CN111672489A - Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil - Google Patents
Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil Download PDFInfo
- Publication number
- CN111672489A CN111672489A CN202010484665.XA CN202010484665A CN111672489A CN 111672489 A CN111672489 A CN 111672489A CN 202010484665 A CN202010484665 A CN 202010484665A CN 111672489 A CN111672489 A CN 111672489A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- acid
- titanium dioxide
- ethyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 150000002148 esters Chemical class 0.000 title claims abstract description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005303 weighing Methods 0.000 claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- FYWVMROQEMIMSK-UHFFFAOYSA-N butane-1-sulfonic acid;hydrogen sulfate;3-methyl-1h-imidazol-3-ium Chemical compound OS([O-])(=O)=O.C[N+]=1C=CNC=1.CCCCS(O)(=O)=O FYWVMROQEMIMSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- -1 thermal stability Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002429 nitrogen sorption measurement Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- AOZDHFFNBZAHJF-UHFFFAOYSA-N [3-hexanoyloxy-2,2-bis(hexanoyloxymethyl)propyl] hexanoate Chemical compound CCCCCC(=O)OCC(COC(=O)CCCCC)(COC(=O)CCCCC)COC(=O)CCCCC AOZDHFFNBZAHJF-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nano titanium dioxide catalyst prepared by taking ionic liquid as a template agent, which is prepared by the following method: a. weighing a certain amount of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate in a round-bottom flask, respectively weighing tetrabutyl titanate and absolute ethyl alcohol, adding into the flask, and uniformly stirring to obtain a solution a. b. Respectively weighing deionized water, absolute ethyl alcohol and acetic acid in a dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, performing water bath aging after dropwise adding is finished, and performing vacuum drying and roasting to obtain the nano titanium dioxide catalyst. The invention also discloses application of the catalyst in preparation of synthetic ester lubricating oil. The catalyst has high activity, stable performance and easy separation, and this speeds up the industrial application.
Description
Technical Field
The invention relates to a titanium dioxide catalyst prepared by taking ionic liquid as a template agent and application thereof in synthesis of ester lubricating oil.
Background
Synthetic esters are lubricants which are born and developed along with the demand for high-performance lubricating materials in the technical progress of aero-engines, and have excellent high and low temperature properties, lubricating properties and other good comprehensive properties, so that the synthetic esters have been taken as key components of aviation lubricating oil materials to play an indispensable role in the aviation field; one of the advantages of synthetic ester as a lubricating material is the adjustability of molecular structure, and various properties of the synthetic ester, including thermal stability, oxidation stability, hydrolytic stability, viscosity grade and viscosity-temperature performance, lubricity, solubility, biodegradability and the like, show great difference along with the change of molecular composition and structure. Meanwhile, the material has the characteristics of renewable raw material sources, environmental friendliness and the like, so that the material has important potential application in industries such as automobiles, metallurgy, cement and the like. In the international aspect, a great deal of research work is carried out on the aspects of structure-activity relationship, preparation process, performance, application and the like of synthetic ester, but the aspects of research depth, systematicness and the like of the synthetic ester still need to be further deepened and perfected. The basic theory and key technology of the synthetic ester in China are deficient, the synthetic ester industry is basically in the blank, and the breakthrough of high and new technology industries such as aviation and the like in China and the development of energy-saving technology in the industries such as transportation and the like are restricted. Therefore, the development of satisfactory high-performance synthetic ester lubricating base oils is a key factor in solving the above problems.
The synthetic ester is a product obtained by esterification reaction of organic alcohol and organic acid, the esterification reaction can be carried out without a catalyst, but the reaction speed is slow, so in the production practice, the esterification reaction is generally added with the catalyst. The traditional homogeneous catalyst can obtain high esterification rate but is not widely applied due to the defects of equipment corrosion, easy environmental pollution and the like. The environmental-friendly catalysts (resins, solid acids, etc.) developed in recent years can overcome the above problems, but their low mass transfer capacity and easy deactivation become obstacles to the efficient progress of the reaction under stoichiometric conditions, and further the residual fatty acids adversely affect the lubricity of the synthetic esters.
For many years, the unique properties of nano materials have made them to play an important role in the scientific and technical field. The nano titanium dioxide has a plurality of special properties such as surface effect, volume effect, quantum size effect, macroscopic quantum tunneling effect and the like, so that the nano titanium dioxide has a plurality of characteristics compared with common titanium dioxide. The nanometer titanium dioxide has wide application in the fields of water treatment, catalysts, ultraviolet absorbers, sunscreen and skin care cosmetics, coatings, photoelectronic devices and the like. The nano titanium dioxide has larger specific surface area, pore volume and abundant pore structure, so that the diffusion and transmission of substrates and products in the catalytic reaction process are facilitated, and the catalytic activity of the catalyst is greatly improved; and the pore structure is controllable. Therefore, the nano titanium dioxide has important application prospect as the catalyst.
Disclosure of Invention
The invention aims to provide a catalyst prepared by taking ionic liquid as a template agent and application thereof in preparation of synthetic ester lubricating oil. The invention uses an ionic liquid as a template agent to prepare nano titanium dioxide (TiO) by a sol-gel method2) The catalyst is used for synthesizing pentaerythritol polyol ester lubricating oil.
A nanometer titanium dioxide catalyst is characterized in that the catalyst is prepared by the following method:
a. weighing a certain amount of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate in a container, respectively weighing tetrabutyl titanate and absolute ethyl alcohol, adding into the container, and uniformly stirring to obtain a solution a.
b. Respectively weighing deionized water, absolute ethyl alcohol and acetic acid in a dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, performing water bath aging after dropwise adding is finished, and performing vacuum drying and roasting to obtain the nano titanium dioxide catalyst.
Further, the catalyst of the invention is prepared by the following method:
a. weighing a certain amount of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate into a 100mL round-bottom flask, respectively weighing 5.3mL tetrabutyl titanate and 26mL absolute ethyl alcohol, adding into the flask, and uniformly stirring to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, aging in a water bath at 60 ℃ for 24h after the dropwise adding is finished, drying in vacuum at 150 ℃ for 4h, and roasting at 550 ℃ for 5 h. Thus obtaining the nano titanium dioxide catalyst.
Further, the amount of the 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate is 0.066-1.88 g.
The application of the catalyst in the preparation of synthetic ester lubricating oil is characterized in that pentaerythritol and organic acid are used as raw materials, the nano titanium dioxide catalyst prepared by the method is used as the catalyst, toluene is used as a water removal agent, the reaction is carried out at the reaction temperature of 150-170 ℃, and after 10 hours of reaction, the ester lubricating oil synthesized by pentaerythritol polyol ester is obtained through centrifugal separation and rotary evaporation.
The molar ratio of pentaerythritol to organic acid is 4: 1.
The mass ratio of the mesoporous nano titanium dioxide catalyst to pentaerythritol is 1: 9.
The organic acid is n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid or n-decanoic acid.
Compared with the prior art, the invention has the following advantages:
the catalyst related by the invention has simple synthesis method and high catalyst activity, and greatly accelerates the process of industrial application.
The characterization shows that the catalyst has the pore size distribution of 3-49 nm and is a typical mesoporous material.
The invention adopts a sol-gel method to regulate and control the appearance, the pore volume, the pore diameter and the specific surface area of the nano titanium dioxide catalyst by changing the dosage of the template agent, so that the pore volume is between 0.022 and 0.16cm3A pore diameter of 3 to 49nm and a specific surface area of 10 to 59m3Adjustable in the range of/g.
The catalytic synthesis of pentaerythritol polyol ester lubricating oil is carried out according to the stoichiometric ratio, the catalytic reaction can be completed at a lower reaction temperature within a shorter reaction time, and a high-purity product can be obtained.
Drawings
FIG. 1 shows TiO prepared in example 3 of the present invention2-3 nitrogen sorption isotherm of the catalyst.
FIG. 2 shows TiO prepared in example 3 of the present invention2-3 XRD pattern of the catalyst.
FIG. 3 shows TiO prepared in example 3 of the present invention2-3 transmission electron micrographs.
Detailed Description
The invention is further illustrated by the following examples, which are intended to provide a better understanding of the subject matter of the invention.
Example 1
a. 0.066g of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate is weighed in a 100mL round-bottom flask, 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol are respectively weighed and added into the flask, and the mixture is uniformly stirred to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, carrying out aged bloom in a water bath at 60 ℃ for 24 hours after dropwise adding, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2-1 catalyst.
Example 2
a. 0.14g of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate is weighed in a 100mL round-bottom flask, 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol are respectively weighed and added into the flask, and the mixture is uniformly stirred to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, carrying out aged bloom in a water bath at 60 ℃ for 24 hours after dropwise adding, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2-2 catalyst.
Example 3
a. 0.22g of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate is weighed in a 100mL round-bottom flask, 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol are respectively weighed and added into the flask, and the mixture is uniformly stirred to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, carrying out aged bloom in a water bath at 60 ℃ for 24 hours after dropwise adding, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2-3 catalyst.
Example 4
a. 0.31g of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate is weighed in a 100mL round-bottom flask, 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol are respectively weighed and added into the flask, and the mixture is uniformly stirred to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, and mixing the solution bDropwise adding into the solution a, after dropwise adding, carrying out aging in a water bath at 60 ℃ for 24 hours, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2-4 catalyst.
Example 5
a. 0.83g of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate is weighed in a 100mL round-bottom flask, 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol are respectively weighed and added into the flask, and the mixture is uniformly stirred to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, carrying out aged bloom in a water bath at 60 ℃ for 24 hours after dropwise adding, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2-5 catalyst.
Example 6
a. Weighing 1.88g of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate in a 100mL round-bottom flask, respectively weighing 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol, adding the tetrabutyl titanate and the absolute ethyl alcohol into the flask, and uniformly stirring to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, carrying out aged bloom in a water bath at 60 ℃ for 24 hours after dropwise adding, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2-6 catalysts.
Comparative example 1
a. 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol are weighed and added into a 100mL round-bottom flask to be uniformly stirred, so as to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a 100mL dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, carrying out aged bloom in a water bath at 60 ℃ for 24 hours after dropwise adding, carrying out vacuum drying at 150 ℃ for 4 hours, and roasting at 550 ℃ for 5 hours. To obtain TiO2A catalyst.
The performance test of the nano titanium dioxide catalyst prepared by the invention comprises the following steps:
FIG. 1 shows TiO prepared in example 3 of the present invention2-3 nitrogen sorption isotherm of the catalyst. As shown in FIG. 1, the material hasThe obvious IV-type adsorption isotherm shows that the material has a typical mesoporous structure.
FIG. 2 shows TiO prepared in example 3 of the present invention2-3 catalyst XRD pattern. It can be seen from the figure that the titanium dioxide is in anatase form.
FIG. 3 shows TiO prepared in example 3 of the present invention2-3 transmission electron microscopy and electron diffraction patterns of the catalyst. As can be seen from the figure, the catalytic material is polycrystalline.
Example 7
And (3) catalytic reaction: pentaerythritol and hexanoic acid are subjected to esterification reaction to obtain pentaerythritol tetra-hexanoate serving as a model reaction, 1.8g of pentaerythritol and 6.13g of hexanoic acid are respectively weighed according to a stoichiometric ratio of 4:1 (molar ratio) and put into a 100mL three-neck flask, 0.2g of the nano titanium dioxide catalyst prepared in the example 1 is added, 2mL of toluene is used as a water removal agent and reacts for 10 hours at 160 ℃, and the product is subjected to centrifugal separation and rotary evaporation to obtain pentaerythritol polyol ester synthetic ester lubricating oil. The acid value of the product is measured by referring to the national standard GB/T4945-2002, and the esterification degree of the product is analyzed by the acid value. Wherein the calculation formula of the esterification rate is as follows:
esterification ratio (%) - (1-product acid value/initial acid value) × acid-alcohol molar ratio ÷ 4] × 100%
The nano titania catalysts prepared in examples 2 to 6 were tested in the same manner as in example 7, and the test results are shown in Table 1.
Table 1 performance test of esterification reaction of pentaerythritol with n-hexanoic acid catalyzed by different catalysts
The difference of catalytic activity of nano titanium dioxide catalyst prepared by ionic liquid template agent with different content is given in table 1, and we can know TiO from the table2The catalyst has the optimal catalytic activity when the addition amount of the-3, namely the ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate is 0.22 g.
Example 8
And (3) catalytic reaction: according to the molar ratio of pentaerythritol to n-pentanoic acid1.8g of pentaerythritol and 5.45g of n-pentanoic acid were weighed in a 100mL three-necked flask for 4:1, respectively, and 0.2g of TiO was added2And (3) reacting the toluene with the volume of-3, 2mL serving as a water removing agent at 150 ℃ for 10 hours, and performing centrifugal separation and rotary evaporation on the product to obtain the synthetic ester lubricating oil. Adding a certain mass of triphenylmethane as an internal standard, and carrying out quantitative analysis on the product through nuclear magnetic resonance.
Example 9
And (3) catalytic reaction: the procedure was repeated as in example 8 except that n-pentanoic acid was changed to an equimolar amount of n-hexanoic acid and the reaction temperature was 160 ℃.
Example 10
And (3) catalytic reaction: the procedure was repeated as in example 8 except that n-pentanoic acid was changed to an equimolar amount of n-heptanoic acid and the reaction temperature was 160 ℃.
Example 11
And (3) catalytic reaction: the procedure was repeated as in example 8 except that n-pentanoic acid was changed to an equimolar amount of n-octanoic acid and the reaction temperature was 160 ℃.
Example 12
And (3) catalytic reaction: the procedure was repeated as in example 8 except that n-pentanoic acid was changed to an equimolar amount of n-nonanoic acid and the reaction temperature was 165 ℃.
Example 13
And (3) catalytic reaction: the procedure was followed as in example 8 except that n-pentanoic acid was replaced by an equimolar amount of n-decanoic acid and the reaction temperature was 170 ℃.
TABLE 2 TiO2-3 study on performance of catalytic synthesis ester lubricating base oil
Table 2 lists TiO2-3 test results for the catalytic synthesis of several ester base lubricants. From the table, the catalyst shows excellent performance for catalyzing and synthesizing the polyol ester base lubricating oil, the esterification reaction yield of more than 95 percent is obtained at relatively low reaction temperature and in relatively short time, and the catalyst is easy to separate. The catalyst also shows better catalytic performance for the synthesis of pentaerythritol ester with other structures, and the productThe yield can reach 96 percent at most.
Claims (7)
1. The nanometer titanium dioxide catalyst is characterized by being prepared by the following method:
a. weighing a certain amount of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate in a container, respectively weighing tetrabutyl titanate and absolute ethyl alcohol, adding into the container, and uniformly stirring to obtain a solution a.
b. Respectively weighing deionized water, absolute ethyl alcohol and acetic acid in a dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, performing water bath aging after dropwise adding is finished, and performing vacuum drying and roasting to obtain the nano titanium dioxide catalyst.
2. The catalyst of claim 1, wherein the catalyst is prepared by:
a. weighing a certain amount of ionic liquid 1-butyl sulfonic acid-3-methylimidazole hydrogen sulfate in a round-bottom flask, respectively weighing 5.3mL of tetrabutyl titanate and 26mL of absolute ethyl alcohol, adding into the flask, and uniformly stirring to obtain a solution a.
b. Respectively weighing 5mL of deionized water, 25mL of absolute ethyl alcohol and 8.5mL of acetic acid in a dropping funnel, uniformly mixing to obtain a solution b, dropwise adding the solution b into the solution a, aging in a water bath at 60 ℃ for 24h after dropwise adding is finished, drying in vacuum at 150 ℃ for 4h, and roasting at 550 ℃ for 5h to obtain the nano titanium dioxide catalyst.
3. The catalyst of claim 2, wherein the amount of ionic liquid 1-butylsulfonic acid-3-methylimidazole hydrogensulfate is from 0.066g to 1.88 g.
4. The application of the catalyst of any one of claims 1 to 3 in the preparation of synthetic ester lubricating oil is characterized in that pentaerythritol and organic acid are used as raw materials, the catalyst of any one of claims 1 to 3 is used as the catalyst, toluene is used as a water removal agent, the reaction is carried out for 10 hours at the temperature of 150 ℃ to 170 ℃, and then the centrifugal separation and the rotary evaporation are carried out to obtain the synthetic ester lubricating oil.
5. Use according to claim 4, characterized in that the molar ratio of pentaerythritol to organic acid is 4: 1.
6. the use of claim 4, wherein the mass ratio of the nano titanium dioxide catalyst to pentaerythritol is 1: 9.
7. the use of claim 4, wherein the organic acid is n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, or n-decanoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010484665.XA CN111672489A (en) | 2020-06-01 | 2020-06-01 | Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010484665.XA CN111672489A (en) | 2020-06-01 | 2020-06-01 | Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111672489A true CN111672489A (en) | 2020-09-18 |
Family
ID=72434690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010484665.XA Pending CN111672489A (en) | 2020-06-01 | 2020-06-01 | Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111672489A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911325A (en) * | 2012-09-29 | 2013-02-06 | 浙江工业大学 | Supercritical carbon dioxide (CO2) foaming nucleating agent and preparation method thereof |
| CN103160205A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院兰州化学物理研究所 | Ionic liquid marine antifouling coating |
| CN105879907A (en) * | 2016-03-02 | 2016-08-24 | 中国科学院兰州化学物理研究所 | Immobilized ionic-liquid catalyst and application thereof to synthesizing ester lubricating oil |
| WO2016183102A1 (en) * | 2015-05-10 | 2016-11-17 | Ross Technology Corporation | Non-stick siloxane compositions having a low water roll off angle |
| CN107694601A (en) * | 2017-10-31 | 2018-02-16 | 李俊霞 | A kind of high selectivity and conversion ratio catalyst and preparation method thereof |
-
2020
- 2020-06-01 CN CN202010484665.XA patent/CN111672489A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160205A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院兰州化学物理研究所 | Ionic liquid marine antifouling coating |
| CN102911325A (en) * | 2012-09-29 | 2013-02-06 | 浙江工业大学 | Supercritical carbon dioxide (CO2) foaming nucleating agent and preparation method thereof |
| WO2016183102A1 (en) * | 2015-05-10 | 2016-11-17 | Ross Technology Corporation | Non-stick siloxane compositions having a low water roll off angle |
| CN105879907A (en) * | 2016-03-02 | 2016-08-24 | 中国科学院兰州化学物理研究所 | Immobilized ionic-liquid catalyst and application thereof to synthesizing ester lubricating oil |
| CN107694601A (en) * | 2017-10-31 | 2018-02-16 | 李俊霞 | A kind of high selectivity and conversion ratio catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 葛翔宇: ""电力复合脂在输变电设备中的导电理论与润滑技术研究"", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅱ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kesserwan et al. | Hybrid CaO/Al2O3 aerogel as heterogeneous catalyst for biodiesel production | |
| CN109603912B (en) | Metal organic framework structure catalyst and application thereof | |
| CN104619680B (en) | The production method of polyol ester | |
| Sharma et al. | Synthesis of bio-lubricant from epoxy canola oil using sulfated Ti-SBA-15 catalyst | |
| Abukhadra et al. | Sonication induced transesterification of castor oil into biodiesel in the presence of MgO/CaO nanorods as a novel basic catalyst: Characterization and optimization | |
| CN103833549B (en) | A kind of preparation method of polyol esters of fatty acids | |
| CN105879907B (en) | A kind of immobilized ionic-liquid catalyst and its application in ester oil preparation | |
| Zięba et al. | Activity and stability of polyaniline-sulfate-based solid acid catalysts for the transesterification of triglycerides and esterification of fatty acids with methanol | |
| Liu et al. | Preparation of bamboo-shaped BiVO4 nanofibers by electrospinning method and the enhanced visible-light photocatalytic activity | |
| Liao et al. | Preparation of fibrous sulfated zirconia (SO42−/ZrO2) solid acid catalyst using collagen fiber as the template and its application in esterification | |
| Narasimharao et al. | Effect of Si precursor on structural and catalytic properties of nanosize magnesium silicates | |
| Wang et al. | Mild synthesis of biofuel over a microcrystalline S2O82−/ZrO2 catalyst | |
| Sachse et al. | Improved silica–titania catalysts by chitin biotemplating | |
| Aghabarari et al. | Modified bentonite as catalyst for esterification of oleic acid and ethanol | |
| Wang et al. | Synthesis of molybdenum oxide hollow microspheres by ethanol and PEG assisting hydrothermal process | |
| CN104528743A (en) | Preparation method of mesoporous one-dimensional silicon dioxide nanofiber with high specific surface area | |
| Yuan et al. | Characterization of SO 4 2−/TiO 2 and its catalytic activity in the epoxidation reaction | |
| CN111672489A (en) | Nano titanium dioxide catalyst and application thereof in preparation of synthetic ester lubricating oil | |
| CN106883120B (en) | MIL-101(Cr) crude sample, and preparation method and application of MIL-101(Cr) material | |
| Hu et al. | Green synthesis of ester base oil with high viscosity–Part Ⅰ: Catalyst preparation, characterization, evaluation, and mechanism analysis | |
| Sisca et al. | Synthesis and Characterization of CaO Limestone from Lintau Buo Supported by TiO 2 as a Heterogeneous Catalyst in the Production of Biodiesel | |
| Manga et al. | Synthesis and modification of mesoporous silica with sulfated titanium dioxide as a heterogeneous catalyst for biodiesel production from palm fatty acid distillate | |
| JP2014504945A (en) | Process for producing supported catalysts and use of said catalysts for esterification of free fatty acids in vegetable oils | |
| Saravani et al. | Synthesis and Characterization of Lanthanum Oxide and Lanthanumoxid Carbonate Nanoparticles from Thermalizes of [La (acacen)(NO | |
| CN102671687A (en) | Composite metal nitrogen-doped carbon nanotube catalyst, preparation method thereof and method for catalyzing biodiesel by utilizing catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |