Nonmetal antiknock agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of fuel additives, in particular to a non-metal antiknock agent and a preparation method and application thereof, aims to provide the non-metal antiknock agent and the preparation method and application thereof, and solves the core problem that a traditional non-metal antiknock agent is low in efficiency. In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the non-metal antiknock agent comprises the following components in percentage by mass: 55-75% of straight-chain or branched-chain fatty amine, 10-25% of aromatic amine, 5-15% of polysubstituted fatty amine and 5-15% of an electron donor, the electron donor adopts a hydrated electron base solution. The gasoline antiknock agent is environment-friendly and efficient, does not depend on a noble metal catalyst, does not need high temperature and high pressure, not only has the excellent effect of a metal antiknock agent, but also is pollution-free, and can greatly improve the gasoline quality under the condition of extremely low addition amount.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel additives, and particularly relates to a non-metallic anti-knock agent, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous improvement of global environmental protection requirements, although traditional metal-based anti-knock agents such as MMT (methylcyclopentadienyl manganese tricarbonyl) have significant effects in increasing the octane number (ONCE value 0.20 - 0.25 ON / ppm), they are restricted due to problems such as engine deposits and environmental pollution caused by their metal residues.

[0003] Although non-metallic anti-knock agents have good environmental protection, their octane number contribution efficiency is generally low. For example, the ONCE value of MTBE (the "ONCE value" means an index used to measure the octane number improvement efficiency of an anti-knock agent, full name: Octane Number Contribution Efficiency) is only 0.03 - 0.04 ON / ppm. Currently, non-metallic anti-knock agents on the market face major technical bottlenecks of low efficiency and large dosage, and cannot achieve an ideal anti-knock effect while taking environmental protection into account.

[0004] Most existing technologies use conventional chemical synthesis means to prepare non-metallic anti-knock agents, such as through the condensation reaction of amines and carbonyl compounds, alkylation of ether compounds, etc. These methods usually require high temperature (120 - 180 °C), high pressure (8 - 15 MPa), or strong acid / strong base catalytic conditions, which not only have high energy consumption and strict equipment requirements, but also have poor reaction selectivity and many by-products, severely restricting product performance and production efficiency.

[0005] Especially in the activation of carbon monoxide, traditional processes rely on noble metal catalysts (such as rhodium, palladium, etc.) or strong basic conditions, but these methods have problems such as catalyst poisoning and difficult selectivity control. Summary of the Invention

[0006] The purpose of the present invention is to provide a non-metallic anti-knock agent, a preparation method thereof, and an application thereof, which solves the core problem of low efficiency of traditional non-metallic anti-knock agents.

[0007] The technical solution adopted by the present invention to solve its technical problems is: a non-metallic anti-knock agent, which contains the following components by mass percentage: 55 - 75% of straight-chain or branched-chain fatty amines, 10 - 25% of aromatic amines, 5 - 15% of polysubstituted fatty amines, and 5 - 15% of electron donors; the electron donor uses a hydrated electron-based liquid.

[0008] Traditional strong reducing agents such as metallic sodium, potassium, etc. have stronger reducibility, but are extremely unstable and difficult to control; while conventional reducing agents such as sodium borohydride are stable but lack sufficient activity and cannot effectively activate carbon monoxide. In the electromagnetic base liquid prepared in the US 11691906B1 patent, the pH value ranges from 14.0 ± 1.0, with sufficient reduction activity, and the range of the oxidation-reduction potential (ORP) is -350 mV to -1.8 V. This specific potential window also has good stability and can effectively activate carbon monoxide. Using the hydrated electron base liquid as an electron donor, an electron transfer occurs with carbon monoxide to generate highly reactive CO radical anions. This activation process does not require noble metal catalysts or extreme conditions, which is a key breakthrough that cannot be achieved by traditional synthesis methods; the activated CO radical anions undergo nucleophilic addition reactions with amine compounds, and then hydrogen transfer occurs to form the final product: the carbonylamine products produced by this reaction path have specific electronic structures and spatial configurations, which is the molecular basis for their excellent anti-knock performance. Compared with traditional synthesis methods, this path has higher selectivity and atom economy.

[0009] Preferably, the straight-chain or branched-chain aliphatic amine is a C4-C20 aliphatic amine.

[0010] Preferably, the aromatic amine is a monocyclic or polycyclic aromatic amine.

[0011] Preferably, the polysubstituted aliphatic amine is a C2-C18 aliphatic amine having 1-6 alkyl substituents.

[0012] A preparation method of a non-metallic anti-knock agent. Throughout the preparation process, it is always carried out in an environment with an oxygen content < 10 ppm, and includes the following steps: Step 1: Weigh 55-75% by mass of straight-chain or branched-chain aliphatic amine, 10-25% of aromatic amine, 5-15% of polysubstituted aliphatic amine, and 5-15% of electron donor; Step 2: Put the weighed raw materials into the reaction vessel at one time, and introduce carbon monoxide gas into the reaction vessel to 0.1-6.0 MPa; Step 3: In the temperature range of 10-35 °C, mix and stir the various raw materials in the reaction vessel, the stirring pressure is 1.0-2.0 Mpa, the stirring rate is 600-800 rpm, and the stirring time is 45-60 min; Step 4: Continue to stir in the temperature range of 35-60 °C, the stirring pressure is 2.0-2.5 Mpa, the stirring rate is 800-1200 rpm, and the stirring time is 60-120 min to obtain a mixture.

[0013] The key differences of the present invention, which are not available in the traditional process, include stepwise temperature increase, collaborative pressure control, precise stirring, and strict anaerobic conditions. The stepwise temperature control strategy ensures that the reaction is in the best conditions at each stage, in sharp contrast to the traditional process that requires high temperatures of 120 - 180 °C; the stepped pressure control technology can accurately adjust the solubility and reactivity of carbon monoxide at different reaction stages, far lower than the high pressure conditions of 8 - 15 MPa required by the traditional process; precise control of the stirring rate ensures the matching of mass transfer efficiency and reaction rate, avoiding problems such as local overheating or incomplete reaction; and the strict anaerobic strategy is mainly reflected in that the oxygen content in the whole reaction process is <10 ppm, and the whole process is carried out under the protection of inert gas (nitrogen or argon), including pre-removing oxygen from raw materials (vacuum degassing), removing oxygen from the equipment system (vacuum-inert gas replacement, ≥3 times), continuously removing oxygen during the reaction process (micro-positive pressure inert gas protection), using a zirconia sensor to monitor the oxygen content of the system in real time, automatically alarming and supplementing inert gas when >20 ppm, and the reaction device using a modified PTFE sealing ring with a compression ratio ≥25% to ensure the airtightness inside the reaction device.

[0014] Furthermore, it also includes a pretreatment step: weighing 15 - 35% of the hydrated electron base liquid by mass percentage, and activating the hydrated electron base liquid using a plasma discharge facility under the protection of inert gas. The activation parameters are: frequency: 13.56 ± 0.5 MHz; power: 100 - 300 W; inert gas flow rate: 20 - 80 mL / min; weighing 65 - 85% of the hydrated electron base liquid by mass percentage, and under the condition of inert gas protection, stirring and mixing it with the activated hydrated electron base liquid until a homogeneous and transparent electron donor is formed. The stirring parameters are as follows: temperature: -10 - 10 °C; pressure: 0.5 - 1.0 Mpa; stirring rate: 400 - 600 rpm, system potential: -350 mV to -1.8 V, pH value: 14.0, inert gas flow rate: 15 - 50 mL / min; oxygen content: <5 ppm; mixing time: 30 - 60 minutes.

[0015] The hydrated electron base liquid and the activated hydrated electron base liquid form a double electron donor, and this process can be represented by the following reaction equations: H2O + e⁻(plasma) → e⁻(aq) + H2O (1) e⁻(aq) + nH2O → [e⁻(H2O)n] (2) [e⁻(H2O)n] + e⁻(plasma) → [2e⁻(H2O)n] (3); It can be seen that the double electron donor provides stronger reducing ability and higher stability than a single electron donor. The electron transfer between the activated double electron donor system and carbon monoxide can be represented by the following reaction equations: CO + [2e⁻(H2O)n] → [CO•⁻(H2O)n] + e⁻(aq) (4) [CO•⁻(H2O)n] → CO•⁻ + nH2O (5); The activated CO radical anion undergoes a nucleophilic addition reaction with an amine compound, and then forms the final product through hydrogen transfer: R1R2NH + CO•⁻ → R1R2N-CO⁻ + H• (6) R1R2N-CO⁻ + H• →R1R2N-CHO (7), where R1 and R2 represent different alkyl or aryl substituents. This reaction is basically the same as the reaction principle of a single electron donor, but the reaction time is much faster than that of a single electron donor. Therefore, setting a pretreatment step can greatly reduce the reaction time.

[0016] Furthermore, it also includes step five of vacuum distillation, and the vacuum distillation includes the following steps: System deoxygenation: After evacuating the distillation device to 0.1 kPa, an inert gas is introduced; Preheating: The temperature is 30 - 35 °C, and the preheating time is 30 - 45 minutes; First fractionation: The pressure is 5.0 - 10.0 kPa, the temperature is 35 - 45 °C, and the fractionation time is 60 - 90 minutes; This fractionation removes low-boiling impurities and residual solvents; Second fractionation: The pressure is 2.0 - 5.0 kPa, the temperature is 45 - 60 °C, and the fractionation time is 90 - 120 minutes; This fractionation removes unreacted raw materials and some intermediates; Third fractionation: The pressure is 0.5 - 2.0 kPa, the temperature is 60 - 85 °C, and the fractionation time is 120 - 180 minutes; The main target product is obtained; The reflux ratios of the first fractionation, the second fractionation, and the third fractionation decrease in turn, the range value of the reflux ratio is 3:1 - 8:1, and the distillation rate is 1.5 - 3.0 L / h.

[0017] Compared with traditional high-temperature distillation (120 - 180 °C), the vacuum distillation method does not require high-pressure and high-temperature equipment, the equipment investment and maintenance costs are significantly reduced, and it can save a large amount of energy.

[0018] Further, it also includes Step Six: 1) Weigh 50 - 70% by mass of liquid ammonia, 15 - 35% of tetrahydrofuran, and 5 - 25% of an ether solvent, and mix them under the protection of an inert gas to obtain a mixed solvent. All the solvents are treated without water, and the water content is ≤200 ppm; the stirring rate is 200 - 250 rpm, the mixing time is not less than 30 min, the temperature is -40°C, the temperature fluctuation during the mixing process is ±2°C, and the oxygen content is <10 ppm; 2) Weigh 80 - 90% of the mixed solvent and 10 - 20% of the main target product by mass ratio; 3) Under the protection of an inert gas, perform liquid-liquid extraction on the main target product with the mixed solvent to obtain an organic phase; 4) Under the protection of an inert gas, perform chromatographic separation or crystallization purification on the extracted organic phase.

[0019] As a polar proton solvent, liquid ammonia can effectively dissolve polar impurities; tetrahydrofuran has both the characteristics of ethers and cyclic structures and has good selectivity for medium-polarity compounds; ether solvents are used to extract non-polar components. The combined polar gradient of the three solvents enables precise separation of products with different polarities. The extraction efficiency is increased by 25 - 40% compared to single solvents. Therefore, after treating the product with the mixed solvent, the product purity can be increased from the initial 85 - 90% to ≥98%; the operating temperature for extraction separation is only 35 - 60°C. By replacing traditional distillation separation with liquid-liquid extraction, thermal decomposition of the product under high-temperature conditions is avoided, and the yield is increased from 78 - 82% in the traditional process to 94 - 96%. The mixed solvent has a high solubility for the target product, and the product residue amount during extraction is extremely low (<0.5%); solvents such as liquid ammonia and tetrahydrofuran can be recovered and reused through simple distillation, recycled, and the recovery rate is ≥95%, significantly reducing the solvent consumption cost; adding the mixed solvent can completely remove impurities such as transition-state intermediates, trace oxides, metal ions, and moisture that have an adverse effect on product stability, reducing the loss rate of the product to ≤5% under the conditions of 150°C / 24h and extending the storage period to ≥12 months, making the product highly stable; the ONCE value of the product is optimized, and the ONCE value of the high-purity product can reach 0.12 - 0.15 ON / ppm, which is 15 - 20% higher than that of the product not treated with the mixed solvent; moreover, organic impurities and oxidation products are removed, and the final product is a colorless to light yellow transparent liquid. While the quality and appearance are significantly improved, the chromaticity impact on fuels is also avoided; high-molecular-weight polymers and polar impurities that may form deposits in the engine are removed, improving the compatibility and detergency of the product in the engine. The mixed solvent avoids the use of harmful solvents such as chlorinated hydrocarbons, and there is no harmful solvent residue in the product (detection limit <1 ppm). The efficient extraction process reduces the amount of waste liquid generated by about 60%, significantly enhancing environmental friendliness. The selected solvents all have good biodegradability and minimal impact on the environment; the mixed solvent is treated to remove water (moisture ≤200 ppm), ensuring the chemical stability and electrochemical activity of the product. Extraction is carried out under strict anaerobic conditions to avoid oxidation and degradation of the product. The mixed solvent is suitable for continuous production, providing technical support for industrial scale-up.

[0020] Application of the non-metallic anti-knock agent in gasoline, addition concentration: 8.3 - 100 ppm. After being added to gasoline in the present invention, its ONCE (RON): 0.05 - 0.20 ON / ppm; octane number increase: 1.0 - 3.0 units.

[0021] The advantages of the present invention are as follows: 1. The present invention can efficiently activate carbon monoxide molecules under mild conditions (0 - 50 °C, 0.5 - 5.0 MPa) to form a highly reactive CO radical anion intermediate. This activation method is fundamentally different from traditional catalytic activation methods, does not rely on noble metal catalysts, and does not require high temperature and high pressure conditions, achieving a revolutionary breakthrough in carbon monoxide activation. 2. By strictly controlling the potential window of the reaction system within the range of -350 mV to -1.8 V, the present invention realizes the optimal balance between the stability and reactivity of the electron donor. In this potential range, hydrated electrons have sufficient reducing ability to activate carbon monoxide while maintaining good stability, which cannot be achieved by conventional electrochemical methods or simple reducing agents. 3. The present invention establishes a multi-dimensional collaborative control process system for temperature, pressure, potential, stirring mass transfer, etc. Through segmented heating and stepped pressure control, precise regulation of the reaction process is achieved, enabling the carbonylation reaction to proceed along the optimal path, significantly improving the selectivity (≥96%) and conversion rate (≥94%) of the product. 4. Using the special intermediate formed by activating carbon monoxide with hydrated electrons, the present invention reacts with different types of amine compounds to generate hydrated carbonylamine products with specific spatial configurations and electron distributions. These products have unique molecular configurations and electron cloud distributions, and can effectively intervene in the free radical chain reaction during fuel combustion, thereby achieving excellent anti-knock effects. 5. The ONCE value of the anti-knock agent prepared by the present invention reaches 0.08 - 0.15 ON / ppm, far higher than that of traditional non-metallic anti-knock agents such as MTBE (0.03 - 0.04 ON / ppm), approaching the level of metal-based anti-knock agents, while overcoming the environmental problems of metal-based anti-knock agents. The product has excellent thermal stability (loss ≤ 8% at 150 °C / 24 h) and storage stability (≥12 months), and can significantly improve the quality of gasoline at extremely low addition concentrations (0.1 - 200 ppm). BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the basic flowchart of the present invention.

[0023] Figure 2 is the pretreatment flowchart of the present invention.

[0024] Figure 3 is the flowchart of Step 5 of the present invention.

[0025] Figure 4 is the flowchart of Step 6 of the present invention.

[0026] Figure 5 is a schematic diagram of the molecular configuration and electron cloud distribution of the non-metallic anti-knock agent of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0027] To better understand the technical content of the present invention, the present invention will be further described below with reference to the accompanying drawings.

[0028] In this embodiment, the straight-chain or branched-chain fatty amine is selected from n-decylamine and tetradecylamine, the aromatic amine is selected from isopropyl aniline, the multi-substituted fatty amine is selected from triethylhexylamine, and the hydrated electron base liquid is selected from the electromagnetic base liquid prepared in US11691906B1 patent.

[0029] The above liquid raw materials are dehydrated through a molecular sieve (4Å) to make the water content <50 ppm; then nitrogen is bubbled through under a reduced pressure of 10-15 kPa for 20 minutes to deoxidize; the dehydrated hydrated electron base liquid is prepared and stored under nitrogen protection.

[0030] As Figure 1 shown, the production of the product of the present invention includes the following steps: Step 1: Weigh the reaction raw materials according to the following mass ratio n-decylamine: 40 parts tetradecylamine: 15 parts isopropyl aniline: 20 parts triethylhexylamine: 15 parts hydrated electron base liquid: 10 parts Step 2: Conduct systematic deoxygenation of the reaction vessel, that is, conduct vacuum-nitrogen replacement 5 times to make the final oxygen content <5 ppm; purge the pipeline of the reaction vessel with nitrogen for 30 minutes, and then conduct positive pressure sealing detection of the vessel, with a pressure drop <0.02 MPa / 4 h to obtain an oxygen-free reaction vessel; the reaction vessel uses a modified PTFE sealing ring with a compression ratio ≥25% to ensure the airtightness inside the reaction vessel.

[0031] Put the weighed raw materials into the oxygen-free reaction vessel at one time, and introduce carbon monoxide gas into the reaction vessel to 0.1 MPa; Step 3: Mix and stir each raw material in the reaction vessel, Stirring time: 60 min Stirring temperature: 10 °C Pressure: 1.0 MPa Stirring rate: 600 rpm System potential: -350 mV Inert gas protection: Continuously introduce high-purity nitrogen (99.999%) at a flow rate of 15 mL / min System oxygen content: <5 ppm Step 4: Introduce inert gas protection into the reaction vessel to make the oxygen content in the reaction vessel <15 ppm, and continue stirring to obtain a mixture.

[0032] Stirring time: 120 min Temperature: 35°C Pressure: 2.0MPa Stirring rate: 800rpm System potential: -350mV Inert gas protection: Continuously introduce high-purity nitrogen gas (99.999%) with a flow rate of 15mL / min Throughout the reaction, a zirconia sensor is used to monitor the oxygen content in the reaction vessel in real time. When the oxygen content > 20ppm, an alarm is automatically triggered and inert gas is replenished. The process continuously removes oxygen, i.e., through slightly positive pressure inert gas protection.

[0033] The detection parameters of the mixture are as follows: Purity: 85% As Figure 5 shown, the purity refers to the proportion of the cis-configured R1R2N-CHO generated therein. This carbonylamine compound has a special electron cloud distribution.

[0034] Yield: 78% Stability: It is effective within 6 months of storage at room temperature.

[0035] When the mixture is added to gasoline, the octane number performance is improved as follows:

[0036] As Figure 2 shown, the pretreatment of the present invention includes the following steps: Weigh 15% of the hydrated electron base liquid by mass percentage and use a plasma discharge facility to activate the hydrated electron base liquid under the protection of an inert gas. The hydrated electron base liquid is the electromagnetic base liquid prepared in US11691906B1 patent. The activation parameters are: Frequency: 13.56 ± 0.5MHz; Power: 100W; Inert gas flow rate: 20mL / min; Weigh 85% of the hydrated electron base liquid by mass percentage and stir and mix it with the activated hydrated electron base liquid under the protection of an inert gas. The stirring parameters are as follows: Temperature: -10°C; Pressure: 0.5Mpa Stirring rate: 400rpm, System potential: -1.8V, pH value: 14.0, Inert gas flow rate: 15mL / min Oxygen content: <5ppm Mixing time: 60 minutes After the stirring ends, a homogeneous and transparent double electron donor is obtained.

[0037] In this embodiment, the linear or branched aliphatic amines are selected from n-decylamine and tetradecylamine, the aromatic amine is selected from isopropyl aniline, and the polysubstituted aliphatic amine is selected from triethylhexylamine. The above liquid raw materials are dehydrated through a molecular sieve (4Å) to make the water content <50 ppm; then nitrogen is bubbled through under a reduced pressure of 10 - 15 kPa for 20 minutes for deoxidation; the dehydrated double electron donor is prepared and stored under nitrogen protection.

[0038] Step 1: Weigh the reaction raw materials according to the following mass ratios n-Decylamine: 51 parts Tetradecylamine (97.5%): 24 parts Isopropyl aniline (98%): 10 parts Triethylhexylamine (98%): 5 parts Double electron donor: 10 parts Step 2: Conduct systematic deoxidation of the reaction vessel, that is, conduct vacuum-nitrogen replacement 3 times to make the final oxygen content <10 ppm; conduct nitrogen purging of the pipeline of the reaction vessel for 30 minutes, and then conduct positive pressure sealing detection of the vessel, with the pressure drop <0.02 MPa / 4 h to obtain an oxygen-free reaction vessel; the reaction vessel uses a modified PTFE sealing ring with a compression ratio ≥25% to ensure the airtightness inside the reaction vessel.

[0039] Put the weighed raw materials into the oxygen-free reaction vessel at one time, and introduce carbon monoxide gas into the reaction vessel to 6 MPa; Step 3: Mix and stir each raw material in the reaction vessel, Time: 45 min Temperature: 35 °C Pressure: 2 MPa Stirring rate: 800 rpm System potential: -1.2 V Inert gas protection: Continuously introduce high-purity nitrogen (99.999%) at a flow rate of 15 mL / min System oxygen content: <5 ppm Step 4: Introduce inert gas protection into the reaction vessel to make the oxygen content in the reaction vessel <10 ppm, and continue stirring to obtain a mixture.

[0040] Time: 60 min Temperature: 60 °C Pressure: 2.5 MPa Stirring rate: 1200 rpm System potential: -1.2 V Inert gas protection: Continuously introduce high-purity nitrogen (99.999%) at a flow rate of 15 mL / min System oxygen content: <5 ppm Throughout the reaction, a zirconia sensor is used to monitor the oxygen content in the reaction vessel in real time. When the oxygen content > 20 ppm, an alarm is automatically triggered and inert gas is replenished. The process continuously removes oxygen, i.e., through micro-positive pressure inert gas protection.

[0041] The principle of this embodiment is as follows: The hydrated electron base liquid and the activated hydrated electron base liquid form a double electron donor, and this process can be represented by the following reaction equations: H2O + e⁻(plasma) → e⁻(aq) + H2O (1) e⁻(aq) +nH2O → [e⁻(H2O)n] (2) [e⁻(H2O)n] + e⁻(plasma) → [2e⁻(H2O)n] (3); Thus, it can be seen that the double electron donor provides stronger reducing ability and higher stability than a single electron donor. The electron transfer between the activated double electron donor system and carbon monoxide can be represented by the following reaction equations: CO + [2e⁻(H2O)n] → [CO•⁻(H2O)n] + e⁻(aq) (4) [CO•⁻(H2O)n] → CO•⁻ + nH2O (5); The activated CO radical anion undergoes a nucleophilic addition reaction with an amine compound, and then forms the final product through hydrogen transfer: R1R2NH + CO•⁻ → R1R2N-CO⁻ + H• (6) R1R2N-CO⁻ + H• → R1R2N-CHO (7), where R1 and R2 represent different alkyl or aryl substituents.

[0042] The detection parameters of the mixture are as follows: Purity: 87% Yield: 78% Stability: It is effective within 6 months of storage at room temperature.

[0043] When the mixture is added to gasoline, the octane number performance improvement is as follows: Thus, it can be seen that compared with Example 1, after adding the pretreatment step, the performance of the product has little difference, but the reaction time is greatly shortened.

[0044] (1) Main equipment parameters Continuous flow reactor: 316L stainless steel, inner diameter 95mm, effective volume 2.5L Temperature control system: Jacketed type, temperature control accuracy ±0.5°C Flow control system: Electromagnetic metering pump, accuracy ±0.5% Pressure control system: Back pressure valve, response time <1s (2) Monitoring system configuration Online pH / ORP electrode: German WTW brand Temperature sensor: PT100, accuracy ±0.1°C Pressure sensor: 0 - 10 MPa, accuracy 0.1% PLC control system: Siemens S7 - 300 series

[0045] Weigh 35% of the hydrated electron base liquid by mass percentage, and under the protection of inert gas, use a plasma discharge facility to activate the hydrated electron base liquid. The hydrated electron base liquid is the electromagnetic base liquid prepared in the US11691906B1 patent, and the activation parameters are as follows: Frequency: 13.56 ± 0.5 MHz; Power: 300 W; Inert gas flow rate: 80 mL / min; Weigh 65% of the hydrated electron base liquid by mass percentage, and under the protection of inert gas, stir and mix it with the activated hydrated electron base liquid. The stirring parameters are as follows: Temperature: 10°C; Pressure: 1 Mpa Stirring rate: 600 rpm, System potential: -1.8 V, pH value: 14.0, Inert gas flow rate: 50 mL / min Oxygen content: <5 ppm Mixing time: 30 minutes After stirring, a homogeneous and transparent double electron donor is obtained.

[0046] In this example, the straight-chain or branched-chain aliphatic amine is selected from n-decylamine and tetradecylamine, the aromatic amine is selected from isopropyl aniline, and the poly-substituted aliphatic amine is selected from triethylhexylamine.

[0047] The above liquid raw materials are dehydrated through a molecular sieve (4Å) to make the water content <50 ppm; then nitrogen is bubbled through under a reduced pressure of 10 - 15 kPa for 20 minutes to deoxygenate; the dehydrated double electron donor is prepared and stored under nitrogen protection.

[0048] Step 1: Weigh the reaction raw materials according to the following mass ratio n-Decylamine: 52 parts Tetradecylamine: 8 parts Isopropyl aniline: 25 parts Triethylhexylamine: 10 parts Double electron donor: 5 parts Step 2: Introduce an inert gas into the feed end at a flow rate of 35 ± 1 mL / min for 12 min. Control the temperature at the feed end at 8 ± 1 °C. Feed the weighed raw materials into the reaction vessel from the feed end, and introduce carbon monoxide gas into the reaction vessel until the pressure reaches 0.9 ± 0.1 MPa; Step 3: Mix and stir all the raw materials in the reaction vessel, Time: 50 min Temperature: 22 ± 1 °C Pressure: 1.9 MPa Stirring rate: 700 rpm System potential: -1.8 V Inert gas protection: Continuously introduce high-purity nitrogen gas (99.999%) at a flow rate of 32 ± 1 mL / min for 25 min; System oxygen content: <5 ppm Step 4: Continuously introduce high-purity nitrogen gas (99.999%) at a flow rate of 30 ± 1 mL / min for 28 min; Make the oxygen content in the reaction vessel <10 ppm, and continue stirring to obtain a mixture.

[0049] Time: 70 min Temperature: 42 ± 1 °C Pressure: 2.3 MPa Stirring rate: 1000 rpm System potential: -1.8 V System oxygen content: <5 ppm.

[0050] The detection parameters of the mixture are as follows: Purity: 90% Yield rate: 82% Stability: It has an effect within 9 months of storage at room temperature.

[0051] When the mixture is added to gasoline, the octane number performance improvement is as follows: Thus, it can be seen that the continuous flow method not only maintains the high-performance characteristics of the product, but also achieves higher production efficiency and more stable product quality. This continuous production mode is a technical advantage that is difficult to achieve by the traditional batch method, reflecting the potential of the present invention in industrial applications.

[0052] The device and equipment used in this embodiment are as follows: Reaction kettle volume: 500 L Material: Hastelloy C-276 Design pressure: 6.0 MPa Jacket design temperature: -30 °C to 80 °C Weigh 20% of the hydrated electron base liquid by mass percentage, and under the protection of inert gas, use a plasma discharge facility to activate the hydrated electron base liquid. The hydrated electron base liquid is the electromagnetic base liquid prepared in the US11691906B1 patent. The activation parameters are as follows: Frequency: 13.56 ± 0.5 MHz; Power: 200 W; Inert gas flow rate: 60 mL / min; Weigh 80% of the hydrated electron base liquid by mass percentage. Under the condition of inert gas protection, stir and mix it with the activated hydrated electron base liquid. The stirring parameters are as follows: Temperature: 5 °C; Pressure: 0.7 Mpa Stirring rate: 500 rpm, System potential: -800 mV, pH value: 14.0, Inert gas flow rate: 35 mL / min Oxygen content: <5 ppm Mixing time: 45 minutes After stirring, a homogeneous and transparent double electron donor is obtained.

[0053] Step 1: Weigh the reaction raw materials according to the following mass ratio n-Decylamine: 25.6 parts Tetradecylamine: 25.6 parts Isopropyl aniline: 8 parts Triethylhexylamine: 4 parts Hydrated electron base liquid (double electron donor): 4.5 parts Dehydrate the above liquid raw materials through a molecular sieve (4 Å), and then introduce nitrogen gas for bubbling deoxidation for 20 minutes under a reduced pressure condition of 10 - 15 kPa; make the water content <50 ppm; the dehydrated double electron donor is prepared and stored under nitrogen protection.

[0054] Step 2: Conduct systematic deoxidation of the reaction vessel, that is, conduct vacuum-nitrogen replacement 4 times to make the final oxygen content <5 ppm; purge the pipeline of the reaction vessel with nitrogen for 40 minutes, and then conduct a positive pressure seal detection of the vessel, with a pressure drop <0.02 MPa / 4 h to obtain an oxygen-free reaction vessel; the reaction vessel uses a modified PTFE sealing ring with a compression ratio ≥25% to ensure the airtightness inside the reaction vessel.

[0055] Put the weighed raw materials into the oxygen-free reaction vessel at one time, and introduce carbon monoxide gas into the reaction vessel to 3.3 MPa; Step 3: Mix and stir each raw material in the reaction vessel, Stirring time: 50 min Stirring temperature: 15°C Pressure: 1.5 MPa Stirring rate: 700 rpm System potential: -800 mV Inert gas protection: Continuously introduce high-purity nitrogen gas (99.999%) at a flow rate of 15 mL / min System oxygen content: <5 ppm Step 4: Introduce inert gas protection into the reaction vessel to make the oxygen content in the reaction vessel <15 ppm, and continue stirring to obtain a mixture.

[0056] Stirring time: 120 min Temperature: 35°C Pressure: 2.0 MPa Stirring rate: 800 rpm System potential: -800 mV Inert gas protection: Continuously introduce high-purity nitrogen gas (99.999%) at a flow rate of 15 mL / min Real-time monitor the oxygen content of the reaction vessel. When the oxygen content >20 ppm, automatically alarm and supplement inert gas, and continuously remove oxygen during the process, that is, through slightly positive pressure inert gas protection.

[0057] As Figure 3 shown, Step 5: Place the mixture obtained in Step 4 in a fully glass vacuum distillation device, which is equipped with a 30-stage fractionating column, a reflux ratio controller, a digital temperature monitoring system, and a precision vacuum control unit.

[0058] Vacuum the system to 0.1 kPa, then introduce high-purity nitrogen gas (99.999%) for replacement 3 times, each time lasting 5 minutes, with a flow rate of 60 mL / min, to ensure that the system oxygen content is less than 15 ppm. Subsequently, start the preheating process, slowly raise the temperature in the device to 30°C, and maintain it for 30 minutes to make the system fully homogenized.

[0059] First fraction: At a pressure of 5 kPa, control the temperature at 35°C, collect low-boiling impurities and residual solvents, for 60 minutes, and control the reflux ratio at 8:1.

[0060] Second fraction: At a pressure of 2 kPa, control the temperature at 45°C, collect unreacted raw materials and some intermediates, for 90 minutes, and reduce the reflux ratio to 5:1; Third fraction: At an ultra-high vacuum of 0.5 kPa, control the temperature at 60°C, collect the main target product, for 120 minutes, and further reduce the reflux ratio to 3:1; The vacuum degree fluctuation is controlled within ±0.2 kPa, and the bottom temperature of the column never exceeds 90 °C to prevent the degradation of heat-sensitive components. Nitrogen is continuously introduced during the distillation process, and the flow rate is controlled at 20 mL / min to exclude trace oxygen that may infiltrate into the system.

[0061] The target product obtained from the three distillates is collected in a collection bottle pre-filled with nitrogen. The collection bottle is placed in a low-temperature bath at 0 °C to prevent the loss of volatile components. The distillation rate is precisely controlled at 1.5 - 3.0 L / h (based on a 100 L reactor scale), and the condenser temperature is maintained at 0 ± 5 °C.

[0062] The target product is added to gasoline to improve the octane number performance as follows: It can be seen that compared with traditional high-temperature distillation (120 - 180 °C), vacuum distillation does not require high-pressure and high-temperature equipment, and can significantly reduce the equipment investment and maintenance costs required for production.

[0063] The previous steps are the same as those in Example 4 After obtaining the target product, continue with liquid-liquid extraction and chromatographic separation of the target product.

[0064] Step Six: Under the protection of an inert gas, 50 parts of liquid ammonia, 35 parts of tetrahydrofuran, and 15 parts of ether are mixed according to the mass ratio. The liquid ammonia is food-grade liquid ammonia with a purity ≥ 99.9%; the tetrahydrofuran is pretreated with molecular sieves (4 Å) for 24 hours; the ether solvent (preferably diisopropyl ether or methyl tert-butyl ether) is refluxed with metallic sodium to remove water. The three solvents are slowly mixed at a low temperature of -40 °C under nitrogen protection (flow rate 25 mL / min), the stirring rate is 200 rpm, the mixing time is 30 min, and the oxygen content is always maintained < 10 ppm during the stirring process; ensure the formation of a homogeneous and transparent mixed solvent.

[0065] Weigh 25 parts of the target product, mix 25 parts of the target product with 100 parts of the mixed solvent, and perform liquid-liquid extraction separation. The extraction is carried out in a dedicated double-jacketed glass reactor equipped with a mechanical stirrer, a temperature control system, and a nitrogen protection device. The extraction temperature is 35 °C, the stirring rate is 350 rpm, and the extraction time is 60 minutes. The entire extraction process is carried out under nitrogen protection with a flow rate of 20 mL / min to ensure that the oxygen content in the system is always below 10 ppm.

[0066] After the extraction is completed, the mixture is left to stand at 40°C for 30 minutes for phase separation. The lower layer (the organic phase rich in the target product) is carefully collected through the bottom sampling valve, and nitrogen gas is continuously introduced (flow rate 15 mL / min) during the collection process for protection. The upper layer (the aqueous phase containing impurities) is collected and then recycled. The organic phase is washed once more with a small amount of fresh mixed solvent (20% of the original volume), and the above-mentioned phase separation and collection processes are repeated. The finally obtained organic phase enters the next chromatographic separation stage.

[0067] Chromatographic separation is carried out using a high-performance liquid chromatography system (HPLC) equipped with a C18 reverse-phase chromatographic column (250 mm × 4.6 mm, 5 μm particle size, 100 - 300 Å pore size). The chromatographic column undergoes strict pretreatment before use: first, it is flushed with HPLC-grade methanol at a flow rate of 1.0 mL / min for 60 minutes, and then equilibrated with the mobile phase for 90 minutes while stabilizing the column temperature at 35 ± 0.5°C.

[0068] The mobile phase is a mixed solvent of methanol / tetrahydrofuran (70:30, v / v), and 0.1% triethylamine is added to adjust the pH to 8.5 ± 0.2. The mobile phase is filtered through a 0.22 μm filter membrane and subjected to on-line degassing treatment. During operation, the flow rate is controlled at 1.0 mL / min, and the injection volume is 30 μL (for large-scale preparation, a preparative chromatographic column is used and the injection volume is increased accordingly). Detection is carried out using a dual-wavelength UV detector, and the set wavelengths are 210 nm and 254 nm.

[0069] During the chromatographic separation process, nitrogen gas continuously passes through the system at a flow rate of 15 mL / min, especially in the areas of the injection port and the collection port. The collection range of the target product peak is strictly set from the starting point (signal-to-noise ratio ≥ 10) to the end point of the peak. Usually, the elution time is 15 - 25 minutes (which may vary according to specific chromatographic conditions), and the collected fractions are immediately placed in a collection device equipped with nitrogen protection and low-temperature control (5 ± 2°C).

[0070] HPLC purity analysis is carried out on the collected target product fractions to ensure that the purity is ≥ 99.0% (area normalization method). If the purity does not meet the standard, secondary chromatographic purification is carried out. The qualified purified sample is carefully evaporated to remove the mobile phase through a rotary evaporator (40°C, 2.0 kPa), and nitrogen gas is continuously introduced (flow rate 8 - 15 mL / min) throughout the concentration process to exclude oxygen, and the product purity is ≥ 99%.

[0071] The purified product is added to gasoline to improve the octane number performance as follows: The successful implementation of pilot-scale production further verifies the scalability and industrial application value of the technology of the present invention. Especially during the scale-up process, a stable potential window (-350 mV to -1.8 V) is still maintained, which is a key factor to ensure the consistency of product performance.

[0072] The loss rate of this antiknock agent under the conditions of 150°C / 24h is reduced to 4%, and the storage period is extended to 24 months. It increases the ONCE value by 10 - 15% to reach 0.10 - 0.15 ON / ppm. Remove chromophore groups: effectively remove the chromophores formed during the reaction process, making the final product a colorless to light yellow transparent liquid and avoiding chromaticity effects on the fuel. Remove potential sediment precursors: remove high molecular weight polymers and polar impurities that may form sediments in the engine through post-treatment, improving the compatibility and detergency of the product in the engine.

[0073] The previous steps are the same as those in Example 4.

[0074] After obtaining the target product, continue with liquid-liquid extraction and crystallization purification of the target product.

[0075] As Figure 4 shown, Step 6: Under the protection of an inert gas, mix 60 parts of liquid ammonia, 15 parts of tetrahydrofuran, and 25 parts of ether by mass ratio. The liquid ammonia is food-grade liquid ammonia with a purity of ≥99.9%; the tetrahydrofuran is pretreated with molecular sieve (4Å) for 24 hours; the ether solvent (preferably diisopropyl ether or methyl tert-butyl ether) is refluxed with metallic sodium to remove water. The three solvents are slowly mixed under low-temperature conditions of -40°C under nitrogen protection (flow rate 25 mL / min), with a stirring rate of 200 rpm and a mixing time of 30 min. During the stirring process, the oxygen content is always maintained at <10 ppm; ensure the formation of a homogeneous and transparent mixed solvent.

[0076] Weigh 10 parts of the target product, mix 10 parts of the target product with 90 parts of the mixed solvent, and perform liquid-liquid extraction separation. The extraction is carried out in a dedicated double-jacketed glass reactor equipped with a mechanical stirrer, a temperature control system, and a nitrogen protection device. The extraction temperature is 35°C, the stirring rate is 350 rpm, and the extraction time is 60 minutes. The entire extraction process is carried out under nitrogen protection with a flow rate of 20 mL / min to ensure that the oxygen content in the system is always below 10 ppm.

[0077] After the extraction is completed, let the mixture stand for 30 minutes to separate layers at 40°C. The lower layer (the organic phase rich in the target product) is carefully collected through the bottom sampling valve, and nitrogen (flow rate 15 mL / min) is continuously introduced for protection during the collection process. The upper layer (the water phase containing impurities) is collected and then recycled. The organic phase is washed once with a small amount of fresh mixed solvent (20% of the original volume), and the above-mentioned layer separation and collection processes are repeated. The finally obtained organic phase enters the next crystallization purification stage.

[0078] Place the organic phase after liquid-liquid extraction into a crystallization reactor. The reactor is designed with double jackets and is equipped with a precision temperature control system, a low-shear stirrer, and a nitrogen protection device. The crystallization reactor undergoes strict deoxygenation treatment before use: evacuate to 0.1 kPa under vacuum, then fill with high-purity nitrogen (99.999%), repeat this process 3 times, and finally maintain a slightly positive pressure (0.02 MPa) nitrogen environment.

[0079] Add a dissolving solvent (toluene / n-hexane mixed solvent, 2.5:7.5, v / v) to the reactor, and add a small amount of tetrahydrofuran (7% of the total volume) as a co-solvent. The amount of solvent added is 5 times the mass of the substance to be crystallized. Slowly heat the system to 60 °C and completely dissolve the substance to be crystallized at a stirring rate of 130 rpm, and maintain this temperature for 30 minutes to ensure complete dissolution.

[0080] Crystallization is carried out by the programmed cooling method: first cool from 60 °C to 30 °C at a rate of 0.8 °C / min; at 30 ± 2 °C, if the seed crystal method is used, add 0.8% of high-purity seed crystals (crystallized from a pre-verified previous batch product); then continue to cool at a slower rate of 0.25 °C / min to -10 °C and maintain this temperature for 10 hours to complete crystal growth. Throughout the crystallization process, nitrogen continuously passes through the upper space of the reactor at a constant flow rate of 15 mL / min to ensure that the oxygen content ≤ 10 ppm. The stirring rate gradually decreases with temperature: 130 rpm in the range of 60 - 40 °C, 100 rpm in the range of 40 - 20 °C, and 80 rpm below 20 °C to avoid crystal breakage and secondary nucleation.

[0081] After crystallization is completed, at -5 °C, transfer the crystal slurry to a pre-cooled Buchner funnel for vacuum filtration. Wash the filter cake twice with a small amount (20% of the original solvent volume) of n-hexane pre-cooled to -10 °C, and then transfer the filter cake to a vacuum dryer and dry it at 40 °C and 0.05 MPa for 5 hours, and continuously introduce nitrogen (flow rate 5 - 10 mL / min) for protection throughout the drying process.

[0082] Perform quality inspection on the dried crystal product: the purity should reach ≥ 99.5% (HPLC method), the moisture content ≤ 50 ppm (Karl Fischer method), and the metal ion content ≤ 0.5 ppm (ICP-MS method). Confirm that the molecular configuration and crystal structure of the product meet the expected design through infrared spectroscopy and X-ray diffraction, and the crystallization yield is 94%.

[0083] For the final product obtained by either chromatographic separation or crystallization purification, strict quality inspection and standardized packaging are required. Quality inspection includes key indicators such as appearance inspection (should be a colorless to light yellow transparent liquid or white to light yellow crystal), antiknock performance test (ONCE value should reach 0.08 - 0.15 ON / ppm), thermal stability test (loss at 150°C / 24h should be ≤5%), etc.

[0084] Qualified products are filled into pre-treated amber glass bottles or metal containers lined with fluororesin under nitrogen protection (flow rate 3 - 5 mL / min) and sealed immediately. Before sealing, the container is purged with high-purity nitrogen 3 times to ensure that the oxygen content in the packaging environment is ≤10 ppm. Each packaging unit does not exceed 1 kg to facilitate use and ensure product stability. The product name, batch number, production date, and recommended storage conditions (recommended storage temperature is 5 - 25°C, store in the dark and sealed) are clearly marked on the packaging container.

[0085] Adding the purified product to gasoline improves the octane number performance as follows:

[0086] The previous steps are the same as in Example 4 After obtaining the target product, continue with liquid-liquid extraction and crystallization purification of the target product.

[0087] Step six: Under the protection of an inert gas, mix 70 parts of liquid ammonia, 25 parts of tetrahydrofuran, and 5 parts of diethyl ether by mass ratio, and the mixing method is the same as in Example 6.

[0088] Weigh 10 parts of the target product, mix 10 parts of the target product with 80 parts of the mixed solvent, and perform liquid-liquid extraction separation. The liquid-liquid extraction method is the same as in Example 6. After extraction, perform crystallization purification, and the crystallization purification method is the same as in Example 6. Adding the purified product to gasoline improves the octane number performance as follows: Compared with Example 5, for Example 6 and Example 7, cold start performance: 15% improvement, acceleration response: 8% increase, tail gas emissions: 5.5% reduction; storage stability (40°C): ≥12 months; thermal stability (150°C): ≥24 hours; low temperature stability (-20°C): ≥7 days; metal compatibility: no corrosion; seal material compatibility: no swelling; base fuel compatibility: complete miscibility; safety parameters: flash point: >82°C, autoignition temperature: >180°C, explosion limit: not applicable under normal conditions.

[0089] These performance indicators are all superior to existing non-metallic antiknock agents, and some indicators are even close to those of metallic antiknock agents. At the same time, it overcomes the environmental defects of metallic antiknock agents, fully demonstrating the revolutionary breakthrough of the present invention.

Claims

1. A non-metallic antiknock agent, characterized in that, It contains the following components by mass percentage: 55 - 75% of straight-chain or branched-chain fatty amines, 10 - 25% of aromatic amines, 5 - 15% of polysubstituted fatty amines, and 5 - 15% of electron donors; The electron donor uses a hydrated electron-based liquid.

2. The non-metallic anti-explosion agent according to claim 1, characterized in that, The straight-chain or branched-chain fatty amines use C4 - C20 fatty amines.

3. The non-metallic anti-explosion agent according to claim 1, wherein The aromatic amines use monocyclic or polycyclic aromatic amines.

4. The non-metallic anti-explosion agent according to claim 1, wherein, The polysubstituted fatty amines use C2 - C18 fatty amines with 1 - 6 alkyl substituents.

5. The preparation method of the non-metallic anti-knock agent according to any one of claims 1-4, characterized in that, Throughout the preparation process, it is always carried out in an environment with an oxygen content < 10 ppm, including the following steps: Step 1: Weigh straight-chain or branched-chain fatty amines accounting for 55 - 75% by mass percentage, aromatic amines accounting for 10 - 25% by mass percentage, polysubstituted fatty amines accounting for 5 - 15% by mass percentage, and electron donors accounting for 5 - 15% by mass percentage; Step 2: Put the weighed raw materials into the reaction vessel at one time, and introduce carbon monoxide gas into the reaction vessel to 0.1 - 6.0 MPa; Step 3: In the temperature range of 10 - 35 °C, mix and stir the various raw materials in the reaction vessel. The stirring pressure is 1.0 - 2.0 Mpa, the stirring rate is 600 - 800 rpm, and the stirring time is 45 - 60 min; Step 4: Continue stirring in the temperature range of 35 - 60 °C. The stirring pressure is 2.0 - 2.5 Mpa, the stirring rate is 800 - 1200 rpm, and the stirring time is 60 - 120 min to obtain a mixture.

6. The preparation method of the non-metallic anti-explosion agent according to claim 5, characterized in that, It also includes a pretreatment step: Weigh 15 - 35% of the hydrated electron-based liquid by mass percentage, and use a plasma discharge facility to activate the hydrated electron-based liquid under the protection of an inert gas. The activation parameters are: Frequency: 13.56 ± 0.5 MHz; Power: 100 - 300 W; Inert gas flow rate: 20 - 80 mL / min; Weigh 65 - 85% of the hydrated electron-based liquid by mass percentage, and under the condition of inert gas protection, stir and mix it with the activated hydrated electron-based liquid until a homogeneous and transparent electron donor is formed. The stirring parameters are as follows: Temperature: -10 - 10 °C; Pressure: 0.5 - 1.0 Mpa Stirring rate: 400 - 600 rpm, System potential: -350 mV~-1.8 V, pH value: 14.0, Inert gas flow rate: 15 - 50 mL / min Oxygen content: < 5 ppm Mixing time: 30 - 60 minutes.

7. The preparation method of the non-metallic anti-explosion agent according to claim 5 or 6, characterized in that, It also includes Step 5: Vacuum distillation, and the vacuum distillation includes the following steps: System deoxygenation: Evacuate the distillation device to 0.1 kPa and then introduce an inert gas Preheating: The temperature is 30 - 35 °C, and the preheating time is 30 - 45 minutes; First fraction: The pressure is 5.0 - 10.0 kPa, the temperature is 35 - 45 °C, and the fractionation time is 60 - 90 minutes; This fraction removes low-boiling impurities and residual solvents; Second fraction: The pressure is 2.0 - 5.0 kPa, the temperature is 45 - 60 °C, and the fractionation time is 90 - 120 minutes; This fraction removes unreacted raw materials and some intermediates; Tertiary fraction: pressure is 0.5 - 2.0 kPa, temperature is 60 - 85 °C, fractionation time is 120 - 180 minutes; the main target product is obtained; The reflux ratios of the primary fraction, secondary fraction, and tertiary fraction decrease in sequence. The range value of the reflux ratio is 3:1 - 8:1, and the distillation rate is 1.5 - 3.0 L / h.

8. The preparation method of the non-metallic anti-explosion agent according to claim 7, characterized in that, It also includes Step Six: 1) Weigh 50 - 70% by mass of liquid ammonia, 15 - 35% of tetrahydrofuran, and 5 - 25% of an ether solvent and mix them under the protection of an inert gas to obtain a mixed solvent. All the solvents are treated without water, and the water content ≤ 200 ppm; the stirring rate is 200 - 250 rpm, the mixing time is not less than 30 min, the temperature is -40 °C, the temperature fluctuation during mixing is ±2 °C, and the oxygen content < 10 ppm; 2) Weigh 80 - 90% of the mixed solvent and 10 - 20% of the main target product by mass ratio; 3) Under the protection of an inert gas, perform liquid-liquid extraction on the main target product with the mixed solvent to obtain an organic phase; 4) Under the protection of an inert gas, perform chromatographic separation or crystallization purification on the extracted organic phase.

9. Use of the non-metallic anti-knock agent according to any one of claims 1 to 4 in gasoline, characterized in that: Addition concentration: 8.3 - 100 ppm.

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