Power boosting type diesel oil additive as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of automotive diesel additives, and particularly relates to a power boosting type diesel additive as well as a preparation method and application thereof. The additive contains 10-30 g / L of an organic lanthanum peroxide component in terms of La, and is a solution prepared from lanthanum carbonate or lanthanum oxide, acetylacetone, hydrogen peroxide and an inert and hydrophobic hydrocarbon solvent; in the preparation raw materials, the molar ratio of La to acetylacetone to H2O2 is 1: (3.0-3.2): (3.3-3.5); the hydrocarbon solvent is composed of a solvent A and a solvent B, the normal-pressure boiling point of the solvent A is 75-100 DEG C and accounts for 20-40 wt% of the total amount of the hydrocarbon solvent, and the normal-pressure distillation range of the solvent B is 70-300 DEG C. The additive is suitable for being added into vehicle diesel oil of a gas station, the adding amount is 0.05-2 v per thousand, the power performance of a diesel oil vehicle can be remarkably improved, and the additive has a certain application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of vehicle diesel additives, and particularly relates to a power-enhancing diesel additive, a preparation method thereof, and an application thereof. Background Art

[0002] For vehicle diesel engines, due to the high intake pressure in the cylinder after turbocharging, large compression ratio in the compression stroke, and high working pressure, they have a high output torque at low rotational speeds, are easy to achieve a relatively high thermal efficiency of about 45% and are fuel-efficient, so they are widely used in heavy-duty transport vehicles and large construction machinery. Vehicle diesel, as a blended oil, is wholesaled to gas stations for further retail by production manufacturers by appropriately adding various additives such as pour point depressants, stabilizers, detergents, cetane improvers, etc. according to the composition and combination of base oils. However, due to the complexity and instability of base oils and additives, diesel vehicle owners can often feel obvious fluctuations in fuel consumption and power performance even for the same grade of diesel added at the same gas station. That is, for the same diesel vehicle, with basically the same load, basically the same driving mode, road conditions, and weather conditions, obvious differences in fuel consumption and / or power performance can be felt among different batches of diesel. Although there is a high correlation between the fuel consumption and power performance of diesel vehicles, fuel consumption is mainly an economic indicator, while power performance mainly reflects the acceleration ability. Gas stations generally focus on providing diesel with better economy and pay less attention to the power performance of the diesel sold.

[0003] As the end-sale unit of finished diesel, gas stations have a certain choice in the purchase channels and performance of vehicle diesel. However, due to technical level and business scope limitations, for diesel vehicle owners who are concerned about vehicle performance, they usually only provide small-capacity packaged additives of the fuel additive type, which are injected into the fuel tank at a ratio of about 1‰ before or during refueling. This addition method has the disadvantage that the fuel additive and diesel cannot be fully mixed. Diesel additives of the fuel additive type usually include maintenance type, cleaning type, and power-enhancing type. Among them, the main function of the maintenance type fuel additive is to prevent the formation of carbon deposits, thereby maintaining the good state of the engine and preventing the increase in fuel consumption caused by the accumulation of carbon deposits. The cleaning type fuel additive is mainly used to remove carbon deposits and sediments inside the engine, thereby restoring the performance of the engine. The power-enhancing type fuel additive generally improves the power performance of the engine by improving the combustion efficiency of diesel, including improving the spray effect and combustion performance of diesel, but often causes a slight increase in fuel consumption. Coupled with the high cost, and the disadvantage of not being fully mixed with diesel due to being injected into the fuel tank at a ratio of only about 1‰ before or during refueling, its actual use effect is relatively limited, so the power-enhancing type fuel additive basically has no market.

[0004] Among the additive components incorporated during the blending of National VI diesel for vehicles in the prior art, components capable of controlling diesel atomization and combustion effects are relatively important, such as β-diketone cerium compounds, ferrocene compounds, and oxygenated organic compounds such as nitrate esters, peroxide compounds, and ether ester compounds. These components can be used alone or two or more of them can be added simultaneously, which can increase the cetane number of diesel, reduce engine fuel consumption, and the emissions of harmful components; incorporating β-diketone cerium compounds at a cerium content of, for example, 50 mg / kg can also significantly reduce the regeneration frequency and regeneration temperature of the diesel particulate filter (DPF); the overall effect of ferrocene compounds is significantly lower than that of β-diketone cerium compounds, and nitrate ester compounds will cause an increase in the production of NOx (resulting in more consumption of the urea aqueous solution); ether ester compounds have problems such as complex preparation processes and low cost performance. The power-boosting diesel fuel additive injected into the fuel tank at a ratio of about 1‰ before or during vehicle refueling at gas stations is to add appropriate combustion-promoting and controlling components to commercial vehicle diesel that already contains these combustion-promoting and controlling components to further improve the power performance of diesel.

[0005] For the power-boosting diesel fuel additive mentioned above, improved β-diketone cerium compounds or peroxide organic compounds can be used as the main components, but it is found that their effects are not significant enough, and there are still problems such as unreasonable preparation processes, large addition amounts, and high costs, so the potential for further development and application is not great. Diesel additives in the form of oil-soluble nano-metals or oxides (such as nano-iron, nano-copper, nano-ceria) grafted with components such as long-chain fatty acids, long-chain organic esters, and long-chain alcohol ethers on the surface can also be used in the form of fuel additives, which have a certain power-boosting effect, but the effect is usually relatively limited and the cost performance is not high.

[0006] Therefore, it is necessary to develop a power-boosting diesel additive with a reasonable preparation process and low production cost, which can be used in the blended vehicle diesel already containing various additive components such as pour point depressants, stabilizers, detergents, and cetane improvers at gas stations. Under the condition of a low addition amount, it can significantly enhance the power, and has high cost performance and application prospects. Summary of the Invention

[0007] To solve the above technical problems, the present invention provides a power-boosting diesel additive containing an organolanthanum peroxide component at 10 - 30 g / L in terms of La, which is a solution prepared from lanthanum carbonate or lanthanum oxide, acetylacetone, hydrogen peroxide, and an inert and hydrophobic hydrocarbon solvent; in the preparation raw materials, the molar ratio of La, acetylacetone, H 2 O 2 is 1:(3.0 - 3.2):(3.3 - 3.5); the hydrocarbon solvent consists of solvent A and B, where the normal boiling point of solvent A is 75 - 100 °C and it accounts for 20 - 40 wt% of the total amount of the hydrocarbon solvent, and the normal boiling range of solvent B is within 70 - 300 °C.

[0008] The power-enhanced diesel additive of the present invention, wherein solvent A can be cyclohexane or benzene. Its main function is as a reaction solvent, and its secondary function is to carry out the water generated by the reaction out through gasification, and after condensation, it is separated from water and then flows back to the reaction feed liquid; solvent B can be light white oil or hydrogenated 0# diesel. The normal boiling points of cyclohexane and benzene are both about 80°C, and the normal boiling points of hydrogen peroxide and acetylacetone are about 150°C and 140°C respectively. Industrial cyclohexane conforming to the SH / T 1673-2023 standard and industrial pure benzene conforming to the Q / SH PRD118-2011 standard both have high purity (such as 99.9%), are widely used, are easy to purchase and have low prices.

[0009] Most grades of the light white oil conforming to the NB / SH / T 0913-2015 standard can be used; however, grades with an end boiling point lower than 285°C are preferably used. These grades of light white oil have lower viscosities, which can enable the additive to be better mixed when circulating and mixing with diesel in the storage tank at the gas station, especially in the low-temperature winter and spring seasons. The light white oil has undergone deep hydrogenation, and its main components are alkanes, and the contents of sulfur and olefins are very low. The hydrogenated 0# diesel is a high-quality diesel component oil produced by a hydrotreating process, and the contents of sulfur and olefins are also very low. Solvent B cannot use olefin-containing solvent oil such as No. 120 solvent oil, and the olefins contained therein will react with the peroxy groups in the effective components of the additive, resulting in the loss of peroxy groups and the performance degradation of the additive.

[0010] Both lanthanum carbonate or lanthanum oxide used are powdery raw materials. Among them, lanthanum carbonate and lanthanum oxide prepared by calcining lanthanum carbonate at a temperature below 600°C have relatively high reaction activities, react quickly with acetylacetone, and can be completely dissolved. Lanthanum oxide is a rare earth material with a large quantity and the lowest price, has high purity, stable quality, and the price per ton can be within 5000 yuan; lanthanum carbonate is the main intermediate material for producing lanthanum oxide and can also be purchased at a low price.

[0011] The hydrogen peroxide used is the industrial product with an H 2 O 2 concentration of 25-50wt%; the small amounts of stabilizers contained therein, such as a few tens of mg / kg of pyrophosphoric acid and hydroxyethylidene diphosphonic acid, do not affect the reaction effect and the stability and application effect of the prepared additive.

[0012] The power-enhanced diesel additive can be prepared through the following steps: (1) In a stirring reactor with a condensation reflux device, after purging with nitrogen, add the required amounts of solvent A, acetylacetone, lanthanum carbonate or lanthanum oxide, start stirring, heat the feed liquid and control the temperature at 70-85°C, and react until the feed liquid becomes a transparent solution to obtain a solution containing La(acac) 3solution; the intake end of the condensation reflux device is connected to the top space of the reactor, and the condensation temperature is 0-25°C; (2) Transfer the solution containing La(acac) 3 into a stirred reactor equipped with a evacuation-condensation reflux-water separation device, displace with nitrogen, start stirring, cool the solution to 20-30°C, add the required amount of resin catalyst swollen with solvent A, or the resin catalyst in the organic lanthanum peroxide-containing solution obtained by filtering the feed liquid in step (3) during the preparation of the previous batch, or the bottom feed liquid of the organic lanthanum peroxide-containing solution and the resin catalyst obtained by sedimentation separation of the feed liquid in step (3) during the preparation of the previous batch; then add hydrogen peroxide and control the temperature of the feed liquid at 25-30°C and the hydrogen peroxide feeding time at 8-12 h. After adding hydrogen peroxide, continue to react for 1-2 h to obtain a feed liquid containing organic lanthanum peroxide; in the feed liquid containing organic lanthanum peroxide, the content of the resin catalyst based on dry basis is 8-15 wt%. The intake end of the evacuation-condensation reflux-water separation device is connected to the top space of the reactor, the condensation temperature is 0-5°C, and the outlet end is connected to a vacuum system; the upper organic phase obtained by condensation flows back to the reactor, and the lower aqueous phase is discharged and collected; control the pumping pressure of the vacuum system to remove the water in the feed liquid in the reactor. The resin catalyst is a hydrogen-type macroporous weak acid cation exchange resin microsphere, and its active group is a carboxyl group; based on the dry basis of the resin microsphere, the carboxyl group content is 10-12 mmol / g. (3) The feed liquid containing organic lanthanum peroxide in step (2) is subjected to solid-liquid separation to obtain a solution containing organic lanthanum peroxide, and a resin catalyst containing the organic lanthanum peroxide solution or a concentrated feed liquid of the resin catalyst containing the organic lanthanum peroxide solution; the obtained resin catalyst containing the organic lanthanum peroxide solution or the concentrated feed liquid of the resin catalyst containing the organic lanthanum peroxide is continuously used in step (2); in the solution containing organic lanthanum peroxide, add the solvent B, mix well, and filter precisely to obtain a power-enhanced diesel additive.

[0013] In the preparation step (2), the hydrogen-type macroporous weak acid cation exchange resin microsphere, preferably with the brand D113, preferably has an average wet ball diameter of 0.5-0.8 mm after being fully swollen in the reaction feed liquid of step (2). The D113 macroporous weak acid cation exchange resin is made by copolymerization of acrylic acid, and the carboxyl group (-COOH) is introduced by acrylic acid. It has good chemical and physical stability, strong antioxidant ability, relatively balanced hydrophilicity and lipophilicity, moderate acidity in the preparation reaction of the additive of the present invention, good use effect and long service life. When the reaction effect declines, its performance can be basically restored by leaching with a benzene solution of trichloroacetic acid.

[0014] In preparation step (2), the condition control of the evacuation-condensation reflux-water separation device and its vacuum system should ensure that the liquid material in the reactor boils, and the significant reflux of the upper organic phase condensed in the evacuation-condensation reflux-water separation device and the formation rate of the lower aqueous phase are basically matched (in a proportional relationship) with the rate of water introduced during the addition of hydrogen peroxide into the reactor, so as to control the water content in the liquid material in the reactor to a relatively low level and enable the peroxidation reaction to proceed well.

[0015] In preparation step (3), the solid-liquid separation of the organic lanthanum peroxide-containing liquid material can be carried out in the reactor or outside the reactor. When a filtration component is set at the liquid discharge port at the bottom of the reactor, all the resin catalysts can be intercepted and directly used in the reaction of step (2) in the next batch preparation process. When the static sedimentation separation method is adopted, the upper layer solution is discharged to obtain a solution containing organic lanthanum peroxide; the bottom liquid material is a mixture of the solution and resin microspheres, but the resin microspheres are enriched. When sedimentation separation is carried out in the reactor, it is directly used in the reaction of step (2) in the next batch preparation process. When sedimentation separation is carried out outside the reactor, it can be recycled to the reaction of step (2) in the subsequent batch preparation process by means of pressure feeding.

[0016] In the solution containing organic lanthanum peroxide obtained in step (3), the total content of hydroperoxy group (-OOH) and peroxyl group (-OO-) expressed by the molar concentration of active oxygen, and the ratio with the molar concentration of La (i.e., the ratio of the molar concentration of active oxygen to the molar concentration of La) is 2.9 - 3.0, and is basically not affected by the molar ratio of La to acetylacetone in the preparation feedstock. The molar concentration of active oxygen is determined by the KI-Na 2 S 2 O 3 method, and the molar concentration of La is obtained by material balance or determined by the solution evaporation-ignition weight loss method.

[0017] The power-enhanced diesel additive of the present invention has good stability, that is, storage performance. When stored in a closed container for 30 days, there is no visible change in transparency and no obvious performance decline. It is suitable for adding to the blended vehicle diesel already incorporated with various conventional components such as pour point depressant, stabilizer, detergent, cetane number improver, etc. at a dosage of 0.5 - 2 v‰ (volume), and has certain application prospects; during application, it can be first diluted and mixed with commercial diesel with a volume of 3 - 5 times, and then further mixed into a large amount of diesel in the underground storage tank by the circulating injection method to quickly and effectively mix in large quantities; for the diesel incorporated with the additive of the present invention, when the incorporation amount is 10 - 30 mg / L in terms of La, its power is significantly improved or even remarkably improved, and it has certain storage stability; after applying the additive of the present invention to the national VI diesel, it can significantly improve the power performance and driving experience of the national IV and national V diesel vehicles.

[0018] Based on the effects of the following examples, comparative examples, and application test examples, the main principle of the present invention is considered as follows: 1. For the power-enhanced diesel additive, La(acac) 3 is subjected to a peroxidation reaction treatment. The active ingredient in the additive is the generated organolanthanum peroxide; the organolanthanum peroxide is dissolved in the additive solution in a solute state, and the selected hydrocarbon solvent has a lower viscosity than diesel, so that the organolanthanum peroxide component can be better mixed when circulating and mixing with the diesel in the storage tank at the gas station without the need for a solubilizing component; after the organolanthanum peroxide is mixed into the diesel in the storage tank and within 40 days after vehicle refueling, it can remain basically stable. Even if it combines or reacts with some components in the incoming diesel, it basically does not affect the power performance of the diesel. In the diesel additive with Ce(acac) 3 as the main active ingredient, when the dosage in diesel is 50 mg / kg (i.e., 40 mg / L) in terms of cerium, a solubilizer such as alcohols, ethers, esters or their combinations is usually required to ensure the dispersion and mixing effect in diesel; this shows that the organolanthanum peroxide in the additive of the present invention has a very different polarity of the molecular structure and solubility in diesel from La(acac) 3 and Ce(acac) 3 .

[0019] 2. During the preparation process of the power-enhanced diesel additive, since there is no problem of valence change of La 3+ and its combination with the peroxy group, and the hydrocarbon solvent basically does not react with H 2 O 2 or the reaction between the two is relatively slow, the peroxidation reaction occurs between H 2 O 2 and the acac ligand, and the generated organolanthanum peroxide is an oxygen-containing organometallic compound bonded with a hydroperoxy group (-OOH) and / or a peroxy group (-OO-). Acetylacetone, i.e., 2,4-pentanedione (Hacac), is a commonly used bidentate ligand that chelates with La 3+ through two carbonyl oxygens to form La(acac) 3 . In steps (1)-(2) of the preparation, the purpose of using the inert and hydrophobic hydrocarbon solvent A (cyclohexane or benzene) is mainly that the feed liquid has a low viscosity, good fluidity, the by-product water in the reaction can be separated by the evacuation-condensation reflux-water separation device, and the reaction temperature conditions can be controlled by the endothermic vaporization, and a solution of La(acac) 3 and organolanthanum peroxide can be obtained; the light white oil or hydrogenated 0# diesel (solvent B) added in step (3) has properties closer to diesel. In the raw material ratio of the preparation, H 2 O 2There is a surplus of about 10% to ensure the concentration in the reaction feed liquid for sufficient reaction. During the long-term reaction and evacuation process in step (2), there are also certain losses and a small amount of decomposition, mainly the loss of condensed water entering the evacuation-condensation reflux-water separation device; in the solution containing organolanthanum peroxide in step (3), there is basically no H 2 O 2 remaining.

[0020] 3. During the reaction process of step (2), the ratio of the total content of hydroperoxy (-OOH) and peroxy (-OO-) expressed by the molar concentration of active oxygen to the molar concentration of La is 2.9 - 3.0, and it is basically not affected by the molar ratio of La to acetylacetone in the preparation feed. This indicates that during the reaction process of step (2), under the catalysis of the hydrogen-type macroporous weak acid cation exchange resin microspheres such as D113, the acac ligand of La(acac) 3 can be peroxidized by H 2 O 2 , and it basically reacts according to the ratio (molar ratio) of one acac ligand bonding one hydroperoxy (-OOH) and / or peroxy (-OO-), and the resin catalyst has very stable reaction performance during the operation of step (2) and can be recycled, which have not been disclosed or taught in the prior art of the relevant preparation process; at the same time, there is basically no reaction between acetylacetone and H 2 O 2 , which is also slightly different from the relevant prior art.

[0021] In step (2), the main reason why La(acac) 3 can react more fully with H 2 O 2 and there is basically no reaction between acetylacetone and H 2 O 2 is that the concentrations of La(acac) 3 and H 2 O 2 in the feed liquid are both appropriate. When the amount of solvent A is relatively large, such as accounting for 60 - 100% of the inert and hydrophobic hydrocarbon solvent, the ratio of the molar concentration of active oxygen in the obtained solution containing organolanthanum peroxide, that is, the total content of hydroperoxy (-OOH) and peroxy (-OO-), to the molar concentration of La decreases to less than 2.5. The main reason should be that the concentrations of H 2 O 2 and La(acac) 3 are both low, and the peroxidation reaction is not sufficient, or more H 2 O 2 is required. When hydrogen peroxide is injected too fast, the ratio of the molar concentration of active oxygen in the obtained solution containing organolanthanum peroxide to the molar concentration of La also decreases to less than 2.5. The main reason should be that H2 O 2 When the amount of solvent A is too small or the hydrogen peroxide is injected too quickly, the free acetylacetone will react with H 2 O 2 The reaction generates acetylacetone peroxide with high polarity, which can easily cause turbidity in the feed solution.

[0022] Acetylacetone, H 2 O 2 The reaction of acetylacetone peroxide is a basic method in related organic synthesis technology; however, under the conditions of inert and hydrophobic hydrocarbon solvents such as cyclohexane or benzene, acetylacetone, H 2 O 2 The product of the peroxidation reaction is easily precipitated, and the solubility of the separated acetylacetone peroxide in cyclohexane or benzene is very low, but its solubility in water is relatively high.

[0023] The solution containing the organic lanthanum peroxide in step (3) is sampled and the solvent is fully removed under room temperature and vacuum conditions. The resulting solute is substantially insoluble in water, indicating that the organic lanthanum peroxide contained in the additive of the present invention has properties that are very different from those of the peroxide of acetylacetone.

[0024] The solution containing the organic lanthanum peroxide in step (3) does not release bubbles or gases (including oxygen) when stored for a long time, and it is considered that there is basically no H 2 O 2 Residue is relatively stable and safe; some acetylacetone peroxide will decompose and release oxygen during storage.

[0025] 4. The liquid containing organic lanthanum peroxide (unseparated resin catalyst) is relatively stable. During the process of heat preservation or cooling and sealing for 100 hours, the peroxide content, i.e., the active oxygen content of the solution, does not change substantially due to long-term contact with the resin catalyst. The acetylacetone immersion can completely capture the La in the La-type macroporous weak acid cation exchange resin microspheres D113. The excess acetylacetone in the ingredients can also ensure that the carboxylic acid groups of the D113 resin do not bind to La and can exert the catalytic effect of all carboxylic acid groups. Therefore, the hydrogen-type macroporous weak acid cation exchange resin microspheres are more suitable for use as catalysts in the preparation method of the present invention. In step (2), the hydrogen-type macroporous strong acid cation exchange resin microspheres cannot be used as catalysts (the catalyst for the preparation of acetylacetone peroxidation by acetylacetone and hydrogen peroxide in the prior art) because the hydrogen-type macroporous strong acid cation exchange resin can quickly capture La (acac). 3 In La.

[0026] In step (1), if lanthanum carbonate is replaced by cerium carbonate (both are trivalent), the feed liquid can also quickly become a transparent solution, that is, it is easy to react and produce Ce(acac) 3Adding an appropriate amount of hydrogen peroxide to a solution containing Ce(acac) 4 However, the hydrogen-type macroporous weak acid cation exchange resin, such as D113, has a higher binding ability between the carboxylic acid group and tetravalent cerium, and can capture Ce(acac) 4 The cerium in the reaction is difficult to maintain in the step (2) of the present invention.

[0027] 5. The diesel fuel with the additive of the present invention, when used in diesel engine vehicles, mainly includes: the engine power, i.e., the output power, can be increased by more than 8% or even more than 10%, the vehicle fuel consumption can be reduced by more than 3.5% or even more than 5%, the exhaust temperature can be reduced by more than 10°C or even more than 20°C, the amount of urea aqueous solution used in the exhaust gas purification system can be reduced by more than 20%, the regeneration cycle (km) of the particulate trap, i.e., DPF, can be extended by more than 30%, and the regeneration time (minutes) can be shortened by more than 20%; it is believed that similar effects can be achieved when used in excavation, loading vehicles and generator sets powered by diesel engines. The main reason for the above effects should be that the combustion process of the diesel fuel with the additive of the present invention after being sprayed into the cylinder in the form of droplets has been further optimized to a certain extent, and is more compatible with the process of pushing the piston to do work; rather than increasing the cetane number of the diesel fuel, changing the particle size distribution of the sprayed diesel fuel droplets, or simply improving the in-cylinder combustion efficiency of the diesel fuel (i.e., not releasing more heat from the in-cylinder combustion).

[0028] The improvement in engine power can be manifested as an increase in engine output power and power under basically the same vehicle weight, speed and fuel consumption conditions, including improved acceleration ability under the same gear and the same instantaneous fuel consumption per 100 kilometers, improved climbing ability under the same gear, the same speed and the same fuel consumption per 100 kilometers, and increased vehicle speed under the same gear and the same stable instantaneous fuel consumption per 100 kilometers.

[0029] The reduction in the amount of urea aqueous solution used in the exhaust gas purification system indicates that the engine's NOx generation and the combustion temperature of diesel droplets in the cylinder are reduced; the extension of the regeneration cycle of the particle filter, namely DPF, indicates that the engine's carbon particle capture is reduced, and the shortened DPF regeneration time indicates that carbon particles are easily oxidized and burned. Most National IV diesel vehicles do not have DPFs, some National V diesel vehicles are equipped with DPFs, and National VI diesel vehicles are basically equipped with DPFs.

[0030] After diesel is sprayed into the cylinder, the combustion process of the droplets includes the ignition delay period (delayed combustion period), rapid combustion period (fast combustion period), slow combustion period (main combustion period), and afterburning period, which gradually unfolds and is completed with the movement of the piston and the changes in the volume, temperature, and pressure in the cylinder. The combustion time of diesel sprayed into the cylinder is usually a few milliseconds.

[0031] 6. The additive of the present invention can achieve the above-mentioned power improvement effect when used in diesel fuel with organic cerium, organic iron, nitrate ester, organic peroxide, organic ether ester or their compound as cetane number improving components. The reason why the effect can still be obtained in diesel fuel added with organic cerium, organic peroxide or their compound should be that organic lanthanum is combined with peroxy group in one component of the organic lanthanum peroxide, and the way and process of this component playing a role in the in-cylinder combustion process are slightly different from those of conventional organic cerium, organic peroxide or their compound; and it is considered that the thermal stability of the organic lanthanum peroxide molecule is relatively high, and the temperature at which its hydroperoxy group and / or peroxy group pyrolyze to generate oxygen-containing free radicals is higher than that of the organic peroxide conventionally used or the peroxide of Hacac without La coordination.

[0032] 7. At present, there are still a large number of diesel vehicles meeting the national IV and national V emission standards (hereinafter referred to as national IV and national V diesel vehicles) in operating vehicles. It is generally considered that the power performance of the engines of the mainstream national VI emission standard diesel vehicles (hereinafter referred to as national VI diesel vehicles) is higher than that of the engines with the same displacement of national IV and national V diesel vehicles; to a certain extent, this has led to the disadvantage of the power performance of the old national IV and national V diesel vehicles with basically the same displacement and model (usually licensed before June 30, 2021) compared with national VI diesel vehicles. The evaporation performance and lubrication performance of the currently commercially available national VI standard vehicle diesel fuel (hereinafter referred to as national VI diesel) are lower than those of the national V standard vehicle diesel fuel (hereinafter referred to as national V diesel, which was taken off the market on December 31, 2018), resulting in the lower power performance of national VI diesel than that of national V diesel; this further causes the significant decline in the power performance of national IV and national V diesel vehicles after using national VI diesel in recent years. After applying the additive of the present invention, national VI diesel can significantly improve the power performance and driving experience of national IV and national V diesel vehicles. Detailed implementation manners

[0033] The technical solutions of the present invention will be specifically described and illustrated below in conjunction with embodiments.

[0034] Example 1: The power-improving diesel additive of this Example 1 contains 20 g / L of organic lanthanum component calculated as La, and is a solution prepared from lanthanum carbonate (powder, purity 99 wt%), acetylacetone (industrial product with a purity of 99.8 wt%, the main impurity being acetic acid), hydrogen peroxide (industrial product with a concentration of 27.5 wt%, the stabilizer being 30 mg / kg of pyrophosphoric acid), and an inert and hydrophobic hydrocarbon solvent; among the preparation raw materials, La, acetylacetone, H 2 O 2The molar ratio is 1:3.2:3.5; the hydrocarbon solvent consists of solvent A and B. Solvent A is benzene (atmospheric boiling point is 80.1 °C, accounting for 40 wt% of the total amount of hydrocarbon solvent, purity 99.9 wt%, industrial pure benzene meeting the Q / SHPRD118-2011 standard), and solvent B is light white oil W1-60 (meeting the NB / SH / T 0913-2015 standard, atmospheric distillation range is 185-225 °C). The power-boosting diesel additive is prepared through the following steps in a fume hood: (1) A stirring reactor with a condensation reflux device (a 1000 mL round-bottomed, three-necked glass flask with magnetic stirring) is fixed on a magnetic stirrer, purged with nitrogen, and the required amounts of solvent A (benzene), acetylacetone, and lanthanum carbonate are added. A stirring bar with an outer fluoroplastic seal is placed, stirring is started, the liquid material is heated and the temperature is controlled at 70-73 °C. After 1 h of reaction, the liquid material becomes a transparent solution, and a 620 mL solution containing La(acac) 3 is obtained; the inlet end of the condensation reflux device is connected to the top space of the reactor, the condensation temperature is 25 °C, and the outlet end is purged with nitrogen to isolate air. (2) A stirring reactor with a vacuum-condensation reflux-water separation device (a 1000 mL, kettle-type, stainless steel reactor with a jacket, mechanical stirring; the inlet end of the vacuum-condensation reflux-water separation device is connected to the top space of the reactor, and the outlet end is connected to a vacuum system). The temperature of the reactor jacket is controlled at 28 °C with circulating water, purged with nitrogen, and the required amount of resin catalyst (macroporous weak acid cation exchange resin microspheres D113 of polyacrylic acid series, hydrogen form, which has been pre-swollen with a sufficient amount of solvent A (benzene) for 10 h and drained of the intermediate benzene between the microspheres) is added. The weight before swelling with benzene is anhydrous and dry, 90 g; the wet weight is 173 g, and the average diameter is between 0.6-0.7 mm; based on the dry basis of the resin microspheres, the carboxyl group content is 11.2 mmol / g). The vacuum-condensation reflux-water separation device is started, and the condensation temperature is controlled at 5 °C and the internal vacuum of the kettle is maintained at about -10 kPa (gauge pressure, the same below). All the solution containing La(acac) 3 prepared in step (1) is pumped in, stirring is started, and the solution is cooled to 30 °C; the internal vacuum of the kettle is adjusted (about -90 kPa) to make the organic phase condensed in the vacuum-condensation reflux-water separation device reach significant reflux. Then, hydrogen peroxide is injected evenly and continuously (through a stainless-steel tube with an outer diameter of 0.6 mm into the bottom of the liquid in the inner side of the reactor), and the temperature of the liquid is controlled at 29 - 30 °C by slightly adjusting the vacuum degree in the kettle. The feeding time of hydrogen peroxide is controlled at 10 h (the flow rate of hydrogen peroxide is adjusted by the weight loss rate of the solution bottle and the opening degree of the needle valve). After adding hydrogen peroxide, continue the reaction for 1.2 h until the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases; close the evacuation-condensation reflux-water separation device, fill the reactor with nitrogen to normal pressure, stop stirring, and obtain a liquid containing organolanthanum peroxide; in the liquid containing organolanthanum peroxide, the content of the resin catalyst on a dry basis is 12 - 13 wt%; during the reaction of injecting hydrogen peroxide, the upper organic phase condensed by the evacuation-condensation reflux-water separation device flows back into the reactor, and the lower aqueous phase is quantitatively discharged and collected. The formation rate of the lower aqueous phase should be basically matched with the rate of water introduced during the process of adding hydrogen peroxide into the reactor; (3) Open the reactor in step (2), remove all the liquid containing organolanthanum peroxide, filter it through a 100-mesh stainless-steel filter to obtain 640 mL of a solution containing organolanthanum peroxide and a resin catalyst containing the solution of organolanthanum peroxide; the resin catalyst containing the solution of organolanthanum peroxide obtained is immediately bagged and stored in a sealed manner; the obtained solution containing organolanthanum peroxide is transferred into a 2000 mL round-bottom glass flask fixed on a magnetic stirrer (which has been replaced with nitrogen), add the required amount of solvent B, put in a magnetic stir bar, stir for 2 h, and filter it precisely through a polypropylene non-woven filter cloth to obtain a power-boosting diesel additive and store it in a bottle.

[0035] The results include: Take 300 μL of parallel samples from the solution containing organolanthanum peroxide obtained in step (3), and determine the molar concentration of active oxygen (the total content of hydroperoxy -OOH and peroxy -OO-) by the KI-Na 2 S 2 O 3 method. The ratio of the molar concentration of active oxygen to the molar concentration of La (obtained by material balance) is 2.96.

[0036] Take 10.0 g of the solution containing organolanthanum peroxide obtained in step (3), and determine the molar concentration of La by the solution evaporation - ignition weight loss method, which is basically consistent with the molar concentration of La obtained by material balance.

[0037] Example 2: After the operation in step (3) of Example 1 is completed, with the raw materials and experimental conditions unchanged, using the same raw material ratio, basically operate according to its steps (1)-(3) to prepare the power-boosting diesel additive of this Example 2. The main difference is that: in the operation of step (2), all the resin catalysts of the solution containing organolanthanum peroxide obtained by filtration in step (3) of Example 1 and stored in a sealed manner in bags are used.

[0038] The results include: in the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.1 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. For the solution containing organolanthanum peroxide obtained in step (3), 300 μL of parallel samples are taken, the molar concentration of active oxygen is measured, and the ratio to the La molar concentration (obtained by material balance) is 2.93.

[0039] Example 3: After the operation of step (3) in Example 2 is completed, with the raw materials and experimental conditions remaining unchanged, the operation is basically carried out according to steps (1)-(3) of Example 2 to prepare the power-enhanced diesel additive of this Example 3. The main difference is that: in the operation of step (2), all the resin catalysts of the organolanthanum peroxide solution obtained by filtration in step (3) of Example 2 and stored in sealed bags are used; during the injection of hydrogen peroxide, the temperature of the feed liquid is controlled at 25-26 °C by finely adjusting the vacuum degree in the kettle, and the hydrogen peroxide feeding time is controlled to be 12 h.

[0040] The results include: in the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.5 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. For the solution containing organolanthanum peroxide obtained in step (3), 300 μL of parallel samples are taken, the molar concentration of active oxygen is measured, and the ratio to the La molar concentration (obtained by material balance) is 2.95.

[0041] Example 4: After the operation of step (3) in Example 3 is completed, with the raw materials and experimental conditions remaining unchanged, the operation is basically carried out according to steps (1)-(3) of Example 3 to prepare the power-enhanced diesel additive of this Example 4. The main difference is that: in the raw material ratio, the molar ratio of La, acetylacetone, H 2 O 2 is changed to 1:3.0:3.2, and in the operation of step (2), all the resin catalysts of the organolanthanum peroxide solution obtained by filtration in step (3) of Example 3 and stored in sealed bags are used.

[0042] The results include: in the operation of step (1), the feed liquid becomes a transparent solution when the reaction lasts for 1.7 h. In the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.4 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. For the solution containing organolanthanum peroxide obtained in step (3), 300 μL of parallel samples are taken, the molar concentration of active oxygen is measured, and the ratio to the La molar concentration (obtained by material balance) is 2.92.

[0043] Example 5: After the operation in step (3) of Example 4 is completed, the raw materials other than hydrogen peroxide and the experimental conditions remain unchanged. The operation is basically carried out according to steps (1)-(3) of Example 3 to prepare the power-enhanced diesel additive of this Example 5. The main difference is that the industrial product with a concentration of 50 wt% of hydrogen peroxide (the stabilizer is 1-hydroxyethylidene-1,1-diphosphonic acid with a content of 40 mg / kg) is used instead of hydrogen peroxide, and the molar ratio of La, acetylacetone, and H 2 O 2 in the raw material ratio is changed to 1:3.1:3.4. In the operation of step (2), all the resin catalysts of the organic lanthanum peroxide-containing solution obtained by filtration in step (3) of Example 4 and stored in a sealed bag are used.

[0044] The results include: In the operation of step (1), the feed liquid becomes a transparent solution when the reaction lasts for 1.4 h. In the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.2 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. For the organic lanthanum peroxide-containing solution obtained in step (3), 300 μL of parallel samples are taken, and the ratio of the molar concentration of active oxygen to the molar concentration of La (obtained by material balance) is 2.93.

[0045] Example 6: After the operation in step (3) of Example 5 is completed, the raw materials and the experimental conditions remain unchanged. The operation is basically carried out according to steps (1)-(2) of Example 3. The main difference is that in the operation of step (2), all the resin catalysts of the organic lanthanum peroxide-containing solution obtained by filtration in step (3) of Example 5 and stored in a sealed bag are used.

[0046] After the reaction in step (2) is completed, stop stirring, let the feed liquid stand and settle for 10 min, open the reactor, and extract 120 mL of the upper layer solution; then close the reactor, displace the space above the feed liquid with nitrogen, start stirring for 3 min every 1 h, place the feed liquid for 30 h, open the reactor, extract 60 mL of the upper layer solution, and then basically carry out the operation according to step (3) of Example 3 to prepare the power-enhanced diesel additive of this Example 6.

[0047] 120 mL of the upper-layer solution extracted after the reaction in step (2) and 60 mL of the upper-layer solution extracted after the feed liquid was left standing for 30 h were each sampled to determine the molar concentration of active oxygen (total content of hydroperoxy -OOH and peroxyl -OO-), and the ratios to the molar concentration of La (obtained by material balance) were 2.94 and 2.97 respectively; another 50 mL of each was taken, and after the solvent was completely removed under room temperature and vacuum conditions, multiple 1.0 g parallel samples were taken from the two resulting solid substances. 100 mL of water was added to each, and two portions of each were heated to 50 °C and placed in an oven at 50 °C for 2 h, and two portions were placed at room temperature for 15 h. It was found that both solid substances were basically insoluble in water. The remaining 70 mL of the upper-layer solution extracted after the reaction in step (2) was sealed with a perforated rubber stopper at the mouth of the glass bottle in which it was stored. The hole of the rubber stopper was connected to a U-shaped water seal. During the 30 h of standing at room temperature, there was no change in the water levels on both sides of the U-shaped water seal; the rubber stopper and the U-shaped water seal were removed, and a slurry prepared from 0.2 g of powdered manganese dioxide and 2 mL of benzene was injected into the solution, and no bubbles were generated within 10 min.

[0048] Example 7: After the operation in step (3) of Example 6 was completed, with the raw materials and experimental conditions remaining unchanged, the operations were basically carried out according to steps (1)-(2) of Example 5, with the main difference being that: in the operation of step (2), all the resin catalysts of the organolanthanum peroxide-containing solution obtained by filtration in step (3) of Example 6 and stored in sealed bags were used.

[0049] After the reaction in step (2) ended, the stirring was stopped, the feed liquid was allowed to settle for 10 min, the reactor was opened, and 120 mL of the upper-layer solution was extracted; then the reactor was sealed again, the space above the feed liquid was replaced with nitrogen, the stirring was started for 3 min every 1 h, the feed liquid was left standing for 30 h, the reactor was opened, 60 mL of the upper-layer solution was extracted, and then the operation was basically carried out according to step (3) of Example 5 to prepare the power-boosting diesel additive of this Example 7.

[0050] 120 mL of the upper-layer solution extracted after the reaction in step (2) and 60 mL of the upper-layer solution extracted after the feed liquid was left standing for 30 h were each sampled to determine the molar concentration of active oxygen (total content of hydroperoxy group -OOH and peroxy group -OO-), and the ratios to the molar concentration of La (obtained by material balance) were 2.95 and 2.94 respectively; another 50 mL of each was taken and the solvents were completely removed under room temperature and vacuum conditions. Multiple 1.0 g parallel samples were taken from the two resulting solid substances, 100 mL of water was added to each, two portions of each were heated to 50 °C and placed in an oven at 50 °C for 2 h, and two portions were left standing at room temperature for 15 h. It was found that both solid substances were basically insoluble in water. The remaining 70 mL of the upper-layer solution extracted after the reaction in step (2) was sealed with a perforated rubber stopper at the mouth of the glass bottle where it was stored, and the rubber stopper hole was connected to a U-shaped water seal. During the 30 h of standing at room temperature, there was no change in the water levels on both sides of the U-shaped water seal; the rubber stopper and the U-shaped water seal were removed, and a slurry prepared from 0.2 g of powdered manganese dioxide and 2 mL of benzene was injected into the solution, and no bubbles were generated within 10 min.

[0051] Example 8: After the operation in step (3) of Example 7 was completed, the raw materials other than lanthanum carbonate remained unchanged, and the operation was basically carried out according to steps (1)-(3) of Example 3 to prepare the power-boosting diesel additive of this Example 8. The main difference was that: lanthanum carbonate was replaced with lanthanum oxide (powdered, prepared by calcining the lanthanum carbonate used in Examples 1-7 at 600 °C for 2 h, with a purity higher than 99.5 wt%); the molar ratio of La, acetylacetone, H 2 O 2 in the raw material ratio was changed to 1:3.1:3.3, and all the resin catalysts of the organic lanthanum peroxide-containing solution obtained by filtration in step (3) of Example 7 and stored in sealed bags were used in the operation of step (2).

[0052] The results included: in the operation of step (1), the feed liquid became a transparent solution when the reaction lasted for 2 h. In the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.3 h, the total amount of the lower-layer aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increased. Parallel samples of 300 μL each were taken from the solution containing organic lanthanum peroxide obtained in step (3) to determine the molar concentration of active oxygen, and the ratio to the molar concentration of La (obtained by material balance) was 2.97.

[0053] Example 9: After the operation in step (3) of Example 8 is completed, the raw materials other than lanthanum carbonate and the experimental conditions remain unchanged, and the operation is basically carried out according to steps (1)-(3) of Example 3 to prepare the power-enhanced diesel additive of this Example 9. The main differences are as follows: Solvent A is changed from benzene to cyclohexane (atmospheric boiling point is 80.7 °C, accounting for 30 wt% of the total amount of hydrocarbon solvents, purity is 99.9 wt%, and it is industrial cyclohexane meeting the SH / T 1673-2023 standard), and solvent B is changed from light white oil to a certain hydrotreated 0# diesel (atmospheric distillation range is 70-300 °C); in the raw material ratio, the molar ratio of La, acetylacetone, H 2 O 2 is changed to 1:3.1:3.5; in the operation of step (2), all the resin catalysts of the organic lanthanum peroxide-containing solution obtained by filtration in step (3) of Example 8 and stored in sealed bags are used.

[0054] The results include: In the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.4 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. For the solution containing organic lanthanum peroxide obtained in step (3), 300 μL of parallel samples are taken, and the molar concentration of active oxygen is measured. The ratio to the La molar concentration (obtained by material balance) is 2.99.

[0055] Comparative Example 1: After the operation in step (3) of Example 9 is completed, the raw materials and experimental conditions remain unchanged, and the same raw material ratio is used. The operation is basically carried out according to steps (1)-(2) of Example 1. The main differences are as follows: In the operation of step (1), the amount of solvent A used is changed to 60% of the inert and hydrophobic hydrocarbon solvents; in the operation of step (2), all the resin catalysts of the organic lanthanum peroxide-containing solution obtained by filtration in step (3) of Example 9 and stored in sealed bags are used.

[0056] The results include: In the operation of step (1), the liquid material becomes a transparent solution when the reaction lasts for 1.8 h. In the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.6 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. After the reaction in step (2) is completed, the stirring is stopped, the liquid material is allowed to stand and settle for 10 min, the reactor is opened, and the upper layer solution is extracted to measure the molar concentration of active oxygen. The ratio to the La molar concentration (obtained by material balance) is 2.2.

[0057] In Example 1 and Comparative Example 1, the difference in the ratio of the molar concentration of active oxygen to the La molar concentration in the obtained solution containing organic lanthanum peroxide indicates that when the amount of solvent A used in the operation of step (1) is excessive, the peroxidation reaction of La(acac) 3 is insufficient.

[0058] Comparative Example 2: After the operation in step (2) of Comparative Example 1 was completed, the liquid material was removed and filtered. All the resin catalysts in the obtained lanthanum organic peroxide-containing solution were washed repeatedly with a sufficient amount of benzene until the washing liquid was transparent and the molar concentration of active oxygen was close to 0. With the raw materials and experimental conditions unchanged and the same raw material ratio used, the operation was basically carried out according to steps (1)-(2) of Example 1, with the main difference being that: in the operation of step (1), the amount of solvent A (benzene) was changed to 15% of the inert and hydrophobic hydrocarbon solvent; in the operation of step (2), all the resin catalysts washed with benzene in this comparative example were used.

[0059] The results included: in the operation of step (1), the liquid material became a transparent solution when the reaction lasted for 1 h. In the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.3 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increased. After the reaction in step (2) ended, the stirring was stopped, the liquid material was allowed to stand and settle for 10 min, the reactor was opened, and the upper layer liquid drawn was a turbid liquid. The ratio of the molar concentration of active oxygen to the molar concentration of La (obtained by material balance) was measured to be 2.4; 50 mL of the turbid upper layer liquid was taken, 20 mL of solvent A (benzene) was added, stirred evenly, and it remained turbid during the 5 h of standing; another 50 mL of the turbid upper layer liquid was taken, 10 mL of water was added, stirred for 10 min, and allowed to stand for 1 h. The upper organic phase and the bottom aqueous phase were both transparent solutions.

[0060] The above effect situations of Example 1 and Comparative Example 2 show that when the amount of solvent A in step (1) is too small, in step (2), the free acetylacetone will react with H 2 O 2 to generate acetylacetone peroxide with a relatively large polarity, resulting in the turbidity of the liquid material, and the peroxidation reaction of La(acac) 3 is not sufficient; the reason should be that the concentration of H 2 O 2 is too high and the evaporation loss is large.

[0061] Comparative Example 3: After the operation in step (2) of Comparative Example 2 was completed, the liquid material was removed and filtered. All the resin catalysts in the obtained lanthanum organic peroxide-containing solution were washed repeatedly with a sufficient amount of benzene until the molar concentration of active oxygen in the washing liquid was close to 0. With the raw materials and experimental conditions unchanged and the same raw material ratio used, the operation was basically carried out according to steps (1)-(2) of Example 1, with the main difference being that: in the operation of step (2), all the resin catalysts washed with benzene in this comparative example were used, and the injection time of hydrogen peroxide was changed to 4 h.

[0062] The results include: in the operation of step (2), after adding hydrogen peroxide and continuing the reaction for 1.5 h, the total amount of the lower aqueous phase condensed by the evacuation-condensation reflux-water separation device no longer increases. After the reaction in step (2) is completed, stop stirring, let the liquid material stand and settle for 10 min, open the reactor, and the extracted upper layer liquid is a turbid liquid. The ratio of the measured molar concentration of active oxygen to the molar concentration of La (obtained by material balance) is 2.0; take 50 mL of the turbid upper layer liquid, add 20 mL of solvent A (benzene), stir well, and it remains turbid during the 5 h of standing; take another 50 mL of the turbid upper layer liquid, add 10 mL of water, stir for 10 min, and let it stand for 1 h. Both the upper organic phase and the bottom aqueous phase are transparent solutions.

[0063] The above effect description of Example 1 and Comparative Example 3 shows that in the operation of step (2), when the injection rate of hydrogen peroxide is too fast, the free acetylacetone will react with H 2 O 2 to generate acetylacetone peroxide with a relatively large polarity, resulting in the turbidity of the liquid material and insufficient peroxidation reaction of La(acac) 3 ; the reason should also be the too high concentration of H 2 O 2 and the large evaporation loss.

[0064] Comparative Example 4: After the operation of step (2) in Comparative Example 3 is completed, remove the liquid material and filter it. All the resin catalysts (macroporous weak acid type cation exchange resin microspheres D113 of polyacrylic acid series, hydrogen form, dry basis 90 g) of the obtained organic lanthanum peroxide solution are washed twice with sufficient benzene and three times with sufficient isopropanol until the washing liquid is transparent and the molar concentration of active oxygen is close to 0, then washed five times with sufficient water until there is no isopropanol smell, the moisture between the resin microspheres is blotted dry with filter paper, impregnated with a sufficient amount of lanthanum acetate aqueous solution (concentration 1 mol / L) for 2 h (stirred once every 10 min), and the resin is converted to the La type; the aqueous solution between the resin microspheres is blotted dry with filter paper, washed three times with sufficient isopropanol, and washed five times with sufficient benzene until there is no isopropanol smell.

[0065] With the raw materials and experimental conditions unchanged, basically operate according to steps (1)-(2) of Example 1. The main difference is that: in the raw material ratio, the molar ratio of La, acetylacetone, and H 2 O 2 is changed to 1:3.1:3.5, and in step (2), the macroporous weak acid type cation exchange resin microspheres D113 of the La type prepared in this comparative example are used.

[0066] The results include: in the operation of step (1), the liquid material becomes a transparent solution after reacting for 1.8 h. After the reaction in step (2) is completed, stop stirring, let the liquid material stand and settle for 10 min, open the reactor, and for the extracted upper layer liquid, measure the ratio of the molar concentration of active oxygen to the molar concentration of La (obtained by material balance) is 0.5.

[0067] Example 10: After the operation in step (2) of Comparative Example 4 was completed, the feed liquid was removed and filtered. All the obtained resin catalysts (wet materials, with the measured average diameter still between 0.6 - 0.7 mm, which was basically the same as that before the first use in Example 1) were washed repeatedly with sufficient benzene until the washing liquid was transparent and the molar concentration of active oxygen was close to 0. The liquid between the resin microspheres was blotted dry with filter paper. The resin was impregnated with a sufficient amount of benzene solution of trichloroacetic acid (concentration 0.8 mol / L) for 2 h (stirred every 10 min). The aqueous solution between the resin microspheres was blotted dry with filter paper. The resin was washed repeatedly with sufficient benzene until the washing liquid was basically not acidic. The resin was converted to the hydrogen form (1.0 g of the sample was taken, replaced step by step with isopropanol and water, and then washed with 1.5 mol / L hydrochloric acid aqueous solution. The total amount of La in all the washing liquids was detected and was basically 0. The resin microspheres were replaced step by step with water, isopropanol, and benzene and then put back into the catalyst material), thus completing the regeneration process of the resin catalyst.

[0068] With the raw materials and experimental conditions unchanged, using the same raw material ratio, the operation was basically carried out according to steps (1) - (3) of Example 1. Using the regenerated resin catalyst, the power-boosting diesel additive of this Example 10 was prepared.

[0069] The results included: The operation effects of steps (1) and (2) were basically the same as those in Example 1. For the solution containing organolanthanum peroxide obtained in step (3), 300 μL of parallel samples were taken. Through the KI-Na 2 S 2 O 3 method to determine the molar concentration of active oxygen (total content of hydroperoxy -OOH and peroxy -OO-), the ratio to the molar concentration of La (obtained through material balance) was 2.95.

[0070] Example 11: All the resin catalysts (D113) of the solution containing organolanthanum peroxide obtained by filtration in step (3) of Example 10 were washed 2 times with sufficient benzene and 3 times with sufficient isopropanol until the washing liquid was transparent and the molar concentration of active oxygen was close to 0. Then, it was washed 5 times with sufficient water until there was no smell of isopropanol. The water between the resin microspheres was blotted dry with filter paper. The resin was impregnated with a sufficient amount of lanthanum acetate aqueous solution (concentration 0.8 mol / L) for 2 h, and the resin was converted to the La form. The aqueous solution between the resin microspheres was blotted dry with filter paper. The resin was washed 3 times with sufficient isopropanol and 5 times with sufficient benzene until there was no smell of isopropanol.

[0071] The obtained macroporous weakly acidic cation exchange resin microspheres D113 in the La form were washed 2 times with sufficient benzene and acetylacetone, 2 h each time (stirred every 10 min), filtered, and the liquid between the resin microspheres was blotted dry with filter paper. Then, using the treated resin catalyst, the operation was basically carried out according to steps (1) - (3) of Example 1 to prepare the power-boosting diesel additive of this Example 10. With the raw materials and experimental conditions unchanged, in the raw material ratio, La, acetylacetone, H 2O 2 The molar ratio was changed to 1:3.1:3.4.

[0072] The results included: the operation effect of step (2) was basically the same as that in Example 1; for the solution containing organolanthanum peroxide obtained in step (3), 300 μL of parallel samples were taken, and the molar concentration of active oxygen (total content of hydroperoxy -OOH and peroxy -OO-) was measured by the KI-Na 2 S 2 O 3 method, and the ratio to the La molar concentration (obtained by material balance) was 2.97.

[0073] Example 12: After the operation of step (3) in Example 11 was completed, the operations of steps (1)-(3) in Example 4 were repeated (using lanthanum carbonate, and the molar ratio of La, acetylacetone, and H 2 O 2 was 1:3.0:3.3). The main differences were: in the operation of step (2), all the resin catalysts of the organolanthanum peroxide-containing solution obtained by filtration in step (3) of Example 11 and stored in sealed bags were used; the solution obtained in step (3) contained 20 g / L of organolanthanum component in terms of La, the ratio of the molar concentration of active oxygen to the La molar concentration was 2.92, and the weight ratio of solvent A (benzene) to solvent B (light white oil W1-60) was 40:60. Then, an appropriate amount of benzene and light white oil W1-60 were added and stirred evenly to obtain a transparent solution containing 10 g / L of organolanthanum component in terms of La, the ratio of the molar concentration of active oxygen to the La molar concentration was 2.92, and the weight ratio of solvent A (benzene) to solvent B (light white oil W1-60) was 40:60, which was used as the power-enhancing diesel additive in this Example 12.

[0074] In the solutions containing organolanthanum peroxide obtained in step (3) of the above Examples 1-12, the ratio of the molar concentration of active oxygen to the La molar concentration was within the range of 2.9-3.0, and was basically not affected by the molar ratio of La to acetylacetone in the preparation feed. This indicated that under the catalytic action of the hydrogen-form macroporous weak-acid cation exchange resin microspheres D113 in the reaction conditions and reaction process of step (2), the acac ligand of La(acac) 3 could be peroxidized by H 2 O 2 , and basically reacted according to the ratio (molar ratio) of one acac ligand bonding one hydroperoxy group (-OOH) and / or peroxy group (-OO-); at the same time, basically no reaction occurred between acetylacetone and H 2 O 2 . This also indicated that the hydrogen-form macroporous weak-acid cation exchange resin microspheres D113 used had a very low binding or adsorption amount of La or La compounds in the preparation processes of steps (2) and (3).

[0075] Regarding the above effects of Examples 1-12 and Comparative Example 4, the macroporous weakly acidic cation exchange resin microsphere D113 in hydrogen form has good chemical and physical stability, strong antioxidant ability, relatively balanced hydrophilicity and lipophilicity, moderate acidity in the preparation reaction of the additive of the present invention, good use effect and long service life. When the reaction effect decreases, its performance can be basically restored by washing with a benzene solution of trichloroacetic acid or acetylacetone.

[0076] Comparative Example 5: The diesel additive of this Comparative Example 5 was prepared from raw materials other than hydrogen peroxide in Example 1 and contains La(acac) 3 at 20 g / L in terms of La, which is a solution prepared from lanthanum carbonate, acetylacetone, and an inert and hydrophobic hydrocarbon solvent; in the preparation raw materials, the molar ratio of La to acetylacetone is 1:3.3; the hydrocarbon solvent consists of Solvent A and B, where Solvent A is benzene (accounting for 40 wt% of the total amount of the hydrocarbon solvent), and Solvent B is light white oil W1-60; Basically, operate according to steps (1) and (3) of Example 3 to prepare the diesel additive of this Comparative Example, with the difference in step (3): (3) Fix a 2000 mL round-bottom glass flask on a magnetic stirrer, replace with nitrogen, transfer all the solution containing La(acac) prepared in step (1) 3 into it, add the required amount of Solvent B, put in a magnetic stir bar, stir for 2 h, and filter precisely through a polypropylene non-woven filter cloth to obtain the diesel additive (transparent solution) of this Comparative Example.

[0077] Comparative Example 6: Using some raw materials and experimental conditions of Example 1, prepare a solution containing La(acac) 3 (without peroxidation reaction) as follows: A stirring reactor with a condensation reflux device (a 1000 mL round-bottom, three-neck glass flask, magnetic stirring) is fixed on a magnetic stirrer, replaced with nitrogen, add 500 g of benzene, 100 g (1 mol) of acetylacetone, and 74.5 g of lanthanum carbonate (containing 0.323 mol of La, and the molar ratio of La to acetylacetone is 1:3.1), put in a magnetic stir bar, start stirring, heat the feed liquid and control the temperature at 70-73 °C. When the reaction reaches 1.5 h, the feed liquid becomes a transparent solution to obtain a solution containing La(acac) 3 ; the inlet end of the condensation reflux device is connected to the top space of the reactor, the condensation temperature is 25 °C, and the outlet end is connected to nitrogen to isolate air.

[0078] The obtained solution containing La(acac) 3Take 50 mL of the solution and put it in a beaker, add hydrogen-type macroporous strong acid cation exchange resin microspheres (Amberlyst-35, pre-swollen with sufficient benzene for 10 hours, filtered and the liquid between the resin microspheres was dried with filter paper; the resin skeleton is polystyrene, the sulfonic acid group content is 5.1 mmol / g, and it is 40 g in anhydrous and dry state before swelling with benzene; the average wet bulb diameter is about 0.9 mm), stir for 2 hours, filter out the liquid between the resin microspheres with rapid filter paper, take a sample of 10.0 g and determine the La content by solution evaporation-ignition loss method, and the result is that the filtrate basically does not contain La.

[0079] The effect of this comparative example 6 shows that the hydrogen-type macroporous strong acid cation exchange resin microsphere Amberlyst-35, whose sulfonic acid group can capture a large amount of La(acac) 3 La.

[0080] Comparative Example 7: Using some of the raw materials and experimental conditions of Example 1, the peroxide of acetylacetone was prepared according to the following method: A stirred reactor with an evacuation-condensation reflux-water separation device (1000mL, kettle type, jacketed stainless steel reactor, mechanical stirring; the air inlet end of the evacuation-condensation reflux-water separation device is connected to the top space of the reactor, and the air outlet end is connected to the vacuum system), the reactor jacket circulating water temperature is controlled at 28°C, nitrogen replacement, 500g of benzene, 100g (1mol) of acetylacetone are added, and the required amount of resin catalyst (40g of anhydrous and dry state before swelling with benzene; hydrogen-type macroporous strong acid cation exchange resin microspheres Amberlyst-35, the same brand as used in Comparative Example 6; wet bulb average diameter of about 0.9mm) is added. The evacuation-condensation reflux-water separation device is started and the condensation temperature is controlled to 5°C, and the vacuum degree in the kettle is adjusted (about -90kPa) to make the organic phase condensed in the evacuation-condensation reflux-water separation device reach a significant reflux; then uniformly and continuously inject hydrogen peroxide (concentration 27.5wt%, injected into the feed liquid at the bottom of the inner side of the reactor through a stainless steel tube with an outer diameter of 0.6mm) 148g (1.2mol) and control the feed liquid temperature at 20-23°C by fine-tuning the vacuum degree in the reactor, the hydrogen peroxide feeding time is controlled to be 10h (the flow rate of hydrogen peroxide is adjusted by the weight loss rate of the solution bottle and the opening of the needle valve), and after the hydrogen peroxide is added, the reaction is continued for 45min, and the total amount of the lower aqueous phase condensed by the vacuum-condensation reflux-water separation device no longer increases; the vacuum-condensation reflux-water separation device is closed, nitrogen is filled into the reactor to normal pressure, and stirring is stopped to obtain a feed liquid containing acetylacetone peroxide; during the reaction of injecting hydrogen peroxide, the upper organic phase condensed by the vacuum-condensation reflux-water separation device flows back to the reactor, and the lower aqueous phase is quantitatively discharged and collected, and the formation rate of the lower aqueous phase should be basically matched with the rate of water introduced during the process of adding hydrogen peroxide into the reactor; After the reaction is completed, stop stirring, let the liquid material stand and settle for 10 min, open the reactor, and extract 50 mL of the upper layer liquid as the first sample liquid; then close the reactor, displace the space above the liquid material with nitrogen, start stirring for 3 min every 1 h, place the liquid material for 12 h, open the reactor, and extract 50 mL of the upper layer liquid as the second sample liquid.

[0081] Both the first sample liquid and the second sample liquid are emulsions that can slowly separate into layers. After being stirred evenly respectively and sampled to measure the molar concentration of active oxygen, the result is that the molar concentration of active oxygen in the second sample liquid is 35% lower than that in the first sample liquid.

[0082] The first sample liquid and the second sample liquid are tested respectively according to the following methods, and the following results are obtained: After stirring evenly, take 20 mL of the sample liquid, add 80 mL of solvent A (benzene), stir evenly, and it is still an emulsion; take another 20 mL of the sample liquid, add 80 mL of water, stir for 10 min, and let it stand for 1 h. The upper organic phase and the lower water phase are both transparent solutions.

[0083] The effect of this Comparative Example 7 shows that from acetylacetone, H 2 O 2 The peroxide of acetylacetone prepared by the above method has a very low solubility in the inert and hydrophobic hydrocarbon solvent benzene, but a relatively high solubility in water; while for the solution containing organolanthanum peroxide described in step (3) of the present invention, after sampling and fully removing the solvent under room temperature and vacuum conditions, the obtained solute is basically insoluble in water, indicating that the organolanthanum peroxide contained in the additive of the present invention has very different properties from the peroxide of acetylacetone.

[0084] The effect situations of Comparative Examples 6 and 7 show that the hydrogen-type macroporous strong acid cation exchange resin microsphere Amberlyst-35 cannot be used in the preparation process of the diesel additive of the present invention.

[0085] Comparative Example 8: Repeat the operation of step (1) of Example 1, replace lanthanum carbonate with cerium carbonate (trivalent cerium), and change the molar ratio of Ce to acetylacetone in the raw material ratio to 1:4.3. React for 1 h to obtain a solution containing Ce(acac) 3 ; According to the molar ratio of Ce to H 2 O 2 of 1:0.6, add the hydrogen peroxide used in Example 1 (industrial product with a concentration of 27.5 wt%, and the stabilizer is pyrophosphoric acid at 30 mg / kg), stir and react for 20 min, and then naturally cool to room temperature. It is considered that Ce(acac) 3 in the solution is basically converted to Ce(acac) 4; Additionally, macroporous weakly acidic cation exchange resin microspheres D113 of the hydrogenation type (new resin, pre-swollen with sufficient benzene for 10 h, filtered, and the liquid between the resin microspheres was blotted dry with filter paper; it was anhydrous and in a dry state of 20 g before swelling with benzene; the average wet ball diameter was 0.6 - 0.7 mm). After stirring for 2 h, it was filtered, and the resin microspheres were washed with sufficient benzene until it was considered that the inner pore liquid did not contain Ce. All the resin microspheres were dried, and the Ce content was determined by the loss on ignition method. The result was that the Ce content in the resin microspheres, calculated on the dry basis of the resin, exceeded 10 wt%.

[0086] The effect of Comparative Example 8 shows that for the macroporous weakly acidic cation exchange resin microspheres D113 of the hydrogen type, its carboxyl group has a relatively high binding ability with tetravalent cerium and can capture the cerium in Ce(acac) 4 . In the operation of step (2) of the present invention, it is difficult to maintain the reaction performance, and it is difficult to prepare a Ce-containing additive similar to that in the examples by the method of the present invention.

[0087] Comparative Example 9: The diesel additive of this Comparative Example 9 was prepared from raw materials other than hydrogen peroxide in Example 1 and contained La(acac) 3 at 20 g / L in terms of La, which was a solution prepared from lanthanum carbonate, acetylacetone, and an inert and hydrophobic hydrocarbon solvent; in the preparation raw materials, the molar ratio of La to acetylacetone was 1:3.3; the hydrocarbon solvent consisted of solvent A and B, where solvent A was benzene (accounting for 40 wt% of the total amount of the hydrocarbon solvent), and solvent B was light white oil W1 - 60; Basically, the operations of steps (1) and (3) in Example 3 were carried out to prepare the diesel additive of this Comparative Example, with the difference in step (3): (3) Fix a 2000 mL round-bottom glass flask on a magnetic stirrer, displace with nitrogen, transfer all the solution containing La(acac) prepared in step (1) 3 , add the required amount of di-tert-butyl peroxide (CAS No. 110 - 05 - 4, purity 99 wt%) and solvent B (the amount used was based on subtracting the amount of di-tert-butyl peroxide from the amount of solvent B used in Example 3 to obtain a La concentration basically the same as that in the above examples), put in a magnetic stir bar, and stir for 2 h to obtain the diesel additive (transparent solution) of this Comparative Example.

[0088] For the diesel additive of this Comparative Example 9, the ratio of the measured molar concentration of active oxygen (total content of hydroperoxy - OOH and peroxy - OO -) to the molar concentration of La (obtained by material balance) was 2.98, which was basically in line with the raw material usage.

[0089] Comparative Example 10: The diesel additive of this Comparative Example 10 had the same formulation and preparation method as Comparative Example 9 and contained La(acac) 320 g / L in terms of La, the ratio of the molar concentration of active oxygen to the molar concentration of La is 3.0 (basically consistent with the raw material dosage). The main difference is that an appropriate amount of 2,2-di-tert-butylperoxide butane (CAS No. 2167-23-9, purity 98 wt%) is used to replace di-tert-butyl peroxide.

[0090] Comparative Example 11: The diesel additive of this Comparative Example 11 has the same formulation and preparation method as Comparative Example 9 and contains La(acac). 3 20 g / L in terms of La, the ratio of the molar concentration of active oxygen to the molar concentration of La is 3.0 (basically consistent with the raw material dosage). The main difference is that an appropriate amount of tert-butyl peroxybenzoate (CAS No. 614-45-9, purity 98.5 wt%) is used to replace 2,2-di-tert-butylperoxide butane.

[0091] Application Example 1: An application test of the additives prepared in Examples 1-12, Comparative Example 5, and Comparative Examples 9-11 was carried out on a National VI diesel pickup truck (the engine is a four-cylinder 2.0T, direct injection in the cylinder, maximum torque 400N·m, maximum torque speed 1400-2600rpm, maximum power speed 3600rpm; six-speed manual transmission, fuel tank volume 70L, the exhaust gas treatment system includes a lean NOx trap (LNT), a diesel particulate filter (DPF), and selective catalytic reduction (SCR) in the gas flow direction; it had traveled 12,000 km before the test and was in good normal condition). The performance of each additive in terms of engine power performance, fuel consumption, and noise was investigated under the required road conditions and controlled driving conditions; before the test, a low-ash full synthetic oil of SP grade with a suitable viscosity was used (to avoid the impact of carbon dust generated by possible slight oil burning on the particulate filter), and no obvious carbon deposits were found in each cylinder and each valve. The temperature during the test was 10-15°C, and the wind speed was ≤2m / s; the air quality of the driving route was excellent most of the time and good for a small part of the time, and no sand and dust were encountered; the intake filter, engine oil, and filter element were replaced every 6000 km, and the test results within 100 km after replacing the intake filter and engine oil were not included in the statistical calculation; 2 people were fixed in the vehicle, and the total vehicle weight was about 2050 kg. The main repeated test items included: (A) Comparison of the stable instantaneous fuel consumption per 100 km, noise, and exhaust gas temperature before the DPF when the vehicle was traveling at a constant speed of 60 km / h (4th gear), 90 km / h (5th gear), and 120 km / h (6th gear) on a relatively new asphalt road surface of a basically flat highway; (B) Comparison of the stable instantaneous fuel consumption per 100 km, noise, and exhaust gas temperature before the DPF when the vehicle was traveling at a constant speed of 60 km / h (4th gear), 80 km / h (5th gear), and 100 km / h (5th gear) on a relatively new asphalt road surface of a highway with a slope of about 4%; (C) Comparison of the stable vehicle speed and exhaust gas temperature before the DPF when the vehicle was traveling at a constant gear (5th gear) and a constant fuel consumption (stable instantaneous fuel consumption per 100 km) of 6.0L / km and 8.0L / km on a relatively new asphalt road surface of a basically flat highway. The vehicle speed, stable instantaneous fuel consumption per 100 km, noise, and exhaust gas temperature before the DPF were recorded by the co-pilot at any time, and the exhaust gas temperature before the DPF was obtained in real time from an OBD diagnostic instrument connected to the corresponding interface of the vehicle.

[0092] When Example 1 of this application was implemented, 1600 L of national standard VI diesel fuel (national standard, with isooctyl nitrate as the cetane improver, and the daily fuel for the national standard VI diesel pickup truck) purchased from a gas station at one time was used as the base oil and the comparative diesel fuel. It was stored in 200 L stainless steel barrels, and the application tests of various additives were completed within twelve days. Before refueling the pickup truck, first take 30 L of diesel fuel and place it in a 50 L stainless steel oil mixing barrel with stirring. Add 30 mL of the additive prepared within ten days (the addition amount is 1 v‰), stir for 4 h to mix evenly, and then inject it into the fuel tank (the remaining amount of diesel fuel in the tank before injection is less than 3 L, and it is replaced once with about 5 L of diesel fuel mixed with the additive. The extracted replacement oil is collected and used for vehicles other than those of the present invention). After obtaining reliable results for each test item more than 3 times in the application test of each additive, the DPF is manually regenerated once under driving conditions, and then the remaining diesel fuel in the fuel tank is pumped out until the remaining amount is less than 3 L. The pumped-out diesel fuel, which is mixed with the additive of the example, is transferred to a 200 L stainless steel barrel for mixed storage and reserved for continued testing in Example 5; the pumped-out diesel fuel, which is mixed with the additive of the comparative example, is transferred to another 200 L stainless steel barrel for mixed storage. During the test process, the liquid level of the urea aqueous solution is ensured.

[0093] Application Example 2: Using the national standard VI diesel pickup truck used in Application Example 1, continue to conduct the application tests of the additives prepared in Examples 1 - 11, Comparative Example 5, and Comparative Examples 9 - 11; the test methods and items are basically the same as those in Application Example 1, except that 800 L of another national standard VI diesel fuel (national standard, with a combination of organic cerium and organic peroxide as the cetane improver, and the occasional fuel for the national standard VI diesel pickup truck) purchased at one time is used as the base oil and the comparative diesel fuel (stored in 200 L stainless steel barrels, and the application tests of various additives are completed within ten days). The remaining diesel fuel in the fuel tank after each additive test is also pumped out; the pumped-out diesel fuel, which is mixed with the additive of the example, is transferred to a 200 L stainless steel barrel for mixed storage.

[0094] Application Example 3: Using a national standard IV diesel pickup truck (the engine is a four-cylinder 2.0T, direct injection in the cylinder, the maximum torque is 315 N•m, the maximum torque speed is 1350 - 2800 rpm, the maximum power speed is 4000 rpm; a six-speed manual transmission, the fuel tank volume is 70 L, and the exhaust gas treatment system has urea reduction, i.e., SCR; it has traveled 93000 km before the test, and the carbon deposits in the cylinder and valves have been cleaned by physical methods, and the overall vehicle condition is good; it is fixed with 2 passengers, and the total vehicle weight is about 1900 kg), continue to conduct the application tests of the additives prepared in Examples 1 and 5; the test methods and items are basically the same as those in Application Example 1, and the national standard VI diesel fuel (national standard, with isooctyl nitrate as the cetane improver) described in Application Example 1 is used as the base oil, and the dosage of each additive is 1 v‰ of the diesel fuel.

[0095] The No. 0 National VI diesel (national standard, the cetane number enhancer is isooctyl nitrate) described in Application Example 1 and the No. 0 National VI diesel (national standard, the cetane number enhancer is a combination of organic cerium and organic peroxide) described in Application Example 2 are both daily fuels for the National IV diesel pickup trucks.

[0096] Application Example 4: In the National VI diesel pickup and the National IV diesel pickup, the additive prepared in Example 5 was further tested for application, using the National VI diesel No. 0 (national standard, the cetane number enhancer is isooctyl nitrate) described in Application Example 1 and the National VI diesel No. 0 (national standard, the cetane number enhancer is a combination of organic cerium and organic peroxide) described in Application Example 2 as base oils, and the addition amount was 1.5 v‰; two types of diesel were tested for each vehicle. The test methods and items were basically the same as those in Application Example 1.

[0097] The tests of the above application examples 1-4 were carried out crosswise to ensure that the tests of each additive were completed within fifteen days after preparation; during the test, the mileage of the National VI diesel pickup truck was about 4,200 km, and the mileage of the National IV diesel pickup truck was about 800 km.

[0098] Application Example 5: After the test process of Application Examples 1-4 is completed, the two types of diesel fuels (mixed and stored in 200L stainless steel barrels respectively) extracted from the fuel tank and mixed with the example additives during the test process are stirred separately, and then further applied to the National IV diesel pickup truck for application testing. The test was completed within 3 days, and the mileage of each type of diesel fuel was about 1000km. In addition to the test items (A)-(C) in Application Example 1, emphasis was also placed on the power performance and driving experience during normal driving.

[0099] Application Example 6: The No. 0 National VI diesel (national standard, the cetane number enhancer is isooctyl nitrate) described in Application Example 1 and the No. 0 National VI diesel (national standard, the cetane number enhancer is a combination of organic cerium and organic peroxide) described in Application Example 2 are used as base oils, and the additives prepared in Example 5 (prepared within ten days, stirred for 4 hours) are added in an amount of 1v‰ through a 50L stainless steel mixing barrel with stirring used in Application Example 1. The two portions of diesel with additives, each 60L in size, are sealed and stored in plastic barrels (200L) for 42 days, and are immediately used for application tests in the National VI diesel pickup and the National IV diesel pickup. The test methods and items are basically the same as those in Application Example 1, and the corresponding diesel stored in barrels for 47 days is used as a comparison.

[0100] Application Example 7: Take 100 mL of the additive prepared in Example 5 on the day of preparation and place it in a transparent glass reagent bottle (250 mL). Cover it and store it in the dark. On the 50th day, use the 0# National VI diesel (national standard, the cetane number improver is isooctyl nitrate) stored in a barrel for 48 days in Application Example 1 as the base oil. Through the 50 L stainless steel oil mixing barrel with stirring used in Application Example 1, add it at a dosage of 1 v‰ (stir for 4 h), and operate twice to obtain 60 L of diesel with the additive added. Conduct application tests on the National VI diesel pickup truck and the National IV diesel pickup truck; the test methods and items are basically the same as those in Application Example 1.

[0101] Application Example 8: On the National VI diesel pickup truck, continue the application test on the additive prepared in Example 5 (57 days after preparation). Use the 0# National VI diesel (national standard, the cetane number improver is isooctyl nitrate, the normal fuel for the National VI diesel pickup truck) described in Application Example 1 as the base oil, with an addition amount of 1.5 v‰, and the driving mileage is about 4000 km, which is completed within 9 days; in addition to conducting the test items (A)-(C) in Application Example 1, focusing on the power performance and driving experience during normal driving, the automatic regeneration cycle and automatic regeneration time consumption of the exhaust gas purification system DPF, and the consumption rate of the urea aqueous solution (fill up the urea aqueous solution before and after the test respectively, and record the addition amount) are also investigated.

[0102] The specific test results of the above Application Examples 1-8 include: 1. Under the driving conditions of a constant speed and constant gear of 60 km / h (4th gear), 90 km / h (5th gear), and 120 km / h (6th gear) on a relatively new asphalt road surface highway that is basically flat, and under the driving conditions of a constant speed and constant gear of 60 km / h (4th gear), 80 km / h (5th gear), and 100 km / h (5th gear) on a relatively new asphalt road surface highway with a slope of about 4%, compared with the direct application of the two kinds of diesel (without using additives), when using the additives prepared in Examples 1-11, the stable instantaneous fuel consumption per 100 kilometers of the engine can be reduced by more than 5% when the additive dosage is 1 v‰ of the diesel (the addition amount of organolanthanum peroxide in the fuel tank diesel is 20 mg / L in terms of La), and can be reduced by more than 6% when the additive dosage is 1.5 v‰ of the diesel (the addition amount of organolanthanum peroxide in the fuel tank diesel is 30 mg / L in terms of La). The noise has no obvious change, and the exhaust gas temperature before the DPF of the National VI vehicle can be reduced by more than 15 °C (more than 20 °C when the dosage is 1.5‰ of the diesel); when using the additive prepared in Example 12, the stable instantaneous fuel consumption per 100 kilometers of the engine can be reduced by more than 3.5% when the additive dosage is 1 v‰ of the diesel (the addition amount of organolanthanum peroxide in the fuel tank diesel is 10 mg / L in terms of La). The additives prepared in Comparative Examples 5, 9-11 cannot achieve these effects.

[0103] 2. When driving at a fixed gear (5th gear) and a fixed fuel consumption (stable instantaneous fuel consumption per 100 km) of 6.0 L / km and 8.0 L / km on a relatively new asphalt highway with a basically flat surface, compared with when no additive is used, the stable vehicle speed when the additives of Examples 1-11 are incorporated into diesel can be increased by more than 4% (corresponding to an increase in engine output power, i.e., power, of more than 8%) when the dosage is 1 v‰ of diesel, and can be increased by more than 5% (corresponding to an increase in engine output power, i.e., power, of more than 11%) when the dosage is 1.5 v‰. The additives prepared in Comparative Examples 5 and 9-11 cannot achieve these effects either.

[0104] 3. The test effects of items (A)-(C) in Application Example 5 are basically the same as the test effects of the national IV diesel pickups described in Application Examples 3-4. Moreover, compared with the No. 0 national VI diesel (national standard, the cetane number improver is isooctyl nitrate) described in Application Example 1 and the No. 0 national VI diesel (national standard, the cetane number improver is a combination of organic cerium and organic peroxide) described in Application Example 2, which are used in daily refueling of this vehicle, the two national VI diesels containing the additives of each example all have significantly improved power performance and driving experience. The test effects of items (A)-(C) in Application Examples 6 and 7 are basically consistent with the test effects of the additive of Example 5 in Application Examples 1, 3, and 4.

[0105] 4. In Application Example 8, the test effects of items (A)-(C) are slightly better than the test effects of the additive of Example 5 in Application Example 1; the power performance and driving experience during normal vehicle driving are significantly improved, the automatic regeneration cycle (km) of the particulate trap, i.e., DPF, in the exhaust gas purification system is extended by more than 30% and the automatic regeneration time (minutes) is shortened by more than 20%, and the dosage of the urea aqueous solution is reduced by more than 20% (compared with the daily consumption rate when the additive of Example 5 is not used). After the test of this Application Example 8 is completed, upon inspection of each cylinder and each valve in the engines of the two pickups used, there is no obvious carbon deposition.

[0106] The above effects of the examples and application examples show that the power-enhancing diesel additive of the present invention has good stability and is suitable for use in vehicle diesel after blending with various conventional components such as pour point depressants, stabilizers, detergents, and cetane number improvers that have been incorporated into gas stations. It has certain application prospects; the power of diesel mixed with 0.5-2 v‰ of the additive of the present invention (the addition amount is 10-30 mg / L in terms of La) is significantly improved or even remarkably improved, and it has certain storage stability, can extend the regeneration cycle (km) of DPF and shorten the regeneration time, and the dosage of the urea aqueous solution is reduced; after the national VI diesel is applied with the additive of the present invention, the power performance and driving experience of national VI diesel vehicles can be significantly improved, and the power performance and driving experience of national IV and national V diesel vehicles can be remarkably improved.

Claims

1. A power-boosting diesel additive, containing 10-30 g / L of organic lanthanum peroxide component, calculated as La, and is a solution prepared from lanthanum carbonate or lanthanum oxide, acetylacetone, hydrogen peroxide, and an inert and hydrophobic hydrocarbon solvent; in the preparation raw materials, the molar ratio of La, acetylacetone, and H2O2 is 1:(3.0-3.2):(3.3-3.5); the hydrocarbon solvent is composed of solvents A and B, wherein the atmospheric boiling point of solvent A is 75-100°C and accounts for 20-40wt% of the total amount of hydrocarbon solvents, and the atmospheric distillation range of solvent B is in the range of 70-300°C.

2. The power-enhancing diesel additive according to claim 1, characterized in that: Solvent A is cyclohexane or benzene; solvent B is light white oil or hydrogenated 0# diesel.

3. The power-enhancing diesel additive according to claim 1, characterized in that: The lanthanum oxide is prepared by calcining lanthanum carbonate at a temperature below 600°C.

4. The power-enhancing diesel additive according to claim 1, characterized in that: The hydrogen peroxide is an industrial product containing 25-50wt% H2O2.

5. The method for preparing the power-enhancing diesel additive according to claim 1, comprising the following steps: (1) In a stirred reactor with a condensation reflux device, nitrogen replacement is performed, and the required amount of solvent A, acetylacetone, lanthanum carbonate or lanthanum oxide is added, stirring is started, and the feed liquid is heated and the temperature is controlled at 70-85°C, and the reaction is carried out until the feed liquid becomes a transparent solution to obtain a solution containing La(acac)3; the air inlet end of the condensation reflux device is connected to the top space of the reactor, and the condensation temperature is 0-25°C; (2) The La(acac)3-containing solution of step (1) is transferred into a stirred reactor equipped with an evacuation-condensation reflux-water separation device, replaced with nitrogen, stirred, cooled to 20-30°C, and added with a required amount of resin catalyst swollen with solvent A, or a resin catalyst containing organic lanthanum peroxide solution obtained by filtering the feed liquid in step (3) in the previous batch preparation process, or a bottom feed liquid containing organic lanthanum peroxide solution and resin catalyst obtained by sedimentation separation of the feed liquid in step (3) in the previous batch preparation process; then hydrogen peroxide is added and the feed liquid temperature is controlled at 25-30°C, the hydrogen peroxide addition time is 8-12h, and the reaction is continued for 1-2h after the addition of hydrogen peroxide to obtain a feed liquid containing organic lanthanum peroxide; the content of the resin catalyst in the feed liquid containing organic lanthanum peroxide is 8-15wt% on a dry basis; The air inlet end of the vacuum-condensation reflux-water separation device is connected to the top space of the reactor, the condensation temperature is 0-5°C, and the air outlet end is connected to the vacuum system; the upper organic phase obtained by condensation flows back to the reactor, and the lower aqueous phase is discharged and collected; the vacuum pressure of the vacuum system is controlled to remove the water in the feed liquid in the reactor; The resin catalyst is a hydrogen-type macroporous weakly acidic cation exchange resin microsphere, whose active group is a carboxylic acid group; based on the dry basis of the resin microsphere, the carboxylic acid group content is 10-12 mmol / g; (3) The liquid containing organic lanthanum peroxide in step (2) is subjected to solid-liquid separation to obtain a solution containing organic lanthanum peroxide, and a resin catalyst containing the organic lanthanum peroxide solution or a concentrated liquid of the resin catalyst containing the organic lanthanum peroxide solution; the obtained resin catalyst containing the organic lanthanum peroxide solution or the concentrated liquid of the resin catalyst containing the organic lanthanum peroxide solution is further used in step (2); solvent B is added to the solution containing organic lanthanum peroxide, mixed, and finely filtered to obtain a power-enhancing diesel additive.

6. The method for preparing the power-enhancing diesel additive according to claim 5, characterized in that: In step (2), the grade of the hydrogen-type macroporous weakly acidic cation exchange resin microspheres is D113, and the average diameter of the wet microspheres after being fully swollen in the reaction solution of step (2) is 0.5-0.8 mm.

7. The method for preparing the power-enhancing diesel additive according to claim 5, characterized in that: In the solution containing organic lanthanum peroxide obtained in step (3), the ratio of the molar concentration of active oxygen to the molar concentration of La is 2.9-3.

0.

8. Use of the power-enhancing diesel additive as claimed in claim 1 in diesel for vehicles at gas stations.

9. The use of the power-enhancing diesel additive in diesel fuel for gas stations as claimed in claim 8, characterized in that: The power-enhancing diesel additive is added in an amount of 0.5-2v‰ of the diesel.

10. The use of the power-enhancing diesel additive in diesel fuel for gas stations as claimed in claim 8, characterized in that: The mixed oil of the diesel and the power-enhancing diesel additive contains 10-30 mg / L of La.