CN106811265A - The preparation method of Graphene modification of lubricating oils, the product for obtaining and purposes - Google Patents
The preparation method of Graphene modification of lubricating oils, the product for obtaining and purposes Download PDFInfo
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- CN106811265A CN106811265A CN201610889159.2A CN201610889159A CN106811265A CN 106811265 A CN106811265 A CN 106811265A CN 201610889159 A CN201610889159 A CN 201610889159A CN 106811265 A CN106811265 A CN 106811265A
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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
- C10M125/02—Carbon; Graphite
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- Oil, Petroleum & Natural Gas (AREA)
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- Inorganic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a kind of preparation method of Graphene modification of lubricating oils, methods described includes adding graphite alkenes material dispersion liquid into substrate oil, and after emulsification, the water phase in removal emulsion obtains modification of lubricating oils.The present invention is added into substrate oil by will be dispersed with the aqueous solution of graphite alkenes material and emulsified, and the phase transfer that graphite alkenes material passes through microemulsified is transferred in substrate oil, obtains the modified lubricating oil of Graphene, and method is simple, efficiently, and feasibility is good.
Description
Technical field
The invention belongs to technical field of lubricating oil, the preparation method for being related to Graphene modification of lubricating oils, the product for obtaining and
Purposes.
Background technology
Fretting wear is the main cause for causing energy loss and equipment failure, and the energy that the whole world there are about 1/3~1/2 is damaged
Consumption is caused by friction, and the damage and failure of plant equipment and parts have about 80% to be caused by friction abrasion greatly, and
And the abominable accident of more than 50% mechanized equipment is all due to the excessive wear caused by lubrication failure.China by
The various materials of mechanical wear loss are up to hundreds of hundred million yuan.Therefore, control friction, it is to reduce energy to reduce abrasion and improve lubricating condition
Source is lost, and improves the important measures of plant equipment service life.Lubrication be with lubricator reduce friction surface between frictional force or
The effect of other surfaces failure mode.Lubricating oil plays reduction friction, reduces and wear and tear, cool, preventing rotten candle, transmission dynamic
Power, vibration damping, insulation, cleaning, sealing etc. are acted on, and reduce energy ezpenditure and environmental pollution that friction belt is come, therefore lubricating oil is claimed
It is the blood of machine operation.
Lubricating oil is made up of base oil and additive, and additive can dramatically increase the antiwear and friction reduction property of lubricating oil, tradition
Lube oil additive be generally sulphur phosphorous antiwear additive, the use of these additives can not only corrode friction pair material can also be produced
Exhaust emission environment.
Therefore, the additive tool for finding a kind of novel environment friendly high-efficiency is of great significance.In recent years, with nanometer section
The development of skill, nano material is increasingly extensive as the research of lube oil additive, such as CN1632081A using Nano diamond as
Lube oil additive, significantly improves the abrasion resistance of lubricating oil.CN105316089A uses nano-silicon nitride or the oxygen of nanometer four
Change three-iron as lube oil additive, obtain anti-oxidant, wear-resistant lubricating oil.
Graphene has the unrivaled advantage of many other materials as a kind of novel nano carbon material, such as has good
Mechanical property, thermal conductivity high etc., special two-dimensional slice structure is conducive to reducing and rubs, therefore Graphene is a kind of preferable
Lube oil additive.But Graphene is poor with the compatibility of lubricating oil, Graphene due to surface potential energy higher easily
Reunion is produced, it is not good so as to cause its dispersiveness in lubricating oil, it is also easy to produce layering and precipitates, final influence lubricating oil
Performance.How to solve dispersiveness of the Graphene in lubricating oil is a problem demanding prompt solution.
In order that Graphene has more preferable lipophile, prior art is processed repeatedly using surfactant or coupling agent etc.
Graphene powder, but these techniques are often more complicated, and it is relatively costly.CN101812351A disclose it is a kind of based on individual layer or
The dilute lube oil additive of several layers of graphite, Graphene is modified by surface, in conjunction with dispersant, can have in base oil
Excellent stability and dispersiveness, but its complex process.Usage cycles are short, lubricity for conventional lubrication oil for CN105176628A
The problems such as poor and existing Nanoparticles As Lubricating Oil Additives are reunited and precipitated, disclose a kind of profit of graphene-supported nano-oxide
The preparation method of lubricating oil, although improve greasy property and stability, but either graphene oxide and nano-oxide
Compound prepare or the compound oleophylic be modified will will be relatively costly by the technical process of HTHP, obtain
Lipophilic graphene nano complex oxide be scattered in base oil will also be by compound additive.CN102911762A is disclosed
A kind of high-termal conductivity lubricating oil and preparation method thereof, by the fluorine that adulterated between graphene layer；CN103450967B discloses a kind of oil
Dissolubility nano-graphite and preparation method thereof the, using-OH in substitution reaction and oxidation nanometer graphite ,-COOH group reaction, to it
Oil-soluble is carried out to be modified.
There is technique to the method for adding Graphene in lubricating oil or lube base oil and improving performance and answer in prior art
Miscellaneous, energy consumption is big, high cost, or needs the problems such as adding dispersant, and this area needs to develop a kind of process is simple, divides without introducing
The method of the Graphene modification of lubricating oils of powder.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Graphene modification of lubricating oils, by the dispersion of graphite alkenes material
Liquid is added into substrate oil, and after emulsification, the water phase in removal emulsion obtains modification of lubricating oils.
Preferably, solvent is hydrophilic solvent in the graphite alkenes material dispersion liquid.
Preferably, the hydrophilic solvent includes water.
The effect of the hydrophilic solvent is for dispersed graphite alkenes material, therefore, it is possible to realize the molten of the purpose
Agent can be employed as the solvent of graphite alkenes material dispersion liquid, such as described solvent can also be DMF.
For graphite alkenes material, it is directly dispersing in exist in lubricating oil or base oil such as reunites, disperses unequal
Defect, realize it is dispersed relatively difficult, the present invention will disperse graphite alkenes material hydrophilic solution add to substrate oil in
When, water phase and oil phase are emulsified, and graphite alkenes material can realize the transfer from the opposite oil phase of water, complete graphite alkenes material
It is dispersed in substrate oil.
For graphite alkenes material of the present invention can be understood as being dispersed in water with graphene sheet layer
The material of structure, for the graphite alkenes material, the present invention is not specifically limited, and what can be dispersed in water is miscellaneous with SP2
The material for changing carbon plate Rotating fields is used equally to the present invention.
The specific graphite alkenes material includes Graphene, biomass Graphene, graphene oxide, Graphene derivative
Any a kind or at least 2 kinds of mixing, the Graphene derivative includes the Graphene of element doping.
Wherein, can be that lamella is less for Graphene, such as less than 30 layers, less than 10 layers, or even fewer layers,
And the mixture of different Sheet Graphite alkene；Lamella is fewer, and agglomeration is more serious, it is therefore desirable to which its dispersion soln is surpassed
Sonication is suitably added dispersant, dispersant such as N- methyl-pyrrols compound (alkanone), neopelex
(SDBS), polyvinylpyrrolidone (PVP), anionic surfactant：Sodium lignin sulfonate (SLS), addition is generally
Less than the 10% of Graphene content, or even less than 1%.
Wherein, biomass Graphene is to contain single-layer graphene, few layer graphene, graphite with biomass as prepared by raw material
Alkene nano-lamellar structure, and carried metal/nonmetallic compound, the number of plies are not more than 10 layers of two-dimensional nano Carbon Materials, or even can
Be more than on the basis of the carbon composite comprising graphitized charcoal, metal/non-metal compound；The biomass Graphene is also
Including the Graphene by being prepared to biomass resource hydrothermal carbonization method.
Preferably, the biomass Graphene uses the biomass Graphene of Jinan holy well company, i.e., with agriculture and forestry organic waste material
It is primary raw material, the carbon nanomaterial compound containing Graphene obtained by steps such as hydrolysis, catalytic treatment, heat treatments,
It is mainly characterized by containing Graphene, agraphitic carbon and non-carbon nonoxygen element, and the non-carbon nonoxygen element includes Fe, Si and Al unit
Element, the non-carbon nonoxygen element content is the 0.5wt%~6wt% of compound.If number of patent application is 201510819312.X
The product of preparation.The leading indicator of the biomass Graphene it is exemplary can be：Electrical conductivity ＞ 3000S/m, preferably ＞
5000S/m；Specific surface area ＞ 150m2/ g, preferably ＞ 300m2/g；Raman spectrum IG/ID ＞ 2, preferably ＞ 3；C/O ＞ 35.0.
Preferably, the Graphene derivative includes any 1 in element doping Graphene or functional group's graphite alkene thing
Kind or at least 2 kinds of combination.
Preferably, the element doping Graphene is including in metal-doped Graphene or nonmetal doping Graphene
Any a kind or at least 2 kinds of combination.
The metal-doped metallic element it is typical but non-limiting including potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium,
Any a kind or at least 2 kinds of combination in vanadium or cobalt.
The nonmetal doping Graphene it is typical but non-limiting including nitrogen, phosphorus, silicon, boron or oxygen in any 1
Kind or at least 2 kinds of combination.
Doped chemical in the element doping Graphene it is exemplary can be potassium and nitrogen combination, iron, titanium and silicon
Combination, the combination of vanadium, cobalt and phosphorus, gold, the combination of nickel and oxygen, the combination of nickel, chromium and vanadium, the combination of potassium, nitrogen and phosphorus, iron, potassium,
Combination of nitrogen, phosphorus and oxygen etc..
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping
Any a kind or at least 2 kinds of combination in Graphene.
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group.
Preferably, functional group's graphite alkene includes any a kind or at least 2 be grafted with hydroxyl, carboxyl or amino
The Graphene of the combination planted.
Those skilled in the art are it will be clearly understood that in the Graphene of the function dough, can also be grafted people in the art
It is any to the helpful functional group of dispersed graphite alkenes material that member is obtained in that.
Preferably, the hydroxyl includes-R1- OH, the R1Including alkyl, preferably include methyl, ethyl, propyl group, butyl,
Any a kind or at least 2 kinds of combination in amyl group, hexyl, vinyl, acrylic.
Preferably, the carboxyl includes-R2- COOH, the R2Including alkyl, methyl, ethyl, propyl group, fourth are preferably included
Any a kind or at least 2 kinds of combination in base, amyl group, hexyl.
Preferably, the carboxyl includes R3-NH3, the R3Including alkyl, methyl, ethyl, propyl group, fourth are preferably included
Any a kind or at least 2 kinds of combination in base, amyl group, hexyl.
Preferably, in terms of graphite alkenes material, the graphite alkenes material accounts for 0.005~0.1wt% of substrate oil, for example
0.006wt%, 0.008wt%, 0.014wt%, 0.022wt%, 0.035wt%, 0.065wt%, 0.078wt%,
0.089wt%, 0.093wt% etc., preferably 0.01~0.05wt%.
Preferably, graphite alkenes material dispersion liquid adds the feed postition into substrate oil to be added dropwise.From the side being added dropwise
Formula adds into substrate oil graphite alkenes material dispersion liquid, advantageously in graphite alkenes material dispersion liquid in substrate oil
Dispersion.
The rate of addition is preferably 0.5~20mL/min, such as 0.6mL/min, 0.7mL/min, 1.5mL/min,
1.8mL/min, 3mL/min, 5mL/min, 8mL/min, 12mL/min, 15mL/min, 18mL/min etc..
Preferably, in the dispersion liquid of the graphite alkenes material, the concentration of graphite alkenes material is below 20mg/g, preferably
1.5mg/g、1.8mg/g、2.3mg/g、2.7mg/g、3.5mg/g、4.3mg/g、4.8mg/g、5.5mg/g、6.4mg/g、
7.7mg/g, 8.5mg/g, 9.6mg/g, 10.5mg/g, 12mg/g, 13mg/g, 14mg/g, 15mg/g, 18mg/g etc., preferably 1~
10mg/g, further preferred 3~5mg/g.
Preferably, any a kind or at least 2 including finished lube, semi-finished product lubricating oil and base oil of the substrate oil
The combination planted.Substrate oil of the present invention can be understood as not containing the finished lube of Graphene, not contain the half of Graphene
Finished lube does not contain the base oil for making lubricating oil of Graphene.
The finished lube can be that on sale any in market does not contain the lubricating oil of Graphene, wherein containing basis
Oil, and lube oil additive, the lube oil additive include well known in the art any can be added in lubricating oil
Functional additive, such as antioxidant, antiwear additive, friction modifier, EP agent, detersive, dispersant, foam suppress
Agent, corrosion prevention rust preventer, flow point improver, viscosity index improver etc..
The base oil, alternatively referred to as lube base oil, are the oil bases for being not added with any additive, including mineral base
Any a kind or at least 2 kinds of combination in oil, synthetic base oil or biological basis oil.
The semi-finished product lubricating oil be from base oil to finished lube during, the oil of any processing time section
Product, it is only necessary to which satisfaction does not contain Graphene and can be used as substrate oil of the invention.
Those skilled in the art are it will be clearly understood that what the present invention was modified is not add Graphene (including biomass graphite
The graphite alkenes such as alkene, Graphene derivative material) base oil product oil or semi-finished product oil, for base oil or semi-finished product
Oil, it is modified by step of the present invention, the functional additive of correlation can also be continuously added according to prior art, such as
Antioxidant, antiwear additive, friction modifier, EP agent, detersive, dispersant, foam in hibitors, corrosion prevention rust preventer, stream
Improver, viscosity index improver etc. are selected, addition is referred to the addition of functional additive in the prior art.
Preferably, the base oil for making lubricating oil includes mineral base oil, synthetic base oil or biological basis
Any a kind or at least 2 kinds of combination in oil.
The mode of emulsification of the present invention is not particularly limited, emulsifying manner that any those skilled in the art can be known
It is used equally to the present invention.
Preferably, the mode of the emulsification includes concussion emulsion process, stirring and emulsifying method, syringe emulsion process, ultrasonic wave breast
Any a kind or at least 2 kinds of combination in change method, mortar emulsion process, preferably stirring and emulsifying method and concussion emulsion process.
When stirring and emulsifying method is selected, graphite alkenes material dispersion liquid can be selected with the speed of 0.5~2mL/min, one
While in dropping to substrate oil, while being stirred, realizing emulsification.
Preferably, the mixing speed of the stirring and emulsifying method is 3000~5000r/min, such as 3200r/min, 3500r/
Min, 3700r/min, 4300r/min, 4500r/min, 4700r/min, 4900r/min etc., 70~80 DEG C of whipping temp, for example
71 DEG C, 72 DEG C, 73 DEG C, 74 DEG C, 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79 DEG C etc..
In lubricating oil, the presence of water can influence the lubricant effect of lubricating oil, it is possible to cause the corrosion to lubricating component
Problem, therefore moisture therein is needed away in lubricating oil.The present invention is not specifically limited for removing the method for water phase.
Preferably, the method for going water removal phase of the present invention includes that layering removes water law, heating volatilization water removal except water law, distillation
Method, the combination for drying any a kind or at least 2 kinds removed in water law.
Preferably, the layering removes water law, ultrasonic emulsion breaking layering except water law or centrifugation are broken except water law includes that demulsifier is layered
Breast layering is except the combination of any a kind or at least 2 kinds in water law.
Being meant that for the combination can be the combination of any water removal phase method and/or any group being layered except water law
Close, exemplary can first carry out demulsifier layering except water law, remove most water phase, add drier to be done afterwards
Dry water removal；Or can first carry out ultrasonic emulsion breaking layering except water law, most of water phase is removed, heating volatilization is carried out afterwards to be removed
Water phase etc..
After removing water phase step, the moisture in lubricating oil disclosure satisfy that the relevant regulations of country, such as meets and contains
Water is less than 0.1%, under normal circumstances less than 0.03%, such as requirement of GB GB/T 260-1977.
Preferably, the demulsifier is layered except water law comprises the following steps：To demulsifier is added in the product after emulsification, make
Water phase and oil phase are layered, and remove water phase；It is preferred that continuously adding drier in the oil phase that layering is obtained except water law, remove remaining
Water phase.
The present invention is not particularly limited to demulsifier, and typical but non-limiting demulsifier of the present invention can be selected from amine
With the block copolymer of epoxide condensation product T1001, polyether type high polymer demulsifier DL32, oxirane and expoxy propane
T1002, LZ5957 etc..
Preferably, the distillation removes water law includes atmospheric distillation and/or distillation under vacuum, and the purpose of vacuum distillation is
Accelerate evaporation rate, reduce heating-up temperature.
Preferably, the boiling point of the vapo(u)rizing temperature less than the base oil of the distillation water removal.
Preferably, the vacuum distillation includes rotary evaporation.
Preferably, the heating volatilization is except the boiling point of the heating-up temperature less than the base oil of water law.
Preferably, the drying is except water law is including adding drier water removal.
But if containing the Graphene after function dough or element doping in graphite alkenes material, its functional group contained or
The element of doping there is no baneful influence to lubricating oil quality or also there is benefit may reside in the Graphene for preparing
In modification of lubricating oils, if there is significantly influence inferior for the quality of lubricating oil, it is necessary to be removed, to meet correlation
Regulation.Minimizing technology can be the element that whole functional group or doping are removed by reduction step, or removal part official
The element that can be rolled into a ball or adulterate, the species of specific removal is not specifically limited, it is only necessary to meet the lubricating oil satisfaction after removing related
Regulation, and the mode for removing also is not specifically limited.
Preferably, after the water phase in emulsion process and/or in removal emulsion, reduction treatment is carried out.
The mode of all or part of functional group of removal or doped chemical can include following three kinds of modes：
Mode one：Alternatively, reduction step is carried out in emulsion process, for removing the portion in the graphite alkenes material
Divide or whole functional groups or doped chemical.
Mode two：Alternatively, reduction step is carried out after the water phase in removal emulsion, removes the portion in graphite alkenes material
Divide or whole functional groups or doped chemical.
Mode three：Alternatively, reduction step is carried out in emulsion process, and is carried out after the water phase in removing emulsion
Reduction step, removes the part or all of functional group in graphite alkenes material or doped chemical.
Preferably, the method for the reduction treatment includes reducing agent reducing process and/or heating reducing process.
Preferably, the reducing agent reducing process includes adding reducing agent to be reduced.
Preferably, the addition of the reducing agent is 10~200wt%, the preferably 50~100wt% of graphite alkenes material,
Such as 15wt%, 18wt%, 23wt%, 27wt%, 50wt%, 70wt%, 90wt%, 105wt%, 120wt%, 150wt%,
165wt%, 170wt%, 190wt% etc., preferably 50~100wt%.
Preferably, the reducing agent includes ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, Cys, hydrogen iodine
Any a kind or at least 2 kinds of combination in acid or sodium borohydride.
Preferably, the heating reducing process is included in non-oxidizing atmosphere, and heating is reduced.
Preferably, the heating reducing process step includes：In autoclave, protective atmosphere and/or reduction are passed through
Property atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
Reduction temperature too high destroys the greasy property of lubricating oil, and too low reduction temperature does not reach reduction effect.
Preferably, when the graphite alkenes material is biomass Graphene, reduction step is not carried out.
Method of the Graphene modification of lubricating oils as described in the first purpose is prepared described in the two of the object of the invention.
The third object of the present invention is to improve a kind of purposes of the Graphene modification of lubricating oils described in second purpose, the stone
Black alkene modification of lubricating oils is used for the lubrication of mechanical structure.
Compared with prior art, the invention has the advantages that：
The present invention is directly added to be emulsified in substrate oil by will be dispersed with the solution of graphite alkenes material, realizes stone
The phase transfer that black alkenes material passes through microemulsified, is transferred in substrate oil, obtains the modified lubricating oil of Graphene, method is simple,
Efficiently, feasibility is good.And while lube base quality is met, also improve its lubricant effect.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
Graphene oxide used is provided for Changzhou No.6 Element Material Technology Co., Ltd. in all examples below,
Model SE2430 (powder).
Graphene used is provided for Changzhou No.6 Element Material Technology Co., Ltd. in all examples below, model
It is SE1430.
Biomass Graphene used both can be using the preparation method of biomass Graphene in the prior art in following examples
Prepare, such as number of patent application is the technology of 201510819312.X, it would however also be possible to employ the biomass stone of Jinan holy well group production
Black alkene.
Substrate oil used in example 1 below -12 is Shandong zero kilometer petrochemical industry Co., Ltd-alloy plate armour model
Lubricating oil.
Embodiment 1
(1) a certain amount of graphite oxide powder is taken, is added to the water, the oxidation stone of 5mg/g is obtained after cell pulverization ultrasound
Black aqueous solution；
(2) graphene oxide water solution for taking 70g steps (1) preparation is added in stirring with the speed of 2ml/min
In 1000g substrates oil；
(3) after whole completion of dropping, continue stirring and emulsifying, add polyether type high polymer demulsifier DL32 stratification, go
Water removal phase, adds desiccant dryness, obtains modification of lubricating oils of the water content less than 0.3wt%.
Embodiment 2：
Concrete technology step is essentially identical with embodiments of the invention 1, and the distinctive points with embodiment 1 are, in step (3)
Reduction step is carried out during stirring and emulsifying, substrate oil is specially placed in pressure for 1.6MPa, temperature is that 200 DEG C of high pressure is anti-
Answer and stir 1h in container.
Embodiment 3：
Concrete technology step is essentially identical with embodiments of the invention 1, and the distinctive points with embodiment 1 are, in step (3)
Reduction step is carried out after going water removal phase, 0.1g sodium citrates, high-speed stirred are added in the substrate oil that specially item goes to remove water after phase
1h, then carry out subsequent operation.
Embodiment 4-5
Concrete technology step is essentially identical with embodiments of the invention 3, and the distinctive points with embodiment 3 are, in step (3)
Reducing agent replaces with hydrazine hydrate 0.05g (embodiment 4), ethylenediamine 0.2g (embodiment 5) respectively.
Embodiment 6
Concrete technology step is essentially identical with embodiments of the invention 1, and the distinctive points with embodiment 1 are, in step (1)
Graphene oxide is replaced with into Graphene.
Embodiment 7
Concrete technology step is essentially identical with embodiments of the invention 1, and the distinctive points with embodiment 1 are, in step (1)
Graphene oxide is replaced with into biomass Graphene, and ultrasonically treated, ultrasonic power 800kw, time are carried out to its aqueous solution
20min。
Embodiment 8-12
Concrete technology step is essentially identical with embodiments of the invention 5, and the distinctive points with embodiment 5 are, step 1) in
The concentration of biomass graphene solution is respectively 1mg/g, 4mg/g, 10mg/g, 15mg/g, 20mg/g, the step 2 of its correspondence) in
Biomass graphene aqueous solution is respectively with the rate of addition of 5ml/min, 8ml/min, 12ml/min, 15ml/min, 20ml/min
50g, 25g, 50g, 50g, 50g is added dropwise.
Embodiment 13
Concrete technology step is essentially identical with embodiments of the invention 1, and the distinctive points with embodiment 1 are, by substrate oil
For lubricating oil is replaced by base oil, the base oil is provided for the magnificent mutually beneficial biochemical industry in Beijing, its CAS:8002-05-9.
Comparative example 1
Using Shandong zero kilometer petrochemical industry Co., Ltd-alloy plate armour model lubricating oil.
Comparative example 2
Concrete technology step is essentially identical with embodiments of the invention 5, and the distinctive points with embodiment 5 are, biomass stone
Black alkene is directly added into substrate oil with powder.
Comparative example 3
The base oil provided using the magnificent mutually beneficial biochemical industry in Beijing, its CAS:8002-05-9.
Comparative example 4
Patent publication No. is CN101812351A, entitled " based on individual layer or the dilute lube oil additive of several layers of graphite "
Specification case 2.
Performance test foundation：
Whether precipitation is had：By standing 7 days, bottom sediment is observed.
Kinematic viscosity：Normative reference GB/T265-1988 oil product kinematic viscosity determination methods and dynamic viscosity calculating method.
Coefficient of friction：Normative reference SH/T0189-1992 lubrication oil antiwears damage performance measurement method (four-ball tester method).
From data above analysis, the lube product prepared using graphite olefinic substance aqueous liquid dispersion is all asked in the absence of precipitation
Topic, and use the lubricating oil of graphite olefinic substance powder preparation and the appearance precipitation of comparative example 4；For kinematic viscosity, ordinary circumstance
Lower index is certified products in 13.5-24；For coefficient of friction, the coefficient of friction of general lubricating oil finished product all 0.08 or so,
All decreased by introducing graphite alkenes material coefficient of friction, but incorporation way effect is special in the form of aqueous liquid dispersion
Significantly.
Applicant states that the present invention illustrates process of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of Graphene modification of lubricating oils, it is characterised in that methods described comprises the following steps：
Graphite alkenes material dispersion liquid is added into substrate oil, after emulsification, the water phase in removal emulsion obtains modified lubrication
Oil.
2. the method for claim 1, it is characterised in that the solvent in the graphite alkenes material dispersion liquid is hydrophily
Solvent；
Preferably, the hydrophilic solvent includes water；
Preferably, the graphite alkenes material includes Graphene, biomass Graphene, graphene oxide, Graphene derivative
Any a kind or at least 2 kinds of mixing, the Graphene derivative includes the Graphene of element doping；
Preferably, the Graphene derivative include any a kind in element doping Graphene or functional group's graphite alkene thing or
At least 2 kinds of combination；
Preferably, it is any during the element doping Graphene is including metal-doped Graphene or nonmetal doping Graphene
1 kind or at least 2 kinds of combination；
The metal-doped metallic element include potassium, sodium, gold, silver, iron, copper, nickel, chromium, titanium, vanadium or cobalt in any a kind or
At least 2 kinds of combination；
The nonmetalloid of the nonmetal doping Graphene includes any a kind or at least 2 in nitrogen, phosphorus, silicon, boron or oxygen
The combination planted；
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping graphite
Any a kind or at least 2 kinds of combination in alkene；
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group；
Preferably, functional group's graphite alkene includes any a kind or at least 2 kinds be grafted with hydroxyl, carboxyl or amino
The Graphene of combination；
Preferably, the hydroxyl includes-R1- OH, the R1Including alkyl, preferably include methyl, ethyl, propyl group, butyl, amyl group,
Any a kind or at least 2 kinds of combination in hexyl, vinyl, acrylic；
Preferably, the carboxyl includes-R2- COOH, the R2Including alkyl, methyl, ethyl, propyl group, butyl, penta are preferably included
Any a kind or at least 2 kinds of combination in base, hexyl；
Preferably, the carboxyl includes R3-NH3, the R3Including alkyl, methyl, ethyl, propyl group, butyl, penta are preferably included
Any a kind or at least 2 kinds of combination in base, hexyl.
3. the method as described in one of claim 1 or 2, it is characterised in that the graphite alkenes material accounts for the 0.005 of substrate oil
~0.1wt%, preferably 0.01~0.05wt%；
Preferably, it is described that graphite alkenes substance moisture content dispersion liquid is added into the feed postition into substrate oil to be added dropwise, the dropwise addition
Speed is preferably 0.5~20mL/min.
4. the method as described in one of claims 1 to 3, it is characterised in that in the aqueous dispersions of the graphite alkenes material, stone
The concentration of black alkenes material is below 20mg/g, preferably 1~10mg/g, further preferred 3~5mg/g.
5. the method as described in one of Claims 1 to 4, it is characterised in that the substrate oil includes finished lube, semi-finished product
The combination of any a kind or at least 2 kinds of lubricating oil and base oil；
Preferably, the base oil includes any a kind or at least 2 in mineral base oil, synthetic base oil or biological basis oil
The combination planted.
6. the method as described in one of Claims 1 to 5, it is characterised in that the mode of the emulsification includes concussion emulsion process, stirs
The combination of any a kind or at least 2 kinds in emulsion process, syringe emulsion process, ultrasonic emulsification, mortar emulsion process is mixed, preferably
Stirring and emulsifying method and/or concussion emulsion process；
Preferably, the mixing speed of the stirring and emulsifying method is 3000~5000r/min, 70~80 DEG C of whipping temp.
7. the method as described in one of claim 1~6, it is characterised in that described to go the method for removing water phase to include that layering is removed water
Method, distillation are volatilized except water law, heating and remove water law, dry except the combination of any a kind or at least 2 kinds in water law；
Preferably, the layering removes water law includes that demulsifier layering removes water law or centrifugation demulsification point except water law, ultrasonic emulsion breaking layering
Layer is except the combination of any a kind or at least 2 kinds in water law；
Preferably, the demulsifier is layered except water law comprises the following steps：To demulsifier is added in the product after emulsification, make water phase
With oil phase layering, water phase is removed；It is preferred that continuously adding drier in the oil phase that layering is obtained except water law, remaining water is removed
Phase；
Preferably, the distillation removes water law includes atmospheric distillation and/or distillation under vacuum；
Preferably, the boiling point of the vapo(u)rizing temperature less than the base oil of the distillation water removal；
Preferably, the vacuum distillation includes rotary evaporation；
Preferably, the heating volatilization is except the boiling point of the heating-up temperature less than the base oil of water law；
Preferably, the drying is except water law is including adding drier water removal.
8. the method as described in one of claim 1~7, it is characterised in that in emulsion process and/or in removal emulsion
After water phase, reduction treatment is carried out；
Preferably, the method for the reduction treatment includes reducing agent reducing process and/or heating reducing process；
Preferably, the reducing agent reducing process includes adding reducing agent to be reduced；
Preferably, the addition of the reducing agent is the 10~200wt%, preferably 50~100wt% of graphite alkenes material；
Preferably, the reducing agent include ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, Cys, hydroiodic acid or
Any a kind or at least 2 kinds of combination in sodium borohydride；
Preferably, the heating reducing process is included in non-oxidizing atmosphere, and heating is reduced；
Preferably, the heating reducing process step includes：In autoclave, protective atmosphere and/or reproducibility gas are passed through
Atmosphere, heating reduction；Temperature≤200 DEG C of the heating reduction, pressure≤1.6MPa.
9. a kind of Graphene modification of lubricating oils, it is characterised in that the Graphene modification of lubricating oils is by one of claim 1~8
Described method is prepared.
10. a kind of purposes of Graphene modification of lubricating oils as claimed in claim 9, it is characterised in that the Graphene is modified
Lubricating oil is used for the lubrication of mechanical structure.
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| CN110982600A (en) * | 2019-12-24 | 2020-04-10 | 徐玉琴 | Lubricating oil containing modified graphene and preparation method thereof |
| CN114873586A (en) * | 2022-04-26 | 2022-08-09 | 油湃能源环保科技(天津)有限公司 | Preparation method of graphene material dispersion liquid |
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