CN112210408A - Fatty acid ester diesel antiwear agent with low-temperature fluidity and preparation method thereof - Google Patents
Fatty acid ester diesel antiwear agent with low-temperature fluidity and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of oil additives, and particularly relates to a fatty acid ester diesel antiwear agent with low-temperature fluidity and a preparation method thereof. The antiwear agent comprises unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol; the preparation method of the anti-wear agent comprises the steps of mixing unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol, continuously reacting at a medium temperature, adding alkali into a product after the reaction is finished to neutralize until the pH value is neutral, then carrying out reduced pressure distillation and suction filtration to remove salt, and adding a viscosity reducer to obtain the fatty acid ester diesel anti-wear agent. The diesel anti-wear agent integrates excellent anti-wear property and low-temperature fluidity, and solves the problem of poor fluidity of the ester anti-wear agent under the low-temperature condition. The product has low acid value and small addition amount, when the temperature is lower than-16 ℃, the viscosity is not higher than 300mpa & s, the pump body is convenient to convey, and the blended low-sulfur diesel oil can meet the national VI lubricity standard and the condensation point requirement.
Description
Technical Field
The invention belongs to the technical field of oil additives, and particularly relates to a fatty acid ester diesel antiwear agent with low-temperature fluidity and a preparation method thereof.
Background
With the widespread use of diesel engines, the consumption of diesel fuel is increasing year by year. However, the large consumption of diesel fuel inevitably leads to further aggravation of the emission of harmful substances from vehicles. Since emissions have a serious impact on the ecological environment, human health and economic development, governments in various countries have successively enacted strict emissions regulations, limiting the harmful emissions of diesel vehicles. With the implementation of national standards of V and VI of diesel oil, the sulfur content of the diesel oil is reduced to below 10ppm, and the desulfurized diesel oil is implemented in domestic refineries. At present, sulfur reduction technologies such as hydrotreating, hydrocracking and the like are adopted in China, so that the sulfur content of fuel is greatly reduced, and the content of polar compounds in diesel oil is too low, so that the lubricity of the diesel oil is greatly reduced, the phenomenon of abrasion and damage of a large number of diesel oil pumps is caused, and the service life of the diesel oil pumps is shortened. Therefore, improving the lubricity of low-sulfur diesel is one of the key problems in solving the wide-range popularization of low-sulfur diesel.
In the prior art, an antiwear agent is usually added into low-sulfur diesel oil, and the antiwear agent can be adsorbed on the surface of metal to form a layer of protective film on the surface of the metal, so that the friction force between the metal is reduced, and the lubricity of the low-sulfur diesel oil is effectively improved. The technical requirements of the diesel antiwear agent established by medium petrochemicals mainly include two types of unsaturated fatty acids and unsaturated fatty acid esters thereof in enterprise standards.
With the deterioration of crude oil exploitation, the yield of crude oil with high sulfur content and high acid content is continuously increased, so that the content of polar compounds in diesel oil is greatly reduced by adopting deep sulfur reduction technologies such as hydrotreating and hydrocracking in China, the diameter of the abrasive wear is far larger than 700 mu m, although the lubricity of the diesel oil can be improved by adding the unsaturated fatty acid antiwear agent, the addition of 300ppm is far from meeting the technical requirement that the diameter of the abrasive wear of low sulfur diesel oil is reduced to be below 420 mu m, and more amount needs to be added to reach the standard. With the increase of the addition amount of the fatty acid antiwear agent, the acidity of the diesel oil is often greater than the standard of 7mgKOH/100mL, or the fatty acid antiwear agent reacts with other alkaline additives in the diesel oil to generate precipitates, and at the moment, the fatty acid antiwear agent cannot meet the technical requirements of the diesel oil standard, so that the unsaturated fatty acid ester antiwear agent needs to be added.
At present, a plurality of mechanisms have researched the ester type antiwear agent, and the ester type antiwear agent can also meet the use standard of the solidification point of the ester type antiwear agent not higher than-16 ℃ specified in the Q/SHCG 57-2014 standard. However, in the using process, it is found that although the condensation point of the ester type antiwear agents is very low, the fluidity of the ester type antiwear agents is very poor at low temperature, the ester type antiwear agents cannot be conveyed into a diesel oil tank by a pump body for blending, particularly in cold northern areas, the conveying difficulty is higher, the ester type antiwear agents can be used after being heated to reach a certain temperature, and time and energy are wasted.
Disclosure of Invention
The purpose of the invention is as follows:
the invention provides a grease type diesel antiwear agent with low-temperature fluidity and a preparation method thereof, and aims to solve the problems of poor fluidity and large conveying difficulty of the conventional ester antiwear agent in a low-temperature environment.
The technical scheme is as follows:
the fatty acid ester diesel antiwear agent with low-temperature fluidity is characterized in that: the antiwear agent comprises the following raw materials: unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol;
wherein the molar ratio of the unsaturated monobasic fatty acid to the polyether polyol to the water absorbent is (1-1.5): 1: (0.2-0.3), xylene accounting for 21-40% of the total mass, a catalyst accounting for 3-8% of the total mass, and the addition amount of the viscosity reducer is 0.1-0.3% of the diesel antiwear agent.
The monounsaturated fatty acid is one or more of soybean oleic acid, tall oil acid and cottonseed oleic acid, and is purified by a multi-stage freezing and filter pressing method to obtain the fatty acid with the condensation point of less than-12 ℃.
The polyether polyol is one or two of propoxylated trimethylolpropane or propoxylated pentaerythritol; wherein the amount of propylene oxide in the propoxylated trimethylolpropane is from 3 to 9; the amount of propylene oxide in the propoxylated pentaerythritol is from 4 to 12.
The viscosity reducer added into the diesel antiwear agent is one or more of polyethylene vinyl acetate, polyalkylacrylate and polyethylene-fumaric acid copolymer. The mass ratio of the polyethylene vinyl acetate to the polyalkylacrylate to the polyethylene-fumaric acid copolymer is (7-10): (1-3): (0-1).
The water absorbent is one or two of anhydrous sodium sulfate or anhydrous magnesium sulfate.
The catalyst is prepared by mixing imidazole-tetrafluoroborate ions and p-toluenesulfonic acid in a mass ratio of 1: 2-5, adding 3-8% of alcohol acid.
The preparation method of the fatty acid ester diesel antiwear agent with low-temperature fluidity is characterized by comprising the following steps: mixing unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol, carrying out esterification reaction at medium temperature, adding sodium bicarbonate into a product after the reaction is finished to neutralize the pH value to be neutral, carrying out reduced pressure distillation and suction filtration to remove salt, adding a viscosity reducer, and uniformly stirring to obtain a final product.
The medium temperature range is 200-240 ℃; adding viscosity reducer and stirring for 10-30min after desalting.
The application of the fatty acid ester diesel antiwear agent with low-temperature fluidity as a diesel engine low-temperature high-fluidity antiwear agent.
The advantages and effects are as follows:
the invention has the following advantages and beneficial effects:
according to the invention, unsaturated monobasic fatty acid, polyether polyol and a viscosity reducer are used as raw materials, the prepared grease type diesel antiwear agent can improve the lubricity of low-sulfur diesel, and a large amount of oxygen atoms and alkyl are introduced into molecules after propoxylation, so that the adsorption performance of the molecules can be improved, a diesel engine can be better protected from abrasion, the demulsification performance of the molecules can be improved, the diesel is prevented from being emulsified, the fluidity at low temperature is good, the pump body can be conveniently conveyed, the grease type diesel antiwear agent is suitable for being used for blending diesel in winter in northern cold regions, and the blended low-sulfur diesel can meet the national VI lubricity standard and the condensation point requirement.
The specific implementation mode is as follows:
the fatty acid ester diesel oil antiwear agent with low temperature fluidity adopts a formula comprising: unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol; wherein the molar ratio of the unsaturated monobasic fatty acid to the polyether polyol to the water absorbent is (1-1.5): 1: (0.2-0.3), xylene accounting for 21-40% of the total mass, a catalyst accounting for 3-8% of the total mass, and the addition amount of the viscosity reducer is 0.1-0.3% of the diesel antiwear agent.
The monounsaturated fatty acid is one or more of soybean oleic acid, tall oil acid and cottonseed oleic acid, and is purified by a multi-stage freezing and filter pressing method to obtain the fatty acid with the condensation point of less than-12 ℃.
The polyether polyol is one of propoxylated trimethylolpropane or propoxylated pentaerythritol; the polyether polyol has multiple branched chains, and the oil solubility and the anti-emulsifying property are enhanced after the propoxylation, so that the viscosity of the product is reduced.
Wherein the amount of propylene oxide in the propoxylated trimethylolpropane is from 3 to 9, preferably 3; the amount of propylene oxide in the propoxylated pentaerythritol is from 4 to 12, preferably 4.
After the salt is removed by suction filtration, one or more viscosity reducers, such as polyethylene vinyl acetate, polyalkylacrylate and polyethylene-fumaric acid copolymer, can be added.
The viscosity reducer is a mixture of two or three of polyethylene vinyl acetate, polyalkylacrylate and polyethylene-fumaric acid copolymer, and the mass ratio of the polyethylene vinyl acetate to the polyalkylacrylate to the polyethylene-fumaric acid copolymer is (7-10): (1-3): (0-1), preferably 7: 2: 1; the addition amount is 0.1-0.3%, preferably 0.15% of the diesel antiwear agent.
The water absorbent is one or two of anhydrous sodium sulfate or anhydrous magnesium sulfate.
The catalyst is prepared by mixing imidazole-tetrafluoroborate ions and p-toluenesulfonic acid in a mass ratio of 1: 2-5, preferably 1: 2.5, adding 3-8 percent of alcohol acid, preferably 5 percent.
The preparation method of the fatty acid ester diesel oil antiwear agent with low-temperature fluidity comprises the steps of mixing unsaturated monobasic fatty acid, a water absorbent, dimethylbenzene, a catalyst and polyether polyol, continuing to react at a medium temperature after the addition, adding sodium bicarbonate into a product after the reaction is finished to neutralize the pH value to be neutral, then carrying out reduced pressure distillation and suction filtration to remove salt, adding a viscosity reducer, and uniformly stirring to obtain a final product, namely the fatty acid ester diesel oil antiwear agent.
The medium temperature range is 200-240 ℃, and the reaction is carried out until the water quantity is not increased any more;
adding viscosity reducer after desalting, and stirring for 10-30min, preferably 20 min.
The fatty acid ester diesel oil antiwear agent with low temperature fluidity is applied as the diesel oil low temperature high fluidity antiwear agent.
The method comprises the steps of mixing unsaturated monobasic fatty acid, a water absorbent, dimethylbenzene, a catalyst and polyether polyol, continuing to react at a medium temperature after the unsaturated monobasic fatty acid, adding sodium bicarbonate into a product after the reaction is finished to neutralize until the pH value is neutral, then carrying out reduced pressure distillation, suction filtration and desalination, and adding a viscosity reducer to obtain the final product, namely the fatty acid ester diesel antiwear agent.
The invention adopts the propoxylated polyether glycol to improve the adsorbability of molecules of the antiwear agent, introduces a large amount of oxygen atoms and alkyl into the molecules, can improve the adsorbability of the molecules, better protect a diesel engine from abrasion, can also improve the anti-emulsifying property of the molecules, avoids diesel oil emulsification, has good fluidity at low temperature, and is convenient for conveying a pump body.
The invention is further illustrated by the following specific examples:
example 1
Unsaturated monobasic fatty acid with a condensation point of-18 ℃, propoxylated trimethylolpropane containing three propylene oxides and anhydrous sodium sulfate are mixed according to a molar ratio of 1: 1: 0.25, adding xylene accounting for 30% of the total mass of the alkyd, and adding a catalyst accounting for 5% of the total mass of the alkyd, wherein imidazole-tetrafluoroborate ions are mixed with p-toluenesulfonic acid in a mass ratio of 1: 2.5, stirring uniformly, heating to 200-240 ℃ for esterification reaction, reacting until the water amount in the water separator is not increased, adding sodium bicarbonate into the product after the reaction is finished to neutralize until the pH is neutral, then carrying out reduced pressure distillation to extract xylene, carrying out suction filtration to remove generated salt while the product is hot, and finally mixing polyethylene vinyl acetate, polyalkylacrylate and polyethylene-fumaric acid copolymer according to the mass ratio of 7: 2: 1, compounding, wherein the adding amount is 0.15 percent of the mass of the desalting product, and stirring for 20min to obtain a final product. The viscosity at-16 ℃ is 273mpa · s, as measured by a rotational viscometer.
Example 2
Unsaturated monobasic fatty acid with a condensation point of-18 ℃, propoxylated pentaerythritol containing four propylene oxides and anhydrous magnesium sulfate are mixed according to a molar ratio of 1: 1: 0.25, adding xylene accounting for 35% of the total mass of the alkyd, and adding a catalyst accounting for 6% of the total mass of the alkyd, wherein imidazole-tetrafluoroborate ions are mixed with p-toluenesulfonic acid in a mass ratio of 1: 3, uniformly stirring, heating to 200-240 ℃ for esterification reaction, reacting until the water amount in the water separator is not increased, adding sodium bicarbonate into a product after the reaction is finished to neutralize until the pH is neutral, then carrying out reduced pressure distillation to extract dimethylbenzene, carrying out suction filtration to remove generated salts while the product is hot, and finally mixing polyethylene vinyl acetate, polyalkylacrylate and polyethylene-fumaric acid copolymer according to the mass ratio of 7: 2: 1, compounding, wherein the adding amount is 0.15 percent of the mass of the desalting product, and stirring for 20min to obtain a final product. Viscosity 282mpa · s at-16 ℃ as measured by a rotational viscometer.
Example 3
Unsaturated monobasic fatty acid with a condensation point of-16 ℃, propoxylated pentaerythritol containing 8 propylene oxides and anhydrous magnesium sulfate are mixed according to a molar ratio of 1.2: 1: 0.28, adding xylene accounting for 28 percent of the total mass of the alkyd, and adding a catalyst accounting for 4 percent of the total mass of the alkyd, wherein imidazole-tetrafluoroborate ions are mixed with p-toluenesulfonic acid according to the mass ratio of 1: and 4, uniformly stirring, heating to 200-240 ℃ for esterification reaction, reacting until the water amount in the water separator is not increased, adding sodium bicarbonate into a product after the reaction is finished to neutralize until the pH is neutral, carrying out reduced pressure distillation to extract dimethylbenzene, carrying out suction filtration to remove generated salts while the product is hot, and finally mixing the polyethylene vinyl acetate, the polyalkylacrylate and the polyethylene-fumaric acid copolymer according to the mass ratio of 8: 1: 1, compounding, wherein the adding amount is 0.2 percent of the mass of the desalting product, and stirring for 26min to obtain a final product. The viscosity was 292mpa · s at-16 ℃ as measured by a rotational viscometer.
Example 4
Unsaturated monobasic fatty acid with a condensation point of-17 ℃, propoxylated trimethylolpropane containing 3 propylene oxides and propoxylated pentaerythritol containing 8 propylene oxides, anhydrous magnesium sulfate and a solvent are mixed according to a molar ratio of 1.3: 1: 0.23, adding xylene accounting for 25% of the total mass of the alkyd, and adding a catalyst accounting for 3% of the total mass of the alkyd, wherein imidazole-tetrafluoroborate ions are mixed with p-toluenesulfonic acid in a mass ratio of 1: and 5, uniformly stirring, heating to 200-240 ℃ for esterification reaction, reacting until the water amount in the water separator is not increased, adding sodium bicarbonate into a product after the reaction is finished to neutralize until the pH is neutral, then carrying out reduced pressure distillation to extract dimethylbenzene, carrying out suction filtration to remove generated salt while the product is hot, and finally mixing the polyethylene vinyl acetate and the polyalkylacrylate according to the mass ratio of 8: 2, compounding, wherein the adding amount is 0.2 percent of the mass of the desalting product, and stirring for 15min to obtain a final product. The viscosity was 288 mpa.s at-16 ℃ as measured by a rotational viscometer.
Example 5
Unsaturated monobasic fatty acid with a condensation point of-15 ℃, propoxylated trimethylolpropane containing 6 propylene oxides and propoxylated pentaerythritol containing 4 propylene oxides, anhydrous sodium sulfate and a solvent are mixed according to a molar ratio of 1.4: 1: 0.2, adding the mixture into a reaction kettle, adding dimethylbenzene accounting for 25% of the total mass of the alkyd, and adding a catalyst accounting for 7% of the total mass of the alkyd, wherein imidazole-tetrafluoroborate ions are mixed with p-toluenesulfonic acid, and the mass ratio is 1: 4.5, stirring uniformly, heating to 200-240 ℃ for esterification reaction, reacting until the water amount in the water separator is not increased, adding sodium bicarbonate into the product after the reaction is finished to neutralize until the pH is neutral, then carrying out reduced pressure distillation to extract xylene, carrying out suction filtration to remove generated salt while the product is hot, and finally mixing polyethylene vinyl acetate and polyalkylacrylate according to the mass ratio of 9: 1, compounding, wherein the adding amount is 0.3 percent of the mass of the desalting product, and stirring for 10min to obtain a final product. The viscosity was 295 mPa. multidot.s at-16 ℃ as measured by a rotational viscometer.
Example 6
Unsaturated monobasic fatty acid with a condensation point of-13 ℃, propoxylated pentaerythritol containing 12 propylene oxides and anhydrous magnesium sulfate are mixed according to a molar ratio of 1.4: 1: 0.3, adding the mixture into a reaction kettle, adding dimethylbenzene accounting for 33% of the total mass of the alkyd, and adding a catalyst accounting for 8% of the total mass of the alkyd, wherein imidazole-tetrafluoroborate ions are mixed with p-toluenesulfonic acid, and the mass ratio is 1: 2, stirring uniformly, heating to 200-240 ℃ for esterification reaction, reacting until the water amount in the water separator is not increased, adding sodium bicarbonate into a product after the reaction is finished to neutralize until the pH is neutral, then carrying out reduced pressure distillation to extract dimethylbenzene, carrying out suction filtration to remove generated salts while the product is hot, and finally mixing polyethylene vinyl acetate and polyalkylacrylate according to the mass ratio of 7: 3, compounding, wherein the adding amount is 0.3 percent of the mass of the desalting product, and stirring for 30min to obtain a final product. The viscosity at-16 ℃ was 298mpa · s, as measured by a rotational viscometer.
In examples 1 to 6, the monounsaturated fatty acid is one or more of soybean oleic acid, tall oil acid, and cottonseed oleic acid, and the fatty acid having a condensation point of less than-12 ℃ is obtained by purification through a multi-stage freezing and pressure filtration method.
TABLE 1 viscosity and other properties of diesel antiwear Agents and control of examples 1-61
1The diesel antiwear agent is added in an amount of 300ppm, the blank diesel oil grinding spot diameter is 598 mu m, and the acidity is 3.2mgKOH/100mL
By comparison, the viscosity of the diesel oil antiwear agent prepared in the embodiment of the invention is obviously lower than that of the triglyceride oleate antiwear agent at low temperature, and the acidity and the lubricity of the diesel oil are not influenced. The diesel antiwear agent integrates excellent abrasion resistance and low-temperature fluidity, and solves the problem of poor fluidity of the ester antiwear agent under the low-temperature condition. The product has low acidity and small addition amount, when the temperature is lower than-16 ℃, the viscosity is not higher than 300mpa & s, the pump body is convenient to convey, and the blended low-sulfur diesel oil can meet the national VI lubricity standard and the condensation point requirement.
Claims (10)
1. The fatty acid ester diesel antiwear agent with low-temperature fluidity is characterized in that: the antiwear agent comprises the following raw materials: unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol;
wherein the molar ratio of the unsaturated monobasic fatty acid to the polyether polyol to the water absorbent is (1-1.5): 1: (0.2-0.3), xylene accounting for 21-40% of the total mass, a catalyst accounting for 3-8% of the total mass, and the addition amount of the viscosity reducer is 0.1-0.3% of the total mass of the diesel antiwear agent.
2. The fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 1, characterized in that: the monounsaturated fatty acid is one or more of soybean oleic acid, tall oil acid and cottonseed oleic acid, and is purified by a multi-stage freezing and filter pressing method to obtain the fatty acid with the condensation point of less than-12 ℃.
3. The fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 1, characterized in that: the polyether polyol is one or two of propoxylated trimethylolpropane or propoxylated pentaerythritol; wherein the amount of propylene oxide in the propoxylated trimethylolpropane is from 3 to 9; the amount of propylene oxide in the propoxylated pentaerythritol is from 4 to 12.
4. The fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 1, characterized in that: the viscosity reducer added into the diesel antiwear agent is one or more of polyethylene vinyl acetate, polyalkylacrylate and polyethylene-fumaric acid copolymer.
5. The fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 4, characterized in that: when the viscosity reducer is polyethylene vinyl acetate, polyalkylacrylate or polyethylene-fumaric acid copolymer, the proportion relationship is as follows: the mass ratio of the polyethylene vinyl acetate to the polyalkylacrylate to the polyethylene-fumaric acid copolymer is (7-10): (1-3): (0-1).
6. The fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 1, characterized in that: the water absorbent is one or two of anhydrous sodium sulfate or anhydrous magnesium sulfate.
7. The fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 1, characterized in that: the catalyst is prepared by mixing imidazole-tetrafluoroborate ions and p-toluenesulfonic acid in a mass ratio of 1: 2-5, and the addition accounts for 3-8% of the total mass.
8. The preparation method of the fatty acid ester diesel antiwear agent with low-temperature fluidity as claimed in claims 1 to 7, is characterized in that: mixing unsaturated monobasic fatty acid, a water absorbent, xylene, a catalyst and polyether polyol, carrying out esterification reaction at medium temperature, adding sodium bicarbonate into a product after the reaction is finished to neutralize the pH value to be neutral, carrying out reduced pressure distillation and suction filtration to remove salt, adding a viscosity reducer, and uniformly stirring to obtain a final product.
9. The preparation method of the fatty acid ester diesel antiwear agent with low temperature fluidity according to claim 8, is characterized in that: the medium temperature range is 200-240 ℃; adding viscosity reducer and stirring for 10-30min after desalting.
10. The use of the fatty acid ester diesel antiwear agent with low temperature fluidity of claim 1 as a diesel engine low temperature high fluidity antiwear agent.
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| CN117986243A (en) * | 2024-04-03 | 2024-05-07 | 湖南浩润科技有限公司 | Diesel antiwear agent containing heterocyclic compound and preparation method thereof |
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