Phosphate-based fire-resistant oil with synergistically optimized flame resistance and stability and preparation method of phosphate-based fire-resistant oil

Abstract

The invention relates to the field of fire-resistant oil, in particular to phosphate-based fire-resistant oil with synergistically optimized flame resistance and stability and a preparation method of the phosphate-based fire-resistant oil. The fire-resistant oil comprises base oil and an additive, the base oil is a mixture obtained by esterification of mixed alkylphenol and phosphorus oxychloride; the molar percentage of the mixed alkylphenol is as follows: 4-6% of phenol; 11 to 14 percent of p-methylphenol; 22 to 26 percent of 2, 5-position dimethyl phenol; 0.8 to 1.5 percent of 2, 4-position dimethyl phenol; 2.5 to 4 percent of 2, 3-position dimethyl phenol; 0.4 to 0.6 percent of 4-ethyl phenol; 40 to 48 percent of 3, 5-position dimethyl phenol; 8 to 11% of 3-ethyl phenol; 3 to 5 percent of 3, 4-position dimethyl phenol; the additives comprise an antioxidant, a corrosion inhibitor, an anti-foaming agent and an anti-hydrolysis agent; the addition amount of the antioxidant is 0.05-5% of the total mass of the base oil; the addition amount of the corrosion inhibitor is 0.001%-0.08% of the total mass of the base oil; the addition amount of the anti-foaming agent is 0.001%-0.009% of the total mass of the base oil; the addition amount of the anti-hydrolysis agent is 0.001%-0.005% of the total mass of the base oil. The fire-resistant oil provided by the invention can be safely used under the working conditions of high temperature and extreme pressure.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of anti-combustion oil, in particular to a phosphate-based anti-combustion oil with synergistically optimized anti-combustion and stability and a preparation method thereof. BACKGROUND

[0002] In the power industry, especially in thermal power plants, "anti-combustion oil" is a crucial concept, mainly used in the electro-hydraulic control system of steam turbine generator units. Anti-combustion oil replaces traditional transparent oil as a medium for transmitting pressure and control signals.

[0003] At present, the domestic anti-combustion oil market is mainly monopolized by foreign brands such as ICL (formerly AkzoNobel) and LANXESS (formerly American Great Lakes), whose core components are butyl phenyl phosphate mixtures with MDPP as the main component, combined with traditional phenolic antioxidants. However, due to the influence of international supply chains, there is a risk of supply interruption.

[0004] The existing anti-combustion oil generally has the following problems:

[0005] Low kinematic viscosity and oil film rigidity: usually used in hydraulic systems, unable to meet the requirements of lubrication systems;

[0006] Acid value is prone to exceed the standard: the oxidation and hydrolysis stability of traditional phosphates is low, and acidic substances are generated under high temperature and hydrolysis environment, resulting in an annual increase of 0.1-0.3 mgKOH / g in acid value;

[0007] Resistivity is prone to exceed the standard: after long-term operation, the resistivity exceeds the standard, the servo valve nozzle is prone to electrochemical corrosion, leading to the jamming of the servo valve and affecting the response accuracy of the regulation system;

[0008] Foam characteristics exceed the standard: more than 500 mL / 10 mL at 24℃, leading to false liquid level and affecting the safety of the oil system;

[0009] Air release value exceeds the standard: increases to more than 10 min with the extension of use time, causing system vibration.

[0010] Paint film or sludge is generated: adsorbed on the bearing bush or oil cooler, leading to decreased heat exchange efficiency, increased oil temperature, and exceeded bearing bush temperature.

[0011] For a long time, the research and production of anti-combustion oil have mainly been applied to steam turbine regulation oil systems. The existing technology generally uses tricresyl phosphate as anti-combustion oil. Although TXP has certain advantages over tertiary butyl phosphate in performance, it cannot meet the requirements of the lubrication system under high temperature and extreme pressure conditions in terms of oil film rigidity and the long-term operation of anti-combustion oil due to high temperature and hydrolysis of the oil, leading to the exceeding of indicators such as sludge and paint film precipitation, air release value, and foam characteristics, which poses potential safety hazards to the safe operation of equipment. SUMMARY

[0012] The technical problem solved by the present application is to provide a phosphonate-based fire-resistant oil with synergistically optimized fire resistance and stability, and a preparation method thereof, so as to meet the safe use under high temperature and extreme pressure conditions.

[0013] The present application provides a phosphonate-based fire-resistant oil with synergistically optimized fire resistance and stability, comprising: a base oil and an additive.

[0014] The base oil is a mixture obtained by esterification of mixed alkyl phenol and phosphorus oxychloride;

[0015] The molar percentage of the mixed alkyl phenol is:

[0016] phenol 4-6%;

[0017] p-methylphenol 11-14%;

[0018] 2,5-dimethylphenol 22-26%;

[0019] 2,4-dimethylphenol 0.8-1.5%;

[0020] 2,3-dimethylphenol 2.5-4%;

[0021] 4-ethylphenol 0.4-0.6%;

[0022] 3,5-dimethylphenol 40-48%;

[0023] 3-ethylphenol 8-11%;

[0024] 3,4-dimethylphenol 3-5%;

[0025] The additive comprises an antioxidant, a corrosion inhibitor, an antifoaming agent, and an anti-hydrolysis agent; the addition amount of the antioxidant is 0.05%-5% of the total mass of the base oil; the addition amount of the corrosion inhibitor is 0.001%-0.08% of the total mass of the base oil; the addition amount of the antifoaming agent is 0.001%-0.009% of the total mass of the base oil; and the addition amount of the anti-hydrolysis agent is 0.001%-0.005% of the total mass of the base oil.

[0026] In one specific embodiment of the present application, the molar percentage of the mixed alkyl phenol is: phenol 5%,

[0027] p-methylphenol 12%;

[0028] 2,5-dimethylphenol 25%;

[0029] 2,4-dimethylphenol 1%;

[0030] 2,3-dimethylphenol 3%;

[0031] 4-ethylphenol 0.5%;

[0032] 3,5-dimethylphenol 44%;

[0033] 3-ethylphenol 10%;

[0034] 3,4-dimethylphenol 4%.

[0035] The application provides a preparation method of a phosphonate-based fire-resistant oil with synergistically optimized fire resistance and stability, comprising the following steps:

[0036] Step 1: adding phosphorus oxychloride in two times in mixed alkyl phenol, and performing esterification under the catalysis of a Ca-Mg composite catalyst to obtain a crude product;

[0037] The molar ratio of the mixed alkyl phenol to the phosphorus oxychloride is (1.8-3.2):(0.8-1.6);

[0038] The molar percentage of the mixed alkyl phenol is:

[0039] phenol 4-6%;

[0040] p-cresol 11-14%;

[0041] 2,5-dimethylphenol 22-26%;

[0042] 2,4-dimethylphenol 0.8-1.5%;

[0043] 2,3-dimethylphenol 2.5-4%;

[0044] 4-ethylphenol 0.4-0.6%;

[0045] 3,5-dimethylphenol 40-48%;

[0046] 3-ethylphenol 8-11%;

[0047] 3,4-dimethylphenol 3-5%;

[0048] Step 2: performing negative pressure acid discharge on the reaction product obtained in step 1;

[0049] Step 3: performing vacuum distillation on the product obtained in step 2, and performing adsorption filtration to obtain a base oil;

[0050] In the pressurized distillation process, the vacuum degree is greater than or equal to 0.099 Mpa, the temperature is first increased to 220-250 DEG C for distillation, and then increased to 290-330 DEG C;

[0051] Step 4: blending the base oil with an antioxidant, a corrosion inhibitor, an antifoaming agent and an anti-hydrolysis agent to obtain the fire-resistant oil;

[0052] The addition amount of the antioxidant is 0.05% to 5% of the total mass of the base oil;

[0053] The addition amount of the corrosion inhibitor is 0.001% to 0.08% of the total mass of the base oil;

[0054] The addition amount of the anti-foaming agent is 0.001% to 0.009% of the total mass of the base oil;

[0055] The addition amount of the anti-hydrolysis agent is 0.001% to 0.005% of the total mass of the base oil.

[0056] In one specific embodiment of the present application, the step 1 specifically comprises:

[0057] The mixed alkyl phenol is first added with phosphorus oxychloride, stirred and slowly heated to 50 to 55°C, then the Ca-Mg composite catalyst is added and stirred uniformly;

[0058] After the catalyst is added, the temperature is rapidly increased to 70 to 80°C, preferably 75°C, within 20 minutes, then slowly increased to 95 to 100°C within 120 minutes, and kept constant for 2 to 5 hours for a primary reaction;

[0059] After the primary reaction, the mixed alkyl phenol is secondly added with phosphorus oxychloride, slowly increased to 95 to 100°C within 120 minutes, kept constant for 3 to 6 hours, then slowly increased to 140 to 150°C within 120 minutes, continuously stirred and kept constant for 6 to 9 hours for a secondary reaction.

[0060] In one specific embodiment of the present application, in the step 2, during the negative pressure acid removal, the temperature is kept above 140°C, the negative pressure acid removal is performed for 6 to 8 hours, the hydrogen chloride gas during the acid removal is washed and absorbed with water, and after no hydrogen chloride gas is produced, the reaction product is subjected to the next step.

[0061] In one specific embodiment of the present application, in the step 3, after the excess mixed alkyl phenol is removed by distillation, the excess mixed alkyl phenol is recovered and recycled after being condensed.

[0062] In one specific embodiment of the present application, the step 3 further comprises: detecting the product after the distillation, and the detection standard is that the dimethyl phenol after the distillation is ≤0.1%, the acid value is ≤0.04 mgKOH / g, the chlorine content is ≤30 ppm, and the kinematic viscosity at 40°C is 46 to 50.6 mm 2 / s.

[0063] If the detection is qualified, the adsorption filtration is directly performed;

[0064] If the detection is unqualified, the product is subjected to a supplementary distillation at 290 to 330°C for 1 to 2 hours, and after the qualification, the filtration is performed; if the product is still unqualified, the product is subjected to an alkali boiling treatment.

[0065] In one embodiment of the present application, the caustic boiling treatment is as follows: after vacuum distillation, the crude product is returned to the reaction kettle, 2-3% of the mass of the crude product of sodium hydroxide and hot water at 100°C are added, and normal pressure caustic boiling is carried out for 4-5 minutes.

[0066] In one embodiment of the present application, step 4 specifically comprises:

[0067] The base oil is pumped into a blending kettle and heated to 60-65°C;

[0068] The anti-oxidant is added in a proportion of 0.05%-5% of the total mass of the base oil, the corrosion inhibitor is added in a proportion of 0.001%-0.08% of the total mass of the base oil, the anti-foaming agent is added in a proportion of 0.001%-0.009% of the total mass of the base oil, and the anti-hydrolysis agent is added in a proportion of 0.001%-0.005% of the total mass of the base oil;

[0069] Stirring is carried out under the conditions of 70-90°C and a vacuum of ≤-0.090 MPa for 2-4 hours until the water content is ≤300 mg / L;

[0070] After dehydration, three-stage filtration is carried out to obtain the fire-resistant oil.

[0071] In one embodiment of the present application, the addition amount of the Ca-Mg composite catalyst is 0.15%-0.4% of the total mass of the mixed alkyl phenol.

[0072] Compared with the prior art, the fire resistance and stability of the phosphate-based fire-resistant oil and the preparation method thereof are synergistically optimized, the mixed alkyl phenol is used as a raw material to prepare the base oil, and special additives such as an anti-oxidant, a corrosion inhibitor, an anti-foaming agent, and an anti-hydrolysis agent are compounded with the base oil to obtain the fire-resistant oil, and the present application has the following beneficial effects:

[0073] (1) The mixed alkyl phenol with a specific ratio is used as a raw material to react with phosphorus oxychloride, the ratio is controlled to inhibit side reactions, reduce the generation of chlorophosphonate impurities, ensure the purity and stability of the crude phosphate ester, the reaction kinetics is optimized through stepwise temperature rising to improve the yield of triaryl phosphate ester, and vacuum distillation, caustic boiling, and adsorption filtration are combined to reduce the acid value and chlorine content and improve the purity of the base oil.

[0074] (2) The main reaction is promoted to be complete by overfeeding the alkyl phenol, and the synthesis oil is nontoxic by combining the vacuum distillation and adsorption filtration processes.

[0075] (3) The anti-oxidant, the corrosion inhibitor, the anti-foaming agent, and the anti-hydrolysis agent are compounded to enhance the oxidative stability and use performance of the fire-resistant oil.

[0076] (4) The overfed alkyl phenol is recovered by vacuum distillation and caustic boiling to improve the utilization rate of the raw material.

[0077] (5) The hydrogen chloride gas generated during the acid discharge process is absorbed by water washing to avoid environmental pollution;

[0078] Through experimental verification, the fire-resistant oil of this invention, by introducing a specific proportion of xylenol, achieves an open-cup flash point ≥280℃ and an auto-ignition point ≥700℃, significantly improving its fire-resistant performance. Open-cup aging results show that after oxidation at 120℃ for 936 hours, the acid value increase is ≤0.15mgKOH / g, demonstrating excellent thermal stability. The kinematic viscosity at 40℃ ranges from 41.4 to 50.6 mmHg, typical of fire-resistant oils. 2 / s optimized to 46–50.6 mm 2 / s, lower limit increased by 4.6mm 2 / s, narrowing the range by 50%. Increasing the lower viscosity limit enhances oil film carrying capacity, meets the lubricant's requirements for oil film stiffness, and improves anti-wear performance and system stability. Hydrolytic stability can reach below 0.03 mgKOH / g, exhibiting excellent hydrolysis resistance and meeting long-term use requirements. Detailed Implementation

[0079] To further understand the present invention, embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the present invention.

[0080] Embodiments of the present invention disclose a phosphate ester-based fire-resistant oil with synergistic optimization of fire resistance and stability, comprising: base oil and additives;

[0081] The base oil is a mixture obtained by esterification of mixed alkylphenols and phosphorus oxychloride;

[0082] The mixed alkylphenols include phenol, p-methylphenol, dimethylphenol, 4-ethylphenol, and 3-ethylphenol;

[0083] The dimethylphenol includes its isomers.

[0084] The molar percentage of the mixed alkylphenols is:

[0085] Phenol 4-6%;

[0086] p-Cresol 11-14%;

[0087] 2,5-Dimethylphenol 22-26%;

[0088] 0.8–1.5% of 2,4-dimethylphenol;

[0089] 2,3-Dimethylphenol 2.5-4%;

[0090] 4-Ethylphenol 0.4–0.6%;

[0091] 3,5-dimethylphenol 40-48%;

[0092] 3-ethylphenol 8-11%;

[0093] 3,4-dimethylphenol 3-5%;

[0094] Preferably, the molar percentage of the mixed alkyl phenol is:

[0095] phenol 5%,

[0096] p-cresol 12%;

[0097] 2,5-dimethylphenol 25%;

[0098] 2,4-dimethylphenol 1%;

[0099] 2,3-dimethylphenol 3%;

[0100] 4-ethylphenol 0.5%;

[0101] 3,5-dimethylphenol 44%;

[0102] 3-ethylphenol 10%;

[0103] 3,4-dimethylphenol 4%.

[0104] The additives include antioxidants, corrosion inhibitors, antifoaming agents, anti-hydrolysis agents; the addition amount of the antioxidant is 0.05%-5% of the total mass of the base oil; the addition amount of the corrosion inhibitor is 0.001%-0.08% of the total mass of the base oil; the addition amount of the antifoaming agent is 0.001%-0.009% of the total mass of the base oil;

[0105] The addition amount of the anti-hydrolysis agent is 0.001%-0.005% of the total mass of the base oil;

[0106] The embodiment of the present application discloses a preparation method of a phosphoric acid ester-based fire-resistant oil with synergistically optimized fire resistance and stability, comprising the following steps:

[0107] Step 1: the first time of adding phosphorus oxychloride in the mixed alkyl phenol, stirring and slowly heating to 50-55°C, adding 0.15%-0.4% of the mixed alkyl phenol feeding mass of Ca-Mg composite catalyst, and stirring uniformly;

[0108] Rapidly increase the temperature to 70-80°C, preferably 75°C within 20 minutes after adding the catalyst, then slowly increase the temperature to 95-100°C within 120 minutes, and keep the temperature constant for 2-5 hours for the first reaction; the rapid temperature increase refers to a temperature increase rate of 5-8°C / min, and the slow temperature increase refers to a temperature increase rate of 0.5-1.5°C / min; after the first reaction, add phosphorus oxychloride again, slowly increase the temperature to 95-100°C within 120 minutes, keep the temperature constant for 3-6 hours, slowly increase the temperature to 140-150°C within 120 minutes, continue stirring and keep the temperature constant for 6-9 hours for the second reaction;

[0109] The mixed alkyl phenol includes phenol, p-methyl phenol, dimethyl phenol, 4-ethyl phenol, 3-ethyl phenol;

[0110] The dimethyl phenol includes isomers thereof.

[0111] The molar percentage of the mixed alkyl phenol is:

[0112] phenol 4-6%;

[0113] p-methyl phenol 11-14%;

[0114] 2,5-dimethyl phenol 22-26%;

[0115] 2,4-dimethyl phenol 0.8-1.5%;

[0116] 2,3-dimethyl phenol 2.5-4%;

[0117] 4-ethyl phenol 0.4-0.6%;

[0118] 3,5-dimethyl phenol 40-48%;

[0119] 3-ethyl phenol 8-11%;

[0120] 3,4-dimethyl phenol 3-5%;

[0121] Preferably, the molar percentage of the mixed alkyl phenol is:

[0122] phenol 5%;

[0123] p-methyl phenol 12%;

[0124] 2,5-dimethyl phenol 25%;

[0125] 2,4-dimethyl phenol 1%;

[0126] 2,3-dimethyl phenol 3%;

[0127] 4-ethyl phenol 0.5%;

[0128] 3,5-dimethylphenol 44%;

[0129] 3-ethylphenol 10%;

[0130] 3,4-dimethylphenol 4%;

[0131] The mass of the phosphorus oxychloride added in the first and second times is equal, and the molar ratio of the mixed alkyl phenol to the phosphorus oxychloride is (1.8-3.2):(0.8-1.6).

[0132] Step 2: The reaction product obtained in Step 1 is subjected to negative pressure acid removal;

[0133] Specifically, during the negative pressure acid removal, the temperature is kept above 140°C, the negative pressure acid removal is performed for 6-8 hours, the hydrogen chloride gas during the acid removal is absorbed by water washing, and after no hydrogen chloride gas is produced, the reaction product is subjected to the next step.

[0134] Step 3: The product obtained in Step 2 is subjected to vacuum distillation and adsorption filtration to obtain the base oil.

[0135] Specifically, the vacuum distillation is performed under the following conditions:

[0136] The vacuum degree of the distillation kettle is controlled to be greater than or equal to 0.099 MPa.

[0137] The temperature is raised to 220-250°C, and distillation is performed to remove bis(dicumyl phenyl phosphate), dichlorophosphoric acid (cumyl phenol) ester and other chlorinated phosphate by-products.

[0138] The temperature is raised to 290-330°C, and the target product is collected, and the heating is stopped after no fraction is collected.

[0139] The excess mixed alkyl phenol is removed by distillation, and the excess mixed alkyl phenol is recovered after condensation and recycled.

[0140] The product after the vacuum distillation is detected, and the indicators are detected: the cumyl phenol after the distillation (≤0.1%), the acid value (≤0.04 mgKOH / g), the chlorine content (≤30 ppm), the kinematic viscosity (46-50.6 mm 2 / s at 40°C), and if the product does not meet the requirements, the product is subjected to a supplementary distillation at 290-330°C for 1-2 hours, and if the product meets the requirements, the product is filtered.

[0141] The product that meets the requirements is subjected to adsorption filtration, and the base oil is obtained after the acid value detection meets the requirements. The standard for the acid value detection meeting the requirements is ≤0.04 mgKOH / g.

[0142] The alkali boiling treatment is specifically as follows: after the vacuum distillation, the crude product is returned to the reaction kettle, 2-3% of the mass of the crude product of sodium hydroxide and 100℃ hot water are added, and the crude product is boiled under normal pressure for 4-5 minutes to convert the dimethyl phenol into sodium phenate, thereby reducing the acid value and color. After the alkali boiling, the distillation product and water are separated, the distillation product is pumped into a post-treatment tank, and is prepared for adsorption filtration.

[0143] Step 4: The base oil is blended with the antioxidant, corrosion inhibitor, antifoaming agent and anti-hydrolysis agent to obtain the fire-resistant oil.

[0144] Specifically comprising:

[0145] The base oil is pumped into a blending kettle and heated to 60-65℃;

[0146] The antioxidant is added in a proportion of 0.05%-5% of the total mass of the base oil, the corrosion inhibitor is added in a proportion of 0.001%-0.08% of the total mass of the base oil, the antifoaming agent is added in a proportion of 0.001%-0.009% of the total mass of the base oil, and the anti-hydrolysis agent is added in a proportion of 0.001%-0.005% of the total mass of the base oil.

[0147] The dehydrating is performed at 70-90℃ under a vacuum of ≤-0.090MPa for 2-4h until the water content is ≤300mg / L.

[0148] After the dehydration, the three-stage filtration is performed to obtain the fire-resistant oil.

[0149] The product is detected, and after the detection is qualified, the product is filled.

[0150] The detection is specifically as follows: the cleanliness and foam characteristics are tested first, and after the detection is qualified, the acid value, viscosity, anti-emulsification, dimethyl phenol content and water-soluble acid are tested.

[0151] The viscosity-temperature characteristics of the fire-resistant oil are poorer than those of the mineral oil, and the kinematic viscosity directly affects the oil film thickness and carrying capacity. The increase of the load reduces the oil film thickness, especially in the case that the kinematic viscosity of the lubricating oil is too high under the high-temperature environment (oil temperature above 60℃) to cause the oil film thickness and rigidity to not meet the design requirements.

[0152] The fire-resistant oil produced by the method has the advantages of high kinematic viscosity, high performance, good extreme pressure lubrication characteristics and wide applicability, and can meet the use conditions in the regulating oil system and the lubricating system. The fire-resistant oil can meet the requirements of the oil film rigidity under the extreme pressure working condition of the lubricating system of the steam turbine, and can avoid the situation that the fire-resistant oil sludge, paint film, air release value, foam characteristics and other indicators exceed the standards due to the high temperature and hydrolysis of the oil during the long-term operation, thereby causing potential safety hazards to the safe operation of the equipment.

[0153] For a further understanding of the present application, the anti-flammability and stability synergistically optimized phosphate-based anti-flammable oil and the preparation method thereof provided by the present application are described in detail below in conjunction with examples, and the protection scope of the present application is not limited by the following examples.

[0154] Example 1

[0155] Step 1: Start the vacuum unit, and when the vacuum degree of the reaction kettle is greater than 0.039 MPa, add the mixed alkyl phenol; add phosphorus oxychloride for the first time in the mixed alkyl phenol, stir and slowly heat to 50℃, then add Ca-Mg composite catalyst with a mass of 0.2% of the mixed alkyl phenol charge, and stir uniformly;

[0156] Rapidly heat to 75℃ within 20 minutes after adding the catalyst, then slowly heat to 95℃ within 120 minutes, and keep constant temperature for 2 hours for the first reaction; the rapid heating refers to a heating rate of 5℃ / minute, and the slow heating refers to a heating rate of 0.5℃ / minute;

[0157] After the first reaction, add phosphorus oxychloride for the second time, slowly heat to 95℃ within 120 minutes, keep constant temperature for 3 hours, slowly heat to 140℃ within 120 minutes, continue to stir and keep constant temperature for 6 hours for the second reaction;

[0158] The molar percentage of the mixed alkyl phenol is as follows:

[0159] Phenol 5%;

[0160] p-methylphenol 12%;

[0161] 2,5-dimethylphenol 25%;

[0162] 2,4-dimethylphenol 1%;

[0163] 2,3-dimethylphenol 3%;

[0164] 4-ethylphenol 0.5%;

[0165] 3,5-dimethylphenol 44%;

[0166] 3-ethylphenol 10%;

[0167] 3,4-dimethylphenol 4%;

[0168] The mass of phosphorus oxychloride added for the first time and the second time is equal, and the molar ratio of the mixed alkyl phenol to phosphorus oxychloride is 1.8:1.6.

[0169] Step 2: Open the vacuum valve of the reaction kettle to perform negative pressure acid discharge for 6-8 hours, the temperature in the kettle is kept above 140℃ during the acid discharge, and is kept for at least 3 hours; the hydrogen chloride gas in the acid discharge process is washed and absorbed by water, no hydrogen chloride gas is produced, then the vacuum valve is closed, and the reaction product is subjected to reduced pressure distillation.

[0170] Step 3: Control the vacuum degree of the distillation kettle ≥ 0.099 MPa;

[0171] Warm up to 220-250℃, distill away bis (dimethyl phenol) chlorophosphate, dichlorophosphate (dimethyl phenol) ester and other chlorinated phosphate by-products;

[0172] Warm up to 290-330℃, collect the target product, and stop heating after no distillate.

[0173] Distill away excess mixed alkyl phenol, which is recovered and recycled after condensation;

[0174] Test the product after vacuum distillation, and test the indicators: dimethyl phenol (≤0.1%) after distillation, acid value (≤0.04 mgKOH / g), chlorine content (≤30 ppm), kinematic viscosity (46-50.6 mm 2 / s at 40℃), and if unqualified, supplement distillation at 330℃ for 2h, and if qualified, filter. If still unqualified, proceed to alkali cooking treatment.

[0175] Test the product that meets the standards to filter by adsorption, and obtain the base oil after the acid value test is qualified. The standard for the acid value test to be qualified is ≤0.04 mgKOH / g.

[0176] The alkali cooking treatment specifically refers to: after vacuum distillation, the crude product is returned to the reaction kettle, 2-3% of sodium hydroxide and 100℃ hot water are added, and the crude product is cooked under normal pressure for 4-5 minutes. Care must be taken to prevent over time from causing saponification reaction, converting dimethyl phenol into sodium phenate, and reducing acid value and color. After alkali cooking, the distillation product and water are separated, and the distillation product is pumped into the post-treatment tank, ready for adsorption filtration.

[0177] The adsorption filtration specifically includes:

[0178] Filtering treatment: turn on the vacuum pump, pour the distillation product into the post-treatment tank, add adsorbent, filter aid and activated carbon, and stir evenly. The mixture is pumped into the filter to form a filter cake;

[0179] Acid value test: test the filtrate for acid value ≤0.04 mgKOH / g, and if unqualified, return it for reprocessing until it is qualified, then deliver it to the blending tank to obtain the base oil.

[0180] Step 4: blend the base oil with antioxidants, corrosion inhibitors, antifoaming agents and anti-hydrolysis agents to obtain the anti-flame oil;

[0181] Specifically includes:

[0182] Pump the base oil into the blending kettle and warm it up to 60℃;

[0183] The anti-oxidant is added in a proportion of 0.05% to 5% of the total mass of the base oil, the corrosion inhibitor is added in a proportion of 0.001% to 0.08% of the total mass of the base oil, the anti-foaming agent is added in a proportion of 0.001% to 0.009% of the total mass of the base oil, and the anti-hydrolysis agent is added in a proportion of 0.001% to 0.005% of the total mass of the base oil.

[0184] Dehydrate at 70℃ under a vacuum of ≤-0.090MPa for 2h until the moisture content is ≤300mg / L; after dehydration, carry out three-stage filtration to obtain the fire-resistant oil.

[0185] After the product is detected and qualified, it is filled.

[0186] The detection specifically includes: first test the cleanliness and foam properties, and then test the acid value, viscosity, anti-emulsification, dimethyl phenol content, water-soluble acid and other technical indexes.

[0187] Compared with the same type of fire-resistant oil FYRQUEL-L, the main indexes such as flash point, ignition point, self-ignition point, acid value, chlorine content, foam properties, air release value, resistivity, hydrolysis stability, dimethyl phenol content, four-ball test and other indexes are all better than those of the comparative example.

[0188]

[0189]

[0190] The above examples are only used to help understand the method of the present application and its core idea. It should be noted that for those skilled in the art, without departing from the principles of the present application, some improvements and modifications can be made to the present application, and these improvements and modifications also fall within the protection scope of the claims of the present application.

[0191] The above description of the disclosed embodiments enables a person skilled in the art to implement or use the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A phosphoric ester-based fire-resistant oil with synergistically optimized fire resistance and stability, characterized by, The base oil and additives are included; The base oil is a mixture of mixed alkyl phenol and phosphorus oxychloride esterification; The mole percentage of the mixed alkyl phenol is: Phenol 4-6%; p-methyl phenol 11-14%; 2,5-dimethyl phenol 22-26%; 2,4-dimethyl phenol 0.8-1.5%; 2,3-dimethyl phenol 2.5-4%; 4-ethyl phenol 0.4-0.6%; 3,5-dimethyl phenol 40-48%; 3-ethyl phenol 8-11%; 3,4-dimethyl phenol 3-5%; The additives include antioxidants, corrosion inhibitors, antifoaming agents, and anti-hydrolysis agents; The addition amount of the antioxidant is 0.05%-5% of the total mass of the base oil; The addition amount of the corrosion inhibitor is 0.001%-0.08% of the total mass of the base oil; The addition amount of the antifoaming agent is 0.001%-0.009% of the total mass of the base oil; The addition amount of the anti-hydrolysis agent is 0.001%-0.005% of the total mass of the base oil.

2. The phosphoric ester-based anti-flammability oil synergistically optimized for anti-flammability and stability according to claim 1, characterized by, The mole percentage of the mixed alkyl phenol is: Phenol 5%; p-methyl phenol 12%; 2,5-dimethyl phenol 25%; 2,4-dimethyl phenol 1%; 2,3-dimethyl phenol 3%; 4-ethyl phenol 0.5%; 3,5-dimethyl phenol 44%; 3-ethyl phenol 10%; 3,4-dimethyl phenol 4%.

3. A method for producing a phosphoric acid ester-based fire-resistant oil with which fire resistance and stability are synergistically optimized, characterized by, The method comprises the following steps: Step 1: adding phosphorus oxychloride twice in the mixed alkyl phenol, and esterification occurs under the catalysis of Ca-Mg composite catalyst to obtain a crude product; The mole ratio of the mixed alkyl phenol to phosphorus oxychloride is (1.8-3.2):(0.8-1.6); The mole percentage of the mixed alkyl phenol is: Phenol 4-6%; p-methyl phenol 11-14%; 2,5-dimethyl phenol 22-26%; 2,4-dimethyl phenol 0.8-1.5%; 2,3-dimethyl phenol 2.5-4%; 4-ethyl phenol 0.4-0.6%; 3,5-dimethyl phenol 40-48%; 3-ethyl phenol 8-11%; 3,4-dimethyl phenol 3-5%; Step 2: performing negative pressure acid discharge on the reaction product obtained in step 1; Step 3: performing vacuum distillation on the product obtained in step 2, and performing adsorption filtration to obtain the base oil; In the process of the vacuum distillation, the vacuum degree is greater than or equal to 0.099 Mpa, and the temperature is first raised to 220-250 DEG C for distillation, and then raised to 290-330 DEG C; Step 4: blending the base oil with antioxidants, corrosion inhibitors, antifoaming agents, and anti-hydrolysis agents to obtain the anti-combustion oil; The addition amount of the antioxidant is 0.05%-5% of the total mass of the base oil; The addition amount of the corrosion inhibitor is 0.001%-0.08% of the total mass of the base oil; The addition amount of the antifoaming agent is 0.001%-0.009% of the total mass of the base oil; The addition amount of the anti-hydrolysis agent is 0.001%-0.005% of the total mass of the base oil.

4. The method for producing a phosphoric ester-based anti-flammability oil with which the synergistic optimization of anti-flammability and stability is achieved according to claim 3, characterized by, The step 1 specifically comprises: The first time of adding phosphorus oxychloride in the mixed alkyl phenol, stirring and slowly raising the temperature to 50-55 DEG C, adding Ca-Mg composite catalyst, and stirring uniformly; After the catalyst is added, the temperature is rapidly increased to 70-80°C, preferably 75°C, within 20 minutes, and then slowly increased to 95-100°C within 120 minutes, and kept constant for 2-5 hours for the first reaction; After the first reaction, phosphorus oxychloride is added for the second reaction, and the temperature is slowly increased to 95-100°C within 120 minutes, and kept constant for 3-6 hours, and then slowly increased to 140-150°C within 120 minutes, and kept constant for 6-9 hours.

5. The method for producing a phosphoric ester-based anti-flammability oil with which the synergistic optimization of anti-flammability and stability is achieved according to claim 3, characterized by, In step 2, the temperature is kept above 140°C during the negative pressure acid removal process, and the negative pressure acid removal process lasts for 6-8 hours; the hydrogen chloride gas during the acid removal process is washed by water, and no hydrogen chloride gas is produced after the reaction product is subjected to the next step.

6. The method for producing a phosphoric ester-based anti-flame oil with which the flame resistance and stability are synergistically optimized according to claim 3, characterized by, In step 3, after the excess mixed alkyl phenol is removed by distillation, the excess mixed alkyl phenol is recovered by condensation and recycled.

7. The method for producing a phosphoric ester-based anti-flaming oil with which the synergistic optimization of the anti-flaming property and stability is achieved according to claim 3, characterized by, The step 3 further comprises: detecting the product after distillation, the detection standard being that the detection of dimethyl phenol after distillation is ≤0.1%, the acid value is ≤0.04 mgKOH / g, the chlorine content is ≤30 ppm, the kinematic viscosity at 40°C is 46-50.6 mm 2 / s; If the detection is qualified, the adsorption filtration is directly performed; If the detection is unqualified, the make-up distillation is performed at 290-330°C for 1-2 hours, and the filtration is performed after the detection is qualified; if the detection is still unqualified, the alkali cooking treatment is performed.

8. The method for producing a phosphoric ester-based anti-flame oil synergistically optimized in terms of flame resistance and stability according to claim 7, characterized by, The alkali cooking treatment specifically includes: after the vacuum distillation, the crude product is returned to the reaction kettle, sodium hydroxide with a mass of 2-3% of the crude product and hot water at 100°C are added, and the normal pressure alkali cooking is performed for 4-5 minutes.

9. The method for producing a phosphoric ester-based anti-flame oil synergistically optimized in flame resistance and stability according to claim 3, characterized by, Step 4 specifically includes: The base oil is pumped into a blending kettle and heated to 60-65°C; The antioxidant with a mass of 0.05%-5% of the total mass of the base oil, the corrosion inhibitor with a mass of 0.001%-0.08% of the total mass of the base oil, the antifoaming agent with a mass of 0.001%-0.009% of the total mass of the base oil, and the anti-hydrolysis agent with a mass of 0.001%-0.005% of the total mass of the base oil are added in proportion; The stirring dehydration is performed at 70-90°C under the condition that the vacuum is less than or equal to -0.090MPa for 2-4 hours until the water content is less than or equal to 300mg / L; After the dehydration, the three-stage filtration is performed to obtain the fire-resistant oil.

10. The method for producing a phosphoric ester-based anti-flammability and stability synergistically optimized anti-flammable oil according to claim 4, characterized by, The addition amount of the Ca-Mg composite catalyst is 0.15%-0.4% of the total mass of the mixed alkyl phenol.

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