and the hydrated electronic base liquid into the reactor at one time, seal the reactor, and add CO2; the mass ratio of the amine mixture, the hydrated electronic base liquid, and the CO2 is 6.0-9.0:0.8-1.2:7.0-11.0; Step 4: stirring the mixture at a stirring speed of 400-500 rpm, a stirring temperature of 33-50°C, a stirring pressure of 35-45 kg, and a stirring time of 4-6 hours; Step 5: Keep the stirring pressure and stirring temperature unchanged and let it stand for 10-13 hours to obtain the liquid.

5. The preparation method according to claim 4, characterized in that It also includes step six, which includes the following steps: primary countercurrent extraction: the feed liquid and ethyl acetate are mixed in a volume ratio of 1:2, and stirred at a stirring speed of 300 rpm for 30 minutes at a temperature of 25±2°C to obtain an organic phase and an aqueous phase, and the organic phase is filtered to obtain a primary aqueous phase; secondary countercurrent extraction: ethyl acetate is added to the primary aqueous phase, and the amount of ethyl acetate added is the same as the amount of feed liquid in the primary extraction, and stirred at a stirring speed of 300 rpm for 30 minutes at a temperature of 25±2°C to obtain an organic phase and an aqueous phase, and the organic phase is filtered to obtain a secondary aqueous phase; tertiary countercurrent extraction: ethyl acetate is added to the secondary aqueous phase, and the amount of ethyl acetate added is the same as the amount of feed liquid in the primary extraction, and stirred at a stirring speed of 300 rpm for 30 minutes at a temperature of 25±2°C to obtain an organic phase and an aqueous phase, and the organic phase is filtered to obtain a tertiary aqueous phase; the organic phases obtained from the three-stage countercurrent extraction are combined to obtain an ethyl acetate solution containing formamide compounds.

6. The preparation method according to claim 5, characterized in that The method further includes the following steps: mixing the tertiary aqueous phase obtained in step 6 with n-butanol in a volume ratio of 1:1.5, performing secondary extraction at a temperature of 30° C. for 25 minutes per stage to obtain carbamate; hydrogenating the carbamate in the presence of a 5% Pd / C catalyst, wherein the catalyst amount is 5% of the mass of the carbamate, introducing hydrogen, and carrying out the reaction at a temperature of 80±5° C., a reaction pressure of 2.0 MPa, a reaction time of 4 hours, and a stirring rate of 800 rpm to obtain formamide.

7. The preparation method according to claim 6, characterized in that The process further comprises step eight: using a distillation tower to purify the liquid obtained in step five and the organic phase obtained in step six by distillation, wherein the top temperature of the distillation tower is 145-155° C., the bottom temperature is 180-190° C., the reflux ratio is 3:1, and the vacuum degree is -0.08 MPa, to obtain a formamide anti-explosion agent.

8. The preparation method according to claim 4, characterized in that In the step 3, CO2 is added in a semi-continuous feeding manner, and CO2 is added in three times, with the same amount added each time and the interval time being 2 hours.

9. Use of the hydrated amine carbonylation antiknock agent according to any one of claims 1 to 3 in gasoline, characterized in that: The added concentration is 100-500ppm.

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