CN117658805A - Fatty acid ester diesel antiwear agent and preparation method thereof - Google Patents
Fatty acid ester diesel antiwear agent and preparation method thereof Download PDFInfo
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- CN117658805A CN117658805A CN202211008597.5A CN202211008597A CN117658805A CN 117658805 A CN117658805 A CN 117658805A CN 202211008597 A CN202211008597 A CN 202211008597A CN 117658805 A CN117658805 A CN 117658805A
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- fatty acid
- antiwear agent
- acid ester
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 86
- 239000000194 fatty acid Substances 0.000 title claims abstract description 86
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 86
- -1 Fatty acid ester Chemical class 0.000 title claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 49
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 47
- 239000000047 product Substances 0.000 claims abstract description 44
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 39
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 4
- 235000020778 linoleic acid Nutrition 0.000 claims description 4
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 4
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 4
- 229960003656 ricinoleic acid Drugs 0.000 claims description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 239000002283 diesel fuel Substances 0.000 description 15
- 238000005457 optimization Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of preparation of diesel antiwear agents, in particular to a fatty acid ester diesel antiwear agent and a preparation method thereof, wherein the fatty acid ester diesel antiwear agent is prepared according to the following steps: mixing sulfonic acid resin, fatty acid and propylene glycol, then carrying out reaction, carrying out solid-liquid separation on the obtained first reaction product, adopting a benzene solvent to wash the solid sulfonic acid resin, removing surface residual products, drying and recycling, adopting deionized water to wash the liquid reaction product, carrying out standing separation on the liquid reaction product, roughly separating water in the product, and distilling the obtained roughly separated product to obtain the fatty acid ester diesel antiwear agent. The solid sulfonic acid resin can be reused after separation, and the obtained fatty acid ester diesel antiwear agent has good effect of improving the lubricating performance of hydrogenated diesel, can reduce the grinding mark diameter from 660 mu m to 420 mu m under the condition of 200ppm addition, and does not obviously influence the properties such as condensation point, cold filtration point, viscosity, acidity and the like.
Description
Technical Field
The invention relates to the technical field of preparation of diesel antiwear agents, in particular to a fatty acid ester diesel antiwear agent and a preparation method thereof.
Background
Because of the increasing importance of world countries on environmental protection, diesel oil, which is one of the main products of the modern oil refining industry, is developing towards high quality and cleanliness, and strict requirements are put on sulfur content in the index of diesel oil products. The diesel oil hydrofining desulfurization removes polycyclic aromatic hydrocarbon with lubricating property and other components with lubricating property, thereby reducing the lubricating property of low-sulfur diesel oil and causing abrasion and even damage of a fuel pump in the diesel engine.
In order to improve the lubricity of low sulfur diesel, a method of adding a lubricating additive to low sulfur diesel is currently used. The additive capable of improving the lubricating performance of diesel oil is an alcohol, ether, amide, carboxylic acid and ester compound which are adsorbed on the surface of metal in a coordination bond form to form a compact single-molecule or multi-molecule protective film so as to play roles in reducing friction and lubrication. The lubricating effect of alcohol substances is better than ethers at higher addition levels, probably due to their higher polarity, but the use of alcohol and ether substances is limited because they only show better lubricating properties at high doses. The fatty amine and the amide compounds have the same problem of large addition amount, and when the addition amount reaches 1% of the mass fraction of the diesel oil, the average abrasive spot diameter of the diesel oil can be reduced to below 460 mu m. In comparison, amides have slightly better antiwear effect as diesel antiwear agents than fatty amines, probably due to the presence of oxygen in their molecules. In general, the effective concentration requirements of amine and amide compounds as lubricity improvers are relatively high, the antiwear effect is not very remarkable, and meanwhile, the emission of tail gas pollutants is increased due to the high nitrogen content in the amine and amide compounds. The carboxylic acid compound has strong polar carboxyl in the molecule, so the antiwear effect is obviously better than that of alcohol, ether, amine and amide, the lubricating performance of low-sulfur diesel oil can be improved well, but the corrosiveness of the diesel oil can be improved due to the overlarge acidity of the carboxylic acid compound, meanwhile, the carbon deposit and the sludge in the diesel engine are promoted to be generated, the problem of filter screen blockage is easy to occur, and the requirement of the low-sulfur diesel oil antiwear agent cannot be fully met.
The ester compound as a low-sulfur diesel oil lubricating additive has the advantages that the functional group of the ester molecule contains more oxygen atoms with higher activity, and the bonding strength of the ester compound and the metal surface is better than that of alcohol, ether, amine and amide compounds, so that the ester molecule can be adsorbed on the metal surface more stably to form a firm lubricating protective film, thereby having excellent wear resistance, and the effect is more obvious when the additive amount is high. The ester compound has good wear resistance and has no obvious negative effect on the performance of the diesel oil, and is one of the important research directions of the diesel oil lubricity improver at home and abroad. Many reports on the synthesis research of an ester type lubricity improver, namely, a diesel antiwear agent are reported, and most common synthetic raw materials of the ester type antiwear agent are multipurpose ricinoleic acid, linoleic acid and other fatty acids and glycerol, pentaerythritol and other polyols react to generate esters, and solid sulfonic acid resin is multipurpose concentrated sulfuric acid, sodium hydroxide and the like.
The Chinese patent publication No. CN110240956A discloses a method for synthesizing an ester diesel antiwear agent by taking fatty acid and glycerol as raw materials and paratoluenesulfonic acid as solid sulfonic acid resin, and removing unreacted glycerol and paratoluenesulfonic acid by reduced pressure distillation after the reaction is finished. The specific working steps are as follows: fatty acid and glycerol were mixed according to 1: mixing at a molar ratio of 1.05 to 1.2, adding p-toluenesulfonic acid solid sulfonic acid resin with the mass percent of 0.15 to 0.5 percent of reactants, heating to 180 to 200 ℃ under the protection of nitrogen, stirring and reacting for 2 to 6 hours, carrying out esterification reaction while evaporating generated water, then cooling to 160 to 170 ℃ and distilling under reduced pressure below 2000Pa for 1 to 2 hours to remove excessive unreacted glycerol, solid sulfonic acid resin and residual water, and cooling to room temperature to obtain the fatty acid ester type diesel antiwear agent product with the acid value of 0.35 to 2.11mgKOH/g.
As a method for synthesizing the fatty acid ester antiwear agent, the above-mentioned document has been reported, which uses p-toluene sulfonic acid as a solid sulfonic acid resin, carries out a stirring reaction at a reaction temperature of 180 to 200 ℃, and removes excess glycerol, solid sulfonic acid resin and water by a reduced pressure distillation method. The method adopts p-toluenesulfonic acid as solid sulfonic acid resin, has higher reaction temperature, adopts a reduced pressure distillation method during separation, and has complex actual operation process.
Disclosure of Invention
The invention provides a fatty acid ester diesel antiwear agent and a preparation method thereof, which overcome the defects of the prior art and can effectively solve the problems of complex synthesis process, high operation difficulty and high production cost existing in the prior art when the fatty acid ester diesel antiwear agent is synthesized.
One of the technical schemes of the invention is realized by the following measures: the preparation method of the fatty acid ester diesel antiwear agent comprises the following steps: firstly, mixing required amount of solid sulfonic acid resin, fatty acid and propylene glycol, and then reacting to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; thirdly, adopting benzene solvent to wash solid sulfonic acid resin, removing surface residual products, drying, recycling and reusing; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product to obtain the fatty acid ester diesel antiwear agent.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
in the first step, the weight percentage of the solid sulfonic acid resin is 2 to 10wt%, the mass content of the propylene glycol is 30 to 60%, and the mol ratio of the propylene glycol to the fatty acid is 1:1 to 2:1.
In the first step, the weight percentage of the solid sulfonic acid resin is 6 to 8wt%, the mass content of the propylene glycol is 50 to 60%, and the mol ratio of the propylene glycol to the fatty acid is 3:1 to 4:1.
In the first step, the reaction temperature is 60 ℃ to 120 ℃ and the reaction time is 2 hours to 8 hours; or/and, in the third step, the drying temperature is 40-100 ℃ and the drying time is 2-6 h.
In the first step, the reaction temperature is 90 ℃ to 120 ℃ and the reaction time is 4 hours to 8 hours; or/and, in the third step, the drying temperature is 60-80 ℃ and the drying time is 4-6 h.
The fatty acid is one or more of oleic acid, linoleic acid, palmitic acid and ricinoleic acid.
The fatty acid is one or more of oleic acid and linoleic acid.
In the fifth step, the distillation temperature is 50 to 140 ℃.
In the fifth step, the distillation temperature is 80℃to 100 ℃.
The second technical scheme of the invention is realized by the following measures: a fatty acid ester type diesel antiwear agent is prepared by a preparation method of the fatty acid ester type diesel antiwear agent.
The reaction condition of the invention is safer and milder, the waste acid is not required to be treated, the invention is simple and easy to control, and the product quality is stable. The synthesis method provided by the invention realizes green production of the antiwear agent of the ester diesel oil, obtains the antiwear agent suitable for diesel oil of different brands, and has the product conversion rate reaching more than 90%.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The various chemical reagents and chemical supplies mentioned in the invention are all commonly known and used in the prior art unless specified otherwise; the percentages in the invention are mass percentages unless specified otherwise; the solutions in the invention are aqueous solutions in which the solvent is water unless otherwise specified, for example, the hydrochloric acid solution is hydrochloric acid aqueous solution; the room temperature and the room temperature in the present invention generally refer to temperatures ranging from 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to examples:
example 1: the preparation method of the fatty acid ester diesel antiwear agent comprises the following steps: firstly, mixing required amount of solid sulfonic acid resin, fatty acid and propylene glycol, and then reacting to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; thirdly, adopting benzene solvent to wash solid sulfonic acid resin, removing surface residual products, drying, recycling and reusing; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product to obtain the fatty acid ester diesel antiwear agent.
The fatty acid ester diesel antiwear agent is prepared by adopting the solid sulfonic acid resin which is separated and is subjected to simple regeneration and can be completely recovered in activity as a catalyst, has the characteristics of low reaction temperature and low operation difficulty, can reach more than 90% in raw material conversion rate, is low in production cost, has a good improvement effect on the lubricating property of hydrogenated diesel, can reduce the grinding mark diameter of the hydrogenated diesel of a sample from 660 mu m to 420 mu m under the condition of 200ppm addition, and does not obviously influence the properties such as condensation point, cold filtration point, viscosity, acidity and the like.
Example 2: as an optimization of the above examples, in the first step, the weight percentage of the solid sulfonic acid resin is 2wt% to 10wt%, the mass content of propylene glycol is 30% to 60%, and the molar ratio of propylene glycol to fatty acid is 1:1 to 2:1.
Example 3: as an optimization of the above examples, in the first step, the weight percentage of the solid sulfonic acid resin is 6wt% to 8wt%, the mass content of propylene glycol is 50% to 60%, and the molar ratio of propylene glycol to fatty acid is 3:1 to 4:1.
Example 4: as an optimization of the above examples, in the first step, the reaction temperature is 60 ℃ to 120 ℃ and the reaction time is 2 hours to 8 hours; or/and, in the third step, the drying temperature is 40-100 ℃ and the drying time is 2-6 h.
Example 5: as an optimization of the above examples, in the first step, the reaction temperature is 90 ℃ to 120 ℃ and the reaction time is 4 hours to 8 hours; or/and, in the third step, the drying temperature is 60-80 ℃ and the drying time is 4-6 h.
Example 6: as an optimization of the above embodiment, the fatty acid is one or more of oleic acid, linoleic acid, palmitic acid and ricinoleic acid.
Example 7: as an optimization of the above embodiment, the fatty acid is one or more of oleic acid and linoleic acid.
Example 8: as an optimization of the above examples, in the fifth step, the distillation temperature was 50 ℃ to 140 ℃.
Example 9: as an optimization of the above examples, in the fifth step, the distillation temperature was 80 ℃ to 100 ℃.
Example 10: the fatty acid ester type diesel antiwear agent is obtained by the preparation method of the fatty acid ester type diesel antiwear agent.
Example 11: the fatty acid ester type diesel antiwear agent is prepared according to the following steps: firstly, mixing 12.50g of fatty acid containing oleic acid and linoleic acid, 12.64g of propylene glycol and 2.00g of solid sulfonic acid resin, and then reacting for 8 hours at 105 ℃ to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; step three, taking 5g of benzene as a solvent to wash solid sulfonic acid resin, removing surface residual products, drying for 6 hours at 60 ℃, and recycling; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product at 80 ℃ to obtain the fatty acid ester diesel antiwear agent.
After the fatty acid ester-based diesel antiwear agent obtained in example 11 was treated, the acid value was found to be 23.20mgKOH/g, and the fatty acid conversion was found to be 85.64%.
Example 12: the fatty acid ester type diesel antiwear agent is prepared according to the following steps: firstly, mixing 12.50g of fatty acid containing oleic acid and linoleic acid, 7.59g of propylene glycol and 1.61g of solid sulfonic acid resin, and then reacting for 8 hours at 120 ℃ to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; step three, taking 5g of benzene as a solvent to wash solid sulfonic acid resin, removing surface residual products, drying for 4 hours at 70 ℃, and recycling; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product at 80 ℃ to obtain the fatty acid ester diesel antiwear agent.
After the fatty acid ester-based diesel antiwear agent obtained in example 12 was treated, the acid value was found to be 37.29mgKOH/g, and the fatty acid conversion was found to be 81.54%.
Example 13: the fatty acid ester type diesel antiwear agent is prepared according to the following steps: firstly, mixing 12.50g of fatty acid containing oleic acid and linoleic acid, 7.59g of propylene glycol and 1.61g of solid sulfonic acid resin, and then reacting for 8 hours at 90 ℃ to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; step three, taking 5g of benzene as a solvent to wash solid sulfonic acid resin, removing surface residual products, drying for 4 hours at 80 ℃, and recycling; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product at 80 ℃ to obtain the fatty acid ester diesel antiwear agent.
After the fatty acid ester-based diesel antiwear agent obtained in example 13 was treated, the acid value was found to be 61.30mgKOH/g, and the fatty acid conversion was found to be 60.45%.
Example 14: the fatty acid ester type diesel antiwear agent is prepared according to the following steps: firstly, mixing 12.50g of fatty acid containing oleic acid and linoleic acid, 16.86g of propylene glycol and 2.34g of solid sulfonic acid resin, and then reacting for 8 hours at 110 ℃ to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; step three, taking 2.11g of benzene as a solvent to wash the solid sulfonic acid resin, removing the surface residual product, drying for 6 hours at 60 ℃, and recycling; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product at 80 ℃ to obtain the fatty acid ester diesel antiwear agent.
After the fatty acid ester-based diesel antiwear agent obtained in example 14 was treated, the acid value was found to be 23.99mgKOH/g, and the fatty acid conversion was found to be 88.12%.
Example 15: the fatty acid ester type diesel antiwear agent is prepared according to the following steps: firstly, mixing 12.50g of fatty acid containing oleic acid and linoleic acid, 5.90g of propylene glycol and 1.47g of solid sulfonic acid resin, and then reacting for 8 hours at 90 ℃ to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; step three, taking 5g of benzene as a solvent to wash solid sulfonic acid resin, removing surface residual products, drying for 4 hours at 70 ℃, and recycling; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product at 80 ℃ to obtain the fatty acid ester diesel antiwear agent.
After the fatty acid ester type diesel antiwear agent obtained in example 15 was treated, the acid value was 70.16mgKOH/g, and the fatty acid conversion was 65.27%.
Example 16: the fatty acid ester type diesel antiwear agent is prepared according to the following steps: firstly, mixing 25g of fatty acid containing oleic acid and linoleic acid, 11.80g of propylene glycol and 2.944g of solid sulfonic acid resin, and then reacting for 8 hours at 105 ℃ to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; step three, taking 5g of benzene as a solvent to wash solid sulfonic acid resin, removing surface residual products, drying for 6 hours at 60 ℃, and recycling; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product at 80 ℃ to obtain the fatty acid ester diesel antiwear agent.
After the fatty acid ester type diesel antiwear agent obtained in example 16 was treated, the acid value was 49.54mgKOH/g, and the fatty acid conversion was 75.48%.
The sources of raw material fatty acid and propylene glycol are not limited, and the raw material fatty acid and propylene glycol are commercially available, wherein solid sulfonic acid resin is a reaction catalyst, and the resin model can be KC139 and is provided by Hebei Kai environmental protection technology Co. The solid sulfonic acid resin can be repeatedly used after reaction and washing separation, the single-time supplement does not exceed 5wt%, the conversion rate of fatty acid used for the second time is reduced by 5-10%, the conversion rate of fatty acid used for the third time is continuously reduced by 5-10%, and the solid sulfonic acid resin can be prepared according to the conversion rate in practical use.
In conclusion, the solid sulfonic acid resin can be reused after separation, and the obtained fatty acid ester diesel antiwear agent has good improvement effect on the lubricating performance of hydrogenated diesel, can reduce the grinding mark diameter from 660 mu m to 420 mu m under the condition of 200ppm addition, and does not obviously influence the properties such as condensation point, cold filtration point, viscosity, acidity and the like.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (10)
1. The preparation method of the fatty acid ester diesel antiwear agent is characterized by comprising the following steps of: firstly, mixing required amount of solid sulfonic acid resin, fatty acid and propylene glycol, and then reacting to obtain a first reaction product; secondly, carrying out solid-liquid separation on the first reaction product to obtain a liquid reaction product and solid sulfonic acid resin respectively; thirdly, adopting benzene solvent to wash solid sulfonic acid resin, removing surface residual products, drying, recycling and reusing; washing the liquid reaction product with deionized water, standing for separation, and roughly separating water in the product to obtain a roughly separated product; and fifthly, distilling the crude separation product to obtain the fatty acid ester diesel antiwear agent.
2. The preparation method of the fatty acid ester diesel antiwear agent according to claim 1, characterized in that in the first step, the weight percentage of the solid sulfonic acid resin is 2wt% to 10wt%, the mass content of propylene glycol is 30% to 60%, and the molar ratio of propylene glycol to fatty acid is 1:1 to 2:1.
3. The method for preparing the fatty acid ester diesel antiwear agent according to claim 2, characterized in that in the first step, the weight percentage of the solid sulfonic acid resin is 6wt% to 8wt%, the mass content of the propylene glycol is 50% to 60%, and the molar ratio of the propylene glycol to the fatty acid is 3:1 to 4:1.
4. The method for preparing the fatty acid ester diesel antiwear agent according to claim 1, 2 or 3, characterized in that in the first step, the reaction temperature is 60 ℃ to 120 ℃ and the reaction time is 2 hours to 8 hours; or/and, in the third step, the drying temperature is 40-100 ℃ and the drying time is 2-6 h.
5. The method for preparing the fatty acid ester diesel antiwear agent according to claim 4, characterized in that in the first step, the reaction temperature is 90 ℃ to 120 ℃ and the reaction time is 4 hours to 8 hours; or/and, in the third step, the drying temperature is 60-80 ℃ and the drying time is 4-6 h.
6. The method for producing a fatty acid ester-based diesel antiwear agent according to any one of claims 1 to 4, characterized in that the fatty acid is one or more of oleic acid, linoleic acid, palmitic acid and ricinoleic acid.
7. The method for preparing the fatty acid ester diesel antiwear agent according to claim 6, wherein the fatty acid is one or more of oleic acid and linoleic acid.
8. The method for producing a fatty acid ester-based diesel antiwear agent according to any one of claims 1 to 7, characterized in that in the fifth step, the distillation temperature is 50 ℃ to 140 ℃.
9. The method for producing a fatty acid ester type diesel antiwear agent according to claim 8, characterized in that in the fifth step, the distillation temperature is 80 ℃ to 100 ℃.
10. A fatty acid ester-based diesel antiwear agent obtained by the method for producing a fatty acid ester-based diesel antiwear agent according to any one of claims 1 to 9.
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