CN109772326B - Catalyst for synthesizing fluorenone, preparation method and application thereof - Google Patents
Catalyst for synthesizing fluorenone, preparation method and application thereof Download PDFInfo
- Publication number
- CN109772326B CN109772326B CN201910196205.4A CN201910196205A CN109772326B CN 109772326 B CN109772326 B CN 109772326B CN 201910196205 A CN201910196205 A CN 201910196205A CN 109772326 B CN109772326 B CN 109772326B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- fluorenone
- solution
- synthesizing
- reaction
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for synthesizing fluorenone, a preparation method and application thereof, belonging to the technical field of catalysts, wherein the catalyst comprises the following active components in percentage by mass: the mass percent of the cobaltosic oxide is 0-100%, the mass percent of the copper oxide is 0-100%, and the sum of the mass percent of the cobaltosic oxide and the copper oxide is 100%, and the catalyst for synthesizing the fluorenone is prepared by a sol-gel method or a gel method. The catalyst for synthesizing fluorenone prepared by the invention has the advantages of low cost, high conversion rate, high selectivity, mild reaction conditions, good stability and easy separation of reactants.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for synthesizing fluorenone as well as a preparation method and application thereof.
Background
Fluorenone of formula C13H8O, molecular weight of 180.20, yellow orthorhombic crystal, melting point of 81-85 ℃, 341 ℃ of boiling point, is insoluble in water, can be dissolved in organic solvents such as alcohol, ether and the like, and is an important fine chemical raw material. The intermediate has important application in the fields of macromolecules, dyes, medicines, pesticides, optical materials and the like. In the polymer field, fluorenone can be condensed with phenol to generate bisphenol fluorene, the bisphenol fluorene structure has higher thermal stability, and is widely applied to heat-resistant materials, separation membrane materials and the like, and meanwhile, bisphenol fluorene is also applied to polymer material additives such as epoxy resin, polycarbonate, polymethyl methacrylate (organic glass) and the like. In the dye industry, fluorenones can be used to synthesize aromatic diamine dyes. Fluorenone can also be used as a medical intermediate for synthesizing various medicaments such as an anticancer medicament, an antituberculosis medicament, an antispasmodic agent and the like. In the field of agricultural chemicals, fluorenones are used in the synthesis of herbicides, insecticides, plant growth regulators, and the like.
The fluorenone synthesis can be divided into non-fluorene raw materials according to different raw materials to synthesize fluorenone and fluorene oxidation to prepare fluorenone. The synthesis of fluorenone from non-fluorene raw materials comprises the steps of taking diphenic acid, 2' -dilithiobiphenyl, benzaldehyde oxime, iodobenzene, 1-cyclohexene-1-carboxylic acid, benzene and the like as raw materials, and synthesizing fluorenone through one-step or multi-step reaction. The price of raw materials used for synthesizing fluorenone from non-fluorene raw materials is high, part of catalysts adopt noble metal active components, the product is complex, and part of methods need to be completed in multiple steps and are not suitable for large-scale production of fluorenone. Compared with the preparation of fluorenone by using non-fluorene raw materials, the method for preparing fluorenone by oxidizing fluorene has the advantages of easily obtained raw materials, simple reaction process and only one-step oxidation. The process for preparing fluorenone by oxidizing fluorene can be divided into two reaction systems of gas phase oxidation and liquid phase oxidation. The preparation of fluorenone by gas-solid heterogeneous catalysis system of fluorene gas phase oxidation is carried out in a fixed bed, fluorene is gasified at high temperature and mixed with oxygen/air, and then passes through a solid catalyst bed layer in a gaseous state, and fluorene is subjected to oxidation reaction to obtain the fluorenone. The method realizes continuous operation, but has high reaction temperature, high requirement on equipment and easy coking in the process. The liquid phase oxidation method has relatively low reaction temperature, usually uses water or organic solvent as solvent, and has oxidant and catalyst in the system, and the common oxidant includes solid/liquid oxidant such as peroxide and high valence iodine compound, and gaseous oxidant such as air and oxygen. Phase (C)Compared with solid/liquid oxidants such as peroxide, high-valence iodine compounds and the like, gaseous oxidants such as air, oxygen and the like are clean, cheap and easy to separate, and have obvious advantages. The research of preparing fluorenone by oxidizing fluorene is carried out by using industrial fluorene as raw material, air as oxidant, potassium hydroxide as catalyst and pyridine as solvent, and the yield of fluorenone is more than 98%. Zhoujianlong et al uses NaOH as catalyst, dimethyl sulfoxide as solvent, industrial oxygen as oxidant to oxidize industrial fluorene with over 85% content, the conversion rate of fluorene is over 99%, and the yield of fluorenone is over 96%. Zhao Ming, etc. investigates the performance of fluorene oxidation on different base catalysts such as potassium hydroxide, potassium carbonate, sodium hydroxide, sodium carbonate, etc. to prepare fluorenone, and investigates the influence of the catalyst dosage, the solvent type, the oxygen flow, the reaction temperature, etc. on the catalytic reaction performance. The results show that when NaOH is used as a catalyst and oxygen is used as an oxidant, the conversion rate of fluorene can reach more than 99%, and the yield of fluorenone is more than 95%. Wang et al use potassium tert-butoxide as a catalyst to catalyze and oxidize benzyl C-H bond to prepare ketone, and when fluorene is used as a raw material and potassium tert-butoxide is used as a catalyst, a phase transfer catalyst 18-crown-6 is simultaneously added into a reaction system, a solvent is N, N-dimethylformamide, and the yield of fluorenone reaches 94% under the oxygen pressure of 1 atm. The liquid phase oxidation method mostly uses strong base catalyst, which is easy to generate alkaline waste liquid and is not beneficial to environmental protection, and partial reaction processes are carried out because alkali liquor and fluorene are separated into aqueous phase and organic phase, and phase transfer catalyst is also needed to promote the reaction. In addition to using strong base catalyst, some researches have been carried out on using imide as catalyst, wherein Ishii takes high-efficiency electron carrier N-hydroxyphthalimide (NHPI) as catalyst and molecular oxygen as oxidant to react, and the yield of fluorenone can reach 80%. Miao et al used N-hydroxyphthalimide and ferric nitrate as catalysts and oxygen as oxidant to catalyze fluorene oxidation, and the yield of fluorenone reached 90%. However, the catalyst is a homogeneous catalyst, and the separation of the catalyst after reaction is difficult, thereby increasing the complexity of operation. In addition, a reaction system using a noble metal active component catalyst is provided, for example, a Au nanoparticle-polydopamine (Pda) -reduced graphene oxide (rGO) ternary nano composite material is prepared by Majumdar and the like, 1mmol of fluorene is used as a raw material, and the dosage of the Au-Pda-rGO catalyst (the Au loading is 2 wt%) is 0.02g which is the same as that of the Au-Pda-rGO catalystThen 10mol% of N-hydroxyphthalimide is added, 5mL of acetonitrile is used as a solvent, O2The pressure is 10bar, the stirring speed is 1000rpm, after the reaction is carried out for 15h at 60 ℃, the conversion rate of fluorene is 89.4 percent, the selectivity of fluorenone reaches 97.6 percent, and noble metal serving as an active component has higher catalytic activity, but the noble metal is expensive, so that the catalyst cost is higher, and the control of the production cost is not facilitated.
Disclosure of Invention
The invention aims to provide a heterogeneous catalyst for synthesizing fluorenone by oxidizing fluorene with oxygen as an oxidant, which has the advantages of low cost, high selectivity, high conversion rate, mild reaction conditions and good stability, and a preparation method and application thereof.
The catalyst of the invention is a composite metal oxide consisting of active components of cobaltosic oxide or copper oxide or both, and the composition of the composite metal oxide is that the mass content of the cobaltosic oxide is 0-100 percent, and the mass content of the copper oxide is 0-100 percent.
The catalyst of the invention is prepared as follows:
1. preparing a catalyst for synthesizing fluorenone by adopting a sol-gel method: firstly, preparing 5-60wt% of precursor ethanol solution or water solution from cobalt and/or copper according to the mass percentage of active components in a catalyst, preparing 5-60wt% of citric acid ethanol solution or water solution at the same time, wherein the volume ratio of the citric acid solution to the precursor solution is 0.5-5, slowly adding the prepared citric acid ethanol solution or water solution into the prepared precursor ethanol solution or water solution at the temperature of 10-60 ℃, and continuously stirring for 2-24 hours; secondly, stirring the citric acid ethanol solution or the mixed solution of the aqueous solution and the precursor ethanol solution or the aqueous solution at the temperature of 50-90 ℃, evaporating the solvent, and drying the obtained solid for 2-24 hours at the temperature of 50-150 ℃; finally, calcining for 1-10h at the temperature of 300-800 ℃ to obtain the catalyst for synthesizing fluorenone.
Further, the soluble salt of the metal is acetate or nitrate.
2. Preparing a catalyst for synthesizing fluorenone by a precipitation method:
firstly, respectively preparing cobalt and copper into soluble salts of metals; secondly, according to the active components in the catalyst andrespectively preparing 1-50wt% of precursor aqueous solution and 1-50wt% of precipitant aqueous solution according to mass percentage, slowly adding the precursor aqueous solution into an empty beaker at 20-80 ℃, controlling the pH value of the mixed solution to be 7-13 in the adding process, and aging for 1-24h after the mixed solution is completely precipitated; again, the aged product was washed with deionized water to no residual K+Or Na+Drying the obtained product at 50-150 deg.C for 2-24 hr; finally, calcining for 1-10h at the temperature of 300-800 ℃ to obtain the catalyst for synthesizing fluorenone.
Further, the soluble salt of the metal is acetate, chloride, sulfate or nitrate.
Further, the precipitant is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.
The application of the catalyst for synthesizing fluorenone prepared by the invention is as follows:
the reaction conditions are as follows: dissolving fluorene with the mass percent content of 0.01-50wt% in a solvent, adding a catalyst into the solvent, wherein the mass ratio of the catalyst to fluorenone is 1: 0.001-0.5, carrying out catalytic reaction in a gas atmosphere, wherein the initial gas pressure is 0.1-6MPa, the reaction temperature is 60-180 ℃, and the reaction time is 0.5-24 h.
Further, the solvent is acetonitrile, cyclohexane or cyclohexanone.
Further, the catalytic reaction gas atmosphere is a mixed gas with an oxygen content of 5-100% such as air, oxygen, ozone and the like.
Furthermore, the mixed gas containing 5-100% of oxygen comprises nitrogen or argon.
Compared with the prior art, the invention has the following advantages:
1) the preparation process of the catalyst is simple and easy to implement, and the catalyst has good stability and excellent reusability;
2) the catalyst has excellent performance, is used as a heterogeneous catalyst, is easy to separate from a product, and is easy to realize industrial amplification;
3) the reaction raw materials are cheap and easy to obtain, the product yield is high, almost no by-product is generated, and the economical efficiency of the synthesis process is obvious;
4) the reaction process is simple and easy to operate.
Detailed Description
Example 1:
preparing 60wt% of cobalt nitrate ethanol solution, slowly adding 5wt% of citric acid ethanol solution (the volume ratio of the citric acid ethanol solution to the cobalt nitrate ethanol solution is 5) at 60 ℃, keeping stirring in the process, continuously stirring at 60 ℃ for 24 hours after dropwise adding is finished, then stirring the solution at 90 ℃, evaporating the solvent, drying the obtained product at 150 ℃ for 24 hours, and calcining at 800 ℃ for 10 hours to obtain the cobaltosic oxide catalyst.
The fluorene oxidation reaction is carried out in a stainless steel reaction kettle under the following reaction conditions: dissolving fluorene in cyclohexane (the mass fraction is 50 wt%), adding a certain amount of catalyst (the mass ratio of the catalyst to fluorenone is 0.5), filling oxygen into a reaction kettle, and reacting at 180 ℃ for 24 hours under the initial pressure of 6 MPa. After the reaction, the resultant was centrifuged, and then analyzed for composition by gas chromatography to obtain fluorenone at a yield of 76%.
Example 2:
preparing 5wt% of copper nitrate ethanol solution, slowly adding 5wt% of citric acid ethanol solution (the volume ratio of the citric acid ethanol solution to the copper nitrate ethanol solution is 0.5) at 10 ℃, keeping stirring in the process, continuously stirring at 10 ℃ for 2h after dropwise adding, then stirring the solution at 50 ℃, evaporating the solvent, drying the obtained product at 50 ℃ for 2h, and calcining at 300 ℃ for 1h to obtain the copper oxide catalyst.
The fluorene oxidation reaction is carried out in a stainless steel reaction kettle under the following reaction conditions: dissolving fluorene in cyclohexane (mass fraction of 0.01 wt%), adding a certain amount of catalyst (mass ratio of fluorenone to 0.001), charging oxygen into the reaction kettle at an initial pressure of 0.1MPa, and reacting at 60 deg.C for 0.5 h. After the reaction, the resultant was centrifuged, and then analyzed for composition by gas chromatography to obtain fluorenone at a yield of 37%.
Example 3:
preparing 30wt% of cobalt nitrate and copper nitrate ethanol solution, wherein the molar ratio of cobalt to copper is 1:1, slowly adding 30wt% of citric acid ethanol solution (the volume ratio of the cobalt nitrate to the copper nitrate ethanol solution is 2.5) at 35 ℃, keeping stirring in the process, continuously stirring at 35 ℃ for 12h after dropwise adding is finished, then stirring the solution at 70 ℃, evaporating the solvent to dryness, drying the obtained product at 100 ℃ for 12h, and calcining at 550 ℃ for 6h to obtain the cobalt-copper composite oxide catalyst.
The fluorene oxidation reaction is carried out in a stainless steel reaction kettle under the following reaction conditions: dissolving fluorene in cyclohexane (the mass fraction is 25 wt%), adding a certain amount of catalyst (the mass ratio of the fluorene to fluorenone is 0.3), filling oxygen into a reaction kettle, and reacting at 120 ℃ for 12 hours under the initial pressure of 3 MPa. After the reaction, the resultant was centrifuged, and then analyzed for composition by gas chromatography to obtain fluorenone at a yield of 93%.
Example 4:
the same procedure as in example 3, except for using an aqueous solution of a metal salt instead of the ethanol solution of a metal salt, gave a fluorenone yield of 91%.
Example 5:
the same procedure as in example 3, except that cobalt acetate and copper acetate were used in place of cobalt nitrate and copper nitrate in the ethanol solution of the metal salt, gave a fluorenone yield of 89%.
Example 6:
the same procedure as in example 3, except that acetonitrile was used in place of cyclohexane to dissolve fluorene, gave a fluorenone yield of 78%.
Example 7:
the same procedure as in example 3 was repeated except that cyclohexanone was used in place of cyclohexane to dissolve fluorene, thereby obtaining a fluorenone yield of 91%.
Example 8:
the fluorenone yield was 95% as in example 3, except that the reaction vessel was charged with ozone instead of oxygen.
Example 9:
the same procedure as in example 3, except that the reaction vessel was charged with air instead of oxygen, gave a fluorenone yield of 67%.
Example 10:
the same procedure as in example 3, except that the reaction vessel was charged with 5% oxygen/nitrogen mixed gas instead of oxygen, gave a fluorenone yield of 28%.
Example 11:
the same procedure as in example 3, except that the reaction vessel was charged with 50% oxygen/nitrogen mixed gas instead of oxygen, gave a fluorenone yield of 79%.
Example 12:
the same procedure as in example 3, except that the reaction vessel was charged with 5% oxygen/argon mixed gas instead of air, gave a fluorenone yield of 29%.
Example 13:
the same procedure as in example 3, except that the reaction vessel was charged with 50% oxygen/argon mixed gas instead of air, gave a yield of fluorenone of 79%.
Example 14:
preparing copper acetate into 1wt% aqueous solution, preparing 1wt% sodium hydroxide aqueous solution, dripping into an empty beaker at the same time at 20 ℃, controlling the pH value of the process to be 7, aging for 1h after complete precipitation, and then washing with deionized water until no residual Na exists+Until detected, the obtained product is dried at 50 ℃ for 2h, and finally calcined at 300 ℃ for 1h to obtain the copper oxide catalyst.
The fluorene oxidation reaction is carried out in a stainless steel reaction kettle under the following reaction conditions: dissolving fluorene in cyclohexane (mass fraction of 0.01 wt%), adding a certain amount of catalyst (mass ratio of fluorenone to 0.001), charging oxygen into the reaction kettle at an initial pressure of 0.1MPa, and reacting at 60 deg.C for 0.5 h. After the reaction, the resultant was centrifuged, and then analyzed for composition by gas chromatography to obtain fluorenone at a yield of 34%.
Example 15:
preparing 50wt% aqueous solution of cobalt acetate, preparing 50wt% aqueous solution of sodium hydroxide, dripping into an empty beaker at the same time at 80 ℃, controlling the pH value of the process to be 13, aging for 24h after complete precipitation, and then washing with deionized water until no residual Na exists+Until the detection, the obtained product is dried for 24h at the temperature of 150 ℃, and finally calcined for 1h at the temperature of 800 ℃ to obtain the cobaltosic oxide catalyst.
The fluorene oxidation reaction is carried out in a stainless steel reaction kettle under the following reaction conditions: dissolving fluorene in cyclohexane (the mass fraction is 50 wt%), adding a certain amount of catalyst (the mass ratio of the catalyst to fluorenone is 0.5), filling oxygen into a reaction kettle, and reacting at 180 ℃ for 24 hours under the initial pressure of 6 MPa. After the reaction, the resultant was centrifuged, and then analyzed for composition by gas chromatography to obtain fluorenone at a yield of 69%.
Example 16:
preparing 25wt% aqueous solution of cobalt acetate and copper acetate with a molar ratio of 1:1, preparing 25wt% aqueous solution of sodium hydroxide, dropwise adding into an empty beaker at 50 deg.C, controlling pH to 10, aging for 12 hr after precipitation, and washing with deionized water until no residual Na is left+Until the detection, the obtained product is dried for 12h at 100 ℃, and finally calcined for 6h at 550 ℃ to obtain the cobalt-copper composite oxide catalyst.
The fluorene oxidation reaction is carried out in a stainless steel reaction kettle under the following reaction conditions: dissolving fluorene in cyclohexane (the mass fraction is 25 wt%), adding a certain amount of catalyst (the mass ratio of the fluorene to fluorenone is 0.3), filling oxygen into a reaction kettle, and reacting at 120 ℃ for 12 hours under the initial pressure of 3 MPa. After the reaction, the resultant was centrifuged, and then analyzed for composition by gas chromatography to obtain fluorenone at a yield of 88%.
Example 17:
the same procedure as in example 15 was repeated except that cobalt nitrate and copper nitrate were used in place of cobalt acetate and copper acetate as the aqueous solution of the metal salt, thereby obtaining fluorenone at a yield of 90%.
Example 18:
in the same manner as in example 15 except that cobalt chloride and copper chloride were used instead of cobalt acetate and copper acetate as the aqueous solution of the metal salt, the yield of fluorenone was 85%.
Example 19:
the same procedure as in example 15 was repeated except that cobalt sulfate and copper sulfate were used in place of cobalt acetate and copper acetate as the aqueous solution of the metal salt, thereby obtaining a fluorenone yield of 86%.
Example 20:
the same procedure as in example 15, except that sodium carbonate was used instead of sodium hydroxide as a precipitant, gave a fluorenone yield of 89%.
Example 21:
the same procedure as in example 15, except that sodium bicarbonate was used instead of sodium hydroxide as a precipitant, gave a fluorenone yield of 88%.
Example 22:
except that potassium hydroxide is used as a precipitator instead of sodium hydroxide, and the solution is washed until no residual K exists+In addition, in the same manner as in example 15, the yield of fluorenone was 85%.
Example 23:
except that potassium carbonate is used as a precipitator instead of sodium hydroxide and washed until no residual K exists+In addition, in the same manner as in example 15, the yield of fluorenone was 87%.
Example 24:
except that potassium bicarbonate is used as a precipitator instead of sodium hydroxide, and the mixture is washed until no residual K exists+In addition, in the same manner as in example 15, the yield of fluorenone was 87%.
Example 25:
the same procedure as in example 15 was repeated except that acetonitrile was used in place of cyclohexane to dissolve fluorene, whereby the yield of fluorenone was 74%.
Example 26:
in the same manner as in example 15 except that cyclohexanone was used in place of cyclohexane to dissolve fluorene, the fluorenone yield was 85%.
Example 27:
the same procedure as in example 15, except that the reaction vessel was charged with ozone instead of oxygen, gave a fluorenone yield of 90%.
Example 28:
the same procedure as in example 15, except that the reaction vessel was charged with air instead of oxygen, gave a fluorenone yield of 61%.
Example 29:
the same procedure as in example 15, except that the reaction vessel was charged with 5% oxygen/nitrogen mixed gas instead of oxygen, gave a fluorenone yield of 22%.
Example 30:
the same procedure as in example 15, except that the reaction vessel was charged with 50% oxygen/nitrogen mixed gas instead of oxygen, gave a fluorenone yield of 73%.
Example 31:
the same procedure as in example 15, except that the reaction vessel was charged with 5% oxygen/argon mixed gas instead of air, gave a fluorenone yield of 22%.
Example 32:
the same procedure as in example 15, except that the reaction vessel was charged with 50% oxygen/argon mixed gas instead of air, gave a fluorenone yield of 74%.
In conclusion, under the action of the catalyst, the yield of fluorenone is higher in the fluorene oxidation reaction, and the process has higher reaction activity and selectivity and fewer byproducts. Through the search of documents and patents, the report of similar reaction processes is not found, and the method belongs to innovative work.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. The application of the catalyst for synthesizing fluorenone is characterized by comprising the following steps:
dissolving fluorene with the mass percent content of 0.01-50wt% in a solvent, adding a catalyst into the solvent, wherein the mass ratio of the catalyst to fluorenone is 1: 0.001-0.5, carrying out catalytic reaction in a gas atmosphere, wherein the initial gas pressure is 0.1-6MPa, the reaction temperature is 60-180 ℃, and the reaction time is 0.5-24 h;
the catalyst comprises the following active components in percentage by mass: the mass percent of the cobaltosic oxide is 0-100%, the mass percent of the copper oxide is 0-100%, and the sum of the mass percent of the cobaltosic oxide and the mass percent of the copper oxide is 100%.
2. The use of a catalyst for the synthesis of fluorenone according to claim 1, wherein: the solvent is acetonitrile, cyclohexane or cyclohexanone.
3. The use of a catalyst for the synthesis of fluorenone according to claim 1, wherein: the catalytic reaction gas atmosphere is air, oxygen, ozone or mixed gas with the oxygen content of 5-100%.
4. The use of a catalyst for the synthesis of fluorenone according to claim 3, wherein: the mixed gas with the oxygen content of 5-100% comprises nitrogen or argon.
5. The use of a catalyst for the synthesis of fluorenone according to claim 1, wherein: the preparation method of the catalyst for synthesizing fluorenone comprises the following steps:
firstly, preparing 5-60wt% of precursor ethanol solution or water solution from cobalt and/or copper according to the mass percentage in the catalyst, simultaneously preparing 5-60wt% of citric acid ethanol solution or water solution, wherein the volume ratio of the citric acid solution to the precursor solution is 0.5-5, slowly adding the prepared citric acid ethanol solution or water solution into the prepared precursor ethanol solution or water solution at the temperature of 10-60 ℃, and continuously stirring for 2-24 hours; secondly, stirring the citric acid ethanol solution or the mixed solution of the aqueous solution and the precursor ethanol solution or the aqueous solution at the temperature of 50-90 ℃, evaporating the solvent, and drying the obtained solid for 2-24 hours at the temperature of 50-150 ℃; finally, calcining for 1-10h at the temperature of 300-800 ℃ to obtain the catalyst for synthesizing fluorenone.
6. The use of a catalyst for the synthesis of fluorenone according to claim 1, wherein: the preparation method of the catalyst for synthesizing fluorenone comprises the following steps:
firstly, preparing 1-50wt% of precursor aqueous solution by cobalt and/or copper according to the mass percent of a catalyst, preparing 1-50wt% of precipitator aqueous solution at the same time, slowly adding the precursor aqueous solution into the precipitator aqueous solution at the temperature of 20-80 ℃, controlling the pH value of the mixed solution to be 7-13 in the adding process, and aging for 1-24 hours after the mixed solution is completely precipitated; secondly, the aged product is washed with deionized water until no residual K remains+Or Na+Drying the obtained product at 50-150 deg.C for 2-24 hr; finally, calcining for 1-10h at the temperature of 300-800 ℃ to obtain the catalyst for synthesizing fluorenone.
7. The use of a catalyst for the synthesis of fluorenone according to claim 6, wherein: the precipitant is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910196205.4A CN109772326B (en) | 2019-03-15 | 2019-03-15 | Catalyst for synthesizing fluorenone, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910196205.4A CN109772326B (en) | 2019-03-15 | 2019-03-15 | Catalyst for synthesizing fluorenone, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109772326A CN109772326A (en) | 2019-05-21 |
| CN109772326B true CN109772326B (en) | 2021-11-12 |
Family
ID=66489519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910196205.4A Active CN109772326B (en) | 2019-03-15 | 2019-03-15 | Catalyst for synthesizing fluorenone, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772326B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801858B (en) * | 2019-10-29 | 2021-12-07 | 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 |
| 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 |
| 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376638A (en) * | 2002-04-22 | 2002-10-30 | 戴振华 | Process for preparing Co3O4 |
| CN102000576A (en) * | 2010-11-30 | 2011-04-06 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN102069005A (en) * | 2010-11-22 | 2011-05-25 | 天津市职业大学 | Catalyst for synthesizing vanillin by using a glyoxylic acid method and a one-pot method and preparation method thereof |
| CN104368343A (en) * | 2014-09-26 | 2015-02-25 | 中南民族大学 | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst with controllable mono-dispersed particles |
| CN105271440A (en) * | 2015-09-29 | 2016-01-27 | 曲阜师范大学 | Structured octahedral nanometer cobaltosic oxide, and preparation method and application thereof |
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN105536799A (en) * | 2016-03-01 | 2016-05-04 | 重庆工商大学 | Preparation method and application of nano-Co3O4 catalyst |
| CN107159224A (en) * | 2017-07-01 | 2017-09-15 | 北京石油化工学院 | A kind of nitrous oxide catalytic decomposition industrial catalyst and preparation method and application |
| CN107537495A (en) * | 2017-09-22 | 2018-01-05 | 太原理工大学 | A kind of preparation method and application of synthesis gas ethanol Cu Co catalyst |
| CN108671923A (en) * | 2018-05-10 | 2018-10-19 | 宁波大学 | Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water |
-
2019
- 2019-03-15 CN CN201910196205.4A patent/CN109772326B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376638A (en) * | 2002-04-22 | 2002-10-30 | 戴振华 | Process for preparing Co3O4 |
| CN102069005A (en) * | 2010-11-22 | 2011-05-25 | 天津市职业大学 | Catalyst for synthesizing vanillin by using a glyoxylic acid method and a one-pot method and preparation method thereof |
| CN102000576A (en) * | 2010-11-30 | 2011-04-06 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN104368343A (en) * | 2014-09-26 | 2015-02-25 | 中南民族大学 | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst with controllable mono-dispersed particles |
| CN105271440A (en) * | 2015-09-29 | 2016-01-27 | 曲阜师范大学 | Structured octahedral nanometer cobaltosic oxide, and preparation method and application thereof |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN105536799A (en) * | 2016-03-01 | 2016-05-04 | 重庆工商大学 | Preparation method and application of nano-Co3O4 catalyst |
| CN107159224A (en) * | 2017-07-01 | 2017-09-15 | 北京石油化工学院 | A kind of nitrous oxide catalytic decomposition industrial catalyst and preparation method and application |
| CN107537495A (en) * | 2017-09-22 | 2018-01-05 | 太原理工大学 | A kind of preparation method and application of synthesis gas ethanol Cu Co catalyst |
| CN108671923A (en) * | 2018-05-10 | 2018-10-19 | 宁波大学 | Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water |
Non-Patent Citations (2)
| Title |
|---|
| 纳米氧化铜粉体的制备及应用研究进展;雷涛，等;《化工进展》;20131005;第2429-2433页 * |
| 雷涛，等.纳米氧化铜粉体的制备及应用研究进展.《化工进展》.2013,第2429-2433页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109772326A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109772326B (en) | Catalyst for synthesizing fluorenone, preparation method and application thereof | |
| CN111604055B (en) | Catalyst for preparing acetophenone by oxidizing ethylbenzene and preparation method thereof | |
| CN107602358B (en) | Method for preparing methoxy acetone by using micro-reaction device | |
| CN102206147A (en) | Method for oxidizing cyclohexane | |
| CN114315504B (en) | Method for preparing methyl cyclopentadiene by catalyzing AxByOz type composite metal oxide | |
| CN103143381B (en) | Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method | |
| CN104817520B (en) | Method for preparing cyclohexene oxide by adopting micro-flow field reaction technology | |
| EP3689848A1 (en) | Method for directly producing methyl acetate and/or acetic acid from syngas | |
| CN102557908A (en) | Preparation method of 2- (cyclohex-1' -enyl) cyclohexanone | |
| CN111747831A (en) | Method for preparing cyclopentanone | |
| CN106946668A (en) | A kind of method that phenol hydrogenation prepares cyclohexanone | |
| CN103537301A (en) | Catalyst for coproduction of methylal and methyl formate from methanol through oxidization as well as preparation method and application of catalyst | |
| CN107922302B (en) | Method for producing 2-hydroxy-1, 4-naphthoquinone | |
| CN101817780B (en) | Preparation method of pyridine-2-formaldehyde | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN115043714A (en) | Environment-friendly method for synthesizing benzil | |
| CN114478243A (en) | Method for synthesizing dihydroxy dimethyl terephthalate by oxygen catalytic oxidation method | |
| JPS6165840A (en) | Production of diglycolic acid salt | |
| CN103121979A (en) | Method for realizing epoxidation of olefins and air through catalysis of cobalt-contained catalyst under assistance of ultrasonic waves | |
| CN101121650A (en) | Method for synthesizing methoxyacetone by 1-methoxy-2-propanol gas phase oxidation dehydrogenation | |
| CN113908828B (en) | Bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, and preparation method and application thereof | |
| CN111517984B (en) | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate | |
| CN114733511B (en) | V 2 O 5 /FeVO 4 Application of catalyst in cyclooctene epoxidation reaction | |
| CN113735746B (en) | Preparation method of 2-nitro-4-methylsulfonyl benzoic acid | |
| CN101565368A (en) | A process for the preparation of 2,2'-biphenyldicarboxylic acid |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |