CN115304770B - Environment-friendly petroleum auxiliary agent and preparation method thereof - Google Patents
Environment-friendly petroleum auxiliary agent and preparation method thereof Download PDFInfo
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- CN115304770B CN115304770B CN202211076702.9A CN202211076702A CN115304770B CN 115304770 B CN115304770 B CN 115304770B CN 202211076702 A CN202211076702 A CN 202211076702A CN 115304770 B CN115304770 B CN 115304770B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
Abstract
The invention discloses a preparation method of an environment-friendly petroleum auxiliary agent, which is characterized in that ferrocene is added in the process of preparing carboxyl modified silicone oil, aliphatic olefine acid and a chlorosilane compound are catalyzed to generate carboxyalkyl methylchlorosilane monomers, and the carboxyalkyl methylchlorosilane monomers containing a ferrocene structure are formed by coordination, and finally the environment-friendly petroleum auxiliary agent mainly comprising carboxyl silicone oil compounds containing ferrocene structural units is generated through polymerization reaction. The inert structure of silicone oil is utilized to protect the ferrocene structure, so that the stability and the dispersibility are improved, the granularity and the density of carbon smoke particles are reduced, the diesel oil conversion rate is improved, the power is improved, the exhaust emission is reduced, and the deposition of metal components is prevented. The metal simple substance is further added to promote the polymerization reaction, and meanwhile, the metal element is doped into the ferrocene crystal structure to form the carboxyl silicone oil compound containing the multi-element metallocene structural unit, so that various performances of the diesel oil after the environment-friendly petroleum auxiliary agent is added are further improved.
Description
Technical Field
The invention belongs to the technical field of chemical petroleum additives, and particularly relates to an environment-friendly petroleum additive and a preparation method thereof.
Background
Petroleum products can be largely classified into 6 types of petroleum fuels, petroleum solvents and chemical materials, lubricants, paraffin waxes, petroleum asphalt, petroleum coke, and the like. Petroleum aids primarily refer to chemicals used to improve the performance of petroleum products in use and storage. Such as: lubricating oil additives, fuel oil additives, and the like.
With the continuous improvement of the living standard of people, automobiles are continuously popularized, and automobile fuel becomes a large consumable. Although new energy automobiles are increasingly popular, petroleum fuels still occupy the main place of automobile fuels because of the advantages of higher conversion rate, stronger power supply and the like. Compared with natural gas, petroleum fuel is easier to accumulate carbon, so that the abrasion of engine cylinder parts is caused, and the service life is reduced; and more harmful pollutants are discharged by combustion, so that environmental pollution is caused.
Chinese patent CN 108753383A discloses a fuel auxiliary agent, which takes nitromethane and polyisobutene amine as main components, takes 1, 3-diethylbenzene 4-isopropyl toluene, benzotriazole, methyl tertiary butyl ether and 2, 6-di-tertiary butyl p-cresol as auxiliary components, and achieves the effects of improving fuel efficiency, preventing solid substances from forming and reducing pollution by mutually matching the components. One of the main components of the nitromethane can play a role of a combustion improver, improve the octane number and the combustion efficiency, but belongs to the class 2B carcinogen; the other main component polyisobutene amine is a common component of the third-generation fuel additive, plays a role of a cleaning agent, can reduce sediment of an air inlet valve, avoids fuel waste caused by blockage of the air inlet valve, and is easy to cause deposition of a combustion chamber. Therefore, the fuel oil additive provided by the invention has the problems of cleaning, environmental protection and engine maintenance to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an environment-friendly petroleum auxiliary agent and a preparation method thereof. The idea of the invention is mainly as follows: the petroleum auxiliary agent is prepared by using more environment-friendly chemical substances, and the purposes of improving the power, reducing pollution and protecting the engine are achieved by improving the fuel conversion efficiency and reducing the generation of particles in the combustion process.
The preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, mixing aliphatic olefine acid, solvent and 30-50wt% NaOH aqueous solution according to the weight ratio of (4-7): (5-10): (0.3-0.5), condensing and refluxing for 5-10min at 70-90 ℃ under 200-400rpm to obtain saponified solution;
K2. adding ferrocene into saponified solution according to the ratio of (10-20) mL (1-3) and dropwise adding chlorosilane compound with the weight ratio of (1-1.5) to saponified solution at the speed of 2-3 drops/s (2-5), and after the dropwise adding, preserving heat for 2-5 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then performing reduced pressure distillation at 60-80 ℃ and 0.01-0.03MPa to remove a solvent to obtain a product A;
K4. mixing the product A with a chlorosilane compound according to the weight ratio of (1-3) (0.5-1) to obtain a mixed solution B, dripping the mixed solution B into water at the temperature of 30-50 ℃ stirred at the speed of 200-400rpm at the speed of 2-3 drops/s, keeping the volume ratio of the mixed solution B to the water at 1 (1.5-3), reacting for 3-6 hours at the constant temperature and the stirring speed, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to the volume ratio of 1 (1-2), shaking uniformly, standing for layering, removing the water layer, and repeating the process until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding strong acid into hydrolysate solution according to the weight ratio of (60-80) (1-2) under the stirring condition of 100-200rpm, heating to 40-60 ℃, reacting for 3-6h, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of (1-2), shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid matters to obtain the environment-friendly petroleum auxiliary agent.
Metal compound additives are often added to diesel fuel and during combustion, metal ions act as nucleation centers for soot particle deposition and eventually are expelled with the particles in the form of metal oxides. Ferrocene, because the atomization of ferrocene can enable particles to be formed in the early stage of flame, so that the ignition temperature of carbon smoke particles is reduced, the combustion conversion rate of fuel oil is improved, and the emission of particles can be reduced while the power is improved. The anti-knock additive is directly added into fuel oil, so that the anti-knock additive has the anti-knock effect, improves the octane number, is easy to cause metal deposition in an engine, causes faults such as abrasion of a cylinder, poisoning of a sensor and the like, and is easy to oxidize and lose efficacy in the storage process. The organosilicon compound has physiological inertia and low surface energy, and can improve the atomization dispersion performance of the fuel after entering the cylinder of the internal combustion engine, promote the fuel to be fully combusted, thereby improving the combustion efficiency of the fuel and reducing the smoke intensity of tail gas.
According to the invention, ferrocene is added in the process of preparing carboxyl modified silicone oil, and finally an environment-friendly petroleum auxiliary agent mainly comprising carboxyl silicone oil compounds containing ferrocene structural units is generated. The diesel oil has low viscosity, heat resistance, low temperature resistance, oxidation resistance, good stability and good lubricity, and can effectively improve the diesel oil conversion rate, improve the power and reduce the exhaust emission.
Ferrocene is easily oxidized under an acidic condition to generate blue paramagnetic ferrocenium ions, and can be used as a phase transfer catalyst to catalyze aliphatic olefine acid and chlorosilane compounds to generate carboxyalkyl methylchlorosilane monomers, and carboxyl groups coordinate with iron ions in a negative ion mode to form carboxyalkyl methylchlorosilane monomers containing ferrocene structures; at the same time, ferrocene can also form partial organic metal complex with carboxylate in saponifying liquid. And (3) carrying out cohydrolysis on the carboxyalkyl methylchlorosilane monomer containing the ferrocene structure and dimethyl dichlorosilane, and then carrying out polymerization under the action of strong acid to generate the carboxyl silicone oil compound containing the ferrocene structural unit. In the process, the ferrocene structure has a catalytic effect on the polymerization reaction, and is helpful for improving the speed and conversion rate of the polymerization reaction. The carboxyl silicone oil compound containing the ferrocene structural unit has the advantages that the steric hindrance is increased, the iron ions are protected, the oxidation stability is improved, and the nucleation effect of the metal ions can be effectively exerted in the use process. The compound has better dispersion performance after atomization, and the generated particles have low density, small granularity, light weight and uniform dispersion, are easy to discharge along with gas, and prevent the faults of cylinder abrasion and the like caused by metal component deposition.
Preferably, the preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, mixing aliphatic olefine acid, solvent and 30-50wt% NaOH aqueous solution according to the weight ratio of (4-7): (5-10): (0.3-0.5), condensing and refluxing for 5-10min at 70-90 ℃ under 200-400rpm to obtain saponified solution;
K2. adding ferrocene into saponified solution according to the ratio of (10-20) mL (1-3) and dropwise adding chlorosilane compound with the weight ratio of (1-1.5) to saponified solution at the speed of 2-3 drops/s (2-5), and after the dropwise adding, preserving heat for 2-5 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then performing reduced pressure distillation at 60-80 ℃ and 0.01-0.03MPa to remove a solvent to obtain a product A;
K4. mixing the product A with a chlorosilane compound according to the weight ratio of (1-3) (0.5-1) to obtain a mixed solution B, dripping the mixed solution B into water at the temperature of 30-50 ℃ stirred at the speed of 200-400rpm at the speed of 2-3 drops/s, keeping the volume ratio of the mixed solution B to the water at 1 (1.5-3), reacting for 3-6 hours at the constant temperature and the stirring speed, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to the volume ratio of 1 (1-2), shaking uniformly, standing for layering, removing the water layer, and repeating the process until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding strong acid into hydrolysate solution according to the weight ratio of (1-2) under the stirring condition of 100-200rpm to obtain a preparation solution, adding metal simple substance with the material-liquid ratio of (0.5-0.7) g (20-50) mL, heating to 40-60 ℃, reacting for 3-6h, naturally cooling to room temperature, filtering to remove solids, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of (1-2), shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid substances to obtain the environment-friendly petroleum auxiliary agent.
The aliphatic olefine acid is any one of undecylenic acid and docosahexaenoic acid.
The chlorosilane compound is any one of methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane.
The solvent is any one of toluene, normal hexane and petroleum ether.
The strong acid is any one of concentrated sulfuric acid and trifluoromethanesulfonic acid; preferably, the strong acid is trifluoromethanesulfonic acid.
The metal simple substance is at least one of cerium, barium, calcium and zinc.
Preferably, the metal simple substance is a mixture of cerium and barium.
Further preferably, the metal simple substance is formed by mixing cerium and barium according to the weight ratio of (1-3) to (2-4).
The metal simple substance can further catalyze the polymerization reaction to be carried out, and is doped into a ferrocene crystal structure to form a carboxyl silicone oil compound containing a multi-element metallocene structural unit, so that the conversion rate of diesel oil after the environment-friendly petroleum auxiliary agent is added is further improved, the power is improved, and the exhaust emission is reduced. Meanwhile, the metal simple substance generates organic sulfonate under the action of trifluoromethanesulfonic acid, has the functions of rust prevention, dispersion, solubilization, oxidization promotion and the like, and is beneficial to improving the preservation performance and combustion performance of diesel oil. The cerium-based compound can reduce the concentration of organic carbon compounds, lower the ignition point and increase the oxidation rate. The barium-based compound promotes the combustion of the soot particles and reduces the emissions of the carbon compound particles, known as a smoke abatement additive. When the two are simultaneously present, the diesel performance is improved, and the emission effect of reducing the carbon smoke particles is particularly obvious.
The invention has the beneficial effects that: according to the invention, ferrocene is added in the process of preparing carboxyl modified silicone oil, aliphatic olefine acid and chlorosilane compound are catalyzed to generate carboxyalkyl methylchlorosilane monomers, and the carboxyalkyl methylchlorosilane monomers containing ferrocene structures are coordinated to form the environment-friendly petroleum auxiliary agent which mainly contains carboxyl silicone oil compounds containing ferrocene structural units through polymerization reaction. The inert structure of silicone oil is utilized to protect the ferrocene structure, so that the stability and the dispersibility are improved, the granularity and the density of carbon smoke particles are reduced, the diesel oil conversion rate is improved, the power is improved, the exhaust emission is reduced, and the deposition of metal components is prevented. The metal simple substance is further added to promote the polymerization reaction, and meanwhile, the metal element is doped into the ferrocene crystal structure to form the carboxyl silicone oil compound containing the multi-element metallocene structural unit, so that various performances of the diesel oil after the environment-friendly petroleum auxiliary agent is added are further improved.
Detailed Description
The raw materials used in the examples are as follows:
ferrocene, CAS number: 102-54-5, orange powder, particle size: the 80 mesh screen lower material is more than or equal to 87 percent, the first grade product is Tianyuan aviation materials (Yingkou) science and technology Co.
Example 1
The preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, undecylenic acid, normal hexane and 40wt% NaOH aqueous solution are mixed according to the weight ratio of 5:7:0.4, and the mixture is condensed and refluxed for 8 minutes at 80 ℃ and 300rpm to obtain saponified solution;
K2. keeping the temperature and the stirring speed unchanged, adding ferrocene into the saponified solution according to the ratio of 2g to 17mL of the feed liquid, dropwise adding dimethyl dichlorosilane with the weight ratio of 1.2 to 4 to the saponified solution according to the speed of 2 drops/s, and after the dropwise adding, carrying out heat preservation reaction for 3 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then distilling at 70 ℃ under 0.01MPa under reduced pressure to remove a solvent to obtain a product A;
K4. mixing the product A with dimethyldichlorosilane according to a weight ratio of 2:1 to obtain a mixed solution B, dripping the mixed solution B into water at a temperature of 40 ℃ and stirring at a speed of 300rpm at a volume ratio of 1:2, keeping the temperature and stirring speed unchanged, reacting for 5 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to a volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, and repeating the processes until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding trifluoromethanesulfonic acid into hydrolysate solution according to the weight ratio of 70:1 under the stirring condition of 200rpm, heating to 50 ℃, reacting for 4 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of 1:1, standing for layering after shaking uniformly, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid matters to obtain the environment-friendly petroleum auxiliary agent.
Example 2
The preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, undecylenic acid, normal hexane and 40wt% NaOH aqueous solution are mixed according to the weight ratio of 5:7:0.4, and the mixture is condensed and refluxed for 8 minutes at 80 ℃ and 300rpm to obtain saponified solution;
K2. keeping the temperature and the stirring speed unchanged, adding ferrocene into the saponified solution according to the ratio of 2g to 17mL of the feed liquid, dropwise adding dimethyl dichlorosilane with the weight ratio of 1.2 to 4 to the saponified solution according to the speed of 2 drops/s, and after the dropwise adding, carrying out heat preservation reaction for 3 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then distilling at 70 ℃ under 0.01MPa under reduced pressure to remove a solvent to obtain a product A;
K4. mixing the product A with dimethyldichlorosilane according to a weight ratio of 2:1 to obtain a mixed solution B, dripping the mixed solution B into water at a temperature of 40 ℃ and stirring at a speed of 300rpm at a volume ratio of 1:2, keeping the temperature and stirring speed unchanged, reacting for 5 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to a volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, and repeating the processes until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding trifluoromethanesulfonic acid into hydrolysate solution according to the weight ratio of 70:1 under the stirring condition of 200rpm to obtain a preparation solution, adding metal simple substance with the material-liquid ratio of 0.6g:30mL into the preparation solution, heating to 50 ℃, reacting for 4 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid substances to obtain the environment-friendly petroleum auxiliary agent.
The metal simple substance is barium.
Example 3
The preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, undecylenic acid, normal hexane and 40wt% NaOH aqueous solution are mixed according to the weight ratio of 5:7:0.4, and the mixture is condensed and refluxed for 8 minutes at 80 ℃ and 300rpm to obtain saponified solution;
K2. keeping the temperature and the stirring speed unchanged, adding ferrocene into the saponified solution according to the ratio of 2g to 17mL of the feed liquid, dropwise adding dimethyl dichlorosilane with the weight ratio of 1.2 to 4 to the saponified solution according to the speed of 2 drops/s, and after the dropwise adding, carrying out heat preservation reaction for 3 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then distilling at 70 ℃ under 0.01MPa under reduced pressure to remove a solvent to obtain a product A;
K4. mixing the product A with dimethyldichlorosilane according to a weight ratio of 2:1 to obtain a mixed solution B, dripping the mixed solution B into water at a temperature of 40 ℃ and stirring at a speed of 300rpm at a volume ratio of 1:2, keeping the temperature and stirring speed unchanged, reacting for 5 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to a volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, and repeating the processes until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding trifluoromethanesulfonic acid into hydrolysate solution according to the weight ratio of 70:1 under the stirring condition of 200rpm to obtain a preparation solution, adding metal simple substance with the material-liquid ratio of 0.6g:30mL into the preparation solution, heating to 50 ℃, reacting for 4 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid substances to obtain the environment-friendly petroleum auxiliary agent.
The metal simple substance is cerium.
Example 4
The preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, undecylenic acid, normal hexane and 40wt% NaOH aqueous solution are mixed according to the weight ratio of 5:7:0.4, and the mixture is condensed and refluxed for 8 minutes at 80 ℃ and 300rpm to obtain saponified solution;
K2. keeping the temperature and the stirring speed unchanged, adding ferrocene into the saponified solution according to the ratio of 2g to 17mL of the feed liquid, dropwise adding dimethyl dichlorosilane with the weight ratio of 1.2 to 4 to the saponified solution according to the speed of 2 drops/s, and after the dropwise adding, carrying out heat preservation reaction for 3 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then distilling at 70 ℃ under 0.01MPa under reduced pressure to remove a solvent to obtain a product A;
K4. mixing the product A with dimethyldichlorosilane according to a weight ratio of 2:1 to obtain a mixed solution B, dripping the mixed solution B into water at a temperature of 40 ℃ and stirring at a speed of 300rpm at a volume ratio of 1:2, keeping the temperature and stirring speed unchanged, reacting for 5 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to a volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, and repeating the processes until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding trifluoromethanesulfonic acid into hydrolysate solution according to the weight ratio of 70:1 under the stirring condition of 200rpm to obtain a preparation solution, adding metal simple substance with the material-liquid ratio of 0.6g:30mL into the preparation solution, heating to 50 ℃, reacting for 4 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid substances to obtain the environment-friendly petroleum auxiliary agent.
The metal simple substance is formed by mixing cerium and barium according to a weight ratio of 2:3.
Comparative example 1
The preparation method of the environment-friendly petroleum auxiliary comprises the following steps:
K1. under the protection of nitrogen, undecylenic acid, normal hexane and 40wt% NaOH aqueous solution are mixed according to the weight ratio of 5:7:0.4, and the mixture is condensed and refluxed for 8 minutes at 80 ℃ and 300rpm to obtain saponified solution;
K2. keeping the temperature and the stirring speed unchanged, dropwise adding dimethyl dichlorosilane with the weight ratio of 1.2:4 to the saponified solution at the speed of 2 drops/s, and carrying out heat preservation reaction for 3 hours after the dropwise adding is finished to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then distilling at 70 ℃ under 0.01MPa under reduced pressure to remove a solvent to obtain a product A;
K4. mixing the product A with dimethyldichlorosilane according to a weight ratio of 2:1 to obtain a mixed solution B, dripping the mixed solution B into water at a temperature of 40 ℃ and stirring at a speed of 300rpm at a volume ratio of 1:2, keeping the temperature and stirring speed unchanged, reacting for 5 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to a volume ratio of 1:1, shaking uniformly, standing for layering, removing the water layer, and repeating the processes until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding trifluoromethanesulfonic acid into hydrolysate solution according to the weight ratio of 70:1 under the stirring condition of 200rpm, heating to 50 ℃, reacting for 4 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of 1:1, standing for layering after shaking uniformly, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, filtering to remove solid matters, and adding ferrocene into filtrate, wherein the dosage of ferrocene is as follows: the ratio of the liquid to the saponified liquid obtained in the step K1 is 2g:17mL to obtain the environment-friendly petroleum auxiliary.
Test example 1
According to the technical requirements of GB 19147-2016 "vehicle Diesel", the performance of No. 0 diesel added with the environment-friendly petroleum additive of each embodiment is tested.
The relevant performance of each diesel oil meets the technical requirements of the diesel oil (IV) for vehicles: oxidation stability (calculated by total insoluble matters) is less than or equal to 2.5mg/100mL; sulfur content is less than or equal to 50mg/kg; the acidity (calculated by KOH) is less than or equal to 7mg/100mL;10% of residual carbon (mass fraction) in the steam residue is less than or equal to 0.3%; ash content (mass fraction) is less than or equal to 0.01%; copper sheet corrosion (50 ℃ for 3 hours) is less than or equal to 1 grade; mechanical impurities: the method is free; the lubricity correction mark grinding diameter (60 ℃) is less than or equal to 460 mu m; the content (mass fraction) of polycyclic aromatic hydrocarbon is less than or equal to 11 percent; kinematic viscosity (20 ℃) 3.0-8.0mm 2 S; the condensation point is less than or equal to 0 ℃; the condensation point is less than or equal to 4 ℃; the flash point (closed) is more than or equal to 60 ℃; the cetane number is more than or equal to 49; the cetane index is more than or equal to 46; distillation range: the recovery temperature is less than or equal to 300 ℃ at 50 percent, is less than or equal to 355 ℃ at 90 percent, and is less than or equal to 365 ℃ at 95 percent; density (20 ℃): 810-850kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The content (volume fraction) of fatty acid methyl ester is less than or equal to 1.0 percent.
Test example 2
Referring to HJ845-2017, in-use diesel vehicle exhaust pollutant measurement method and technical requirement (remote sensing method), mobile remote sensing detection is carried out, and an automobile using No. 0 diesel oil added with the environment-friendly petroleum auxiliary agent of each embodiment is tested, wherein the exhaust pipe of the automobile discharges gaseous pollutants (NO) and particulate matters (calculated by opacity and blackness), and the addition amount is as follows: the weight ratio of the environment-friendly petroleum additive to the No. 0 diesel oil is 1:1000. And taking the No. 0 diesel oil without the environment-friendly petroleum auxiliary agent as a control group. The test results are shown in Table 1.
The test vehicle is: m-type four-wheel passenger car.
The test environmental conditions were: wind speed is 4.2m/s; the temperature is 25 ℃; relative humidity 60%; atmospheric pressure is 80kPa.
TABLE 1 exhaust pollutant test results
Test example 3
The fuel consumption of the automobile with the No. 0 diesel oil added with the environment-friendly petroleum auxiliary agent of each embodiment is tested and calculated according to GB/T19233-2020 light automobile fuel consumption test method, and the addition amount is as follows: the weight ratio of the environment-friendly petroleum additive to the No. 0 diesel oil is 1:1000. Specific methods of operation are described in GB 18352.8-2016 "limit and measure of emissions of pollutants for light vehicles (sixth stage of China)". The test vehicle is: the same class M four-wheel passenger car as in test example 2. And taking the No. 0 diesel oil without the environment-friendly petroleum auxiliary agent as a control group. The test results are shown in Table 2.
TABLE 2 Fuel consumption test results
| CO 2 Emission (g/km) | Fuel consumption (L/100 km) | |
| Example 1 | 1232 | 6.5 |
| Example 2 | 1264 | 6.2 |
| Example 3 | 1275 | 6.0 |
| Example 4 | 1285 | 5.7 |
| Control group | 1030 | 7.6 |
| Comparative example 1 | 1106 | 7.2 |
A low fuel consumption indicates an improved diesel power and, at the same time, CO 2 The increase of the emission amount or the decrease of the emission amount of NO also proves that the diesel is combusted more fully, the conversion rate of the diesel is improved, and more sufficient kinetic energy is provided for the automobile. The fuel consumption is based on Hydrocarbon (HC), carbon monoxide (CO), carbon dioxide (CO) 2 ) Calculated from the amount of emissions, CO while the fuel consumption is reduced 2 The emission amount is increased, the emission amount of HC and CO is correspondingly reduced, and the air pollution is reduced. Opacity and ringeman's blackness are mainly indicative of how much particulate matter in the automobile exhaust, which is mainly from liquid and solid particles (soot) formed by unburned or incomplete combustion of diesel fuel.The low opacity may indicate that the exhaust has low total particulate matter and low particle size, where a low ringeman blackness rating may also indicate that the exhaust has low soot particles.
Compared with the control group without the environment-friendly petroleum auxiliary, the fuel consumption of the comparative example 1 is reduced, and CO 2 The environment-friendly petroleum auxiliary agent of the comparative example 1 is formed by mixing an organosilicon compound and ferrocene, the ferrocene reduces the ignition temperature of carbon smoke particles, the organosilicon compound improves the atomization dispersion performance of fuel, the emission of particulate matters can be reduced, the fuel is promoted to be fully combusted, and the conversion rate of the fuel is improved. The fuel consumption of example 1 was significantly reduced compared to comparative example 1, CO 2 The emission is increased, the emission of NO is reduced, and the diesel oil added with the environment-friendly petroleum auxiliary agent is more fully combusted. The opacity is reduced, the ringeman blackness is reduced, and the reduction of the content of particles in the smoke and the smaller granularity are indicated. Example 2 and example 3 the addition of elemental metals in the polymerization reaction based on example 1, the resulting environmentally friendly petroleum additive-containing diesel fuel has further improved properties, the barium-based compound produced in example 2 promotes the combustion of carbon soot particles, reduces the emission of carbon soot particles, and further reduces the opacity; the formation of cerium-based compound in example 3 reduced the concentration of organic carbon compounds, lowered the ignition point, increased the oxidation rate, reduced the NO, CO, HC content, and increased CO 2 And the emission quantity improves the diesel conversion rate. Example 4 when the two are used simultaneously, the conversion rate of diesel oil is synergistically improved, the kinetic energy is improved, the smoke content is reduced, and the emission of harmful ingredients is reduced.
Claims (7)
1. The preparation method of the environment-friendly petroleum auxiliary agent is characterized by comprising the following steps of:
K1. heating, stirring, condensing and refluxing the aliphatic olefine acid, the solvent and the NaOH aqueous solution under the protection of nitrogen to obtain saponified solution;
K2. maintaining the temperature and stirring speed unchanged, adding ferrocene into the saponified solution, dropwise adding a chlorosilane compound into the saponified solution, and carrying out heat preservation reaction for 2-5h after the dropwise adding is finished to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then distilling under reduced pressure to remove a solvent to obtain a product A;
K4. mixing the product A with a chlorosilane compound to obtain a mixed solution B, dripping the mixed solution B into warm water under stirring, keeping the temperature and the stirring speed unchanged, reacting for 3-6h, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, and washing the reaction solution to be neutral to obtain a hydrolysate solution;
K5. adding strong acid into the hydrolysate solution under the stirring condition, heating to 40-60 ℃, reacting for 3-6h, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization liquid, washing the polymerization liquid to be neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solids to obtain the environment-friendly petroleum auxiliary agent;
the chlorosilane compound is any one of methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane.
2. The method for preparing the environment-friendly petroleum auxiliary as claimed in claim 1, comprising the following steps:
K1. under the protection of nitrogen, mixing aliphatic olefine acid, solvent and 30-50wt% NaOH aqueous solution according to the weight ratio of (4-7): (5-10): (0.3-0.5), condensing and refluxing for 5-10min at 70-90 ℃ under 200-400rpm to obtain saponified solution;
K2. adding ferrocene into saponified solution according to the ratio of (10-20) mL (1-3) and dropwise adding chlorosilane compound with the weight ratio of (1-1.5) to saponified solution at the speed of 2-3 drops/s (2-5), and after the dropwise adding, preserving heat for 2-5 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then performing reduced pressure distillation at 60-80 ℃ and 0.01-0.03MPa to remove a solvent to obtain a product A;
K4. mixing the product A with a chlorosilane compound according to the weight ratio of (1-3) (0.5-1) to obtain a mixed solution B, dripping the mixed solution B into water at the temperature of 30-50 ℃ stirred at the speed of 200-400rpm at the speed of 2-3 drops/s, keeping the volume ratio of the mixed solution B to the water at 1 (1.5-3), reacting for 3-6 hours at the constant temperature and the stirring speed, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to the volume ratio of 1 (1-2), shaking uniformly, standing for layering, removing the water layer, and repeating the process until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding strong acid into hydrolysate solution according to the weight ratio of (60-80) (1-2) under the stirring condition of 100-200rpm, heating to 40-60 ℃, reacting for 3-6 hours, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of (1-2), shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid matters to obtain the environment-friendly petroleum auxiliary agent;
the chlorosilane compound is any one of methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane.
3. The method for preparing the environment-friendly petroleum auxiliary as claimed in claim 2, comprising the following steps:
K1. under the protection of nitrogen, mixing aliphatic olefine acid, solvent and 30-50wt% NaOH aqueous solution according to the weight ratio of (4-7): (5-10): (0.3-0.5), condensing and refluxing for 5-10min at 70-90 ℃ under 200-400rpm to obtain saponified solution;
K2. adding ferrocene into saponified solution according to the ratio of (10-20) mL (1-3) and dropwise adding chlorosilane compound with the weight ratio of (1-1.5) to saponified solution at the speed of 2-3 drops/s (2-5), and after the dropwise adding, preserving heat for 2-5 hours to obtain a reaction mixture;
K3. naturally cooling the reaction mixture to room temperature, standing for layering, removing a water layer, and then performing reduced pressure distillation at 60-80 ℃ and 0.01-0.03MPa to remove a solvent to obtain a product A;
K4. mixing the product A with a chlorosilane compound according to the weight ratio of (1-3) (0.5-1) to obtain a mixed solution B, dripping the mixed solution B into water at the temperature of 30-50 ℃ stirred at the speed of 200-400rpm at the speed of 2-3 drops/s, keeping the volume ratio of the mixed solution B to the water at 1 (1.5-3), reacting for 3-6 hours at the constant temperature and the stirring speed, naturally cooling to room temperature, standing for layering, removing a water layer to obtain a reaction solution, adding water into the reaction solution according to the volume ratio of 1 (1-2), shaking uniformly, standing for layering, removing the water layer, and repeating the process until the reaction solution is neutral to obtain a hydrolysate solution;
K5. adding strong acid into hydrolysate solution according to the weight ratio of (1-2) under the stirring condition of 100-200rpm to obtain a preparation solution, adding metal simple substance with the material-liquid ratio of (0.5-0.7) g (20-50) mL, heating to 40-60 ℃, reacting for 3-6h, naturally cooling to room temperature, filtering to remove solids, standing for layering, removing a water layer to obtain a polymerization solution, adding water into the polymerization solution according to the volume ratio of (1-2), shaking uniformly, standing for layering, removing the water layer, repeating the process until the polymerization solution is neutral, adding a small amount of anhydrous sodium sulfate for drying and removing water, and filtering to remove solid substances to obtain the environment-friendly petroleum auxiliary agent;
the chlorosilane compound is any one of methyltrichlorosilane, dimethyldichlorosilane and trimethylchlorosilane;
the metal simple substance is at least one of cerium, barium, calcium and zinc.
4. The method for preparing an environment-friendly petroleum auxiliary as claimed in any one of claims 1 to 3, wherein the aliphatic olefine acid is any one of undecylenic acid and docosahexaenoic acid.
5. The method for preparing an environment-friendly petroleum additive according to any one of claims 1 to 3, wherein the strong acid is any one of concentrated sulfuric acid and trifluoromethanesulfonic acid.
6. The method for preparing an environment-friendly petroleum additive according to any one of claims 1 to 3, wherein the solvent is any one of toluene, n-hexane and petroleum ether.
7. An environmentally friendly petroleum aid prepared by the method of any one of claims 1-6.
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