CN112473676A - Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application - Google Patents
Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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Abstract
The invention provides a multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, a preparation method and application thereof. The catalyst is used for preparing fluorenone by catalytic oxidation of fluorene and comprises the following steps: adding fluorene into a solvent, then adding a catalyst, and introducing oxygen for reaction at 40-80 ℃. The catalyst is prepared by only adopting a mechanical grinding mode to mix precursor raw materials and then directly roasting at high temperature, the precursor raw materials are not required to be mixed and dissolved by water or other organic solvents, complex processes such as recycling of waste water and a large amount of solvents are avoided, the operation is easy, the cost is low, the later-stage separation of the heterogeneous oxide catalyst from products is convenient, and the regeneration treatment of the catalyst after reaction is simple.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a multi-oxide catalyst for preparing fluorenone by oxidizing fluorene, a preparation method and application.
Background
9-fluorenone, alias fluorenone, yellow orthorhombic crystal, molecular formula C13H8O, is easily soluble in organic solvents such as ethanol, diethyl ether, acetone, benzene, toluene and the like, and is insoluble in water. It is an important organic synthetic raw material, and is also an expensive fine chemical intermediate, and has wide application in the fields of medicine, pesticide, dye, high molecular material, photosensitive material, etc. Wherein, in the medical industry, the 9-fluorenone is an important intermediate for synthesizing the antispasmodic 2-hydroxyaminoacetylfluorenone and other anticancer drugs and antituberculosis drugs; in the agricultural field, for the synthesis of pesticides, herbicides, plant growth regulators and the like; in the dye industry, for the synthesis of aromatic diamine dyes; in the plastic industry, bisphenol fluorene products with high thermal stability synthesized from 9-fluorenone are important monomers and modifiers for novel engineering plastics such as heat-resistant materials, separation film materials and the like。
The synthesis of 9-fluorenone is divided into a non-fluorene route and a fluorene oxidation route according to raw materials. The non-fluorene route for preparing fluorenone by using diphenic acid, 2' -dilithiobiphenyl, iodobiphenyl, benzaldehyde oxime and the like as raw materials is gradually eliminated due to the defects that the raw materials are high in price, more in side reactions, difficult in later-stage product separation and the like because a part of the non-fluorene route adopts noble metal catalysts. In contrast, the direct oxidation route for preparing fluorenone from fluorene in coal tar has attracted attention of researchers and enterprises.
Among them, US5902907(1999) and zl.96123084.3(1996) report a high-temperature gas-phase oxidation method for synthesizing fluorenone by catalytic oxidation of fluorene gasified at a high temperature on a fixed bed at a temperature of 400 ℃ or higher, wherein deep oxidation is very likely to occur due to high reaction temperature, and raw materials or products are easily coked during high-temperature use to block the pore structure of the catalyst, thereby causing catalyst deactivation. In contrast, the low-temperature liquid-phase oxidation method is to dissolve fluorene in an organic solvent and prepare 9-fluorenone by catalytic oxidation of the fluorene by using an oxidant, and the method has the advantages of mild reaction conditions, less equipment investment and high yield of 9-fluorenone, and is an ideal industrial method for preparing 9-fluorenone on a small scale.
At present, the preparation of fluorenone by fluorene liquid phase oxidation relates to the problems of recycling of organic solvent, screening and optimization of oxidant, development of high-performance phase transfer catalyst, later separation of homogeneous oxidation catalyst and the like. For example, in the patents of US4218400 and CN1754867A, polar aprotic solvents such as pyridine and dimethyl sulfoxide are used as reaction solvents, alkali metal hydroxide is used as a catalyst, and fluorene is oxidized at 50-100 ℃ by using air/industrial oxygen to prepare fluorenone, so that the process has the disadvantages of large solvent loss and large energy consumption for recycling the solvent. CN102391087A reports that fluorene is air oxidized at normal pressure and above 90 ℃ to prepare fluorenone by using toluene/xylene as a solvent, sodium hydroxide as a catalyst and quaternary ammonium salt as a phase transfer catalyst. Its disadvantages are that no water is added, the quaternary ammonium salt is difficult to perform phase transfer action, the reaction temperature is high and the loss of solvent is large. CA201410074857.8 and CN201310355676.8 report that fluorenone is prepared by oxidizing fluorene in air at 10-80 ℃ by using alkali as a catalyst, an aromatic organic solvent and water as solvents and quaternary ammonium salt as a phase transfer agent. CN102020543A reports that quaternary ammonium salt is used as a phase transfer catalyst, and fluorene is oxidized by air in toluene to prepare fluorenone without adding an alkali metal hydroxide catalyst, but the fluorene conversion rate is extremely low by the method.
In general, the advantage of the liquid phase oxidation process is that the reaction temperature is relatively low, typically less than 100 ℃. However, in the method, homogeneous alkali metal compounds are mostly used as catalysts, quaternary ammonium salts and the like are used as phase transfer catalysts, the later-stage catalysts are difficult to separate and recycle, and part of the homogeneous catalysts have the problem of product pollution.
In order to overcome the defects of the homogeneous catalyst prepared by the liquid-phase oxidation method, in the early stage, CN109772326A participates in the designed heterogeneous Co-Cu composite metal oxide catalyst, and the aim of separation from a reaction system can be achieved through simple filtration after reaction, but in the preparation process of the catalyst, 5-60 wt% of ethanol solution or aqueous solution is adopted to dissolve precursors of cobalt and copper, 5-60 wt% of ethanol solution or aqueous solution is used to dissolve citric acid, the mixture is continuously stirred and mixed for 2-24 hours at 10-60 ℃, then the solvent is stirred and evaporated to dryness at 50-90 ℃, then the mixture is dried for 2-24 hours at 50-150 ℃, and the catalyst is obtained after roasting for 1-10 hours at 300-800 ℃. The whole process consumes a large amount of ethanol/water solution, the operation steps are complex, the preparation conditions of the catalyst are harsh, the yield of the fluorenone is 61-95% when the catalyst is at a high temperature of 120-180 ℃, the yield of the fluorenone is only 22-37% when the catalyst is reacted at a low temperature of 60 ℃, and the catalytic effect is poor.
In summary, the prior art for preparing fluorenone by oxidizing fluorene has the following problems: the homogeneous phase alkali catalyst and the phase transfer catalyst are needed to be used at low temperature (less than 100 ℃), but the homogeneous phase catalyst is easy to pollute products at the later stage, is difficult to separate and recover, and has higher cost. The heterogeneous catalyst is easy to separate, a phase transfer catalyst is not needed during reaction, but the preparation process is complex, and the heterogeneous catalyst needs high temperature (more than 120 ℃) to achieve ideal yield of the fluorenone. Therefore, the development of a heterogeneous catalyst with low temperature, high activity and simple preparation process is very important.
Disclosure of Invention
The invention provides a multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, a preparation method and application, overcomes the defects of the prior art, provides a multi-component Co-Cu-X (X = K, Na, Mg and Ca) heterogeneous catalyst with low temperature, high activity and simple preparation process for preparing fluorenone by oxidizing fluorene, and provides application for preparing fluorenone by oxidizing fluorene by taking oxygen as an oxidant.
The technical scheme for realizing the invention is as follows:
a preparation method of a multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene is characterized in that precursor substances of Co, Cu and X are mixed in a physical mechanical grinding mode, wherein X = K, Na, Mg and Ca, and then the mixture is calcined at high temperature to obtain the multi-component oxide catalyst.
And the precursors of the Co, the Cu and the X are one or two of nitrate or acetate.
The precursor is mechanically ground to more than 200 meshes.
The high-temperature calcination temperature is 300-800 ℃, the calcination time is 2-6 h, and the heating rate is 2-5 ℃/min.
The molar ratio of Co, Cu and X in the multi-component oxide catalyst is (5-7): (2-4): 1-3.
The catalyst is Co-Cu-X, the catalyst is a heterogeneous multi-element metal oxide catalyst, wherein X = K, Na, Mg, Ca, and the molar ratio of Co, Cu and X is (5-7): (2-4): (1-3).
The application of the catalyst in preparing fluorenone by catalytic oxidation of fluorene comprises the following steps: adding fluorene into a solvent, then adding a catalyst, and introducing oxygen for reaction at 40-80 ℃.
The solvent is 1, 3-dimethyl-3, 4,5, 6-tetrachloro-2 (1H) pyrimidone, dimethyl sulfoxide, o-xylene, m-xylene, p-xylene or cyclohexane, oxygen is introduced into each 100mL of the solvent at a volume flow of 60-300 mL/min, and the oxidation reaction time is 4-12H.
The mass percentage of the fluorene is 0.1-30 wt%, and the mass ratio of the catalyst to the fluorene is 1: (0.5 to 150).
And a reflux condensing device is arranged on the reactor of the catalytic reaction to prevent the solvent from volatilizing. Wherein the conversion rate of fluorene is more than 85 percent, and the selectivity of fluorenone is more than 99.1 percent.
The invention has the beneficial effects that:
(1) the catalyst of the invention is only subjected to two steps of mechanical grinding and high-temperature roasting, the preparation process avoids the use of chemical reagents such as water, organic solvent, precipitator and the like, and the preparation process is simple, low in production cost, high in synthesis efficiency and good in repeated stability.
(2) According to the catalyst, the number and strength of alkaline sites on the surface of the catalyst are enhanced by adding the alkali metal K, Na and the alkaline earth metals Mg and Ca, so that weakly acidic 9-site C-H bonds on fluorene molecules are efficiently activated, the conversion rate of fluorene is more than 85%, and the selectivity of fluorenone is more than 99.1% under the reaction condition of a lower reaction temperature of 40-80 ℃.
(3) The alkali metal and alkaline earth metal doped composite metal oxide catalyst avoids the use of homogeneous alkali catalysts, and the heterogeneous characteristic of the composite metal oxide enables the catalyst to be easily separated from a reaction system, and the operation is convenient.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows a fluorenone reaction apparatus for synthesis according to the present invention.
FIG. 2 shows an infrared spectrum (KBr pellet) of a fluorenone product synthesized according to the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The catalyst is prepared by mechanical grinding and high-temperature roasting, and activity evaluation is carried out. 14.55g of Co (NO) are weighed out3)2·6H2O, 7.25g of Cu (NO)3)2·3H2O, 4.72g of Ca (NO)3)2·4H2And (4) transferring the O salt into an agate mortar together, and mechanically grinding to more than 200 meshes. Then directly transferring the catalyst precursor ground into powder into a muffle furnace to be calcined for 4 h at the temperature of 500 ℃, wherein the heating rate is 2 ℃/min, thereby obtaining Co5Cu3Ca2A catalyst.
100mL of cyclohexane, 6g of fluorene and 0.05g of catalyst are taken to be placed in a 250mL three-neck flask, oxygen is introduced into the bottom of a reactor at a reaction temperature of 50 ℃ at a rate of 120 mL/min, oxidation reaction is carried out for 8 hours, the conversion rate of fluorene is 95.1%, and the selectivity of fluorenone is 99.6%.
Example 2
The catalyst preparation method and evaluation conditions differ from example 1 as follows: catalyst precursor 14.55g of Co (NO) was weighed out3)2·6H2O, 7.25g of Cu (NO)3)2·3H2O, KNO 2.02g3The conversion rate of fluorene is 90.1%, and the selectivity of fluorenone is 99.5%.
Example 3
The catalyst preparation method and evaluation conditions differ from example 1 as follows: catalyst precursor 14.55g of Co (NO) was weighed out3)2·6H2O, 7.25g of Cu (NO)3)2·3H2O, 1.70g of NaNO3The conversion rate of fluorene was 91.1%, and the selectivity of fluorenone was 99.2%.
Example 4
The catalyst preparation method and evaluation conditions differ from example 1 as follows: catalyst precursor 14.55g of Co (NO) was weighed out3)2·6H2O, 7.25g of Cu (NO)3)2·3H2O, 5.12g Mg (NO)3)2·6H2O, the conversion rate of fluorene is 94.3%, and the selectivity of fluorenone is 99.3%.
Example 5
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the catalyst precursor is roasted for 6 hours at 300 ℃, the conversion rate of fluorene is 86.1%, and the selectivity of fluorenone is 99.2%.
Example 6
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the catalyst precursor is roasted for 2h at 800 ℃, the fluorene conversion rate is 89.3 percent, and the fluorenone selectivity is 99.1 percent.
Example 7
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the temperature rise rate of the catalyst precursor is 5 ℃/min during roasting, the fluorene conversion rate is 93.4 percent, and the fluorenone selectivity is 99.4 percent.
Example 8
The catalyst preparation method and evaluation conditions differ from example 1 as follows: at the reaction temperature of 80 ℃, the conversion rate of fluorene is 98.7 percent, and the selectivity of fluorenone is 99.7 percent.
Example 9
The catalyst preparation method and evaluation conditions differ from example 1 as follows: at the reaction temperature of 40 ℃, the conversion rate of fluorene is 93.2 percent, and the selectivity of fluorenone is 99.2 percent.
Example 10
The catalyst preparation method and evaluation conditions differ from example 1 as follows: 300 mL/min, the fluorene conversion rate is 96.8 percent, and the fluorenone selectivity is 99.1 percent.
Example 11
The catalyst preparation method and evaluation conditions differ from example 1 as follows: 60 mL/min, the fluorene conversion rate is 92.1 percent, and the fluorenone selectivity is 99.1 percent.
Example 12
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the oxidation reaction was carried out for 4 hours, the conversion of fluorene was 85.3%, and the selectivity of fluorenone was 99.2%.
Example 13
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the oxidation reaction was carried out for 12 hours, the conversion of fluorene was 98.2%, and the selectivity of fluorenone was 99.1%.
Example 14
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the reaction solvent is 100mL of p-xylene, the conversion rate of fluorene is 91.3%, and the selectivity of fluorenone is 99.1%.
Example 15
The catalyst preparation method and evaluation conditions differ from example 1 as follows: 100mL of dimethyl sulfoxide serving as a reaction solvent, 82.4% of fluorene conversion rate and 99.3% of fluorenone selectivity.
Example 16
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the reaction solvent 1, 3-dimethyl-3, 4,5, 6-tetrachloro-2 (1H) pyrimidone is 100mL, the fluorene conversion rate is 87.8 percent, and the fluorenone selectivity is 99.2 percent.
Example 17
The catalyst preparation method and evaluation conditions differ from example 1 as follows: the reaction solvent 1, 3-dimethyl-3, 4,5, 6-tetrachloro-2 (1H) pyrimidone is 100mL, the fluorene conversion rate is 87.8 percent, and the fluorenone selectivity is 99.2 percent.
Example 18
The catalyst preparation method and evaluation conditions differ from example 1 as follows: 20.37g of Co (NO) were weighed out3)2·6H2O, 4.83g of Cu (NO)3)2·3H2O, 2.36g of Ca (NO)3)2·4H2O salt, thereby obtaining Co7Cu2Ca1A catalyst. The conversion rate of fluorene is 96.5%, and the selectivity of fluorenone is 99.5%.
Example 19
The catalyst preparation method and evaluation conditions differ from example 1 as follows: 8.85g of Co (CH) are weighed out3COO)2·4H2O, 5.98g of Cu (CH)3COO)2·H2O, 3.52g of Ca (CH)3COO)2·H2O salt, thereby obtaining Co5Cu3Ca2A catalyst. The conversion rate of fluorene is 94.6%, and the selectivity of fluorenone is 99.2%.
Example 20
The catalyst used in example 1 was centrifuged and added again to carry out the above reaction under the same conditions, and the reaction was repeated 10 times, with the following experimental results:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a multi-oxide catalyst for preparing fluorenone by oxidizing fluorene is characterized by comprising the following steps: mixing precursor substances of Co, Cu and X by a physical mechanical grinding mode, wherein X = K, Na, Mg and Ca, and then calcining at high temperature to obtain the multi-element oxide catalyst.
2. The method of claim 1, wherein: and the precursors of the Co, the Cu and the X are one or two of nitrate or acetate.
3. The method of claim 1, wherein: the precursor is mechanically ground to more than 200 meshes.
4. The method of claim 1, wherein: the high-temperature calcination temperature is 300-800 ℃, the calcination time is 2-6 h, and the heating rate is 2-5 ℃/min.
5. The method of claim 1, wherein: the molar ratio of Co, Cu and X in the multi-component oxide catalyst is (5-7): (2-4): 1-3.
6. A catalyst prepared by the process of any one of claims 1 to 5, characterized in that: the catalyst is Co-Cu-X, the catalyst is a heterogeneous multi-element metal oxide catalyst, wherein X = K, Na, Mg, Ca, and the molar ratio of Co, Cu and X is (5-7): (2-4): (1-3).
7. The use of the catalyst of claim 6 for the catalytic oxidation of fluorene to fluorenone, characterized by the following steps: adding fluorene into a solvent, then adding a catalyst, and introducing oxygen for reaction at 40-80 ℃.
8. Use according to claim 7, characterized in that: the solvent is 1, 3-dimethyl-3, 4,5, 6-tetrachloro-2 (1H) pyrimidone, dimethyl sulfoxide, o-xylene, m-xylene, p-xylene or cyclohexane, oxygen is introduced into each 100mL of the solvent at a volume flow of 60-300 mL/min, and the oxidation reaction time is 4-12H.
9. Use according to claim 8, characterized in that: the mass percentage of the fluorene is 0.1-30 wt%, and the mass ratio of the catalyst to the fluorene is 1: (0.5 to 150).
10. Use according to any one of claims 7 to 9, characterized in that: a reflux condensing device is arranged on a reactor of the catalytic reaction, wherein the conversion rate of fluorene is more than 85%, and the selectivity of fluorenone is more than 99.1%.
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