CN109772326A - A kind of catalyst and its preparation method and application synthesizing Fluorenone - Google Patents
A kind of catalyst and its preparation method and application synthesizing Fluorenone Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst and its preparation method and application for synthesizing Fluorenone, belong to catalyst technical field, the active component and its mass percentage content of the catalyst are as follows: the mass percentage content of cobaltosic oxide is 0-100%, the mass percentage content of copper oxide is 0-100%, the sum of mass percentage content of cobaltosic oxide and copper oxide is 100%, passes through sol-gal process or the catalyst of gel method preparation synthesis Fluorenone.The catalyst of synthesis Fluorenone prepared by the present invention has the advantages of at low cost, high conversion rate, selectivity is high, reaction condition is mild, stability is good, and reactant is easily isolated.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to be it is a kind of synthesize Fluorenone catalyst and preparation method thereof
And application.
Background technique
Fluorenone, molecular formula C13H8O, molecular weight 180.20, be in yellow orthorhombic body, 81-85 DEG C of fusing point, boiling point 341
DEG C, it is not soluble in water, the organic solvents such as alcohol, ether can be dissolved in, are a kind of important fine chemicals raw materials.It is as intermediate in height
The fields such as molecule, dyestuff, medicine, pesticide, optical material have and its important application.In the field of polymers, Fluorenone can be with phenol
Condensation generates bisphenol fluorene, and the fluorene structured thermal stability with higher of bis-phenol is widely used in heat proof material, separation membrane material
Deng, while bisphenol fluorene is also used for the high molecular materials such as epoxy resin, polycarbonate, polymethyl methacrylate (organic glass)
Additive.In dye industry, Fluorenone can be used for synthesizing aromatic diamines dyestuff.Fluorenone can also be used as medicine intermediate, use
Include a variety of drugs such as anticarcinogen, anti-tubercular drug, convulsion relieving agent in synthesis.Pesticide production in, Fluorenone be used to synthesize herbicide,
Insecticide and plant growth regulator etc..
Fluorenone synthesis can be divided into non-fluorene Material synthesis Fluorenone by the difference of raw material and fluorenes oxidation prepares Fluorenone.Non-fluorene raw material closes
It include with diphenic acid, 2,2 '-two lithium biphenyl, benzaldoxime and iodobenzene, 1- cyclohexene -1- carboxylic acid and benzene etc. for original at Fluorenone
Material reacts synthesis Fluorenone by one or more steps.Cost of material used in non-fluorene Material synthesis Fluorenone is higher, partial catalyst
Using noble metal active component, product is complicated, and Part Methods need multistep to complete, and is not suitable for large-scale production Fluorenone.Compared to
Fluorenone is prepared with non-fluorene raw material, fluorenes oxidation prepares Fluorenone raw material and is easy to get, and reaction process is simple, it is only necessary to step oxidation.Fluorenes oxidation system
The technique of standby Fluorenone can be divided into gaseous oxidation and the big reaction system of liquid phase oxidation two.Fluorenes gaseous oxidation prepares Fluorenone using gas-solid
Heterogeneous catalysis system, reaction carry out in fixed bed, and fluorenes is gasified by high temperature and is mixed with oxygen/air, with gaseous
By solid catalyst bed, fluorenes occurs oxidation reaction and obtains Fluorenone form.The method realizes continuous operation, but reaction temperature
Height, and the high requirements on the equipment, the easy coking of process.Liquid phase oxidation reaction temperature is relatively low, is usually made with water or organic solvent
Solvent, oxidant and catalyst are existed simultaneously in system, and common oxidant includes that peroxide, hypervalent iodine compounds etc. are solid
The gaseous oxidizers such as state/liquid oxidizer and air, oxygen.Compared to the liquid/solids oxygen such as peroxide, hypervalent iodine compounds
Agent, the cleaning of the gaseous oxidizers such as air, oxygen is cheap, is easily isolated, with the obvious advantage.Hu Xin etc. is empty using Industrial fluorene as raw material
Gas is oxidant, and potassium hydroxide is catalyst, and pyridine is that solvent has carried out the research that fluorenes oxidation prepares Fluorenone, and the yield of Fluorenone is big
In 98%.For Zhou Jianrong etc. using NaOH as catalyst, dimethyl sulfoxide is solvent, and industrial oxygen is oxidizing content greater than 85%
Industrial fluorene, the conversion ratio of fluorenes are greater than 99%, and the yield of Fluorenone is greater than 96%.Zhao Ming etc. has investigated potassium hydroxide, potassium carbonate, hydroxide
Fluorenes oxidation prepares the performance of Fluorenone on the difference base catalyst such as sodium, sodium carbonate, has studied catalyst amount, solvent type, oxygen
Influence of the factors such as flow, reaction temperature to catalytic perfomance.The result shows that oxygen is oxidation when using NaOH as catalyst
When agent, the conversion ratio of fluorenes is up to 99% or more, and Fluorenone yield is 95% or more.Wang etc. is aoxidized by catalyst of potassium tert-butoxide
Benzyl c h bond prepares ketone, and when using fluorenes as raw material, potassium tert-butoxide is catalyst, and phase transfer catalyst is added simultaneously in reaction system
18- crown- 6, solvent are n,N-Dimethylformamide, and under oxygen pressure 1atm, the yield of Fluorenone reaches 94%.The above liquid phase oxidation
Fado uses alkali catalyst, is also easy to produce alkaline waste liquor, is unfavorable for environmental protection, and part reaction process is since lye and fluorenes are respectively in water phase
With organic phase, also need to promote reaction to carry out using phase transfer catalyst.In addition to using alkali catalyst, there are also part researchs to use
Acid imide substance is as catalyst, and wherein Ishii etc. is with efficient electron carrier n-Hydroxyphthalimide (NHPI)
It for catalyst, is reacted by oxidant of molecular oxygen, the yield of Fluorenone is up to 80%.Miao etc. is with N- hydroxyl phthalyl
Imines and ferric nitrate are catalyst, and oxygen is the oxidation of oxidizer catalytic fluorenes, and the yield of Fluorenone has reached 90%.But such is catalyzed
Agent is homogeneous catalyst, and the separation of post catalyst reaction is difficult, increases the complexity of operation.In addition there are use noble metal living
The reaction system of property component catalyst, such as Majumdar are prepared for Au nano particle-poly-dopamine (Pda)-oxygen reduction fossil
Black alkene (rGO) ternary nano composite material, using 1mmol fluorenes as raw material, Au-Pda-rGO catalyst (Au load capacity is 2wt%) is used
Amount is 0.02g, while the n-Hydroxyphthalimide of 10mol% is added, and 5mL acetonitrile is solvent, O2Pressure is 10bar, is stirred
Rate 1000rpm is mixed, after reaction carries out 15h at 60 DEG C, the conversion ratio of fluorenes is 89.4%, and the selectivity of Fluorenone reaches 97.6%,
Noble metal is as active component although catalytic activity with higher, but it is expensive, causes catalyst higher cost, no
Conducive to the control of production cost.
Summary of the invention
The object of the present invention is to provide a kind of inexpensive, selectivity height, high conversion rate, reaction conditions relatively mildly, stability
It is good, using oxygen as the heterogeneous catalysis and preparation method and application of the fluorenes oxidative synthesis Fluorenone of oxidant.
Catalyst of the invention is aoxidized by the composition metal that active component cobaltosic oxide or copper oxide or both form
Object, consisting of the mass content of cobaltosic oxide is 0-100%, the mass content of copper oxide is 0-100%.
Catalyst preparation of the invention is as follows:
1, the catalyst of synthesis Fluorenone is prepared using sol-gal process: firstly, by cobalt and/or copper according to the active group in catalyst
The precursor ethanol solution or aqueous solution for dividing mass percent to prepare 5-60wt%, while the citric acid ethyl alcohol for preparing 5-60wt% is molten
The volume ratio of liquid or aqueous solution, citric acid solution and precursor solution is 0.5-5, by prepared citric acid ethanol solution or water
Solution is slowly added into prepared precursor ethanol solution or aqueous solution under the conditions of 10-60 DEG C, persistently stirs 2-24h；
Secondly, by the mixed solution of citric acid ethanol solution or aqueous solution and precursor ethanol solution or aqueous solution in 50-90 DEG C of condition
Obtained solid is dried 2-24h by lower stirring, solvent evaporated under the conditions of 50-150 DEG C；Finally, under the conditions of 300-800 DEG C
1-10h is calcined, the catalyst of synthesis Fluorenone is obtained.
Further, the soluble-salt of the metal is acetate or nitrate.
2, the catalyst of synthesis Fluorenone is prepared using the precipitation method:
Firstly, cobalt and copper to be prepared into the soluble-salt of metal respectively；Secondly, according to active component and its quality in catalyst
Degree prepares the precursor water solution of 1-50wt% respectively, while preparing the precipitating reagent aqueous solution of 1-50wt%, by forerunner
Body aqueous solution is slowly added into sky beaker simultaneously under the conditions of 20-80 DEG C, and the pH value that mixed solution is controlled in adding procedure is
7-13, the completely rear aging 1-24h of solution precipitating to be mixed；Again, product that aging obtains is washed with deionized to noresidue
K+Or Na+Until detection, then by obtained product under the conditions of 50-150 DEG C dry 2-24h；Finally, in 300-800 DEG C of condition
Lower calcining 1-10h obtains the catalyst of synthesis Fluorenone.
Further, the soluble-salt of the metal is acetate, chloride, sulfate or nitrate.
Further, the precipitating reagent is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or carbonic acid
Hydrogen potassium.
The application of the catalyst of the synthesis Fluorenone prepared in the present invention is as follows:
Reaction condition are as follows: the fluorenes that mass percentage content is 0.01-50wt% is dissolved in solvent, catalyst is added into solvent,
The mass ratio of catalyst and Fluorenone is 1:0.001-0.5, and atmosphere catalysis is reacted, initial gas pressure 0.1-6MPa, instead
Answering temperature is 60-180 DEG C, reaction time 0.5-24h.
Further, the solvent is acetonitrile, hexamethylene or cyclohexanone.
Further, the catalysis reaction gas atmosphere is the mixing that the oxygen content such as air, oxygen, ozone are 5-100%
Gas.
Further, the oxygen content is including nitrogen or argon gas in the gaseous mixture of 5-100%.
Compared with the prior art, the invention has the following advantages:
1) catalyst preparation process is simple and easy, there is good stability, and repeat performance is excellent；
2) catalyst performance is excellent, as heterogeneous catalysis, easily separates with product, it is easy to accomplish industry amplification；
3) reaction raw materials are cheap and easy to get, product yield high, almost no coupling product, and synthesis process economy is significant；
4) reaction process is simple, easily operated.
Specific embodiment
Embodiment 1:
The cobalt nitrate ethanol solution for preparing 60wt%, by the citric acid ethanol solution of 5wt% (with cobalt nitrate ethanol solution at 60 DEG C
Volume ratio is 5) to be slowly added to, and is kept stirring in the process, continues stirring after dripping at 60 DEG C for 24 hours, then by solution in 90
It is stirred at DEG C, solvent evaporated, for 24 hours, 800 DEG C of calcining 10h obtain cobaltosic oxide catalysis to obtained product for drying at 150 DEG C
Agent.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
50wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.5) is added, oxygen, initial pressure are filled with into reaction kettle
6MPa reacts for 24 hours at 180 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 76%.
Embodiment 2:
The copper nitrate ethanol solution for preparing 5wt%, by the citric acid ethanol solution of 5wt% (with copper nitrate ethanol solution at 10 DEG C
Volume ratio is 0.5) to be slowly added to, and is kept stirring in the process, continues to stir 2h at 10 DEG C after dripping, then by solution in 50
It is stirred at DEG C, solvent evaporated, obtained product dry 2h, 300 DEG C of calcining 1h at 50 DEG C obtain copper oxide catalyst.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
0.01wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.001) is added, oxygen is filled with into reaction kettle, it is initial to press
Power 0.1MPa reacts 0.5h at 60 DEG C.Through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtain fluorenes
Ketone yield is 37%.
Embodiment 3:
Prepare the cobalt nitrate and copper nitrate ethanol solution of 30wt%, the molar ratio of cobalt and copper is 1:1, by the lemon of 30wt% at 35 DEG C
Sour ethanol solution (being 2.5 with the volume ratio of cobalt nitrate and copper nitrate ethanol solution) is slowly added to, and is kept stirring, is added dropwise in the process
Continue to stir 12h at 35 DEG C after complete, then stir solution at 70 DEG C, solvent evaporated, obtained product is done at 100 DEG C
Dry 12h, 550 DEG C of calcining 6h, obtains cobalt copper composite oxide catalysts.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
25wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.3) is added, oxygen, initial pressure are filled with into reaction kettle
3MPa reacts 12h at 120 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 93%.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
25wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.3) is added, oxygen, initial pressure are filled with into reaction kettle
3MPa reacts 12h at 120 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 93%.
Embodiment 4:
In addition to using the aqueous solution of metal salt to replace the ethanol solution of metal salt, with embodiment 3, obtaining Fluorenone yield is for other
91%。
Embodiment 5:
In addition to the ethanol solution of metal salt replaces cobalt nitrate and copper nitrate using cobalt acetate and copper acetate, other are obtained with embodiment 3
It is 89% to Fluorenone yield.
Embodiment 6:
In addition to using acetonitrile that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 3, obtaining Fluorenone yield is 78% for other.
Embodiment 7:
In addition to using cyclohexanone that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 3, obtaining Fluorenone yield is 91% for other.
Embodiment 8:
In addition to being filled with ozone in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is 95% for other.
Embodiment 9:
In addition to being filled with air in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is 67% for other.
Embodiment 10:
In addition to being filled with 5% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is for other
28%。
Embodiment 11:
In addition to being filled with 50% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is for other
79%。
Embodiment 12:
In addition to being filled with 5% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 3, obtaining Fluorenone yield is for other
29%。
Embodiment 13:
In addition to being filled with 50% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 3, obtaining Fluorenone yield is for other
79%。
Embodiment 14:
Copper acetate is configured to the aqueous solution of 1wt%, the sodium hydrate aqueous solution of 1%wt is prepared, is added drop-wise to empty burning simultaneously at 20 DEG C
In cup, the pH value of control process is 7, and aging 1h, is then washed with deionized to the Na of noresidue after precipitating completely+Detection is
Only, the product obtained finally calcines 1h at 300 DEG C, obtains copper oxide catalyst in 50 DEG C of dry 2h.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
0.01wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.001) is added, oxygen is filled with into reaction kettle, it is initial to press
Power 0.1MPa reacts 0.5h at 60 DEG C.Through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtain fluorenes
Ketone yield is 34%.
Embodiment 15:
Cobalt acetate is configured to the aqueous solution of 50wt%, the sodium hydrate aqueous solution of 50%wt is prepared, is added drop-wise to sky simultaneously at 80 DEG C
In beaker, the pH value of control process is 13, and aging for 24 hours, is then washed with deionized to the Na of noresidue after precipitating completely+Inspection
Until out, obtained product is dried for 24 hours at 150 DEG C, is finally calcined 1h at 800 DEG C, is obtained cobaltosic oxide catalyst.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
50wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.5) is added, oxygen, initial pressure are filled with into reaction kettle
6MPa reacts for 24 hours at 180 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 69%.
Embodiment 16:
Cobalt acetate and copper acetate be configured to the aqueous solution of 25wt%, the molar ratio of cobalt and copper is 1:1, prepares the hydroxide of 25%wt
Sodium water solution is added drop-wise in sky beaker simultaneously at 50 DEG C, and the pH value of control process is 10, and aging 12h, is then used after precipitating completely
Deionized water is washed to the Na of noresidue+Until detection, obtained product is finally calcined at 550 DEG C in 100 DEG C of dry 12h
6h obtains cobalt copper composite oxide catalysts.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
25wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.3) is added, oxygen, initial pressure are filled with into reaction kettle
3MPa reacts 12h at 120 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 88%.
Embodiment 17:
In addition to the aqueous solution of metal salt replaces cobalt acetate and copper acetate using cobalt nitrate and copper nitrate, other are obtained with embodiment 15
It is 90% to Fluorenone yield.
Embodiment 18:
In addition to the aqueous solution of metal salt replaces cobalt acetate and copper acetate using cobalt chloride and copper chloride, other are obtained with embodiment 15
It is 85% to Fluorenone yield.
Embodiment 19:
In addition to the aqueous solution of metal salt replaces cobalt acetate and copper acetate using cobaltous sulfate and copper sulphate, other are obtained with embodiment 15
It is 86% to Fluorenone yield.
Embodiment 20:
Except use sodium carbonate replace sodium hydroxide as precipitating reagent in addition to, with embodiment 15, obtaining Fluorenone yield is 89% for other.
Embodiment 21:
Except use sodium bicarbonate replace sodium hydroxide as precipitating reagent in addition to, with embodiment 15, obtaining Fluorenone yield is 88% for other.
Embodiment 22:
Except using potassium hydroxide to replace sodium hydroxide as precipitating reagent, wash to the K of noresidue+Detection is outer, other same embodiments
15, obtaining Fluorenone yield is 85%.
Embodiment 23:
Except using potassium carbonate to replace sodium hydroxide as precipitating reagent, wash to the K of noresidue+Detection is outer, other with embodiment 15,
Obtaining Fluorenone yield is 87%.
Embodiment 24:
Except using saleratus to replace sodium hydroxide as precipitating reagent, wash to the K of noresidue+Detection is outer, other same embodiments
15, obtaining Fluorenone yield is 87%.
Embodiment 25:
In addition to using acetonitrile that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 15, obtaining Fluorenone yield is 74% for other.
Embodiment 26:
In addition to using cyclohexanone that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 15, obtaining Fluorenone yield is 85% for other.
Embodiment 27:
In addition to being filled with ozone in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is 90% for other.
Embodiment 28:
In addition to being filled with air in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is 61% for other.
Embodiment 29:
In addition to being filled with 5% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is for other
22%。
Embodiment 30:
In addition to being filled with 50% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is for other
73%。
Embodiment 31:
In addition to being filled with 5% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 15, obtaining Fluorenone yield is for other
22%。
Embodiment 32:
In addition to being filled with 50% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 15, obtaining Fluorenone yield is for other
74%。
In conclusion fluorenes oxidation reaction is under the effect of the catalyst, Fluorenone yield is higher, process reaction with higher
Activity and selectivity, by-product are few.Through document and patent retrieval, the report of similar reaction process was not met, belongs to innovative work
Make.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
It is familiar with those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of catalyst for synthesizing Fluorenone, it is characterised in that: the active component and its mass percentage content of the catalyst
Are as follows: the mass percentage content of cobaltosic oxide is 0-100%, and the mass percentage content of copper oxide is 0-100%, four oxidations three
The sum of mass percentage content of cobalt and copper oxide is 100%.
2. a kind of preparation method of the catalyst of synthesis Fluorenone as described in claim 1, it is characterised in that the following steps are included:
Firstly, cobalt and/or copper are prepared the precursor ethanol solution of 5-60wt% or water-soluble according to the mass percent in catalyst
Liquid, while the citric acid ethanol solution or aqueous solution of 5-60wt% are prepared, the volume ratio of citric acid solution and precursor solution is
Prepared citric acid ethanol solution or aqueous solution are slowly added into prepared presoma by 0.5-5 under the conditions of 10-60 DEG C
In ethanol solution or aqueous solution, 2-24h is persistently stirred；Secondly, citric acid ethanol solution or aqueous solution and precursor ethanol is molten
The mixed solution of liquid or aqueous solution stirs under the conditions of 50-90 DEG C, solvent evaporated, by obtained solid under the conditions of 50-150 DEG C
Dry 2-24h；Finally, calcining 1-10h under the conditions of 300-800 DEG C, the catalyst of synthesis Fluorenone is obtained.
3. it is according to claim 2 synthesis Fluorenone catalyst preparation method, it is characterised in that: the metal it is solvable
Property salt be acetate or nitrate.
4. a kind of preparation method of the catalyst of synthesis Fluorenone as described in claim 1, it is characterised in that the following steps are included:
Firstly, cobalt and/or copper to be prepared to the precursor water solution of 1-50wt% according to the mass percent in catalyst, match simultaneously
Precursor water solution is slowly added into precipitating reagent aqueous solution by the precipitating reagent aqueous solution of 1-50wt% processed under the conditions of 20-80 DEG C
In, the pH value that mixed solution is controlled in adding procedure is 7-13, the completely rear aging 1-24h of solution precipitating to be mixed；Secondly, spending
The product that ion water washing aging obtains to noresidue K+Or Na+Until detection, then by obtained product in 50-150 DEG C of condition
Lower dry 2-24h；Finally, calcining 1-10h under the conditions of 300-800 DEG C, the catalyst of synthesis Fluorenone is obtained.
5. it is according to claim 4 synthesis Fluorenone catalyst preparation method, it is characterised in that: the metal it is solvable
Property salt be acetate, chloride, sulfate or nitrate.
6. the preparation method of the catalyst of synthesis Fluorenone according to claim 4, it is characterised in that: the precipitating reagent is hydrogen
Sodium oxide molybdena, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or saleratus.
7. a kind of application of the catalyst of synthesis Fluorenone as described in claim 1, it is characterised in that include the following steps:
The fluorenes that mass percentage content is 0.01-50wt% is dissolved in solvent, catalyst, catalyst and fluorenes are added into solvent
The mass ratio of ketone is 1:0.001-0.5, atmosphere catalysis reaction, initial gas pressure 0.1-6MPa, reaction temperature 60-
180 DEG C, reaction time 0.5-24h.
8. a kind of application of catalyst for synthesizing Fluorenone according to claim 7, it is characterised in that: the solvent is second
Nitrile, hexamethylene or cyclohexanone.
9. a kind of application of catalyst for synthesizing Fluorenone according to claim 7, it is characterised in that: catalysis reaction gas atmosphere
It encloses for air or is oxygen or is ozone or is the gaseous mixture that oxygen content is 5-100%.
10. a kind of application of catalyst for synthesizing Fluorenone according to claim 9, it is characterised in that: the oxygen content
For in the gaseous mixture of 5-100% include nitrogen or argon gas.
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| CN110801858A (en) * | 2019-10-29 | 2020-02-18 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing carbonyl compound by catalyzing benzyl compound oxidation, preparation method and application thereof |
| CN110961113A (en) * | 2019-12-16 | 2020-04-07 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing carbonyl compound by catalyzing benzyl compound oxidation, preparation method and application thereof |
| CN112473676A (en) * | 2021-01-13 | 2021-03-12 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
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| CN112473676A (en) * | 2021-01-13 | 2021-03-12 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
| CN112473676B (en) * | 2021-01-13 | 2022-12-13 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
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