Application of phosphite antioxidant in improving oxidation resistance of phosphate fire-resistant oil
By adding bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP-36) to phosphate fuel-resistant oil as an antioxidant, the performance degradation caused by oxidation and hydrolysis reaction of phosphate fuel-resistant oil during use is solved, significantly improving its antioxidant performance, extending its service life, and bringing dual benefits of economic and social value.
Patent Information
- Application Number
- CN202411354481.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2025-05-13
AI Technical Summary
Phosphate fuel-resistant oil is prone to oxidation and hydrolysis reactions during use, resulting in a degradation of oil performance and affecting the stable operation of the equipment. The prior art is difficult to effectively solve this problem, and the added antioxidants are poor in compatibility, making it difficult to determine the selection and addition amount.
Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP-36) is used as a phosphite antioxidant and added to the phosphate fuel-resistant oil. It is dissolved and evenly dispersed at a specific temperature under a sealed state to ensure its uniform distribution and sufficient effect in the oil.
It significantly improves the antioxidant performance of phosphate esters, extends its service life, reduces equipment failures and maintenance costs caused by oil deterioration, reduces operating costs in the power industry, and reduces waste generation, which is conducive to environmental protection.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of phosphate fire-resistant oil, and in particular to application of a phosphite antioxidant in improving the anti-oxidation performance of phosphate fire-resistant oil. Background Art
[0002] In the speed control system of steam turbines and gas turbines, phosphate ester fire-resistant oil is used as a hydraulic transmission medium to transmit power, control valve opening and closing, and adjust the speed, ensuring that the unit can quickly respond to load changes and achieve precise control. In addition, its excellent lubrication performance can effectively reduce wear between mechanical parts and extend the service life of equipment. However, as the service time increases, the antioxidant performance of phosphate ester fire-resistant oil becomes a key factor affecting its long-term stable operation.
[0003] During the use of phosphate fire-resistant oil, due to exposure to high temperature, oxygen and moisture, oxidation and hydrolysis reactions are prone to occur, resulting in a decrease in oil performance. Oxidation reactions will generate acidic substances, which will increase the acid value of the oil, and then corrode system components, such as servo valves, control valves and other precision components, causing problems such as jamming and leakage. At the same time, the reduction in resistivity will affect the insulation performance of electrical equipment and increase the risk of electrical failure. In addition, the deepening of oxidation and hydrolysis reactions will also form sludge, block the oil circuit, affect the smoothness and response speed of the system, and in severe cases may cause abnormal shutdown of the unit, affecting production safety.
[0004] In order to improve the antioxidant performance of phosphate ester fire-resistant oil, a strict oil monitoring and maintenance system has been established, and phosphate ester fire-resistant oil is regularly tested and replaced to ensure that the oil performance is always in good condition. However, this method will increase operating costs and downtime, which will have a certain impact on production. It is also possible to improve the antioxidant capacity of phosphate ester fire-resistant oil by adjusting its molecular structure and composition. This requires in-depth research on the synthesis process of oil products and considers factors such as cost and environmental protection. However, this method is technically difficult and has a long cycle, and it may not completely solve the problem of antioxidant performance. It is also possible to improve the use environment of oil products and reduce the occurrence of oxidation reactions by measures such as lowering the system temperature, reducing oxygen and water contact, and strengthening oil filtration. Although this can delay the deterioration of oil products to a certain extent, it cannot fundamentally solve the problem. Adding an appropriate amount of antioxidant to the oil is the most convenient method, such as compounds such as phenols and amines, which can effectively inhibit the progress of oxidation reactions and delay the deterioration process of oil products. However, due to the poor compatibility of phosphate ester fire-resistant oil with additives, selecting a suitable antioxidant and determining its optimal addition amount has become a major problem. In addition, some antioxidants may become ineffective at high temperatures, resulting in unsatisfactory long-term effects. Summary of the invention
[0005] In order to overcome the problems of the prior art, the present invention provides an application of a phosphite antioxidant in improving the antioxidant performance of phosphate fire-resistant oil, wherein the phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, also known as PEP-36. After adding the antioxidant to the phosphate fire-resistant oil, the antioxidant performance of the phosphate fire-resistant oil can be improved, the stability of the phosphate fire-resistant oil product can be enhanced, and the safe operation of the generator set can be guaranteed.
[0006] To achieve the above object, the present invention provides the following technical solution: application of a phosphite antioxidant in improving the antioxidant performance of phosphate fire-resistant oil, wherein the phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
[0007] Furthermore, in terms of weight percentage, the added amount of the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is 0.0020% to 0.0100% of the weight of the phosphate fire-resistant oil.
[0008] Furthermore, in terms of weight percentage, the added amount of the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is 0.0050% of the weight of the phosphate fire-resistant oil.
[0009] Furthermore, the main component of the phosphate fire-resistant oil is trixylene phosphate.
[0010] The present invention also provides a method for improving the oxidation stability of phosphate fire-resistant oil. In terms of weight percentage, 0.0020% to 0.0100% of a phosphite antioxidant is added to the phosphate fire-resistant oil. The phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite. The main component of the phosphate fire-resistant oil is trixylyl phosphate.
[0011] Furthermore, the adding method is specifically as follows: in a closed state, at 60°C±5°C, di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is dissolved in a new phosphate fire-resistant oil with a mass of 10000±3% times that of di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite to obtain an additive mother liquor, and the additive mother liquor is added into the phosphate fire-resistant oil.
[0012] The present invention also provides a phosphate fire-resistant oil with high oxidation stability. The main component of the phosphate fire-resistant oil is trixyl phosphate. In terms of weight percentage, 0.0020% to 0.0100% of a phosphite antioxidant is added to the phosphate fire-resistant oil. The phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
[0013] Furthermore, the added amount of the phosphite antioxidant is 0.0050% by weight of the phosphate fire-resistant oil.
[0014] Furthermore, the method for adding the phosphite antioxidant is as follows: in a closed state, at 60°C±5°C, dissolving bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite in a new phosphate fire-resistant oil with a mass of 10000±3% times that of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite to obtain an additive mother liquor; adding the additive mother liquor to the phosphate fire-resistant oil to obtain a phosphate fire-resistant oil with high oxidation stability.
[0015] The invention also provides a phosphate ester fire-resistant oil with high oxidation stability for use in a steam turbine or gas turbine speed control system of a power plant.
[0016] Compared with the prior art, the present invention has at least the following beneficial effects: The present invention provides an application of a phosphite antioxidant in improving the antioxidant performance of phosphate fire-resistant oil. As a high-efficiency antioxidant, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP-36) can effectively neutralize free radicals in phosphate fire-resistant oil, significantly slow down the oxidation reaction rate, and thus significantly improve its antioxidant performance, which reduces equipment failures and maintenance costs caused by oil deterioration, and improves the overall stability and reliability of the unit. By inhibiting the oxidation reaction, PEP-36 slows down the deterioration process of phosphate fire-resistant oil, reduces the rate of increase in the acid value and decrease in the resistivity of the oil, significantly prolongs its operating time before sludge is generated, and thus achieves an extension of the service life of phosphate fire-resistant oil. Moreover, PEP-36 has low cost, a simple addition method, and is easy to implement in the existing production process. This not only reduces the operating cost of the power industry, but also reduces the waste generated by frequent oil changes, is beneficial to environmental protection, and has high economic and social value.
[0017] The invention provides a method for improving the oxidation stability of phosphate fire-resistant oil. The method ensures the maximization of the antioxidant effect by accurately controlling the addition amount of PEP-36 (0.0020% to 0.0100%), while avoiding the negative effects that may be caused by excessive addition. When adding, the additive mother solution is prepared under a closed state at a specific temperature (60°C±5°C), ensuring the uniform dispersion and full dissolution of the antioxidant in the phosphate fire-resistant oil, thereby improving the utilization efficiency of the antioxidant. The method is simple to operate, easy to realize automated production, and improves the production efficiency and product quality of the phosphate fire-resistant oil.
[0018] The present invention provides a phosphate ester fire-resistant oil with high oxidation stability. Due to the addition of PEP-36, the anti-oxidation performance of the phosphate ester fire-resistant oil is significantly improved, and the oil can maintain stable performance under harsh working conditions. High oxidation stability means that the oil can maintain excellent performance for a longer period of time, reducing the number of shutdowns and maintenance caused by oil deterioration, and improving the operating efficiency and reliability of the unit. The oil is suitable for various occasions requiring high-oxidation-resistant phosphate ester fire-resistant oil, such as power plant steam turbines, gas turbine speed control systems, etc.
[0019] The present invention also provides an application of a phosphate fire-resistant oil with high oxidation stability in a speed control system of a steam turbine or a gas turbine in a power plant. The phosphate fire-resistant oil with high oxidation stability can ensure the stable operation of the speed control system, avoid malfunctions such as jamming and leakage caused by oil deterioration, thereby ensuring the safe operation of the generator set; reduce the downtime for maintenance due to oil problems, and improve the power generation efficiency and overall economic benefits of the unit; due to the stable performance of the oil, reduce the frequency of equipment maintenance and component replacement, and reduce the maintenance cost of the power industry; reduce the waste generated by frequent oil replacement, reduce pollution to the environment, and meet the requirements of sustainable development. DETAILED DESCRIPTION
[0020] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0021] In the present invention, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.
[0022] In the present invention, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.
[0023] In the present invention, unless otherwise specified, percentage (%) or part refers to the weight percentage or weight part relative to the composition.
[0024] In the present invention, unless otherwise specified, the components or preferred components involved can be combined with each other to form a new technical solution.
[0025] In the present invention, unless otherwise specified, the numerical range "a-b" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "6-22" represents that all real numbers between "6-22" are listed in this document, and "6-22" is just an abbreviation of these numerical combinations.
[0026] The “range” disclosed in the present invention is in the form of a lower limit and an upper limit, which can be one or more lower limits, and one or more upper limits, respectively.
[0027] In the present invention, the term "and / or" used herein refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.
[0028] In the present invention, unless otherwise specified, each reaction or operation step can be carried out sequentially or in accordance with the sequence. Preferably, the reaction method herein is carried out sequentially.
[0029] Unless otherwise specified, the professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content may also be applied to the present invention.
[0030] The invention provides an application of a phosphite antioxidant in improving the antioxidant performance of a phosphate fire-resistant oil. The phosphite antioxidant is specifically bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite. The bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite has low cost, a simple adding method and high economic value and social value. When used, the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is mixed with the phosphate fire-resistant oil. The adding method is simple. After the addition, the oxidation stability of the phosphate fire-resistant oil can be improved, the acid value, resistivity and sludge precipitation stability of the phosphate fire-resistant oil can be enhanced during the use of the phosphate fire-resistant oil, the speed of the acid value increase and resistivity decrease of the phosphate fire-resistant oil product can be reduced, and the running time before sludge is generated can be extended, thereby achieving the extension of the service life of the phosphate fire-resistant oil.
[0031] The main component of the phosphate ester fire-resistant oil mentioned here is trixylene phosphate.
[0032] Preferably, in terms of weight percentage, the additive amount of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is 0.0020% to 0.0100% of the weight of the phosphate fire-resistant oil.
[0033] Preferably, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, also known as PEP-36, with the brand name of Elico; In the present invention, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is mixed with phosphate fire-resistant oil to obtain a phosphate fire-resistant oil with high oxidation stability. The specific steps of the preparation method are as follows: 1. Determine the dosage of phosphate ester fire-resistant oil; 2. Weigh 0.0020% to 0.0100% of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite based on the weight of the phosphate ester fire-resistant oil; 3. In a sealed state, at 60°C±5°C, dissolve bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite in 10000±3% times the mass of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite in new phosphate fire-resistant oil to obtain an additive mother solution; 4. In a sealed state, the additive mother liquid is added into the phosphate ester fire-resistant oil to obtain a phosphate ester fire-resistant oil with high oxidation stability.
[0034] Example 1 Preparation of No. 1 phosphate fire-resistant oil test sample with high oxidation stability, the specific steps are as follows: 1) Take a sample bottle equipped with a sealed bottle stopper, weigh a certain amount of phosphate ester fire-resistant oil and put it in the sample bottle, calculate the mass of antioxidant added according to the mass of phosphate ester fire-resistant oil in the sample bottle, weigh it with an analytical balance and add it to the corresponding sample bottle, and cover the bottle cap to seal it.
[0035] The phosphite antioxidant is specifically: bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, the addition amount is 0.0050% by weight; Preferably, the volume of the sample bottle is 1000 mL, and the sealing stopper of the sample is a stopper made of polytetrafluoroethylene.
[0036] 2) Place the sealed sample bottle on the mixing device, which includes a vertically arranged triangular bracket, the bottom of which is fixed in a drying oven, a motor is arranged on the top of the triangular bracket, and the motor shaft is detachably connected to the sample bottle fixing plate. When the motor shaft is connected to the sample bottle fixing plate, the sample bottle fixing plate is driven by the motor to realize continuous rotation in the vertical direction at a speed of 5r / min to 10r / min. A plurality of sample bottle fixing clamps are arranged along the circumference of the sample bottle fixing plate for fixing the mouths of the plurality of sample bottles toward the center of the sample bottle fixing plate.
[0037] Preferably, the sample bottle fixing clamp comprises a bottle bottom fixing clamp, a bottle body fixing clamp and a bottle top fixing clamp, wherein the bottle top fixing clamp is a movable fixing clamp, which can prevent the sample bottle from falling off during rotation after being tightened.
[0038] 3) Connect the sample bottle fixing plate with the sample bottles to the motor shaft. Keep the temperature in the drying oven constant at 60℃±5℃. Rotate the sample bottle fixing plate to mix the samples for 1 hour to ensure that the additives are dissolved in the phosphate fire-resistant oil and mixed evenly.
[0039] 4) The sample is taken out of the drying oven and cooled to room temperature to obtain a test sample No. 1 of phosphate fire-resistant oil with high oxidation stability.
[0040] Full analysis and testing of the No. 1 phosphate ester fire-resistant oil sample with high oxidation stability and phosphate ester fire-resistant oil: In order to detect the actual effect of the phosphite antioxidant of the present invention on improving phosphate fire-resistant oil after being added to phosphate fire-resistant oil, the test samples of phosphate fire-resistant oil and No. 1 phosphate fire-resistant oil were fully analyzed. The test results are shown in Table 1.
[0041] Table 1 Test results of samples after adding composite additives to base oil
[0042] It can be seen from Table 1 that the phosphite antioxidant of the present invention can improve the antioxidant properties of phosphate ester fire-resistant oils and has no negative impact on other properties of phosphate ester fire-resistant oils. Therefore, the phosphite antioxidant of the present invention is suitable as an additive for phosphate ester fire-resistant oils; compared with phosphate ester fire-resistant oils, the phosphate ester fire-resistant oil with high oxidation stability of the present invention has improved antioxidant capacity, especially antioxidant capacity, which is improved by about 50% compared with the base oil.
[0043] Example 2 The difference from Example 1 is that, by weight percentage, the phosphite antioxidant is specifically bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite: the added amount of the phosphite antioxidant is 0.0100%; the test results of key indicators are shown in Table 2.
[0044] Table 2 Test results of samples after adding composite additives to base oil
[0045] Example 4 Different from Example 1, commercially available Aksu EHC fire-resistant oil is selected, and the phosphite antioxidant is specifically bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite: by weight percentage, the added amount of the phosphite antioxidant is 0.0020%; the test results of key indicators are shown in Table 3.
[0046] Table 3 Test results of samples after adding composite additives to base oil
[0047] It can be seen from Table 3 that after adding the antioxidant of the present invention, the antioxidant capacity of Aksu EHC fire-resistant oil is significantly improved.
[0048] The present invention mainly discusses the application of phosphite antioxidants, especially bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP-36), in improving the antioxidant performance of phosphate fire-resistant oil (the main component is tris-tolyl phosphate). The present invention selects bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP-36) as an antioxidant, which can effectively improve the oxidation stability of phosphate fire-resistant oil; the addition amount of the antioxidant is preferably 0.0020% to 0.0100% of the weight of the phosphate fire-resistant oil, and this ratio range can significantly enhance the antioxidant performance of the fire-resistant oil. In a closed state, the antioxidant is dissolved in a small amount of new phosphate fire-resistant oil to prepare an additive mother liquid. Subsequently, the additive mother liquid is added to the phosphate fire-resistant oil in a sealed state and mixed evenly to obtain a phosphate fire-resistant oil with high oxidation stability, which significantly improves the oxidation stability of the phosphate fire-resistant oil, prolongs its service life, enhances the stability of the acid value, resistivity and sludge precipitation of the phosphate fire-resistant oil during use, reduces the rate at which the acid value of the phosphate fire-resistant oil product increases and the resistivity decreases, and reduces the generation of sludge; prolongs the operating time of the phosphate fire-resistant oil before sludge is generated, reduces equipment failures and maintenance costs caused by sludge generation, and has low cost, a simple adding method, and is easy to implement, thereby improving the use efficiency of the phosphate fire-resistant oil and reducing the replacement frequency, thereby reducing the overall operating cost, reducing the waste generated by frequent replacement of the fire-resistant oil, and being beneficial to environmental protection.
[0049] In summary, the present invention effectively improves the antioxidant properties of phosphate fire-resistant oil, prolongs its service life, and brings significant economic and social value by adding an appropriate amount of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
Claims
1. The application of phosphite antioxidant in improving the antioxidant performance of phosphate fire-resistant oil is characterized in that: The phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
2. The application according to claim 1, characterized in that: In terms of weight percentage, the added amount of the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is 0.0020% to 0.0100% of the weight of the phosphate fire-resistant oil.
3. The application according to claim 1, characterized in that: In terms of weight percentage, the added amount of the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is 0.0050% of the weight of the phosphate fire-resistant oil.
4. The use according to claim 1, characterized in that: The main component of the phosphate fire-resistant oil is trixylene phosphate.
5. A method for improving the oxidation stability of phosphate ester fire-resistant oil, characterized in that: In terms of weight percentage, 0.0020% to 0.0100% of a phosphite antioxidant is added to the phosphate fire-resistant oil, wherein the phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and the main component of the phosphate fire-resistant oil is trixylene phosphate.
6. A method for improving the oxidation stability of phosphate ester fire-resistant oil according to claim 5, characterized in that: The specific adding method is: in a closed state, at 60°C±5°C, di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is dissolved in 10000±3% times the mass of new phosphate fire-resistant oil of di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite to obtain an additive mother liquor, and the additive mother liquor is added into the phosphate fire-resistant oil.
7. A phosphate fire-resistant oil with high oxidation stability, characterized in that: The main component of the phosphate fire-resistant oil is trixyl phosphate. In terms of weight percentage, 0.0020% to 0.0100% of a phosphite antioxidant is added to the phosphate fire-resistant oil. The phosphite antioxidant is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
8. The phosphate ester fire-resistant oil with high oxidation stability according to claim 7, characterized in that: The added amount of the phosphite antioxidant is 0.0050% of the weight of the phosphate fire-resistant oil.
9. The phosphate ester fire-resistant oil with high oxidation stability according to claim 7, characterized in that: The method for adding the phosphite antioxidant is as follows: in a sealed state, at 60°C±5°C, di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is dissolved in a new phosphate fire-resistant oil with a mass of 10000±3% of di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite to obtain an additive mother liquor; and the additive mother liquor is added to the phosphate fire-resistant oil to obtain a phosphate fire-resistant oil with high oxidation stability.
10. Use of the phosphate ester fire-resistant oil with high oxidation stability as claimed in any one of claims 7 to 9 in a speed control system of a steam turbine or a gas turbine in a power plant.