CN107376999A - Organo-functional group composite catalyzing material and its production and use is modified after polyacid aluminum oxide - Google Patents
Organo-functional group composite catalyzing material and its production and use is modified after polyacid aluminum oxide Download PDFInfo
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- CN107376999A CN107376999A CN201710592736.6A CN201710592736A CN107376999A CN 107376999 A CN107376999 A CN 107376999A CN 201710592736 A CN201710592736 A CN 201710592736A CN 107376999 A CN107376999 A CN 107376999A
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
Abstract
The invention provides organo-functional group composite catalyzing material and its production and use is modified after polyacid aluminum oxide.The present invention is prepared for ionic liquid, hydrophobic long-chain and the multi-functional composite catalyzing material of sulfonic group@polyacid@aluminum oxide.Polyoxometallate selected by above-mentioned three kinds of composite catalysts has high oxidation state and makes it have excellent oxidation susceptibility.Covalent modification is modified to inorganic carrier surface by organosilicon functional molecular, the mass transfer effect of catalysis material has been effectively promoted, has significantly improved catalytic effect.The consumption and loss of organic functional molecular are avoided simultaneously.It is to have high conversion ratio and selectivity in benzaldehyde and 1,3 propane diols cascade reactions that composite catalyst is separately into desulfurizing oil and benzyl alcohol oxidation.
Description
Technical field
The invention belongs to composite catalyzing field of material technology, more particularly to different organo-functional groups and polyacid@aluminum oxide shapes
Function and service catalysis material in pairs and preparation method thereof, prepared composite catalyzing material can be used for desulfurizing oil and phenmethylol oxygen
Turn in benzaldehyde and 1,3- propane diols cascade reactions.
Background technology
Polyacid compound is a kind of poly-metal deoxide containing metals such as V, Mo, W, Nb, is had because of its distinctive structure
There is high oxidation state so that it has a wide range of applications in catalysis oxidation field.But polyacid in the solution solubility it is high and easily from
Crystallize and separate out in solution.Which has limited application of the polyacid on industrial reaction.Therefore, heterogeneous more acid catalysts are studied as carrying
One important directions of high more acidic group catalyst recovery yields, selectivity and heat endurance.
Research report before, polyacid covalently immobilized can load polyacid on alumina support, solving conventional method
It is easy to run off, cyclical stability difference and active component the problem of being difficult to differentiate between.But the composite catalyzing material of polyacid@aluminum oxide for
Many reaction mass transfers are poor, and reaction substrate is difficult contact catalytic active component, greatly limit catalytic reaction conversion ratio.Therefore need
Catalyst mass transfer is improved, the role of phase transfer is most important for catalytic reaction.
Alumina material has many excellent properties, such as：Good aperture structure, high-specific surface area.Wherein, spherical oxygen
Changing aluminium has good physical stability, high impact strength and excellent controllability.This causes it to be widely used in chemistry and stone
Oily chemical field.
The content of the invention
The purpose of the present invention is synthesizing new organo-functional group@polyacid@alumina composite catalysis materials.
A kind of organo-functional group@polyacid@alumina composite catalysis materials, by organo-functional group and polyacid@alumina supports
Reacted in reflux in toluene so that different organic molecules are modified in the form of covalent bond to oxidation aluminium surface, realize organo-functional group
Jointly stabilizing is immobilized on alumina with polyoxometallate.
Preferably, polyacid is room type polyacid, and its molecular formula is Na12[α-P2W15O56]·24H2O, Na9[A-PW9O34]·
7H2O, K7[PW11O39]·12H2O, K8[α-SiW11O39]·13H2O and K10[α2-P2W17O61]·20H2Any one in O.
A kind of preparation method of ionic liquid@polyacid@alumina composite catalysis materials, including step in detail below：
1) by 0.125-0.25mol N- methylimidazoles and 0.125-0.25mol 3- r-chloropropyl trimethoxyl silanes in 60-
At 80 DEG C, lead to N2, 45-48h is reacted, after reaction terminates, is cooled to room temperature, obtained sticky liquid is washed with the ether of drying
For several times, vacuum drying obtains IL-Cl；
2) 4-5mmol IL-Cl are added in the round-bottomed flask of drying, diluted with 20-25mL acetone, keep N2Atmosphere,
And by 4-5mmol KPF6It is added in the flask of another drying, is diluted with 15-20mL dry acetones, keeps N2Atmosphere；So
Afterwards by KPF6Solution is transferred in IL-Cl solution, is reacted 10-12h at room temperature, after reaction terminates, white precipitate is filtered, filtrate
Vacuum drying, obtains orange stickiness ionic liquid IL-PF6；
3) by IL-PF6With polyacid@Al2O3In mass ratio 1:20-30 back flow reactions at 100-110 DEG C dry of toluene
20-24h, after reaction terminates, room temperature is cooled to, solid is filtered, the solid then filtered flows back in dichloromethane washs 20-
24h, filtering, vacuum drying obtain ionic liquid@polyacid@alumina composite catalysis materials.
Above-mentioned ionic liquid@polyacid@alumina composites catalysis material is used for catalyzed oil pint reaction of Salmon-Saxl.
A kind of preparation method of hydrophobic long-chain@polyacid@alumina composite catalysis materials：By 0.01-0.02mol n-octyls three
Ethoxysilane and 1-3g polyacid@Al2O3100-110 DEG C of backflow 20-24h, after reaction terminates, is cooled to room temperature in toluene, will
Solid is filtered, and the solid then filtered is washed with toluene and absolute ethyl alcohol, and vacuum drying obtains hydrophobic long-chain@polyacid@aluminum oxide
Composite catalyzing material.
Above-mentioned hydrophobic long-chain@polyacid@alumina composites catalysis material is used for catalyzed oil pint reaction of Salmon-Saxl.
A kind of preparation method of sulfonic group@polyacid@alumina composite catalysis materials, comprises the following steps：
1) by the mercaptopropyl trimethoxysilanes of 0.1-0.3mol tri- and 1-3g polyacid@Al2O3100-110 DEG C is returned in toluene
30-36h is flowed, after reaction terminates, solid filtering, is washed with absolute ethyl alcohol and removes unreacted three mercaptopropyl trimethoxysilane,
It is dried in vacuo 20-24h；
2) product for obtaining step 1) reacts 10-12h with 4-6mL Peracetic acid in the in the mixed solvent of acetonitrile and water,
After reaction terminates, filtering, vacuum drying obtains sulfonic group@polyacid@alumina composite catalysis materials.
Above-mentioned sulfonic group@polyacid@alumina composites catalysis material is oxidized to benzaldehyde and 1,3- for catalytic phenylmethanol
The application of propylene glycol acetal cascade reaction.
Polyoxometallate selected by above-mentioned three kinds of composite catalysts has high oxidation state and made it have excellent
Oxidation susceptibility.Covalent modification is modified to inorganic carrier surface by organosilicon functional molecular, has been effectively promoted catalysis material
Mass transfer effect, significantly improve catalytic effect.The consumption and loss of organic functional molecular are avoided simultaneously.By composite catalyst point
It is to have high conversion ratio and choosing in benzaldehyde and 1,3- propane diols cascade reactions not to be applied to desulfurizing oil and benzyl alcohol oxidation
Selecting property.
Brief description of the drawings
The FT-IR figures for the ionic liquid@polyacid@alumina composite catalysis materials that Fig. 1 embodiments 1 synthesize.
The solid state nmr 29Si figures for the ionic liquid@polyacid@alumina composite catalysis materials that Fig. 2 embodiments 1 synthesize.
Fig. 3 embodiments it is 2-in-1 into hydrophobic long-chain@polyacid@alumina composite catalysis materials FT-IR figure.
Fig. 4 embodiments it is 2-in-1 into hydrophobic long-chain@polyacid@alumina composite catalysis materials solid state nmr 12C figure.
The FT-IR figures for the sulfonic group@polyacid@alumina composite catalysis materials that Fig. 5 embodiments 3 synthesize.
Embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Embodiment 1
The preparation method of ionic liquid@polyacid@alumina composite catalysis materials is：
By 0.125mol N- methylimidazoles and 0.25mol 3- r-chloropropyl trimethoxyl silanes at 80 DEG C, lead to N2, reaction
48h.After reaction terminates, room temperature is cooled to, obtained sticky liquid is washed for several times with the ether of drying, and vacuum drying obtains
IL-Cl。
5mmol IL-Cl are added in the round-bottomed flask of drying, diluted with 20mL acetone, keep N2Atmosphere.Then, will
5mmol KPF6It is added in the flask of another drying, is diluted with 20mL dry acetones, keeps N2Atmosphere.Finally by KPF6It is molten
Liquid is transferred in IL-Cl solution, reacts 12h at room temperature.After reaction terminates, white precipitate is filtered, filter vacuum is dried, and is obtained
Orange stickiness ionic liquid IL-PF6。
By IL-PF6 and P2W15@Al2O3In mass ratio 1:20 at 100 DEG C dry of toluene back flow reaction 24h, reaction knot
Shu Hou, room temperature is cooled to, solid is filtered.Then the solid filtered flows back in dichloromethane washs 24h, filtering, and vacuum is done
It is dry to obtain ionic liquid@polyacid@alumina composite catalysis materials.
P2W15For polyacid Na12[α-P2W15O56]·24H2O's writes a Chinese character in simplified form.
As shown in Figure 1, P2W15@Al2O3After loading IL, there is IL eigen vibration peak, wherein 3101cm-1, 2951cm-1With
2876cm-1It is IL C-H stretching vibration characteristic peaks, 1584cm-1It is C-C stretching vibration peak.It is worth noting that, 1060cm-1
It is the feature stretching vibration peak of the Si-O-Al on ionic liquid IL, this demonstrate ionic liquid IL and Al2O3The hydroxyl on surface takes off
Alcohol forms covalent bond, realizes IL in P2W15@Al2O3Surface-stable loads.
As shown in Figure 2,29The reflection of Si NMR spectras is composite IL@P2W15@Al2O3Si in upper ionic liquid IL
Chemical environment.This demonstrate that ionic liquid IL is successfully modified in P2W15@Al2O3It is upper.
Ionic liquid polyacid alumina composite catalysis material prepared by the present embodiment can be used for catalysis desulfurizing oil anti-
Should.
Embodiment 2
The preparation method concrete operation step of hydrophobic long-chain@polyacid@alumina composite catalysis materials is：
By 0.01mol n-octytriethoxysilanes and 2g P2W15@Al2O3110 DEG C of backflow 24h in toluene.Reaction knot
Shu Hou, room temperature is cooled to, solid is filtered.Then the solid filtered is washed with toluene and absolute ethyl alcohol, and vacuum drying is dredged
Water long-chain@polyacid@alumina composite catalysis materials.
From the figure 3, it may be seen that P2W15@Al2O3After loading different alkane long-chains, there is the eigen vibration peak of hydrophobic long-chain, wherein
3101cm-1, 2951cm-1And 2876cm-1It is IL C-H stretching vibration characteristic peaks, 1584cm-1 is C-C stretching vibration peak, value
Obtain it is noted that 1060cm-1The feature stretching vibration peak of the Si-O-Al on ionic liquid IL, this demonstrate hydrophobic long-chain with
Al2O3The hydroxyl dealcoholysis on surface forms covalent bond, realizes hydrophobic long-chain in P2W15@Al2O3Surface-stable loads.
As shown in Figure 4,13The reflection of C NMR spectras is the hydrophobic long-chain@P of composite2W15@Al2O3C in upper carbon long-chain
Chemical environment.This proves that hydrophobic long-chain is successfully modified in P2W15@Al2O3It is upper.
Hydrophobic long-chain polyacid alumina composite catalysis material prepared by the present embodiment can be used for catalysis desulfurizing oil anti-
Should.
Embodiment 3
The preparation method concrete operation step of sulfonic group@polyacid@alumina composite catalysis materials is：
By the mercaptopropyl trimethoxysilanes of 0.2mol tri- and 2g P2W15@Al2O3110 DEG C of backflow 32h in toluene.Reaction knot
Shu Hou, solid filtering, is washed with absolute ethyl alcohol and removes unreacted three mercaptopropyl trimethoxysilane, is dried in vacuo 24h.
By product obtained in the previous step with 6mL Peracetic acid in acetonitrile and water (volume ratio 3:2) 12h is reacted in solution,
After reaction terminates, filtering, vacuum drying obtains sulfonic group@polyacid@alumina composite catalysis materials.
As shown in Figure 5, sulfonic group modification P2W15@Al2O3After composite, there is sulfonic eigen vibration peak,
1190cm-1、1068cm-1、620cm-1、530cm-1Absworption peak be sulfonic group characteristic peak, indicate sulfonic group and successfully modify oxygen
Change aluminium surface.
Sulfonic group@polyacid@alumina composite catalysis materials prepared by the present embodiment are oxidized to available for catalytic phenylmethanol
The application of benzaldehyde and 1,3- propylene glycol acetal cascade reactions.
The present invention contains end the different types of functional molecular of trimethoxy silane, by organic solvent with it is more
Sour@aluminum oxide is flowed back, and makes organic molecule by the form covalent modification of silicon oxygen bond to polyacid@alumina materials surface,
Polyacid is realized to load from the jointly stabilizing of different organo-functional groups.Ionic liquid, hydrophobic long-chain and sulphur are successfully prepared respectively
The multi-functional composite catalyzing material of acidic group@polyacid@aluminum oxide.Polyoxometallate selected by above-mentioned three kinds of composite catalysts
Excellent oxidation susceptibility is made it have with high oxidation state.Covalent modification is modified to inorganic carrier by organosilicon functional molecular
Surface, the mass transfer effect of catalysis material is effectively promoted, has significantly improved catalytic effect.Avoid organic functional molecular simultaneously
Consumption and loss.It is that benzaldehyde is connected with 1,3- propane diols that composite catalyst is separately into desulfurizing oil and benzyl alcohol oxidation
There is high conversion ratio and selectivity in reaction.
It is understood that above is in order to illustrate the example of the principle of the present invention and exploitativeness, not office of the invention
It is limited to this.For those skilled in the art, without departing from the spirit and substance in the present invention, can be with
All variations and modifications are made, these variations and modifications are also considered as protection scope of the present invention.
Claims (8)
1. a kind of organo-functional group@polyacid@alumina composite catalysis materials, it is characterised in that by organo-functional group and polyacid@oxygen
Change alumina supporter to react in reflux in toluene so that organic molecule is modified in the form of covalent bond to oxidation aluminium surface, realizes organic official
Jointly stabilizing is immobilized on alumina with polyoxometallate for energy group.
2. organo-functional group@polyacid@alumina composite catalysis materials according to claim 1, it is characterised in that polyacid is
Room type polyacid, its molecular formula are Na12[α-P2W15O56]·24H2O, Na9[A-PW9O34]·7H2O, K7[PW11O39]·
12H2O, K8[α-SiW11O39]·13H2O or K10[α2-P2W17O61]·20H2Any one in O.
3. a kind of preparation method of ionic liquid@polyacid@alumina composite catalysis materials, it is characterised in that including in detail below
Step：
1) by 0.125-0.25mol N- methylimidazoles and 0.125-0.25mol 3- r-chloropropyl trimethoxyl silanes at 60-80 DEG C
Under, lead to N2, 45-48h is reacted, after reaction terminates, is cooled to room temperature, obtained sticky liquid is washed with the ether of drying, very
Sky is dried to obtain IL-Cl；
2) 4-5mmol IL-Cl are added in the round-bottomed flask of drying, diluted with 20-25mL acetone, keep N2Atmosphere, and
By 4-5mmol KPF6It is added in the flask of another drying, is diluted with 15-20mL dry acetones, keeps N2Atmosphere；Then will
KPF6Solution is transferred in IL-Cl solution, is reacted 10-12h at room temperature, after reaction terminates, white precipitate is filtered, filter vacuum
Dry, obtain orange stickiness ionic liquid IL-PF6；
3) by IL-PF6With polyacid@Al2O3In mass ratio 1:20-30 back flow reaction 20- at 100-110 DEG C dry of toluene
24h, after reaction terminates, room temperature is cooled to, solid is filtered, the solid then filtered flows back in dichloromethane washs 20-
24h, filtering, vacuum drying obtain ionic liquid@polyacid@alumina composite catalysis materials.
4. ionic liquid@polyacid@alumina composites catalysis material prepared by claim 3 is used for catalyzed oil pint reaction of Salmon-Saxl.
5. a kind of preparation method of hydrophobic long-chain@polyacid@alumina composite catalysis materials, it is characterised in that by 0.01-
0.02mol n-octytriethoxysilanes and 1-3g polyacid@Al2O3100-110 DEG C of backflow 20-24h, reaction terminate in toluene
Afterwards, room temperature is cooled to, solid is filtered, the solid then filtered is washed with toluene and absolute ethyl alcohol, and vacuum drying obtains hydrophobic
Long-chain@polyacid@alumina composite catalysis materials.
6. hydrophobic long-chain@polyacid@alumina composites catalysis material prepared by claim 5 is used for catalyzed oil pint reaction of Salmon-Saxl.
7. a kind of preparation method of sulfonic group@polyacid@alumina composite catalysis materials, it is characterised in that comprise the following steps：
1) by the mercaptopropyl trimethoxysilanes of 0.1-0.3mol tri- and 1-3g polyacid@Al2O3The 100-110 DEG C of backflow 30- in toluene
36h, after reaction terminates, solid filtering, washed with absolute ethyl alcohol and remove unreacted three mercaptopropyl trimethoxysilane, vacuum is done
Dry 20-24h；
2) product for obtaining step 1) reacts 10-12h, reaction with 4-6mL Peracetic acid in the in the mixed solvent of acetonitrile and water
After end, filtering, vacuum drying obtains sulfonic group@polyacid@alumina composite catalysis materials.
8. sulfonic group@polyacid@alumina composites catalysis materials prepared by claim 7 are oxidized to benzene first for catalytic phenylmethanol
The application of aldehyde and 1,3- propylene glycol acetal cascade reactions.
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Cited By (4)
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| CN109046464A (en) * | 2018-08-21 | 2018-12-21 | 东北师范大学 | A kind of diatomite immobilized polyacid Quito hole bionic catalysis material and preparation method thereof |
| CN109180711A (en) * | 2018-08-27 | 2019-01-11 | 河南师范大学 | A kind of organic boronic-rare earth-HPAs complex and preparation method thereof and the application in photo luminescent devices |
| CN112939783A (en) * | 2021-01-27 | 2021-06-11 | 三峡大学 | Method for preparing aldehyde or ketone by selectively oxidizing alcohol with oxygen |
| CN112939783B (en) * | 2021-01-27 | 2022-05-17 | 三峡大学 | Method for preparing aldehyde or ketone by selectively oxidizing alcohol with oxygen |
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