Vanadium inhibitor, preparation method thereof, petroleum additive and application

Abstract

The invention discloses a vanadium inhibitor and a preparation method thereof, a petroleum additive and application, and the vanadium inhibitor comprises the following components in percentage by mass: 45%-70% of a magnesium-containing compound, 5%-22% of a dispersing agent, 15%-45% of a solvent and 0.5%-8% of an anti-settling agent. Wherein the mass percent of the magnesium element in the vanadium inhibitor is 20%-36%, the particle size D100 of the vanadium inhibitor is smaller than 350 nm, and the magnesium-containing compound comprises one or more of magnesium oxide, magnesium hydroxide and magnesium carbonate. The vanadium inhibitor with high magnesium element content and small particle size range is obtained by selecting the specific magnesium-containing compound and optimizing the formula of the vanadium inhibitor, can be efficiently combined with the vanadium element in an oil material to generate magnesium vanadate, has a good vanadium inhibition effect, still keeps excellent flowability in a water-containing environment or high and low-temperature environments, and can be used for preparing magnesium vanadate. Decomposition and curing do not occur, and good stability is achieved.

Description

Technical Field

[0001] The present invention relates to the field of chemical materials, and particularly to a vanadium inhibitor, a preparation method thereof, a petroleum additive and an application thereof. Background Art

[0002] With the gradual reduction of crude oil resources, the trend of heavy and inferior crude oil is becoming increasingly obvious. The content of impurity elements in crude oil is getting higher and higher, such as vanadium, nickel, sodium, sulfur, chlorine, etc. These elements will gradually accumulate during the whole process of crude oil processing. Among them, vanadium elements will form low-melting corrosive substances during oil processing or use. In special equipment such as large ships, fuel power plants, industrial boilers, etc., heavy oil is commonly used as fuel. Vanadium in fuel oil usually exists in the form of vanadyl porphyrin. In the combustion chamber boiler burning heavy oil, vanadyl porphyrin will be transformed into V2O5. The melting point of V2O5 is about 670 °C. When the temperature is lower than this temperature, it is in a solid state and will not adhere to the pipe wall. However, when the temperature exceeds this temperature, V2O5 will melt and adhere to the device or corrode the inner wall of the pipeline. If V2O5 and Na2SO4 exist simultaneously, a low-melting compound mNa2O·nV2O5 will be generated, which is more likely to adhere to the pipe wall and exacerbate the corrosion. High-temperature corrosion occurs in parts with higher temperatures such as the superheater tubes and combustion chamber walls of boilers. This kind of corrosion will not only increase the maintenance cost of the equipment, but also shorten the service life of the equipment, and even increase the safety risk. In a gas turbine, the metal temperature is higher than 1000 °C, and the corrosion proceeds quite rapidly at this temperature. If no measures are taken to prevent corrosion, the hot part of the gas turbine will be damaged within 1 week. On the other hand, V2O5 is toxic. If its emission is not restricted, it will cause serious pollution to the environment. In view of this, controlling vanadium elements in fuel oil will become increasingly important. In order to solve the corrosion problem of V elements in fuel oil to gas turbines, industrial boilers, etc., magnesium elements are added to the vanadium-containing oil. During combustion, V2O5 will react with magnesium elements preferentially to generate magnesium vanadate with a melting point higher than 1100 °C, thereby preventing the corrosion brought by V2O5 to the device and equipment.

[0003] Traditional vanadium inhibitors are mainly prepared by some surface treatments or dissolutions to form magnesium compounds with certain fluidity or oil solubility. However, these products generally have the problem of low active ingredient content, and the magnesium element content is about 4%. And due to the characteristics of magnesium compounds themselves, they are prone to hydrolysis to form solid substances when encountering moisture during storage and transportation. These solid substances will seriously affect the normal use of equipment. If the magnesium element content in traditional vanadium inhibitors is increased, there will be problems of uneven dispersion and long-term preservation. There are also vanadium inhibitors that convert magnesium compounds into magnesium carbonate or basic magnesium carbonate. Although it can alleviate the problem of magnesium salt hydrolysis to a certain extent, the use conditions of modified magnesium salts are harsh, the industrial production difficulty is large, and the solubility of modified magnesium salts in fuel oil is small, resulting in a low decomposition rate of modified magnesium salts. Summary of the Invention

[0004] Based on this, it is necessary to provide a vanadium inhibitor with good stability and vanadium inhibition effect, its preparation method, a petroleum additive, and applications thereof.

[0005] The present application provides a vanadium inhibitor, which, in terms of mass percentage, comprises 45% - 70% of a magnesium-containing compound, 5% - 22% of a dispersant, 15% - 45% of a solvent, and 0.5% - 8% of an anti-settling agent;

[0006] Among them, the mass percentage of magnesium element in the vanadium inhibitor is 20% - 36%, the particle size D100 of the vanadium inhibitor is < 350 nm, and the magnesium-containing compound includes one or more of magnesium oxide, magnesium hydroxide, and magnesium carbonate.

[0007] In one embodiment, the magnesium-containing compound includes one or more of light magnesium oxide, active light magnesium oxide, magnesium hydroxide, and basic magnesium carbonate hydrate.

[0008] In one embodiment, the magnesium-containing compound satisfies one or more of the following conditions:

[0009] (1) The specific surface area of the light magnesium oxide is 2 m 2 / g - 18 m 2 / g;

[0010] (2) The specific surface area of the active light magnesium oxide is 2 m 2 / g - 18 m 2 / g;

[0011] (3) The specific surface area of the basic magnesium carbonate hydrate is 10 m 2 / g - 60 m 2 / g;

[0012] (4) The specific surface area of the magnesium hydroxide is 5 m 2 / g - 25 m 2 / g.

[0013] In one embodiment, the dispersant includes one or two of aliphatic amine compounds and aliphatic amide compounds.

[0014] In one embodiment, the solvent includes one or more of aromatic hydrocarbons, mineral oils, vegetable oils, and animal oils.

[0015] In one embodiment, the solvent includes one or more of C6 - C10 aromatic hydrocarbons, white oil, rapeseed methyl ester, diesel oil, palm oil, and tall oil.

[0016] In one embodiment, the anti-settling agent includes one or more of heavy alkyl benzene sulfonic acid, oleic acid, stearic acid, palmitic acid, boric acid, and boron oxide.

[0017] The present application provides a preparation method of the vanadium inhibitor as described above, including the following steps:

[0018] Mix and grind according to the mass ratio of each component until the particle size D100 < 350 nm.

[0019] The present application also provides a petroleum additive including the vanadium inhibitor as described above.

[0020] Furthermore, the present application also provides the use of the above-mentioned vanadium inhibitor or the above-mentioned petroleum additive in reducing vanadium elements in petroleum products.

[0021] By selecting specific magnesium-containing compounds and optimizing the formula of the vanadium inhibitor, the present application obtains a vanadium inhibitor with a high magnesium element content and a small particle size range, which can efficiently combine with vanadium elements in oil to form magnesium vanadate, having a good vanadium inhibition effect. At the same time, it still maintains excellent fluidity in a water-containing environment, or high and low temperature environments, without decomposition and solidification, and has good stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0023] Figure 1 It is a particle size detection diagram of the vanadium inhibitor in Example 1, where the abscissa is the particle size and the ordinate is the distribution rate.

[0024] Figure 2 It is a particle size detection diagram of the vanadium inhibitor in Example 2, where the abscissa is the particle size and the ordinate is the distribution rate.

[0025] Figure 3 It is a particle size detection diagram of the vanadium inhibitor in Example 3, where the abscissa is the particle size and the ordinate is the distribution rate.

[0026] Figure 4 It is a particle size detection diagram of the vanadium inhibitor in Example 4, where the abscissa is the particle size and the ordinate is the distribution rate.

[0027] Figure 5 It is a particle size distribution diagram of a commercially available vanadium inhibitor, where the abscissa is the particle size and the ordinate is the distribution rate. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] To facilitate the understanding of the present application, the present application will be described more comprehensively below with reference to the relevant drawings. Preferred embodiments of the present application are shown in the drawings. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this application belongs. The terms used in the description of this application herein are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0030] The term "and / or" as used herein includes any one of two or more related listed items, as well as any and all combinations of the related listed items. The said any and all combinations include any two related listed items, any more related listed items, or the combination of all related listed items. For example, "A and / or B" includes three parallel options: A, B, and "the combination of A and B".

[0031] In this article, unless otherwise stated, "one or more" means any one of the listed items or any combination of the listed items. Similarly, in other cases where "one or more" and other expressions indicating "one or more" are used, the same understanding shall be made unless otherwise stated.

[0032] In this article, terms such as "further", "even further", "especially", "for example", "such as", "example", "for illustration" are used for descriptive purposes, indicating that there is an association in the content covered between the different technical solutions before and after. However, it should not be understood as a limitation on the previous technical solution, nor as a limitation on the protection scope of this article. In this article, unless otherwise stated, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0033] In this article, "optionally", "optional", "option" mean "may or may not", that is, any one of the two parallel options of "yes" or "no". If "optional" appears in a technical solution in multiple places, unless otherwise specified and there are no contradictions or mutual restrictions, each "optional" is independent. In this application, descriptions such as "optionally contain" and "optionally include" mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means containing or not containing this component X.

[0034] In this text, in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are only for descriptive purposes, and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly specifying the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive listing and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0035] In this text, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, as well as an open technical solution containing the listed features.

[0036] In this text, regarding a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the selectable numerical values within this numerical interval is considered continuous, and it includes the two numerical endpoints of this numerical interval (i.e., the minimum value and the maximum value), as well as each numerical value between these two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within this numerical interval, it includes the two endpoint integers of this numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed in this text should be understood to include any and all sub-ranges subsumed therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows for a broad inclusion of numerical interval types such as a percentage interval, a ratio interval, a ratio value interval, etc.

[0037] In this text, the term "room temperature" or "normal temperature" generally refers to 4°C to 35°C, for example, 20°C ± 5°C. In some embodiments of this text, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this text, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0038] In this text, when a method process involves multiple steps, unless there are clear different descriptions in this text, the execution of these steps has no strict order limit, and it can be executed in an order other than the described one. Moreover, any step can include multiple sub-steps or multiple stages. These sub-steps or stages do not necessarily need to be executed at the same moment, but can be executed at different moments, and their execution order does not necessarily need to be sequential, but can be executed alternately or simultaneously with other steps or a part of the sub-steps or stages of other steps.

[0039] This application provides a vanadium inhibitor. In terms of mass percentage, the composition includes 45% to 70% of a magnesium-containing compound, 5% to 22% of a dispersant, 15% to 45% of a solvent, and 0.5% to 8% of an anti-settling agent;

[0040] Among them, the mass percentage of magnesium element in the vanadium inhibitor is 20% - 36%, the particle size D100 of the vanadium inhibitor is < 350 nm, and the magnesium-containing compound includes one or more of magnesium oxide, magnesium hydroxide, and magnesium carbonate.

[0041] It can be understood that the above limitation on the particle size is a limitation on the solid in the vanadium inhibitor. Generally, the smaller the particle size of the material, the faster the reaction rate. This is because materials with smaller particle sizes have a larger specific surface area. An increase in the specific surface area means that more atoms or molecules are exposed on the surface, increasing the chance of contact with the reactants and thus promoting the progress of the chemical reaction. The particle size of the material can affect the selectivity of the chemical reaction. In some cases, materials with smaller particle sizes may promote the progress of specific reaction paths, thereby improving the selectivity of the reaction. The light magnesium oxide used in this application meets the standard of HG / T 2573 - 2012 "Industrial Light Magnesium Oxide", the activated light magnesium oxide used meets the standard of HG / T 3928 - 2012 "Industrial Activated Light Magnesium Oxide", and the hydrated basic magnesium carbonate used meets the standard of HG / T 2959 - 2023 "Industrial Hydrated Basic Magnesium Carbonate".

[0042] In this application, by selecting specific magnesium-containing compounds and optimizing the formulation of the vanadium inhibitor, a vanadium inhibitor with a high magnesium element content and a small particle size range is obtained, which can efficiently combine with the vanadium element in the oil to form magnesium vanadate, having a good vanadium inhibition effect. At the same time, it still maintains excellent fluidity in an aqueous environment, or high and low temperature environments, does not decompose or solidify, and has good stability.

[0043] Furthermore, the mass percentage of magnesium element in the vanadium inhibitor can be, but is not limited to, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, or 36%.

[0044] Furthermore, particle size D100: It represents that the volume (or mass, etc., depending on the measurement method) of particles smaller than this particle size in the particle group accounts for 100% of the total volume (or total mass) of the particle group. That is, D100 is the maximum particle size in the particle group, and all particle sizes are less than or equal to this value.

[0045] In a specific example, the vanadium inhibitor, by mass percentage, comprises 50% - 65% of magnesium-containing compound, 5% - 20% of dispersant, 15% - 44% of solvent, and 0.5% - 5% of anti-settling agent.

[0046] In a specific example, the magnesium-containing compound includes one or more of light magnesium oxide, activated light magnesium oxide, magnesium hydroxide, and hydrated basic magnesium carbonate.

[0047] Furthermore, the specific surface area of the light magnesium oxide is 2 m 2 / g to 18 m 2 / g. Specifically, the specific surface area of the light magnesium oxide can be, but is not limited to, 2 m 2 / g, 3 m 2 / g, 4 m 2 / g, 5 m 2 / g, 6 m 2 / g, 7 m 2 / g, 8 m 2 / g, 9 m 2 / g, 10 m 2 / g, 11 m 2 / g, 12 m 2 / g, 13 m 2 / g, 14 m 2 / g, 15 m 2 / g, 16 m 2 / g, 17 m 2 / g or 18 m 2 / g.

[0048] The specific surface area of the active light magnesium oxide is 2 m 2 / g to 18 m 2 / g. Specifically, the specific surface area of the active light magnesium oxide can be, but is not limited to, 2 m 2 / g, 3 m 2 / g, 4 m 2 / g, 5 m 2 / g, 6 m 2 / g, 7 m 2 / g, 8 m 2 / g, 9 m 2 / g, 10 m 2 / g, 11 m 2 / g, 12 m 2 / g, 13 m 2 / g, 14 m 2 / g, 15 m 2 / g, 16 m 2 / g, 17 m 2 / g or 18 m 2 / g.

[0049] The specific surface area of the hydrated basic magnesium carbonate is 10 m 2 / g to 60 m 2 / g. Specifically, the specific surface area of the hydrated basic magnesium carbonate can be, but is not limited to, 10 m 2 / g, 15 m 2 / g, 20 m2 / g, 25 m 2 / g, 30 m 2 / g, 35 m 2 / g, 40 m 2 / g, 45 m 2 / g, 50 m 2 / g, 55 m 2 / g or 60 m 2 / g.

[0050] The specific surface area of magnesium hydroxide is 5 m 2 / g ~ 25 m 2 / g. Specifically, the specific surface area of magnesium hydroxide can be, but is not limited to, 5 m 2 / g, 6 m 2 / g, 7 m 2 / g, 8 m 2 / g, 9 m 2 / g, 10 m 2 / g, 11 m 2 / g, 12 m 2 / g, 13 m 2 / g, 14 m 2 / g, 15 m 2 / g, 16 m 2 / g, 17 m 2 / g, 18 m 2 / g, 19 m 2 / g, 20 m 2 / g, 21 m 2 / g, 22 m 2 / g, 23 m 2 / g, 24 m 2 / g or 25 m 2 / g.

[0051] In a specific example, the dispersant includes one or two of aliphatic amine compounds and aliphatic amide compounds. Further, the dispersant includes one or more of oleic acid amide, polyisobutylene succinimide, triethanolamine dodecylbenzenesulfonate, monoalkenyl succinimide, and octadecylamine polyoxyethylene ether.

[0052] It can be understood that the total base number of the dispersant can be, but is not limited to, 10 mgKOH / g ~ 30 mgKOH / g, and the nitrogen content is 1% - 2%.

[0053] Further, the polyisobutylene succinimide can be, but is not limited to, one or more of a mono-polyisobutylene succinimide, a bis-polyisobutylene succinimide, and a borated polyisobutylene succinimide. The molecular weight of the polyisobutylene succinimide is 1,000 to 3,000. Specifically, the molecular weight of the polyisobutylene succinimide can be, but is not limited to, 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, 2,000, 2,100, 2,200, 2,300, 2,400, 2,500, 2,600, 2,700, 2,800, 2,900, or 3,000.

[0054] In a specific example, the solvent includes one or more of an aromatic hydrocarbon, a mineral oil, a vegetable oil, and an animal oil.

[0055] In a specific example, the solvent includes one or more of a C6 - C10 aromatic hydrocarbon, white oil, rapeseed methyl ester, diesel oil, palm oil, and tall oil. It can be understood that the C6 - C10 aromatic hydrocarbon can be, but is not limited to, one or both of a heavy aromatic hydrocarbon and 1,2,4,5 - tetramethylbenzene.

[0056] In a specific example, the anti - settling agent includes one or more of a heavy alkylbenzene sulfonic acid, oleic acid, stearic acid, palmitic acid, boric acid, and boron oxide. The heavy alkylbenzene sulfonic acid can be, but is not limited to, dodecylbenzene sulfonic acid. It can be understood that the anti - settling agent will react with the magnesium - containing compound to a certain extent, and the product synergizes with the dispersant to improve the product stability.

[0057] The present application provides a preparation method of a vanadium - inhibiting agent as described above, including the following steps:

[0058] Mix and grind according to the mass ratio of each component until the particle size D100 < 350 nm.

[0059] The present application also provides a fuel additive including the vanadium - inhibiting agent as described above.

[0060] Specifically, the preparation method of the above - mentioned vanadium - inhibiting agent is from step S10 to step S30:

[0061] Step S10: Input a magnesium - containing compound, a dispersant, a solvent, and a stabilizer into a mixing tank according to a weight ratio and mix evenly.

[0062] Step S20: Pump the premix into a horizontal grinder or a basket grinder for grinding.

[0063] Step S30: Detect the particle size of the material. After the particle size D100 < 350 nm, discharge the material to complete the preparation.

[0064] In a specific example, the stirring form of the mixing tank in step S10 is a planetary stirring paddle or a dispersing disk, and the stirring speed is 400 rpm to 800 rpm. It can be understood that the mixing time depends on the feeding weight, and the mixing time can be but is not limited to 0.5 h to 4 h.

[0065] In a specific example, the maximum linear speed of the grinder in step S20 is > 8 m / s. To grind the target material particles to the nanometer level, the linear speed needs to be greater than 10 m / s. The filter screen gap of the grinder is 0.1 mm to 0.4 mm. Further, the filter screen gap is 0.1 mm. Pulse ultrasound is configured at the filter screen of the grinder to grind the material to a smaller particle size. The pulse frequency is 15 KHz to 30 KHz, and the preferred frequency is 20 KHz.

[0066] Further, the rotor material of the grinder is 95% yttrium zirconia, and the inner cavity material of the grinder is silicon carbide. The grinding medium of the grinder is 95% yttrium zirconia beads. Using yttrium zirconia material for the grinding medium and the rotor, choosing silicon carbide lining, on the one hand, it has excellent thermal conductivity, which is conducive to heat dissipation inside the grinding equipment, and on the other hand, it can prevent the introduction of impurity metals.

[0067] Specifically, the diameter of the 95% yttrium zirconia beads of the grinding medium is 0.1 mm to 0.8 mm, and preferably the diameter of the 95% yttrium zirconia beads is 0.2 mm to 0.4 mm.

[0068] Furthermore, the filling amount of the grinding medium for the grinder is 50% to 85% of the volume of the grinding chamber. To grind the target material particles to the nanometer level, the preferred filling volume is 80%.

[0069] The specific grinding process is as follows: Pump a certain weight of the premix into the circulating stirring tank, and then the premix is circulated and ground in the circulating stirring tank and the grinder. It can be understood that the circulating stirring tank is a single-cycle tank circulation or a double-cycle tank reverse cylinder circulation.

[0070] Further, the pressure in the grinding chamber during the grinding process is 0.05 MPa to 0.25 MPa. Furthermore, the pressure in the grinding chamber is 0.15 MPa to 0.2 MPa.

[0071] The vanadium inhibitor provided by this application is prepared mainly by physical means and supplemented by chemical means. The initial particle size D100 of the premix is between 100 μm and 200 μm. The premix is pumped into a grinder, and the high-speed rotation of the grinder drives the grinding medium to move rapidly and randomly in the grinding cavity. The shear force generated by the grinding medium impacts the magnesium compound particles, causing them to finally exist stably as nano-sized particles in the system. For a multifunctional nano-MgO vanadium inhibitor prepared by the patent with the publication number CN 105238461A of the comparative application, magnesium oxide carboxylate is modified under high-temperature conditions of about 350 °C. After dehydration at high temperature, the structure of the magnesium carboxylate salt is that multiple MgO molecules chelate with each other with a macromolecular acid as the center. During the use of this product, sintering occurs and it agglomerates after combustion in a gas turbine, and its specific surface area is significantly reduced, further reducing the reaction efficiency with V2O5. The environmentally friendly magnesium-based vanadium inhibitor prepared by this application, with the support of a unique dispersion system, makes MgO molecules evenly suspended in the solvent through physical grinding. During combustion, the component dispersant and anti-settling agent will burn rapidly, making the magnesium oxide molecules after combustion appear in a porous form. In this form, the vanadium inhibitor magnesium oxide molecules have a higher specific surface area, meaning more molecules are exposed on the surface, and there are more opportunities to contact V2O5, thus promoting the improvement of the vanadium inhibition effect.

[0072] Furthermore, this application also provides the use of the above-mentioned vanadium inhibitor or the petroleum additive as described above in reducing vanadium elements in petroleum products.

[0073] It can be understood that petroleum products can be but are not limited to heavy oil, crude oil, and fuel oil.

[0074] In a gas turbine or a boiler, the vanadium inhibitor reacts with V2O5 in the oil product to form magnesium vanadate with a melting point higher than 1100 °C, preventing the corrosion of equipment and devices by V2O5. The technical solution of the preparation method of the vanadium inhibitor provided by this application has advanced technology, simple production process, high production efficiency, high production safety, and low production energy consumption. Moreover, the vanadium inhibitor product is green and environmentally friendly. The raw materials used are all ordinary chemicals, which are environmentally friendly and harmless, and no three wastes are generated during the production and use of the product.

[0075] The following further elaborates on this application in detail with specific examples. It should be understood that these examples are only used to illustrate this application and not to limit the scope of this application. For the experimental methods without specific conditions in the following examples, preferentially refer to the guidance given in this application, and it can also be carried out according to the experimental manuals or conventional conditions in the art, or according to the conditions recommended by the manufacturer, or refer to the experimental methods known in the art.

[0076] In the following specific embodiments, regarding the measurement parameters of raw material components, unless otherwise specified, there may be slight deviations within the weighing accuracy range. Regarding temperature and time parameters, acceptable deviations caused by instrument test accuracy or operation accuracy are allowed. "Normal temperature" refers to 25°C; "normal pressure" refers to 100 KPa or 101 KPa.

[0077] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity in description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0078] Example 1

[0079] This example provides a vanadium inhibitor, and its preparation method is as follows:

[0080] Weigh 500 g of light magnesium oxide with a specific surface area of 12 m 2 / g, 60 g of oleic acid amide, 430 g of 1800# aromatic solvent, and 10 g of oleic acid in a 2-L beaker, and use mechanical stirring to stir rapidly for 30 min to make the materials mix evenly. Pour the premix into a 0.2-L laboratory grinder. The rotor material of the grinder is zirconia ceramic, its inner lining material is silicon carbide, the diameter of the grinding medium is zirconia beads with a diameter of 0.2 - 0.3 mm, the filling volume of the grinding medium is 80%, the filter screen gap of the grinder is 0.1 mm, adjust the grinder speed to 2000 rpm - 2500 rpm, and the corresponding linear speed is about 11.8 m / s. Grind cyclically for about 4 h, and when the particle size D100 of the sample is < 350 nm, the sample preparation can be completed. As Figure 1 Shown is the particle size detection diagram of the vanadium inhibitor in Example 1.

[0081] Example 2

[0082] This example provides a vanadium inhibitor, and its preparation method is as follows:

[0083] Weigh 1300 g of magnesium hydroxide with a surface area of 20 m 2 / g, 200 g of polyisobutylene succinimide with a molecular weight of about 2300, 420 g of palm oil, and 80 g of dodecylbenzenesulfonic acid in a 3-L beaker, and use mechanical stirring to stir rapidly for 30 min to make the materials mix evenly. Pour the premix into a 1-L laboratory grinder. The diameter of the grinding medium is zirconia beads with a diameter of 0.3 - 0.4 mm, the filling volume of the grinding medium is 80%, the filter screen gap of the grinder is 0.15 mm, adjust the speed to 1800 rpm - 2300 rpm, grind cyclically for about 6 h, and detect the particle size of the sample. When its D100 < 350 nm, the sample preparation can be completed. As Figure 2 Shown is the particle size detection diagram of the vanadium inhibitor in Example 2.

[0084] Example 3

[0085] This example provides a vanadium inhibitor, and its preparation method is as follows:

[0086] Weigh 550 g of active light magnesium oxide with a specific surface area of 12 m 2 / g in a 3 L beaker, 180 g of boronated polyisobutylene succinimide, 260 g of durene, and 10 g of boric acid. Use mechanical stirring to quickly stir for 30 min to make the materials evenly mixed. Pour the premixed material into a 0.2 L laboratory grinder with zirconia beads with a diameter of 0.3 - 0.4 mm. The filling volume of the grinding medium is 75%. Adjust the grinder speed to 2000 rpm - 2500 rpm and grind cyclically for about 4 h. When the particle size D100 of the sample is detected to be < 350 nm, the sample preparation is completed. As Figure 3 shown is the particle size detection diagram of the vanadium inhibitor in Example 3.

[0087] Example 4

[0088] This example provides a vanadium inhibitor, and its preparation method is as follows:

[0089] Weigh and put 3500 Kg of light magnesium oxide with a specific surface area of 12 m 2 / g, 1080 Kg of mono - polyisobutylene succinimide, 1140 Kg of 10# white oil, and 60 Kg of oleic acid into a 5 m³ dispersion tank. Turn on the dispersion stirring, adjust the speed to 600 rpm - 800 rpm, and mix for about 3 h. After the materials are evenly mixed, use a pneumatic diaphragm pump to pump the premixed material into a double - circulation stirring tank. Turn on the grinder with zirconia beads with a diameter of 0.3 - 0.4 mm. The filling volume of the grinding medium is 75%. Adjust the speed to 400 rpm - 450 rpm, and the corresponding linear speed is about 12 m / s. Grind cyclically for about 10 h. When the particle size D100 of the product is detected to be < 350 nm, discharge and package to complete the production. As Figure 4 shown is the particle size detection diagram of the vanadium inhibitor in Example 4.

[0090] Comparative Example 1

[0091] Compared with Example 1, change the specification of the grinding medium zirconia beads to 0.8 - 1.0 mm, change the filling amount to 40%, and after grinding for 4 h, the particle size of the material is detected to be 7.829 μm. After grinding for 8 h, the particle size of the material is detected to be 5.742 μm. After grinding for 12 h, the particle size of the material is detected to be 5.691 μm. After grinding for 24 h, the physical particle size is detected to be 5.211 μm. Continuing to extend the grinding time, the particle size of the material remains at about 5 μm. Continuing to extend the grinding time can hardly reduce the particle size and wastes energy.

[0092] Comparative Example 2

[0093] Compared with Example 1, the linear velocity was adjusted to 6 m / s. After grinding for 4 h, the particle size of the material was detected to be 10.197 μm. After grinding for 8 h, the particle size of the material was detected to be 9.910 μm. After grinding for 12 h, the particle size of the material was detected to be 9.106 μm. After grinding for 24 h, the particle size of the material was detected to be 8.800 μm. When the grinding time was extended again, the particle size of the detected material remained at about 8.5 μm. Continuing to extend the grinding time could hardly reduce the particle size and was a waste of energy.

[0094] Comparative Example 3

[0095] Compared with Example 1, the light magnesium oxide was replaced with a raw material having a specific surface area of 20 m 2 / g, and the other conditions remained unchanged. After grinding for 2 h, the state of the material changed and became paste-like, losing its fluidity, and this material could not be used as a vanadium inhibitor.

[0096] The characterization data and effect data of the products of the examples and comparative examples and the commercially available vanadium inhibitors are shown in Tables 1 and 2 below. As Figure 5 shown is the particle size distribution diagram of the commercially available vanadium inhibitor.

[0097] Table 1

[0098]

[0099] Table 2

[0100]

[0101] Comparison of hydrolysis stability and filterability (test basis: GEK28150 Appendix2)

[0102] Method overview: This test examines the hydrolysis stability and filterability of the vanadium inhibitor product. Under pressure (1 bar N2), filtration is carried out using a microporous filter membrane with a pore size of 0.8 microns. The duration of filtration is used to check for the presence of colloidal compounds that may clog the filter membrane.

[0103] The experiment includes: a. Blank diesel;

[0104] b. Blank diesel + 0.1% H2O (v / v)

[0105] c. Diesel + 300 mg / Kg vanadium inhibitor;

[0106] d. Diesel fuel + 300 mg / Kg of vanadium inhibitor + 0.1% (v / v) of water, and homogenized using a mechanical stirrer (rotation speed 1000 revolutions per minute) for 5 minutes at room temperature;

[0107] e. Diesel fuel + 300 ppm of vanadium inhibitor + 0.1% (v / v) water, homogenized by mechanical stirrer (rotating speed 1000 rpm) in a hot water bath (90 °C) for 5 minutes, and filtered after the mixture is cooled to room temperature.

[0108] The total volume of the filtered sample is 200 mL.

[0109] The experimental results are shown in the following table:

[0110]

[0111] From the comparison of hydrolysis stability and filterability, it can be seen that the particle size of the commercially available sample is large and the hydrolysis stability is poor, and it cannot completely pass through the 0.8 μm microporous filter membrane under different experimental conditions. The environmentally friendly magnesium-based vanadium inhibitor prepared by this method can quickly pass through the 0.8 μm microporous filter membrane under different experimental conditions. This product has better stability and smaller particle size.

[0112] The above embodiments only represent several implementation manners of the present invention, which are convenient for understanding the technical solution of the present invention specifically and in detail, but should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments based on the technical solutions provided by the present invention are all within the protection scope of the appended claims of the present invention. Therefore, the protection scope of the present invention patent should be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A vanadium inhibitor, characterized in that, By mass percentage, the composition includes 45% - 70% of magnesium-containing compound, 5% - 22% of dispersant, 15% - 45% of solvent, and 0.5% - 8% of anti-settling agent; Among them, the mass percentage of magnesium element in the vanadium inhibitor is 20% - 36%, the particle size D100 of the vanadium inhibitor is < 350 nm, and the magnesium-containing compound includes one or more of magnesium oxide, magnesium hydroxide, and magnesium carbonate.

2. The vanadium inhibitor according to claim 1, wherein The magnesium-containing compound includes one or more of light magnesium oxide, active light magnesium oxide, magnesium hydroxide, and basic magnesium carbonate hydrate.

3. The vanadium inhibitor according to claim 2, characterized in that, The magnesium-containing compound satisfies one or more of the following conditions: (1) The specific surface area of the light magnesium oxide is 2 m 2 / g to 18 m 2 / g; (2) The specific surface area of the active light magnesium oxide is 2 m 2 / g to 18 m 2 / g; (3) The specific surface area of the hydrated basic magnesium carbonate is 10 m 2 / g to 60 m 2 / g; (4) The specific surface area of the magnesium hydroxide is 5 m 2 / g to 25 m 2 / g.

4. The vanadium inhibitor according to claim 1 or 2, characterized in that, The dispersant includes one or two of aliphatic amine compounds and aliphatic amide compounds.

5. The vanadium inhibitor according to claim 1 or 2, characterized in that, The solvent includes one or more of aromatic hydrocarbons, mineral oils, vegetable oils, and animal oils.

6. The vanadium inhibitor according to claim 5, characterized in that, The solvent includes one or more of C6 - C10 aromatic hydrocarbons, white oil, rapeseed methyl ester, diesel oil, palm oil, and tall oil.

7. The vanadium inhibitor according to claim 1 or 2, characterized in that, The anti-settling agent includes one or more of heavy alkylbenzene sulfonic acid, oleic acid, stearic acid, palmitic acid, boric acid, and boron oxide.

8. A preparation method of the vanadium inhibitor according to any one of claims 1 to 7, characterized in that, It includes the following steps: Mix and grind according to the mass ratio of each component until the particle size D100 < 350 nm.

9. An oil additive, characterized in that, It includes the vanadium inhibitor according to any one of claims 1 - 7.

10. Use of the vanadium inhibitor according to any one of claims 1 - 7 or the petroleum additive according to claim 9 in reducing vanadium element in petroleum products.

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