Hydrolysis-resistant oil-soluble vanadium inhibitor as well as preparation method and application thereof
The dispersion and stability of magnesium oxide in the prior art were solved by using tris(maleic anhydride monoester methyl)propane and alkyl mercaptan for surface modification in oil-soluble vanadium inhibitors. The problem of poor performance increases the melting point of vanadium ash in the gas turbine and inhibits corrosion.
Patent Information
- Application Number
- CN202411422478.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2025-01-10
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The dispersion of magnesium oxide in existing oil-soluble vanadium inhibitors is poor, resulting in insufficient stability and active ingredient content in heavy oil, and it is unable to effectively inhibit the impact of vanadium pentoxide on gas turbine blades.
By using tris(maleic anhydride monoester methyl)propane and alkyl mercaptan for mercaptoalkenite click reaction, a surface modifier with multiple carboxyl and alkyl long chains is prepared, magnesium oxide is modified, and its in diesel, etc. Dispersibility in the solvent, and an oil-soluble vanadium inhibitor that is resistant to hydrolysis is prepared by ultrasonic dispersion and heating and stirring.
It significantly improves the dispersion and stability of magnesium oxide in oil-soluble vanadium inhibitors, enhances the reaction capacity with vanadium pentoxide, increases the melting point of vanadium ash, reduces corrosion, and extends the service life of vanadium inhibitors .
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of vanadium inhibitors, in particular to a hydrolysis-resistant oil-soluble vanadium inhibitor and a preparation method and application thereof. Background Art
[0002] Gas turbines mainly use low-cost heavy oil as fuel, but heavy oil contains vanadium, sodium, potassium and other impurities. When burned at high temperatures, they will generate low-melting-point vanadium pentoxide and form sodium-vanadium compounds with sodium, which have a strong corrosive effect on gas turbine blades, seriously affecting the performance of gas turbines and posing a major safety hazard. Adding vanadium inhibitors to heavy oil is an effective way to solve the above problems.
[0003] The current vanadium inhibitors can be divided into water-soluble vanadium inhibitors and oil-soluble vanadium inhibitors. The water-soluble vanadium inhibitors have poor solubility with heavy oil. The oil-soluble vanadium inhibitors have the advantages of solubility with heavy oil, high stability, and high content of effective ingredients. Its effective ingredients are mainly magnesium oxide, magnesium oxide, etc. Improving the dispersibility of magnesium oxide in oil-soluble vanadium inhibitor solutions is a research hotspot. It is usually necessary to add surfactants, such as stearic acid, Span 80, OP-10, etc. However, the interaction between these surfactants and magnesium oxide is low, and the modification effect is poor. Summary of the invention
[0004] The invention solves the problem that magnesium oxide vanadium inhibitor has poor oil solubility
[0005] Technical solution: A hydrolysis-resistant oil-soluble vanadium inhibitor comprises 40-50 parts by weight of modified magnesium oxide and 50-60 parts by weight of a solvent.
[0006] The preparation method of modified magnesium oxide is:
[0007] (1) Add N,N-dimethylformamide, tris(maleic anhydride monoester methyl) propane, alkyl mercaptan, and benzoin dimethyl ether to a container, irradiate under a high-pressure mercury lamp for reaction, distill under reduced pressure, wash with n-hexane and ethanol in turn, and dry to obtain a surface modifier. The reaction formula is as follows:
[0008]
[0009] (2) Add toluene and magnesium oxide into a container, disperse them by ultrasonication, then add a surface modifier, heat and stir to react, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0010] Preferably, the solvent is diesel, synthetic motor oil or mineral oil.
[0011] Preferably, the molar amounts of alkyl mercaptan and benzoin dimethyl ether in (1) are 300-330% and 1.5-2.1% of the molar amount of tris(maleic anhydride monoester methyl)propane, respectively.
[0012] Preferably, the structural formula of alkyl mercaptan is HS-C n H 2n+1 , n is 12-18.
[0013] Preferably, (1) the power of the medium- and high-pressure mercury lamp is 400-600 W, and the reaction time is 1-2 h.
[0014] Preferably, the mass of the surface modifier in (2) is 4-8% of the mass of magnesium oxide.
[0015] Preferably, the average particle size of the magnesium oxide in (2) is 1-3 μm.
[0016] Preferably, the reaction temperature in (2) is 60-80°C and the reaction time is 2-4h.
[0017] Preferably, the preparation method of the hydrolysis-resistant oil-soluble vanadium inhibitor is: adding a solvent to a container, modifying magnesium oxide, and stirring for 20-40 minutes to obtain the hydrolysis-resistant oil-soluble vanadium inhibitor.
[0018] Preferably, the hydrolysis-resistant oil-soluble vanadium inhibitor is used in a gas turbine.
[0019] Technical effect: The present invention utilizes tri(maleic anhydride monoester methyl) propane and alkyl mercaptan to carry out a thiol-ene click reaction to obtain a surface modifier containing multiple carboxyl groups and alkyl long chains. Its multiple active carboxyl groups have a stronger interaction with the surface of magnesium oxide, effectively realizing the surface functionalization modification of magnesium oxide. The hydrophilic carboxyl groups are inwardly bound to the surface of magnesium oxide, and the multiple alkyl long chains are outwardly facing, forming a steric hindrance, reducing the agglomeration and aggregation of magnesium oxide, and the multiple alkyl long chains have a good affinity with aliphatic hydrocarbon substances in solvents such as diesel, which is beneficial to improving the dispersibility of magnesium oxide in solvents such as diesel, and at the same time, it has good anti-hydrolysis performance. The better the dispersibility of magnesium oxide in the oil-soluble vanadium inhibitor, the easier it is to react with vanadium pentoxide to generate high-melting-point vanadates, which is beneficial to increase the melting point of vanadium ash in gas turbines and inhibit its corrosiveness. DETAILED DESCRIPTION
[0020] In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with the examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention. Tris(maleic anhydride monoester methyl)propane was prepared according to the method of the journal "Fine Chemicals", Vol. 28, No. 10, October 2011, document "Esterification Reaction of Maleic Anhydride and Trimethylolpropane".
[0021] Add 5 mmol trimethylolpropane to the container, heat to 70°C, stir and melt, add maleic anhydride in 3 times, 5 mmol each time, and add p-toluenesulfonic acid (0.2% of the total mass of the reactants), heat to 90°C, react for 4 hours, cool and discharge, and obtain tris(maleic anhydride monoester methyl)propane. The structural formula is:
[0022] Example 1
[0023] (1) Add 150 mL of N,N-dimethylformamide, 20 mmol of tris(maleic anhydride monoester methyl)propane, 60 mmol of octadecyl mercaptan, and 0.42 mmol of benzoin dimethyl ether into a container, irradiate under a 400 W high-pressure mercury lamp for 2 h, distill under reduced pressure, wash with n-hexane and ethanol in turn, and dry to obtain a surface modifier.
[0024] (2) Add 600 mL of toluene and 40 g of magnesium oxide into a container, disperse by ultrasonication, then add 1.6 g of surface modifier, heat to 60°C, stir and react for 4 h, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0025] (3) Add 600 g diesel and 400 g modified magnesium oxide into a container and stir for 30 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0026] Example 2
[0027] (1) Add 200 mL of N,N-dimethylformamide, 20 mmol of tris(maleic anhydride monoester methyl)propane, 66 mmol of dodecanethiol, and 0.42 mmol of benzoin dimethyl ether into a container, irradiate under a 400 W high-pressure mercury lamp for 2 h, distill under reduced pressure, wash with n-hexane and ethanol in turn, and dry to obtain a surface modifier.
[0028] (2) Add 600 mL of toluene and 40 g of magnesium oxide into a container, disperse by ultrasonication, then add 2.1 g of surface modifier, heat to 80°C, stir and react for 2 h, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0029] (3) Add 500 g of mineral oil and 500 g of modified magnesium oxide into a container and stir for 40 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0030] Example 3
[0031] (1) Add 200 mL of N,N-dimethylformamide, 20 mmol of tris(maleic anhydride monoester methyl)propane, 63 mmol of dodecanethiol, and 0.36 mmol of benzoin dimethyl ether into a container, irradiate under a 600 W high-pressure mercury lamp for 1 hour, distill under reduced pressure, wash with n-hexane and ethanol in turn, and dry to obtain a surface modifier.
[0032] (2) Add 700 mL of toluene and 40 g of magnesium oxide into a container, disperse by ultrasonication, then add 2.7 g of surface modifier, heat to 80°C, stir and react for 3 h, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0033] (3) Add 550 g of synthetic motor oil and 450 g of modified magnesium oxide into a container and stir for 20 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0034] Example 4
[0035] (1) Add 150 mL of N,N-dimethylformamide, 20 mmol of tris(maleic anhydride monoester methyl)propane, 60 mmol of 1-hexadecanethiol, and 0.3 mmol of benzoin dimethyl ether into a container, irradiate under a 400 W high-pressure mercury lamp for 1.5 h, distill under reduced pressure, wash with n-hexane and ethanol in turn, and dry to obtain a surface modifier.
[0036] (2) Add 700 mL of toluene and 40 g of magnesium oxide into a container, disperse by ultrasonication, then add 3.2 g of surface modifier, heat to 70°C, stir and react for 4 h, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0037] (3) Add 600 g diesel and 400 g modified magnesium oxide into a container and stir for 20 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0038] Comparative Example 1
[0039] (1) Add 600 g diesel and 400 g magnesium oxide into a container and stir for 30 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0040] Comparative Example 2
[0041] (1) Add 600 mL of toluene and 40 g of magnesium oxide into a container, disperse by ultrasonication, then add 1.6 g of stearic acid, heat to 60°C, stir and react for 4 h, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0042] (2) Add 600 g diesel and 400 g modified magnesium oxide into a container and stir for 30 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0043] Comparative Example 3
[0044] (1) Add 600 mL of toluene and 40 g of magnesium oxide into a container, disperse by ultrasonication, then add 1.6 g of Span 80, heat to 60°C, stir and react for 4 h, filter, wash with toluene, and dry to obtain modified magnesium oxide.
[0045] (2) Add 600 g diesel and 400 g modified magnesium oxide into a container and stir for 30 min to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
[0046] Allow the oil-soluble vanadium inhibitor to stand at 25°C and observe its appearance.
[0047] Table 1 Stability test of oil-soluble vanadium inhibitor
[0048]
[0049] The average particle size of magnesium oxide in oil-soluble vanadium inhibitor was tested by laser particle size analyzer.
[0050] Table 2 Average particle size of magnesium oxide in oil-soluble vanadium inhibitor
[0051]
[0052]
[0053] After testing, compared with Comparative Example 1, Examples 1-4 use a surface modifier containing multiple carboxyl groups to modify the surface of magnesium oxide. Multiple hydrophobic alkyl long chains are introduced into the surface of the modified magnesium oxide, which has better dispersibility in solvents such as diesel and mineral oil. The vanadium inhibitor does not stratify and has no precipitation. The average particle size of the magnesium oxide in the vanadium inhibitor is small, only 8.4-15.0um.
[0054] In Comparative Example 2, conventional stearic acid was used to modify the surface of magnesium oxide. After being placed for a long time for 14 days, the vanadium inhibitor was prone to precipitation, and the particle size of magnesium oxide in the vanadium inhibitor was 22.4 um, which was higher than that of the embodiments.
[0055] In Comparative Example 3, Span 80 was used to modify the surface of magnesium oxide, but the modification effect was poor, the stability of the vanadium inhibitor was poor, the average particle size of the magnesium oxide in the vanadium inhibitor was large, and the dispersibility was poor.
[0056] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A hydrolysis-resistant oil-soluble vanadium inhibitor, characterized in that: The hydrolysis-resistant oil-soluble vanadium inhibitor comprises 40-50 parts by weight of modified magnesium oxide and 50-60 parts by weight of a solvent; The preparation method of the modified magnesium oxide is: (1) Add N,N-dimethylformamide, tris(maleic anhydride monoester methyl)propane, alkyl mercaptan, and benzoin dimethyl ether into a container, irradiate under a high-pressure mercury lamp for reaction, distill under reduced pressure, wash, and dry to obtain a surface modifier; (2) Add toluene and magnesium oxide into a container, disperse them by ultrasonication, then add a surface modifier, heat and stir to react, filter, wash, and dry to obtain modified magnesium oxide.
2. The hydrolysis-resistant oil-soluble vanadium inhibitor according to claim 1, characterized in that: The solvent is diesel, synthetic motor oil or mineral oil.
3. The hydrolysis-resistant oil-soluble vanadium inhibitor according to claim 1, characterized in that: The molar amounts of alkyl mercaptan and benzoin dimethyl ether in (1) are 300-330% and 1.5-2.1% of the molar amount of tris(maleic anhydride monoester methyl)propane, respectively.
4. The hydrolysis-resistant oil-soluble vanadium inhibitor according to claim 1, characterized in that: The structural formula of the alkyl mercaptan in (1) is HS-CnH2n+1, where n is 12-18.
5. The hydrolysis-resistant oil-soluble vanadium inhibitor according to claim 1, characterized in that: The power of the medium- and high-pressure mercury lamp in (1) is 400-600W, and the reaction time is 1-2h.
6. The hydrolysis-resistant oil-soluble vanadium inhibitor according to claim 1, characterized in that: The mass of the surface modifier in (2) is 4-8% of the mass of magnesium oxide.
7. The hydrolysis-resistant oil-soluble vanadium inhibitor according to claim 1, characterized in that: The reaction temperature in (2) is 60-80°C and the reaction time is 2-4h.
8. A method for preparing the hydrolysis-resistant oil-soluble vanadium inhibitor according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: adding a solvent into a container, modifying magnesium oxide, and stirring for 20-40 minutes to obtain a hydrolysis-resistant oil-soluble vanadium inhibitor.
9. Use of the hydrolysis-resistant oil-soluble vanadium inhibitor obtained by the preparation method according to claim 8 in a gas turbine.