WO2017066928A1 - Multipurpose nano-mgo vanadium inhibitor, method for preparation and uses thereof - Google Patents

Abstract

A method for the preparation of a multipurpose nano-MgO vanadium inhibitor, the nano-MgO vanadium inhibitor thus obtained, and uses thereof; the preparation method uses as raw ingredients a magnesium compound, organic acids, a resin dispersant, an organic solvent and water that are formed by means of a synthesis reaction into oil-soluble nano-MgO. The nano-MgO thus obtained can be used not only as a vanadium inhibitor, but also as an acid neutralizing agent, inhibiting acid corrosion caused by elements such as sulfur and nitrogen during combustion. The method of preparation is simple, and the nano-MgO vanadium inhibitor obtained has a high concentration of Mg, good dispersability and high stability, and can be stored long-term.

Description

 Multifunctional nano MgO vanadium suppressing agent, preparation method thereof and use thereof

 [0001] The present invention belongs to the field of energy and petrochemical industry, and particularly relates to a preparation method of multifunctional nanometer MgO. The prepared product is a fuel additive, which can be used for suppressing V, S, N, Na, etc. in the fuel combustion process. Impurities corrode equipment and extend the life of the equipment.

 Background technique

[0002] Heavy oil is widely used in gas turbines of power plants because of its low price. However, heavy oil usually contains impurities such as V, S, N, Na, etc., which brings many problems to the operation, maintenance and maintenance of the unit and its auxiliary systems. For example, V in heavy oil exists in the form of porphyrins, which are difficult to remove by conventional methods, while V forms V ₂ 0 ₅ during combustion.

, its low melting point, causing severe molten salt corrosion on gas turbine blades. When S and Na elements are present, compounds such as NaSO ₄ · mNa ₂ 0 · nV ₂ 0 ₅ are further formed. NaSO ₄ alone has no corrosive effect on stainless steel, carbon steel, etc., but when a reducing substance is present, Produces severe corrosion; ma 20 - nV ₂ 0 _{5 has} a lower melting point than V ₂ 0 ₅ and is deposited in a molten state on several gas turbine blades, causing the blade to suffer destructive damage in a short period of time, even causing blade breakage, etc. The occurrence of a serious accident. In addition, sulfur, nitrogen and other elements in the combustion process, such as SO _x , NO and other acidic substances will also strongly corrode the turbine blades. The most economical and effective way to solve this series of problems is to add corrosion inhibitors to heavy oil.

 [0003] At present, such corrosion inhibitors are mainly ruthenium- or magnesium-containing compounds. Since ruthenium is a rare earth element, the price is relatively expensive, and the magnesium compound is more competitive in the market in terms of economy and effect.

[0004] Magnesium-containing corrosion inhibitors are generally classified into three types: 1. Water-soluble magnesium salts such as magnesium sulfate, magnesium acetate, and the like (CN 1055110C, CN 1174877A, etc.). Due to the high pressure of the power equipment, the decomposition rate of magnesium sulfate and the like is very low, and the decomposition of the active ingredient MgO is small, so such inhibitors can only be used in fuels with low V and Na contents. 2. Oil-soluble magnesium salts, such as magnesium sulfonate, magnesium tartrate, etc. (CN 1278550A, CN 02150923. 9, etc.). Such inhibitors can be directly added to the fuel, have a certain vanadium-inhibiting effect, but can not inhibit sulfur and nitrogen corrosion. 3, colloidal suspension, such inhibitors are generally specially treated MgO and Mg (0H) ₂ particles (CN 1804005A, CN 101265422A, etc.), can be suspended in water or organic solvents, both vanadium inhibitors, acid Neutralizer Yes, it is a kind of multifunctional fuel additive. However, at present, such inhibitors have the following disadvantages: First, the particle size is large, which is easy to cause wear of the fuel pump and the flow distributor; secondly, the concentration of the active ingredient MgO is low, the stability is insufficient, and the long-term storage cannot be performed; The preparation process is complicated, requires high-pressure equipment, and has poor safety. Therefore, colloidal suspension inhibitors are currently used less.

[0005] In summary, the development of a multi-functional vanadium-reducing agent with simple synthesis process, high-pressure equipment, high active component, good oil solubility, small particle size and long-term preservation has important practical significance.

 Summary of invention

 technical problem

 [0006] The object of the present invention is to provide a method for preparing a multifunctional nano-MgO vanadium suppressing agent according to the deficiencies of the prior art. The method is simple, easy, low-cost, and does not require high-pressure equipment, and the prepared nano-MgO vanadium-inhibiting agent is effective. High composition, good oil solubility, small particle size, good stability, long-term preservation, and anti-vanadium, acid neutralization and other functions.

 Problem solution

 Technical solution

 [0007] In order to achieve the object, the present invention provides a preparation method of a multifunctional nano-MgO vanadium-inhibiting agent, and the specific steps are as follows:

 [0008] In the reactor, magnesium compound 10~27%, organic acid A 2~10%, organic acid B are added in parts by mass.

0 to 8%, resin dispersant 0 to 3%, organic solvent 50 to 75%, water 0 to 18%, stir evenly;

0~220 ° C, heat preservation l~3h, while steaming off the water in the reaction system;

[0009] Continue to raise the temperature to 260~350 ° C, keep l~5h, and remove part of the solvent in the system (refer to 260-35

0 degree of solvent which can be distilled under normal pressure) and water produced by the reaction process, to obtain a uniform low concentration of multifunctional oil-soluble nano-MgO;

[0010] Distillation under reduced pressure (~200 ° C, l~10 mmHg) In addition to low boilers, a high concentration of nano-M _g 0 is obtained.

[0011] The reactor is a normal pressure or medium and low pressure reactor.

 [0012] The magnesium compound is a mixture of one or more of magnesium oxide, magnesium carbonate, magnesium hydroxide, and magnesium acetate.

[0013] The organic solvent is a high-boiling inert solvent such as a mixture of one or more of mercaptobenzene, heavy aromatic hydrocarbon, olefin oligomer, mineral oil, synthetic oil and the like. [0014] The organic acid A is a mixture of one or more of an organic carboxylic acid having a carbon chain length of C8 to C20, a long-chain sulfonic acid, a nonylbenzenesulfonic acid, and a cyclic citric acid.

[0015] The organic acid B is a mixture of one or more of a lower organic monobasic acid or a polybasic acid such as acetic acid, propionic acid, butyric acid or oxalic acid.

 [0016] The resin dispersant is a mixture of one or more of a terpene resin, an epoxy resin, and an acrylic resin.

 [0017] The nano MgO vanadium inhibitor prepared by the process has the following characteristics:

 [0018] First, the product quality index is superior to the similar products currently on the market, the mass content of Mg can reach 30~45%, the particle size can reach 50~100nm, and the solubility in fuel oil and organic solvent is excellent. It is evenly dispersed and can be stored for a long time. This is because the process uses a composite dispersion system. On the basis of the traditional long-chain organic acid, the addition of a small molecule organic carboxylic acid can effectively reduce the particle size of the MgO particles in the product; and the addition of the resin-type dispersant can not only increase The fluidity of the system can also greatly increase the concentration of MgO and the stability of the product.

 [0019] Secondly, due to the above characteristics, the product prepared by the process as a fuel additive can not only inhibit the corrosion of the V, S, N, Na and other impurities in the fuel combustion process, but also has the function of acid neutralization, and can also be used as lubrication. Additives are used in lubricating oils and are a multifunctional additive.

 Advantageous effects of the invention

 Beneficial effect

 [0020] The method adopts a general pressure reactor to prepare a MgO vanadium suppressing agent, and has the advantages of low investment cost, simple process, good safety, no pollution of three wastes. The process is suitable for both large-scale industrial production and small-scale production applications. It is the first choice for many small and medium-sized additive production and sales enterprises in China. It breaks the monopoly of foreign enterprises on the high-end product market of anti-vanadium agents in China, and enhances the autonomy of anti-vanadium products in China. Research and development capabilities and promotion and application are of great significance.

 Invention embodiment

 Embodiments of the invention

 The invention will be described in more detail by the following examples, but the invention is not limited to these specific examples.

Embodiment 1

[0023] In terms of parts by mass, 20 parts of industrial grade Mg0, 40 parts of heavy decyl benzene, 50 parts of mixed trimethylbenzene were added to the reactor. 1小时的含摩尔树脂, 4 parts of terpene resin, 4 parts of oleic acid, 25 parts of distilled water and 6 parts of glacial acetic acid, the temperature is raised to 105 ° C under stirring, the reaction is kept for 2.5 h, and the water in the reaction system is removed by a water separator to obtain nano-MgO. Precursor.

 [0024] The above-mentioned nano-MgO precursor is heated to 230 ° C, the mixed trimethylbenzene in the system is continuously removed during the heating process, and then the temperature is further raised to 33 CTC and kept for 3 hours, and the distilled solvent is collected and generated during the reaction. Water, the obtained product was a brown-gray translucent fluid containing 17% of Mg, and the physical and chemical properties of the product are shown in Table 1.

 [0025] Example 2

 The product of Example 1 was subjected to distillation under reduced pressure to obtain a product containing Mg in an amount of 25%, 35% and 45%, respectively. These products are translucent fluids with good fluidity, good storage stability, no precipitation after 12 months of storage, no precipitation in water, good dispersion in oil, no insoluble matter, and the physicochemical properties of the products are shown in Table 1. Shown

Table 1

 [] [Table 1]

 Embodiment 3

[0029] In terms of parts by mass, 16 parts of reagent grade Mg0, 30 parts of alkene oligomer, 60 parts of mixed tetramethylbenzene, 2 parts of terpene resin, 8 parts of dodecylbenzenesulfonic acid, 15 were added to the reactor. The distilled water and 2 parts of glacial acetic acid were heated to 110 ° C under stirring, and the reaction was kept for 3 hours, and the water in the reaction system was removed by a water separator to obtain a nano-MgO precursor. [0030] The above-mentioned nano-MgO precursor is heated to 300 ° C, kept for 4 h, and a part of the distilled solvent and water generated during the reaction are collected, and the obtained product is a brownish gray translucent fluid with good fluidity, and the product contains Mg. The amount is 15%, and the physical and chemical properties are shown in Table 2.

 Example 4

 The product of Example 3 was subjected to distillation under reduced pressure to give a product containing 25% and 35% of Mg. These products are translucent fluids with good fluidity, good storage stability, no precipitation after 12 months of storage, no precipitation after water, good dispersion in oil, no insoluble matter, and the physicochemical properties of the products are shown in Table 2. Shown.

 Table 2

 [] [Table 2]

 Example 5

[0035] In parts by mass, 20 parts of Mg (OH) ₂ , 80 parts of high boiling synthetic oil, 1 part of terpene resin, 10 parts of cyclodecanoic acid, 10 parts of distilled water and 8 parts of propionic acid are added to the reactor. The temperature was raised to 140 ° C under stirring, and the temperature was kept for 2 hours, and the water in the reaction system was removed by a water-distributing device; the temperature was further raised to 260 ° C, and the temperature was kept for 5 hours, and the distilled solvent and the water formed during the reaction were collected. The resulting product was a yellow translucent fluid with good fluidity and a Mg content of 12%. Further concentration of the product can also result in a high concentration product containing more than 30% Mg. The above products are yellow translucent fluids with good fluidity, good storage stability, no precipitation after 12 months of storage, no precipitation in water, good dispersion in oil, no insoluble matter, and average particle size is less than 150nm.

 Embodiment 6

[0037] In the reactor, 20 parts of Mg (OH) ₂ , 80 parts of high boiling point mineral oil, 10 parts of cyclodecanoic acid are added to the reactor. 10 parts of distilled water and 8 parts of acetic acid, heated to 160 ° C under stirring, kept for 2 h, the water in the reaction system was removed by a water separator; the temperature was further increased to 260 ° C, and kept for 5 h, and the distilled solvent and reaction were collected. Water generated during the process. The obtained product was a milky white suspension, which was left to stand for 3 months without precipitation.

Example 7

[0039] In the reactor, 35 parts of MgCO ₃ , 80 parts of C8-12 mercaptobenzene, 4 parts of epoxy resin dispersant, 12 parts of tall oil acid, 25 parts of distilled water and 7 parts of butyric acid were added to the reactor. The temperature was raised to 180 ° C under stirring, and the temperature was kept for 1 hour. The water in the reaction system was removed by a water separator; the temperature was further raised to 280 ° C, and the temperature was kept for 4 hours, and the distilled solvent and the water formed during the reaction were collected. The resulting product was a brown translucent fluid with good fluidity and a MF content of 9%. This product can be further concentrated to obtain a high concentration product containing more than 30% Mg. The above products are all brown translucent fluids with good fluidity, good storage stability, no precipitation after 12 months of storage, no precipitation in water, good dispersion in oil, no insoluble matter, and average particle size is less than 200nm.

 Embodiment 8

[0041] In the reactor, 40 parts of Mg (CH ₃ C00) ₂ - 4H ₂ 0, 90 parts of heavy decyl benzene, 60 parts of mixed trimethylbenzene, 3 parts of acrylic resin dispersant, 14 parts by weight are added to the reactor. The oleic acid and 4 parts of distilled water were heated to 220 ° C under stirring, and the temperature was kept for 1.5 h. The water and part of the solvent in the reaction system were removed by a water separator; the temperature was further raised to 350 ° C, and the mixture was kept for 1 hour, and the steamed off was collected. Part of the solvent and water formed during the reaction. 5%。 The product is a very good liquid color of the translucent liquid, containing Mg in an amount of 4.5%. This product can be further concentrated to obtain a high concentration stable product containing a Mg content of more than 30%. The above products are all brown and translucent fluids with good fluidity, good storage stability, no precipitation after 12 months of storage, no precipitation after water, good dispersibility in oil, no insoluble matter, and average particle size less than 100nm .

 Example 9

[0043] In parts by mass, 20 parts of Mg0, 80 parts of high boiling synthetic oil, 1 part of terpene resin, 4 parts of C8-C12-carboxylic acid mixture, 20 parts of distilled water and 4 parts of oxalic acid are added to the reactor, and The mixture was heated to 100 ° C under stirring, and kept for 3 hours. The water in the reaction system was removed by a water separator; the temperature was further raised to 280 ° C, and the temperature was kept for 2 hours, and the distilled solvent and the water formed during the reaction were collected. The resulting product was a very fluid, brown translucent fluid containing 12% Mg. This product can be further concentrated to obtain a high concentration product containing more than 30% Mg. The above products are all brown translucent fluids with good fluidity, good storage stability, no precipitation after 6-12 months, no precipitation in water, good dispersion in oil, no insoluble matter, and the product Average particle size Less than 250 nm.

Claims

Claim  [Claim 1] A method for preparing a multifunctional nano-MgO vanadium suppressing agent, comprising the following synthesizing steps:  i) 10 to 27% of magnesium compound, 2 to 10% of organic acid A, 0 to 8% of organic acid B, 0 to 3% of resin dispersant, 50 to 75% of organic solvent, and water in an amount of water in the reactor 0~18%, stirring evenly; heating to 100~220 ° C, keeping l~3h, while steaming off the water in the reaction system;  The organic acid A is a mixture of one or more of an organic carboxylic acid having a carbon chain length of C8 to C20, a long-chain sulfonic acid, a nonylbenzenesulfonic acid, and a cyclic citric acid;  The organic acid B is a mixture of one or more of a lower organic monobasic acid or a polybasic acid such as acetic acid, propionic acid, butyric acid or oxalic acid;  Ii) continue to raise the temperature to 260~350 °C, and then keep warm for l~5h, while steaming off part of the solvent in the system and the water generated during the reaction to obtain low concentration nano-MgO;  ϋ) Distillation of low-boiling substances under reduced pressure yields a high concentration of nano-Mg. [Claim 2] The method for preparing a multifunctional nano-MgO vanadium suppressing agent according to claim 1, wherein the magnesium compound is in magnesium oxide, magnesium carbonate, magnesium hydroxide or magnesium acetate. a mixture of one or several.  [Claim 3] The method for preparing a multifunctional nano-MgO vanadium suppressing agent according to claim 1, wherein the organic solvent is a high-boiling inert solvent such as nonylbenzene, heavy aromatic hydrocarbon, or low olefin a mixture of one or more of a polymer, a mineral oil, a synthetic oil. [Claim 4] The method for preparing a multifunctional nano-MgO vanadium suppressing agent according to claim 1, wherein the resin dispersing agent is one of terpene resin, epoxy resin and acrylic resin. Or a mixture of several. [Claim 5] according to any of claims 1-4 MgO nano-vanadium a multifunctional inhibitor preparation prepared as nano M _g 0 one of the preceding claims, wherein the particle diameter of MgO nano 5(T250n _m 5〜45百分比。 The mass content of Mg is 4. 5~45%. [Claim 6] The nano-Mg0 prepared by the method for preparing a multifunctional nano-MgO vanadium suppressant according to any one of claims 1 to 4, wherein the nano-MgO particle size is 5 ( At Tl00 _nm , the mass content of Mg is 3 (Γ45%). [Claim 7] The use of a multifunctional nano-MgO vanadium suppressing agent, characterized in that the nano-MgO vanadium suppressing agent is used as a fuel additive for suppressing V, S, N, Na impurity pairing devices in a fuel combustion process Corrosion.