CN116731764B - Preparation method of modified polyol ester aviation lubricating oil - Google Patents
Preparation method of modified polyol ester aviation lubricating oil Download PDFInfo
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- CN116731764B CN116731764B CN202310768384.0A CN202310768384A CN116731764B CN 116731764 B CN116731764 B CN 116731764B CN 202310768384 A CN202310768384 A CN 202310768384A CN 116731764 B CN116731764 B CN 116731764B
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- polyol ester
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- -1 polyol ester Chemical class 0.000 title claims abstract description 33
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 29
- 229920005862 polyol Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 49
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 34
- 239000011572 manganese Substances 0.000 claims abstract description 34
- 239000003930 superacid Substances 0.000 claims abstract description 32
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 description 16
- 230000032050 esterification Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000314 lubricant Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 230000001050 lubricating effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/74—Esters of polyhydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/0405—Phosphate esters used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a preparation method of modified polyol ester aviation lubricating oil. Firstly, preparing solid super acid catalyst ZrO 2 ‑ Al 2 O 3 During the process, metallic cobalt and metallic manganese are added for modification, and the metallic cobalt and the metallic manganese have synergistic effect, so that the tetragonal ZrO is formed 2 The catalyst is stable at room temperature, so that the solid catalyst has higher catalytic activity, and has the advantages of easy separation from products, simple preparation method and the like. And p-chlorobenzoic acid is used for modifying the trimethylol phosphorus oxide, and the modified trimethylol phosphorus oxide can remarkably improve the wear resistance and has better lubricity and biodegradability. The preparation process is simple and convenient to operate, and the wear resistance and lubricity of the lubricating oil are further improved by the modified solid super acid catalyst and the application of the modified trimethylol phosphorus oxide.
Description
Technical Field
The invention relates to preparation of lubricating oil, in particular to polyol ester lubricating oil, and particularly relates to a preparation method of modified polyol ester lubricating oil.
Background
Lubricants have been developed to address the problems encountered during the manufacturing process. Has extremely wide application in the industrial field. The relative motion of the machinery in the working state causes dry friction between contact surfaces, which causes abrasion of parts and reduces the service life, and a layer of oil film or lubricating film can be formed between friction contact surfaces by using the lubricant, and the layer of film can effectively reduce friction between the machinery and physical loss caused by friction. Besides the effects of reducing friction and prolonging service life, which can be directly imagined, the lubricant can also play a role in cooling under certain conditions.
Polyol ester lubricating oil has excellent thermal stability and biodegradability, and has wide application range and excellent lubricating performance due to the artificially controllable molecular structure, and has been widely used in a plurality of fields. In particular, large-scale applications were at the earliest achieved in the field of aviation. Because the working temperature of the aeroengine is extremely high and can reach thousands of degrees centigrade, and meanwhile, the requirements on reliability are not achieved by a common engine, so that extremely severe requirements are put forward on a lubricating system on the aeroengine, the common mineral oil can not meet the operation requirements of the aeroengine far away, and the polyol ester lubricant occupies the market segment by virtue of the polyol ester lubricant and the effective thermal stability. With the further development of the synthetic lubrication industry, synthetic ester lubricants have been gradually used in national defense industry and in the brand-new corner of the common civil market, for example, polyol esters can be used for preparing high-end lubricating oil for special internal combustion engine equipment, and the high-end lubricating oil can well complete tasks which cannot be completed by common mineral oil. In our civil field, fully synthetic engine oils and semi-synthetic engine oils are rapidly gaining popularity, which can bring better, more durable lubrication effect, extend the time interval and mileage of automobile machinery maintenance. In these synthetic engine oils, the synthetic oils of polyol esters occupy a considerable proportion.
Disclosure of Invention
Aiming at the problems, the invention adds metallic cobalt and metallic manganese to modify in the process of preparing the solid super acid catalyst, so that the solid catalyst has higher catalytic activity, and has the advantages of easy separation from products, simple preparation method and the like. And p-chlorobenzoic acid is used for modifying the trimethylol phosphorus oxide, and the modified trimethylol phosphorus oxide can remarkably improve the wear resistance and has better lubricity and biodegradability. The preparation process is simple and convenient to operate, and the wear resistance and lubricity of the lubricating oil are further improved by the modified solid super acid catalyst and the application of the modified trimethylol phosphorus oxide. The preparation method comprises the following specific steps:
S1、2g～5g Al(NO 3 ) 3 .9H 2 the volume ratio of O dissolved in the water is 1:1, adding 0.1 g-1 g sodium citrate into deionized water and ethanol solution, mixing and stirring for 15 min-30 min, transferring into a high-pressure reaction kettle, reacting for 18 h-24 h at 120-200 ℃, naturally cooling to room temperature, centrifuging and drying to obtain spherical Al 2 O 3 A carrier;
s2, weighing 0.4 g-1 g of spherical Al prepared in the step S1 2 O 3 Carrier, adding volume ratio of 10:1 and deionized water, stirring for 8-12 h, continuously stirring and slowly dripping 10-15 mL of zirconium n-butoxide, performing ultrasonic treatment until complete hydrolysis, transferring the suspension to a polytetrafluoroethylene high-pressure reaction kettle, and transferring the suspension to 100-17Heating in water bath at 0 ℃ for 20-24 h, naturally cooling, and centrifugally drying to obtain the solid super catalyst ZrO 2 -Al 2 O 3 ；Al 2 O 3 The specific surface area of the solid super acid is larger, and the special coordination of the surface atoms can generate the forms of different acid properties of the corresponding solid super acid. To ZrO 2 The addition of a small amount of Al can significantly improve the isomerization performance of the catalyst.
S3, adding 5 mL-15 mL0.75mol/L (NH) into 1 g-3 g of the solid super catalyst prepared in the step S2 4 ) 2 S 2 O 8 Stirring the solution for 10-15 min, and centrifugally drying to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 Will S 2 O 8 2- /ZrO 2 -Al 2 O 3 Adding 1-3% of metal cobalt and metal manganese into 10-30 mL of deionized water, soaking for 6-10 h, drying and roasting to obtain a metal cobalt and metal manganese modified solid super acid catalyst; the synergistic effect between the cobalt and manganese metal leads to tetragonal ZrO 2 Is stable at room temperature, so that the activity of the catalyst is improved.
S4, weighing the following components in a molar ratio of 1:1.5, placing the trimethylol phosphorus oxide and p-chlorobenzoic acid into a round bottom flask, uniformly mixing, preheating, continuously heating to 150-220 ℃ under vacuum condition, reacting for 5-10 h, and obtaining modified trimethylol phosphorus oxide after the reaction is finished; the modified trimethylol phosphorus oxide can remarkably improve the antiwear performance, has better lubricating property and biodegradability, and can improve the extreme pressure antiwear property of the lubricant when the lubricant is used in mechanical parts because the benzene ring has a large pi bond sharing electrons.
S5, weighing the following components in a molar ratio of 3:1.2, placing the modified trimethylol phosphorus oxide and oleic acid into a four-necked flask, adding a solid super acid catalyst modified by metal manganese prepared in 0.9% -1.1% S3, uniformly mixing, keeping the vacuum degree at 0.09MPa, and continuously reacting for 8-10 h at 180-200 ℃ to obtain modified crude ester;
s6, placing the modified crude ester obtained in the step S3 into a four-necked flask, then adding 4% -6% of solid magnesium oxide, heating and stirring, reacting for 2-4 hours at 60-80 ℃, and centrifuging to obtain the modified polyol ester lubricating oil.
Preferably: the reaction is carried out in the step S1 in the high-pressure reaction kettle at 200 ℃ for 24 hours in the step S1.
Preferably: the reaction product in the step S2 is heated in a water bath at 170 ℃ for 20 hours.
Preferably: in the step S3, a doping ratio of 1% by mass is added as 1:1, metallic cobalt and metallic manganese.
Preferably: and in the step S4, the temperature is continuously increased to 200 ℃ under the vacuum condition, and the reaction is carried out for 8 hours.
Preferably: and in the step S5, the solid super acid catalyst modified by the metallic cobalt and the metallic manganese, which is prepared in the step S3, is added in the amount of 1.0 percent.
Preferably: in the step S6, 4% of solid magnesium oxide is added.
The invention has the beneficial effects that:
1. the invention relates to a preparation method of modified polyol ester aviation lubricating oil, which uses metallic cobalt and metallic manganese to modify solid super acid catalyst ZrO 2 -Al 2 O 3 The solid catalyst has higher catalytic activity, and has the advantages of easy separation from products, simple preparation method and the like. Al (Al) 2 O 3 The specific surface area of the solid super acid is larger, and the special coordination of the surface atoms can generate the forms of different acid properties of the corresponding solid super acid. To ZrO 2 The addition of a small amount of Al can significantly improve the isomerization performance of the catalyst. And the metal cobalt and the metal manganese have synergistic effect, so that the tetragonal ZrO 2 Is stable at room temperature, so that the activity of the catalyst is improved.
2. The invention uses p-chlorobenzoic acid to modify the trimethylol phosphorus oxide, and the modified trimethylol phosphorus oxide can obviously improve the antiwear performance and has better lubricity and biodegradability. The benzene ring has a large pi bond sharing electrons, and the rigid molecules contained in the benzene ring have excellent antiwear performance in lubrication, so that the extreme pressure antiwear performance of the lubricant in use of mechanical parts can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a ZrO of the invention 2 -Al 2 O 3 SEM images at 1 μm magnification of (a).
FIG. 2 is a SEM image at 500nm magnification of a super solid acid catalyst modified with metallic cobalt and metallic manganese according to the present invention.
FIG. 3 is a graph showing the effect of the addition of different amounts of modified super solid acid catalyst on the esterification rate of polyol ester type aviation lubricants of example 2 and comparative examples 2-6 of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present patent.
Example 1
S1、2g Al(NO 3 ) 3 .9H 2 The volume ratio of O dissolved in the water is 1:1, adding 0.2g of sodium citrate into deionized water and ethanol solution, mixing and stirring for 15min, transferring into a high-pressure reaction kettle, reacting for 24h at 200 ℃, naturally cooling to room temperature, centrifuging and drying to obtain spherical Al 2 O 3 A carrier;
s2, weighing 0.4g of the spherical Al prepared in the step S1 2 O 3 Carrier, adding volume ratio of 10:1 and deionized water, stirring for 8 hours, continuously stirring and slowly dripping 15mL of zirconium n-butoxide, carrying out ultrasonic treatment until complete hydrolysis, transferring the suspension to a polytetrafluoroethylene high-pressure reaction kettle, heating in a water bath at 170 ℃ for 20 hours, naturally cooling, centrifuging and drying to obtain a solidSuper strong catalyst ZrO 2 -Al 2 O 3 ；
S3, adding 15mL of 0.75mol/L (NH) into 1g of the solid super catalyst prepared in the step S2 4 ) 2 S 2 O 8 Stirring the solution for 10min, and centrifugally drying to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 Will S 2 O 8 2- /ZrO 2 -Al 2 O 3 And the doping proportion of 1% by mass is 1:1, adding metal cobalt and metal manganese into 30mL of deionized water, soaking for 6h, drying and roasting to obtain a metal cobalt and metal manganese modified solid super acid catalyst;
s4, weighing the following components in a molar ratio of 1:1.5 (Guangzhou Hijia chemical Co., ltd.) and p-chlorobenzoic acid are placed in a round bottom flask, and after being uniformly mixed, the mixture is preheated, and then is continuously heated to 200 ℃ under the vacuum condition, and reacted for 8 hours, and after the reaction is finished, the modified trimethylol phosphorus oxide is obtained;
s5, weighing the following components in a molar ratio of 3:1.2, placing modified trimethylol phosphorus oxide and oleic acid (Ara Ding Huagong Co., ltd.) in a four-necked flask, adding a solid super acid catalyst modified by metallic cobalt and metallic manganese prepared in 1% S3, uniformly mixing, keeping the vacuum degree at 0.09MPa, and continuously reacting for 8 hours at 180 ℃ to obtain modified crude ester;
s6, placing the modified crude ester obtained in the step S3 into a four-necked flask, then adding 4% of solid magnesium oxide, heating and stirring, reacting for 4 hours at 60 ℃, and centrifugally separating to obtain the modified polyol ester lubricating oil.
Comparative example 1 in step S3, only 1% by mass of metallic cobalt was added, and the rest was the same as in example 1.
Comparative example 2 in step S3, only 1% by mass of metallic manganese was added, and the rest was the same as in example 1.
List one
| Project | Comparative example 1 | Comparative example 2 | Example 1 |
| Esterification rate (%) | 75.8％ | 69.9％ | 90.1％ |
Table I shows the effect of adding 1% by mass of different transition metals on the esterification rate of polyol ester aviation lubricants. FIG. 1 is ZrO 2 -Al 2 O 3 SEM image of (2), spherical Al 2 O 3 The specific surface area of the solid super acid is larger, and the special atomic coordination on the surface of the solid super acid can generate the forms of different acid properties of the corresponding solid super acid. And the second is an SEM image of a solid super acid catalyst modified by metallic cobalt and metallic manganese, the addition of the metallic cobalt and the metallic manganese does not change the morphology of the carrier, the specific surface of the solid super acid catalyst becomes larger, and trace metal elements are distributed on the surface active sites of the carrier. The addition of different transition metals has great influence on polyol ester aviation lubricating oil, S 2 O 8 2- /ZrO 2 -Al 2 O 3 Because of the unique macroporous structure, the reaction flow is smoother, the service life is greatly prolonged, and the catalyst has better activity. As can be seen from Table I, the catalyst for modification by adding 1% by mass of metallic cobalt was used to obtain an esterification rate of 75.8%, and the catalyst for modification by adding 1% by mass of metallic manganese was used to obtain an esterification rate of 69.9%. From the above, the doping ratio of 1% by mass is 1:1 and manganese metals are most active. This is due to ZrO 2 As a oneThe reducible metal oxide contains a large number of oxygen vacancies which are easy to capture negative electrons in the center of zirconia, and the metal cobalt and the metal manganese have synergistic effect, so that tetragonal phase is stable at room temperature, and the activity of the catalyst is improved.
Example 2
S1、2g Al(NO 3 ) 3 .9H 2 The volume ratio of O dissolved in the water is 1:1, adding 0.2g of sodium citrate into deionized water and ethanol solution, mixing and stirring for 15min, transferring into a high-pressure reaction kettle, reacting for 24h at 200 ℃, naturally cooling to room temperature, centrifuging and drying to obtain spherical Al 2 O 3 A carrier;
s2, weighing 0.4g of the spherical Al prepared in the step S1 2 O 3 Carrier, adding volume ratio of 10:1 and deionized water, stirring for 8 hours, continuously stirring and slowly dripping 15mL of zirconium n-butoxide, carrying out ultrasonic treatment until complete hydrolysis, transferring the suspension to a polytetrafluoroethylene high-pressure reaction kettle, heating in a water bath at 170 ℃ for 20 hours, naturally cooling, centrifuging and drying to obtain a solid super-strong catalyst ZrO 2 -Al 2 O 3 ；
S3, adding 15mL of 0.75mol/L (NH) into 1g of the solid super catalyst prepared in the step S2 4 ) 2 S 2 O 8 Stirring the solution for 10min, and centrifugally drying to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 Will S 2 O 8 2- /ZrO 2 -Al 2 O 3 And the doping proportion of 1% by mass is 1:1, adding metal cobalt and metal manganese into 30mL of deionized water, soaking for 6h, drying and roasting to obtain a metal cobalt and metal manganese modified solid super acid catalyst;
s4, weighing the following components in a molar ratio of 1:1.5 (Guangzhou Hijia chemical Co., ltd.) and p-chlorobenzoic acid are placed in a round bottom flask, and after being uniformly mixed, the mixture is preheated, and then is continuously heated to 200 ℃ under the vacuum condition, and reacted for 8 hours, and after the reaction is finished, the modified trimethylol phosphorus oxide is obtained;
s5, weighing the following components in a molar ratio of 3:1.2, placing modified trimethylol phosphorus oxide and oleic acid (Ara Ding Huagong Co., ltd.) in a four-necked flask, adding a solid super acid catalyst modified by metallic cobalt and metallic manganese prepared in 1% S3, uniformly mixing, keeping the vacuum degree at 0.09MPa, and continuously reacting for 8 hours at 180 ℃ to obtain modified crude ester;
s6, placing the modified crude ester obtained in the step S3 into a four-necked flask, then adding 4% of solid magnesium oxide, heating and stirring, reacting for 4 hours at 60 ℃, and centrifugally separating to obtain the modified polyol ester lubricating oil.
Comparative example 3 the same procedure as in example 2 was followed except that 0.6% of a solid super acid catalyst modified with metallic cobalt and metallic manganese was added in step S5.
Comparative example 4 the same procedure as in example 2 was followed except that 0.8% of a solid super acid catalyst modified with metallic cobalt and metallic manganese was added in step S5.
Comparative example 5 the procedure of example 2 was followed except that 1.2% of a solid superacid catalyst modified with metallic cobalt and metallic manganese was added in step S5.
Comparative example 6 the same procedure as in example 2 was followed except that 1.4% of a solid superacid catalyst modified with metallic cobalt and metallic manganese was added in step S5.
And thirdly, the influence of the dosage of the solid super acidic catalyst modified by the metallic cobalt and the metallic manganese on the esterification rate of polyol ester type aviation lubricating oil. It can be seen from the figure that the esterification rate of the reactant is highest when the amount of the modified solid super acid catalyst is 1%, and conversely, the esterification rate of the reactant is lowered when the amount of the modified solid super acid catalyst is higher than 1%. This is probably because the esterification reaction is a reversible reaction, and the catalyst can catalyze not only the forward reaction but also the reverse reaction of the reaction to accelerate, and when the proportion of the catalyst is too high, the forward catalysis effect is not increased with the increase of the catalyst, but the reverse reaction proceeds. In summary, the catalyst should be controlled to 1% most suitably and the esterification rate is highest.
Example 3
S1、2g Al(NO 3 ) 3 .9H 2 The volume ratio of O dissolved in the water is 1:1 to a solution of deionized water and ethanol, 0.2g of lemon was addedSodium carbonate is mixed and stirred for 15min, then transferred into a high-pressure reaction kettle for reaction for 24h at 200 ℃, then naturally cooled to room temperature, centrifugally dried, and spherical Al is obtained 2 O 3 A carrier;
s2, weighing 0.4g of the spherical Al prepared in the step S1 2 O 3 Carrier, adding volume ratio of 10:1 and deionized water, stirring for 8 hours, continuously stirring and slowly dripping 15mL of zirconium n-butoxide, carrying out ultrasonic treatment until complete hydrolysis, transferring the suspension to a polytetrafluoroethylene high-pressure reaction kettle, heating in a water bath at 170 ℃ for 20 hours, naturally cooling, centrifuging and drying to obtain a solid super-strong catalyst ZrO 2 -Al 2 O 3 ；
S3, adding 15mL of 0.75mol/L (NH) into 1g of the solid super catalyst prepared in the step S2 4 ) 2 S 2 O 8 Stirring the solution for 10min, and centrifugally drying to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 Will S 2 O 8 2- /ZrO 2 -Al 2 O 3 And the doping proportion of 1% by mass is 1:1, adding metal cobalt and metal manganese into 30mL of deionized water, soaking for 6h, drying and roasting to obtain a metal cobalt and metal manganese modified solid super acid catalyst;
s4, weighing the following components in a molar ratio of 1:1.5 (Guangzhou Hijia chemical Co., ltd.) and p-chlorobenzoic acid are placed in a round bottom flask, and after being uniformly mixed, the mixture is preheated, and then is continuously heated to 200 ℃ under the vacuum condition, and reacted for 8 hours, and after the reaction is finished, the modified trimethylol phosphorus oxide is obtained;
s5, weighing the following components in a molar ratio of 3:1.2, placing modified trimethylol phosphorus oxide and oleic acid (Ara Ding Huagong Co., ltd.) in a four-necked flask, adding a solid super acid catalyst modified by metallic cobalt and metallic manganese prepared in 1% S3, uniformly mixing, keeping the vacuum degree at 0.09MPa, and continuously reacting for 8 hours at 180 ℃ to obtain modified crude ester;
s6, placing the modified crude ester obtained in the step S3 into a four-necked flask, then adding 4% of solid magnesium oxide, heating and stirring, reacting for 4 hours at 60 ℃, and centrifugally separating to obtain the modified polyol ester lubricating oil.
Comparative example 7 the molar ratio added in step S4 was 2:1 and p-chlorobenzoic acid, the remainder being the same as in example 3.
Comparative example 8 the molar ratio added in step S4 was 1:2 and p-chlorobenzoic acid, the remainder being the same as in example 3.
Watch II
| Project | Comparative example 7 | Example 3 | Comparative example 8 |
| Esterification rate (%) | 50.2％ | 89.6％ | 67.8％ |
| Average value of friction coefficient | 0.044 | 0.031 | 0.053 |
And the second table is the influence of adding the trimethylol phosphorus oxide and p-chlorobenzoic acid with different mole ratios on the esterification rate and friction coefficient of the aviation lubricating oil. As the amount of p-chlorobenzoic acid increases, the viscosity of the lubricating oil becomes greater. It can be seen from the table that the esterification rate and the friction coefficient of the aviation lubricating oil did not increase with increasing amounts of p-chlorobenzoic acid. And found that when the molar ratio of trimethylol phosphorus oxide to p-chlorobenzoic acid is 1:2, the fluidity is deteriorated and the average value of the friction coefficient is increased; when the mole ratio of the trimethylol phosphorus oxide to the p-chlorobenzoic acid is 2: in the case of 1, the esterification rate is relatively low, and the average value of friction coefficients is relatively low; but when the mole ratio of the trimethylol phosphorus oxide to the p-chlorobenzoic acid is 1:1.5, the esterification rate reaches 89.6%, the fluidity is good, and the average value of friction coefficient is the lowest. This is probably due to the fact that the benzene ring has a large pi bond sharing electrons, and its rigid structure gives excellent antiwear properties in lubricants. In summary, the molar ratio of trimethylol phosphorus oxide to p-chlorobenzoic acid should be chosen to be 1:1.5, a better esterification rate and better friction properties.
Claims (7)
1. A preparation method of modified polyol ester aviation lubricating oil is characterized by comprising the following steps: the steps are as follows:
S1、2g～5g Al(NO 3 ) 3 ·9H 2 the volume ratio of O dissolved in the water is 1:1, adding 0.1 g-1 g sodium citrate into deionized water and ethanol solution, mixing and stirring for 15 min-30 min, transferring into a high-pressure reaction kettle, reacting for 18 h-24 h at 120-200 ℃, naturally cooling to room temperature, centrifuging and drying to obtain spherical Al 2 O 3 A carrier;
s2, weighing 0.4 g-1 g of spherical Al prepared in the step S1 2 O 3 Carrier, adding volume ratio of 10:1 and deionized water, stirring for 8-12 h, continuously stirring and slowly dripping 10-15 mL of zirconium n-butoxide, performing ultrasonic treatment until complete hydrolysis, transferring the suspension to a polytetrafluoroethylene high-pressure reaction kettle, heating in a water bath at 100-170 ℃ for 20-24 h, naturally cooling, centrifuging and drying to obtain the solid super-strong catalyst ZrO 2 -Al 2 O 3 ；
S3, adding 5 mL-15 mL0.75mol/L (NH) into 1 g-3 g of the solid super catalyst prepared in the step S2 4 ) 2 S 2 O 8 Stirring the solution for 10-15 min, and centrifugally drying to obtain S 2 O 8 2- /ZrO 2 -Al 2 O 3 Will S 2 O 8 2- /ZrO 2 -Al 2 O 3 The doping proportion of 1-3% by mass is 1:1, adding metal cobalt and metal manganese into 10-30 mL deionized water, soaking for 6-10 h, drying and roasting to obtain a metal cobalt and metal manganese modified solid super acid catalyst;
s4, weighing the following components in a molar ratio of 1:1.5, placing the trimethylol phosphorus oxide and p-chlorobenzoic acid into a round bottom flask, uniformly mixing, preheating, continuously heating to 150-220 ℃ under vacuum condition, reacting for 5-10 h, and obtaining modified trimethylol phosphorus oxide after the reaction is finished;
s5, weighing the following components in a molar ratio of 3:1.2, placing the modified trimethylol phosphorus oxide and oleic acid into a four-necked flask, adding a solid super acid catalyst modified by metal cobalt and metal manganese prepared in 0.9% -1.1% S3, uniformly mixing, keeping the vacuum degree at 0.09MPa, and continuously reacting for 8-10 h at 180-200 ℃ to obtain modified crude ester;
s6, placing the modified crude ester obtained in the step S3 into a four-necked flask, then adding 4% -6% of solid magnesium oxide, heating and stirring, reacting for 2-4 hours at 60-80 ℃, and centrifuging to obtain the modified polyol ester lubricating oil.
2. The method for preparing the modified polyol ester aviation lubricating oil according to claim 1, wherein the method comprises the following steps: the reaction is carried out in the step S1 in a high-pressure reaction kettle at 200 ℃ for 24 hours.
3. The method for preparing the modified polyol ester type aviation lubricating oil according to claim 1 or 2, wherein the method comprises the following steps of: the reaction product in the step S2 is heated in a water bath at 170 ℃ for 20 hours.
4. The method for preparing the modified polyol ester aviation lubricating oil according to claim 1, wherein the method comprises the following steps: in the step S3, a doping ratio of 1% by mass is added as 1:1, metallic cobalt and metallic manganese.
5. The method for preparing the modified polyol ester aviation lubricating oil according to claim 1, wherein the method comprises the following steps: and in the step S4, the temperature is continuously increased to 200 ℃ under the vacuum condition, and the reaction is carried out for 8 hours.
6. The method for preparing the modified polyol ester aviation lubricating oil according to claim 1, wherein the method comprises the following steps: and in the step S5, adding 1% of the solid super acid catalyst modified by the metallic cobalt and the metallic manganese prepared in the step S3.
7. The method for preparing the modified polyol ester aviation lubricating oil according to claim 1, wherein the method comprises the following steps: in the step S6, 4% of solid magnesium oxide is added.
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