CN109161425B - Lubricating oil additive and preparation method thereof - Google Patents
Lubricating oil additive and preparation method thereof Download PDFInfo
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- CN109161425B CN109161425B CN201810925638.4A CN201810925638A CN109161425B CN 109161425 B CN109161425 B CN 109161425B CN 201810925638 A CN201810925638 A CN 201810925638A CN 109161425 B CN109161425 B CN 109161425B
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 68
- 239000000654 additive Substances 0.000 title claims abstract description 55
- 230000000996 additive effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011259 mixed solution Substances 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000502 dialysis Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 238000010790 dilution Methods 0.000 claims abstract description 4
- 239000012895 dilution Substances 0.000 claims abstract description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 13
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 150000005837 radical ions Chemical class 0.000 claims 1
- 230000001050 lubricating effect Effects 0.000 abstract description 9
- -1 cerium ions Chemical class 0.000 description 16
- 229910052684 Cerium Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003879 lubricant additive Substances 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/20—Compounds containing nitrogen
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
-
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
-
- 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
- C10N2030/04—Detergent property or dispersant property
-
- 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
-
- 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
-
- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/04—Oxidation, e.g. ozonisation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a lubricating oil additive and a preparation method thereof, belonging to the field of lubricating oil. The preparation method of the lubricating oil additive comprises the following steps: adding graphene into the first oxidation solution, and sequentially performing first oxidation treatment, dilution, filtration and drying to obtain an intermediate; adding the intermediate into a second oxidation solution, and sequentially carrying out second oxidation treatment, centrifugation, acid washing, dialysis and freeze drying to obtain graphene oxide; placing graphene oxide in a mixed solution of water and ethanol, and performing first ultrasonic operation to obtain a first mixed solution; putting cerium nitrate hexahydrate in a mixed solution of water and ethanol, and obtaining a second mixed solution after a first stirring operation; dripping the second mixed solution into the first mixed solution, and performing second stirring operation and second ultrasonic operation to obtain a third mixed solution; and adding sodium hydroxide into the third mixed solution, reacting at a preset temperature after a third stirring operation, and washing with water and ethanol to obtain the lubricating oil additive with no pollution and good lubricating effect.
Description
Technical Field
The invention relates to the field of lubricating oil, in particular to a lubricating oil additive and a preparation method thereof.
Background
Friction is an inevitable natural phenomenon, and frictional wear shortens the service life of mechanical equipment and increases power consumption. The friction can be reduced by adding lubricating oil, and the friction and the abrasion can be reduced. With the comprehensive adjustment of industrial structures in China, new equipment, instruments and process systems widely use a large amount of lubricating oil, and the requirement on the lubricating performance of the lubricating oil is higher and higher. The lubricating properties of the lubricating oil can be adjusted by adding appropriate additives to the lubricating oil. In view of the above, it is necessary to provide a lubricating oil additive which has good applicability and can improve the lubricating performance of lubricating oil.
The related art provides a lubricating oil additive which contains harmful elements such as phosphorus, sulfur, chlorine and the like, and causes harm to the environment and human health. Further, the lubricating oil containing the lubricating oil additive is inferior in lubricating effect.
Disclosure of Invention
The embodiment of the invention provides a lubricating oil additive and a preparation method thereof, which can solve the technical problems. The specific technical scheme is as follows:
in one aspect, embodiments of the present invention provide a preparation method of a lubricating oil additive, where the preparation method includes:
adding graphene into the first oxidation solution, and sequentially performing first oxidation treatment, dilution, filtration and drying to obtain an intermediate;
adding the intermediate into a second oxidation solution, and sequentially carrying out second oxidation treatment, centrifugation, acid washing, dialysis and freeze drying to obtain graphene oxide;
placing the graphene oxide in a mixed solution of water and ethanol, and performing first ultrasonic operation to obtain a first mixed solution;
putting cerium nitrate hexahydrate in a mixed solution of water and ethanol, and obtaining a second mixed solution after a first stirring operation;
dripping the second mixed solution into the first mixed solution, and performing second stirring operation and second ultrasonic operation to obtain a third mixed solution;
and adding sodium hydroxide into the third mixed solution, reacting at a preset temperature after a third stirring operation, and washing with water and ethanol to obtain the lubricating oil additive.
In one possible design, the first oxidizing fluid includes: concentrated sulfuric acid, potassium peroxodisulfate, phosphorus pentoxide and water;
the volume ratio of the mixed solution of the potassium peroxydisulfate, the phosphorus pentoxide and the water to the concentrated sulfuric acid is 1: 4-5;
the mass ratio of the potassium peroxodisulfate to the phosphorus pentoxide is 1-3: 1-3.
In one possible design, the first oxidation process includes:
and performing magnetic stirring for 5.8-6.5 h under the condition of a water bath at 78-82 ℃.
In one possible design, the second oxidizing liquid includes: concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and water.
In one possible design, the second oxidation treatment includes:
adding the intermediate into 110-120 mL of concentrated sulfuric acid, uniformly stirring, adding 13-18 g of potassium permanganate at the temperature of 8-12 ℃, reacting at the temperature of 33-38 ℃ for 1.8-2.2 h, adding 220-240 mL of water, reacting at the temperature of 40-50 ℃ for 1.8-2.2 h, finally adding 680-720 mL of water and 12-13 mL of hydrogen peroxide, and standing for one day.
In one possible design, the first mixed liquor includes: 72-77 mg of the graphene oxide, 7.2-7.7 mL of ethanol and 28-32 mL of water.
In one possible design, the second mixed liquor includes: 72-77 mg of the cerium nitrate hexahydrate, 7.2-7.7 mL of ethanol and 28-32 mL of water.
In a possible design, the time of the second stirring operation and the time of the second ultrasonic operation are both 28-32 min.
In one possible design, the preset temperature is 138 ℃ to 142 ℃;
and the reaction time at the preset temperature is 11-13 h.
In another aspect, embodiments of the present invention provide a lubricating oil additive prepared by the method for preparing any one of the above-mentioned lubricating oil additives.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
the preparation method of the lubricating oil additive provided by the embodiment of the invention is simple, and a large amount of oxygen-containing (carbonyl) functional groups are formed on the surface of graphene by performing first oxidation treatment and second oxidation treatment on the graphene, so that the graphene and cerium ions in cerium nitrate hexahydrate can form a composite material, namely the lubricating oil additive. The graphene oxide in the lubricating oil additive has good dispersion stability in water and most polar organic solvents, and cerium ions adsorbed on the graphene oxide can improve the lubricating effect of the lubricating oil. In addition, the lubricating oil additive does not contain harmful elements such as phosphorus, sulfur, chlorine and the like, and is harmless to the environment and human health.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a lubricating oil additive according to an embodiment of the present invention;
FIG. 2a is a morphology of graphene oxide under a transmission electron microscope provided by an embodiment of the present invention;
FIG. 2b is a diagram of the morphology of cerium oxide under a transmission electron microscope provided by an embodiment of the present invention;
FIG. 3 is an X-ray diffraction pattern of the lubricating oil additive provided in example 1;
fig. 4 is a raman spectrum of graphene oxide and a lubricant additive provided in example 1.
Detailed Description
Unless defined otherwise, all technical terms used in the examples of the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
In one aspect, the embodiment of the present invention provides a preparation method of a lubricating oil additive, as shown in fig. 1, the preparation method includes:
And 102, adding the intermediate into a second oxidation solution, and sequentially carrying out second oxidation treatment, centrifugation, acid washing, dialysis and freeze drying to obtain the graphene oxide.
103, placing the graphene oxide in a mixed solution of water and ethanol, and performing a first ultrasonic operation to obtain a first mixed solution.
And step 104, placing the cerous nitrate hexahydrate in a mixed solution of water and ethanol, and obtaining a second mixed solution after the first stirring operation.
And 105, dripping the second mixed solution into the first mixed solution, and performing second stirring operation and second ultrasonic operation to obtain a third mixed solution.
And step 106, adding sodium hydroxide into the third mixed solution, reacting at a preset temperature after a third stirring operation, and washing with water and ethanol to obtain the lubricating oil additive.
The preparation method of the lubricating oil additive provided by the embodiment of the invention is simple, and a large amount of oxygen-containing (carbonyl) functional groups are formed on the surface of graphene by performing first oxidation treatment and second oxidation treatment on the graphene, so that the graphene and cerium ions in cerium nitrate hexahydrate can form a composite material, namely the lubricating oil additive. The graphene oxide in the lubricating oil additive has good dispersion stability in water and most polar organic solvents, and cerium ions adsorbed on the graphene oxide can improve the lubricating effect of the lubricating oil. In addition, the lubricating oil additive does not contain harmful elements such as phosphorus, sulfur, chlorine and the like, and is harmless to the environment and human health.
The preparation method of the lubricating oil additive provided by the embodiment of the invention is described in detail as follows:
in step 101, a plurality of first oxidation solutions can be used, and the following examples are given in consideration of the good effect of preliminary oxidation of graphene: the first oxidizing liquid comprises: concentrated sulfuric acid, potassium peroxodisulfate, phosphorus pentoxide and water; the volume ratio of the mixed solution of potassium peroxydisulfate, phosphorus pentoxide and water to concentrated sulfuric acid is 1:4 to 5, for example, 1:4, 1:4.3, 1:4.5, 1:4.7, 1:5, etc.; the mass ratio of potassium peroxodisulfate to phosphorus pentoxide is 1-3: 1-3, and may be, for example, 1:1, 1:2, 1:3, 2:1, 3:2, etc.
The amount of water may be such that potassium peroxodisulfate and phosphorus pentoxide are dissolved. H in concentrated sulfuric acid2SO4Is greater than 70 percent. The mass ratio between the graphene and the first oxidizing solution is not particularly limited, and the graphene may be completely immersed in the first oxidizing solution.
So set up, under the prerequisite of saving raw materials, can carry out preliminary oxidation to the surface of graphite alkene, clear away the protection film and the impurity on its surface to the oxidation forms partial oxygen-containing radical, does benefit to and forms a large amount of oxygen-containing radicals in the second oxidation treatment process.
As an example, the first oxidation process includes: and performing magnetic stirring for 5.8-6.5 h under the condition of a water bath at 78-82 ℃.
For example, the temperature of the water bath may be 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃ and the like, and the time of magnetic stirring may be 5.8h, 5.9h, 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h and the like.
Therefore, the oxidation reaction on the surface of the graphene is facilitated.
After the first oxidation treatment, 480 to 520mL of water may be added to the mixed solution of graphene and the first oxidation solution to dilute the mixed solution. Therefore, impurities on the surface of the graphene subjected to the first oxidation treatment can be removed, and an intermediate can be obtained through filtering and separation.
The drying temperature may be 38 to 43 ℃, for example, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃ or the like, in consideration of the fact that the drying temperature does not affect the performance of the intermediate and does not deteriorate the intermediate.
In step 102, the second oxidizing solution may be selected from a plurality of solutions, and in view of being capable of sufficiently oxidizing the intermediate to form a large number of oxygen-containing functional groups on the surface thereof to facilitate adsorption of cerium ions on the oxygen-containing functional groups, the following examples are given:
the second oxidizing solution comprises: concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and water.
As an example, the second oxidation treatment includes:
adding the intermediate into 110-120 mL of concentrated sulfuric acid, uniformly stirring, adding 13-18 g of potassium permanganate at the temperature of 8-12 ℃, reacting at the temperature of 33-38 ℃ for 1.8-2.2 h, adding 220-240 mL of water, reacting at the temperature of 40-50 ℃ for 1.8-2.2 h, finally adding 680-720 mL of water and 12-13 mL of hydrogen peroxide, and standing for one day.
It should be noted that H in concentrated sulfuric acid2SO4Is greater than 70 percent. The mass ratio between the intermediate and the second oxidizing solution is not particularly limited, and the intermediate can be completely immersed in the second oxidizing solution. The mass concentration of the hydrogen peroxide can be 20-50%.
The volume of the concentrated sulfuric acid may be 110mL, 111mL, 113mL, 114mL, 115mL, 116mL, 117mL, 118mL, 119mL, 120mL, or the like. Potassium permanganate may be added at 8 to 12 ℃ and at 8 ℃ to 9 ℃ and 10 ℃ to 11 ℃ and 12 ℃ to sufficiently dissolve the potassium permanganate, for example, by adding 13g, 14g, 15g, 16g, 17g, 18g and the like.
The reaction is carried out for 1.8h, 1.9h, 2h, 2.1h, 2.2h and the like under the conditions of 33-38 ℃, for example, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃ and the like, and potassium permanganate enables a large amount of oxygen-containing functional groups to be generated on the surface of the intermediate.
Further adding 220 to 240mL of water, for example, 220mL, 225mL, 230mL, 235mL, 240mL, etc., reacting at 40 to 50 ℃ for 1.8 to 2.2 hours, for example, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, etc., and reacting for 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, etc. Thus, potassium permanganate is further allowed to react sufficiently with the surface of the intermediate to form a large amount of oxygen-containing functional groups.
Finally, 680-720 mL of water and 12-13 mL of hydrogen peroxide are added, and the mixture is kept stand for one day. The amount of water added may be 680mL, 685mL, 690mL, 695mL, 700mL, 705mL, 710mL, 715mL, 720mL, or the like. Therefore, the residual oxidant in the mixed liquid can be reduced by the hydrogen peroxide, and pure graphene oxide can be obtained conveniently.
After the second oxidation treatment, the mixture is centrifuged, acid washing is carried out by using hydrochloric acid with the mass fraction of 10%, then the centrifuged substance is filled into a dialysis membrane, and the membrane is soaked in water for one week, and then freeze-dried and frozen for a plurality of times, so that the pure graphene oxide product is obtained.
Therefore, the graphene oxide powder with high purity can be prepared, and the preparation of the lubricating oil additive is facilitated.
In step 103, the first mixed solution may include: 72-77 mg of graphene oxide, 7.2-7.7 mL of ethanol and 28-32 mL of water.
The mass of the graphene oxide may be 72mg, 73mg, 74mg, 75mg, 76mg, 77mg, or the like. The volume of ethanol can be 7.2mL, 7.3mL, 7.4mL, 7.5mL, 7.6mL, 7.7mL, and the like. The volume of water may be 28mL, 29mL, 30mL, 31mL, 32mL, etc.
The mass or volume of each component is set in such a way, so that the graphene oxide can be fully dispersed in water and ethanol.
In step 104, the second mixed liquor may include: 72-77 mg of cerous nitrate hexahydrate, 7.2-7.7 mL of ethanol and 28-32 mL of water.
Wherein, the mass of the cerous nitrate hexahydrate can be 72mg, 73mg, 74mg, 75mg, 76mg, 77mg and the like. The volume of ethanol can be 7.2mL, 7.3mL, 7.4mL, 7.5mL, 7.6mL, 7.7mL, and the like. The volume of water may be 28mL, 29mL, 30mL, 31mL, 32mL, etc.
The mass or volume of each component is set in such a way, so that cerium nitrate hexahydrate is favorably and fully dissolved in water and ethanol.
In step 105, dropping the second mixed solution into the first mixed solution facilitates fully adsorbing cerium ions in the second mixed solution on oxygen-containing functional groups on the graphene oxide. Through the second stirring operation and the second ultrasonic operation, cerium ions and graphene oxide can be uniformly mixed.
It can be understood that the number of moles of cerium ions is controlled to be less than or equal to the number of oxygen-containing functional groups on the graphene oxide, so that the cerium ions are sufficiently adsorbed on the oxygen-containing functional groups of the graphene oxide without wasting a cerium ion raw material.
The following example is given in view of not affecting the performance of graphene oxide and cerium ions, and saving energy:
the time of the second stirring operation and the time of the second ultrasonic operation are both 28-32 min, and for example, may be 28min, 29min, 30min, 31min, 32min, and the like.
In step 106, sodium hydroxide is added to the third mixed solution to neutralize the acid ions in the third mixed solution.
The molar ratio of the sodium hydroxide to the cerium ions (cerium nitrate hexahydrate) added to the third mixed solution may be 1:1 to 3:1, and may be, for example, 1:1, 1:2, 1:3, or the like.
In consideration of sufficient reaction between the graphene oxide and the cerium ions, the preset temperature is, as an example, 138 ℃ to 142 ℃, and may be, for example, 138 ℃, 139 ℃, 140 ℃, 141 ℃, 142 ℃, or the like. The reaction time at the preset temperature is 11-13 h, for example, 11h, 11.5h, 12h, 12.5h, 13h, etc.
Finally, impurities are removed through water washing and ethanol washing to obtain the pure lubricating oil additive.
In another aspect, embodiments of the present invention provide a lubricating oil additive prepared by any one of the above-mentioned methods of preparing a lubricating oil additive.
The graphene oxide in the lubricating oil additive has good dispersion stability in water and most polar organic solvents, and cerium ions adsorbed on the graphene oxide can improve the lubricating effect of the lubricating oil. In addition, the lubricating oil additive does not contain harmful elements such as phosphorus, sulfur, chlorine and the like, and is harmless to the environment and human health.
The present invention will be further described below by way of specific examples.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Example 1
The embodiment provides a lubricating oil additive, which is prepared by the following method:
adding 3g of graphene into a mixed solution of 12.5mL of concentrated sulfuric acid, 2.5mL of potassium peroxodisulfate, phosphorus pentoxide and water, magnetically stirring and reacting for 6h under the condition of water bath at 80 ℃, then adding 500mL of water into the mixed solution for diluting, filtering, and finally drying at 40 ℃ to obtain an intermediate.
Adding the intermediate into 115mL of concentrated sulfuric acid, uniformly stirring in a water bath at 0 ℃, controlling the temperature of the water bath to be 10 ℃, slowly adding 15g of potassium permanganate, reacting for 2h at 35 ℃, then adding 230mL of water, and reacting for 2h at 45 ℃. Finally 700mL of water and 12.5mL of hydrogen peroxide were added and left for one day. And centrifuging the mixture, washing with hydrochloric acid with the mass fraction of 10%, finally filling into a dialysis membrane, soaking in water for one week, and freeze-drying and freezing to obtain the graphene oxide.
Weighing 75mg of graphene oxide, placing the graphene oxide in 30mL of water and 7.5mL of ethanol, and performing first ultrasonic operation to obtain a first mixed solution. And weighing 75mg of cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate in 30mL of water and 7.5mL of ethanol, and performing second stirring operation to obtain a second mixed solution. And dripping the second mixed solution into the first mixed solution, and performing 30min second stirring operation and 30min second ultrasonic operation to obtain a third mixed solution. And (3) adding sodium hydroxide and cerium nitrate hexahydrate into the third mixed solution in a molar ratio of 1:1, uniformly stirring, finally pouring the mixed solution into a reaction kettle, reacting for 12 hours at 140 ℃, and washing with water and ethanol to obtain the lubricating oil additive provided by the embodiment.
Example 2
The embodiment provides a lubricating oil additive, which is prepared by the following method:
adding 3g of graphene into a mixed solution of 10mL of concentrated sulfuric acid, 2.5mL of potassium peroxodisulfate, phosphorus pentoxide and water, magnetically stirring and reacting for 5.8h under the condition of water bath at 78 ℃, then adding 500mL of water into the mixed solution for diluting, filtering, and finally drying at 40 ℃ to obtain an intermediate.
Adding the intermediate into 110mL of concentrated sulfuric acid, uniformly stirring in a water bath at 0 ℃, controlling the temperature of the water bath to be 10 ℃, slowly adding 13g of potassium permanganate, reacting at 33 ℃ for 1.8h, then adding 220mL of water, and reacting at 43 ℃ for 1.8 h. Finally 690mL of water and 12mL of hydrogen peroxide were added and left for one day. And centrifuging the mixture, washing with hydrochloric acid with the mass fraction of 10%, finally filling into a dialysis membrane, soaking in water for one week, and freeze-drying and freezing to obtain the graphene oxide.
Weighing 72mg of graphene oxide, placing the graphene oxide in 28mL of water and 7.2mL of ethanol, and performing first ultrasonic operation to obtain a first mixed solution. And weighing 72mg of cerous nitrate hexahydrate, putting the cerous nitrate hexahydrate in 29mL of water and 7.2mL of ethanol, and performing second stirring operation to obtain a second mixed solution. And dripping the second mixed solution into the first mixed solution, and performing 28min second stirring operation and 28min second ultrasonic operation to obtain a third mixed solution. And (3) adding sodium hydroxide and cerium nitrate hexahydrate into the third mixed solution in a molar ratio of 1:1, uniformly stirring, finally pouring the mixed solution into a reaction kettle, reacting for 11 hours at 138 ℃, and washing with water and ethanol to obtain the lubricating oil additive provided by the embodiment.
Example 3
The embodiment provides a lubricating oil additive, which is prepared by the following method:
adding 3g of graphene into a mixed solution of 12.5mL of concentrated sulfuric acid, 2.5mL of potassium peroxodisulfate, phosphorus pentoxide and water, magnetically stirring and reacting for 6.3h under the condition of water bath at 82 ℃, then adding 500mL of water into the mixed solution for diluting, filtering, and finally drying at 40 ℃ to obtain an intermediate.
Adding the intermediate into 120mL of concentrated sulfuric acid, uniformly stirring in a water bath at 0 ℃, controlling the temperature of the water bath to be 12 ℃, slowly adding 18g of potassium permanganate, reacting for 2.2h at 38 ℃, then adding 240mL of water, and reacting for 2.2h at 50 ℃. Finally, 720mL of water and 13mL of hydrogen peroxide were added and left for one day. And centrifuging the mixture, washing with hydrochloric acid with the mass fraction of 10%, finally filling into a dialysis membrane, soaking in water for one week, and freeze-drying and freezing to obtain the graphene oxide.
77mg of graphene oxide is weighed and placed in 32mL of water and 7.7mL of ethanol, and a first mixed solution is obtained after first ultrasonic operation. 77mg of cerous nitrate hexahydrate is weighed and placed in 32mL of water and 7.7mL of ethanol, and a second mixed solution is obtained after a second stirring operation. And dripping the second mixed solution into the first mixed solution, and performing 32min second stirring operation and 32min second ultrasonic operation to obtain a third mixed solution. And (3) adding sodium hydroxide and cerium nitrate hexahydrate into the third mixed solution in a molar ratio of 1:1, uniformly stirring, finally pouring the mixed solution into a reaction kettle, reacting for 13 hours at 142 ℃, and washing with water and ethanol to obtain the lubricating oil additive provided by the embodiment.
Application examples
The present application example evaluates the performance of the graphene oxide and the lubricant additive provided in example 1. The specific evaluation method comprises the following steps: (1) the morphology and structure of the graphene oxide and cerium oxide provided in example 1 were characterized using a high-resolution transmission electron microscope of type JEM-2100 (HR). See in particular fig. 2a and 2 b. Fig. 2a is a topographic map of graphene oxide prepared in example 1, which has a thin lamellar structure, is large, has a smooth surface, and contains many folds. FIG. 2b is a graph of cerium oxide having a plurality of dots. The two can be easily distinguished from each other from the topography maps of the two, and the later-stage observation of the topography map of the composite material of the graphene oxide lubricating oil additive is facilitated.
(2) The lubricating oil additive provided in example 1 was tested using an X-ray diffractometer model D/MAX2500 PC. An X-ray diffraction pattern for the lubricating oil additive provided in example 1 was obtained using a Cu-ka source with a data collection range of 5 ° to 90 °, as shown in figure 3. As can be seen from FIG. 3, the X-ray diffraction patterns exhibited diffraction peaks (001), (111), (200), (220), (311), (222), (400) and (420), and in contrast to JCPDS cards (NO.89-8436), the diffraction peaks exhibited in FIG. 3 all matched CeO2The appearance of a (001) diffraction peak in the crystal, X-ray diffraction pattern, due to the presence of Graphene Oxide (GO). No other diffraction peak is found, namely the XRD result is confirmedBy this method, CeO was successfully prepared2the/GO composite material is a lubricating oil additive.
(3) The graphene oxide and the lubricant additive provided in example 1 were tested by using a laser raman spectrometer of DXP type. Raman testing was performed by means of a Renishaw microscope system RM2000 with a 532nm 20mW Ar + laser. The specific map is shown in figure 4 in detail, and as can be seen from figure 4, the characteristic peak of the graphene oxide is 1343cm-1And 1602cm-1And the D band and the G band belong to graphene oxide respectively. Example 1 provides a lubricating oil additive at 456.89cm-1A characteristic peak occurs because cerium oxide is present in the composite. In addition, no other types of characteristic peaks were detected, consistent with the results of XRD analysis.
The above analysis shows that cerium ions are adsorbed on the oxygen-containing functional groups on graphene oxide to form CeO2The composite material can be used as a lubricating oil additive to be added into lubricating oil, and can effectively enhance the lubricating effect of the lubricating oil.
The above description is only an illustrative embodiment of the present invention, and should not be taken as limiting the scope of the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a lubricating oil additive, comprising:
adding graphene into the first oxidation solution, and sequentially performing first oxidation treatment, dilution, filtration and drying to obtain an intermediate;
adding the intermediate into a second oxidation solution, and sequentially carrying out second oxidation treatment, centrifugation, acid washing, dialysis and freeze drying to obtain graphene oxide;
placing the graphene oxide in a mixed solution of water and ethanol, and performing first ultrasonic operation to obtain a first mixed solution;
putting cerium nitrate hexahydrate in a mixed solution of water and ethanol, and obtaining a second mixed solution after a first stirring operation;
dripping the second mixed solution into the first mixed solution, and performing second stirring operation and second ultrasonic operation to obtain a third mixed solution;
and adding sodium hydroxide into the third mixed solution, reacting at a preset temperature after a third stirring operation, and washing with water and ethanol to obtain the lubricating oil additive, wherein the sodium hydroxide is used for neutralizing acid radical ions in the third mixed solution.
2. The method of claim 1, wherein the first oxidizing fluid comprises: concentrated sulfuric acid, potassium peroxodisulfate, phosphorus pentoxide and water;
the volume ratio of the mixed solution of the potassium peroxydisulfate, the phosphorus pentoxide and the water to the concentrated sulfuric acid is 1: 4-5;
the mass ratio of the potassium peroxodisulfate to the phosphorus pentoxide is 1-3: 1-3.
3. The method of claim 1, wherein the first oxidation treatment comprises:
and performing magnetic stirring for 5.8-6.5 h under the condition of a water bath at 78-82 ℃.
4. The method of preparing the lubricating oil additive according to claim 1, wherein the second oxidizing solution comprises: concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and water.
5. The method of preparing the lubricating oil additive according to claim 4, wherein the second oxidation treatment comprises:
adding the intermediate into 110-120 mL of concentrated sulfuric acid, uniformly stirring, adding 13-18 g of potassium permanganate at the temperature of 8-12 ℃, reacting at the temperature of 33-38 ℃ for 1.8-2.2 h, adding 220-240 mL of water, reacting at the temperature of 40-50 ℃ for 1.8-2.2 h, finally adding 680-720 mL of water and 12-13 mL of hydrogen peroxide, and standing for one day.
6. The method of any one of claims 1 to 4, wherein the first mixed solution comprises: 72-77 mg of the graphene oxide, 7.2-7.7 mL of ethanol and 28-32 mL of water.
7. The method of any one of claims 1 to 4, wherein the second mixed solution comprises: 72-77 mg of the cerium nitrate hexahydrate, 7.2-7.7 mL of ethanol and 28-32 mL of water.
8. The method for preparing the lubricating oil additive according to any one of claims 1 to 4, wherein the time of the second stirring operation and the time of the second ultrasonic operation are both 28 to 32 min.
9. The method for preparing the lubricating oil additive according to any one of claims 1 to 4, wherein the preset temperature is 138 ℃ to 142 ℃;
and the reaction time at the preset temperature is 11-13 h.
10. A lubricating oil additive, characterized in that the lubricating oil additive is prepared by the method for preparing a lubricating oil additive according to any one of claims 1 to 9.
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