CN109092337B

CN109092337B - Catalyst for preparing fluorenone by gas-phase oxidation of fluorene

Info

Publication number: CN109092337B
Application number: CN201811047260.9A
Authority: CN
Inventors: 鄂永胜; 鄢景森; 贺凤伟; 代文双; 王强; 吕萍
Original assignee: Liaoning Institute of Science and Technology
Current assignee: Liaoning Institute of Science and Technology
Priority date: 2018-09-09
Filing date: 2018-09-09
Publication date: 2021-02-23
Anticipated expiration: 2038-09-09
Also published as: CN109092337A

Abstract

The invention relates to a catalyst for preparing fluorenone by gas phase oxidation of fluorene, which is prepared from V₂O₅、KOH、MnSO₄、Fe₂(SO₄)₃、K₂SO₄、FeSO₄And NH₄H₂PO₄Seven compounds with the mass ratio V₂O₅∶KOH∶MnSO₄∶Fe₂(SO₄)₃∶K₂SO₄∶FeSO₄ ∶NH₄H₂PO₄= 1: 1.1: 0.03: 2.5: 1: 0.05: 0.08. The catalyst can lead the conversion rate of fluorene to reach more than 99.5 percent and the selectivity of fluorenone to reach more than 98 percent in the gas phase oxidation process, and simultaneously has low cost and long service life.

Description

Catalyst for preparing fluorenone by gas-phase oxidation of fluorene

Technical Field

The invention relates to a catalyst for preparing fluorenone by gas phase oxidation of fluorene, belonging to the technical field of chemical industry.

Background

Fluorenone is the basic organic synthetic raw material and has wide application. In the pharmaceutical industry, for the synthesis of anticancer agents, antispasmodics, etc.; in agriculture, for the synthesis of herbicides, insecticides, etc.; in the dye industry, for the synthesis of aromatic diamine dyes; in the xerography industry for making photosensitive materials; in the food industry for the synthesis of preservatives; in the plastics industry, the bisphenol compound is used for synthesizing bisphenol products, is used as a stabilizer and a plasticizer in the polymerization process, is used for preparing functional polymer materials, and can also be used as a raw material of synthetic resin and a modifier. The functional polymer material is mainly used.

The existing production method of fluorenone is mainly prepared by oxidizing fluorene, wherein the oxidation can be divided into two methods of liquid-phase oxidation and gas-phase oxidation, and the gas-phase oxidation method does not use a solvent, so that the environmental pollution is avoided, and the product has high yield, good quality and low cost, and is suitable for industrial production. The gas phase catalytic oxidation reaction of fluorene is composed of parallel reaction and series reaction, except for fluorenone, by-products of phthalic anhydride and maleic anhydride, etc. pointed out in "coal tar engineering" (2 nd edition) (P267-270) by shorea editor, and in order to obtain fluorenone with high yield, the catalyst is selectedSelection is one of the most important factors. In order to oxidize fluorene into fluorenone, improve conversion rate, prevent over-oxidation and avoid selectivity reduction, the catalyst is compounded. V of table 10-6 in the book₂O₅-Fe₂O₃-Cs₂SO₄The catalyst has very good selectivity, the maximum selectivity of fluorenone reaches 99 percent, and the minimum selectivity is more than 85 percent, but Cs₂SO₄It is very expensive and its addition can significantly increase the catalyst cost. In tables 10 to 7, the vanadium-titanium based catalysts had a conversion of about 99% and a selectivity of about 89%, and the selectivity was to be improved.

The catalyst in patent ZL200810137413.9 has better conversion rate and selectivity, but Cs₂The use of O also increases the cost of the catalyst. Three catalysts, potassium vanadium, tin vanadium and titanium vanadium, are mentioned in patent ZL99112742.0, and have long service life, but conversion and selectivity are not mentioned. The conversion rate is about 99 percent and the selectivity is 87.4 to 96.0 percent in the following table 1 of the patent ZL96123084.3 example, and the improvement space is still provided.

The conversion rate and the selectivity are in a pair of contradiction in the process of producing fluorenone by catalytic oxidation of fluorene, if the activity of the catalyst is low, the conversion rate is low, the fluorene reaction is incomplete, and the yield of the final fluorenone is low; if the activity of the catalyst is too high, excessive oxidation occurs, so that although the reaction is complete, the by-products such as phthalic anhydride and maleic anhydride are too much, the selectivity of fluorenone is reduced, and the yield of the final product is not high. At the same time, the cost and service life of the catalyst are also considered.

The invention provides a novel seven-element catalyst which is developed on the basis of fully considering the problems, and the catalyst is composed of V₂O₅、KOH、MnSO₄、Fe₂(SO₄)₃、K₂SO₄、FeSO₄And NH₄H₂PO₄The catalyst is composed of seven compounds and has strict mass proportion limitation, the conversion rate of fluorene can reach more than 99.5%, the selectivity of fluorenone can reach more than 98%, and meanwhile, the catalyst is low in cost and has the service life of more than 5 years.

Disclosure of Invention

Hair brushThe purpose of the invention is to provide a catalyst for preparing fluorenone by gas phase oxidation of fluorene, which is prepared from V₂O₅、KOH、MnSO₄、Fe₂(SO₄)₃、K₂SO₄、FeSO₄And NH₄H₂PO₄Seven compounds with the mass ratio V₂O₅∶KOH∶MnSO₄∶Fe₂(SO₄)₃∶K₂SO₄∶FeSO₄ ∶NH₄H₂PO₄The catalyst has the advantages that the conversion rate of fluorene can reach more than 99.5 percent, the selectivity of fluorenone can reach more than 98 percent, and the catalyst is low in cost and long in service life.

The catalyst is prepared by the following steps:

1.V₂O₅preparation of the solution

Weighing a certain amount of vanadium pentoxide, adding the vanadium pentoxide into a potassium hydroxide solution, heating for dissolving, properly stirring for assisting the dissolution, and controlling the dissolving temperature to be about 70 ℃.

2. Preparation of two cocatalyst solutions

Weighing a certain amount of MnSO₄、Fe₂(SO₄)₃、FeSO₄Adding distilled water, heating to dissolve, stirring properly to help dissolve, and controlling the dissolving temperature at 50-60 deg.C.

In addition, a certain amount of K₂SO₄And NH₄H₂PO₄And adding distilled water to prepare a solution.

3. Preparation of impregnation liquid

Adding the above three solutions together under stirring, and stirring to obtain soaking solution.

4. Impregnation

Adding dry pumice into a flat container, adding the immersion liquid onto the pumice, pouring while flanging and heating to uniformly impregnate the pumice, and heating until there is no immersion liquid in the container.

5. Drying

The impregnated pumice stone is dried in a dryer, and the drying humidity is controlled at 130-150 ℃.

6. Activation of

The dried catalyst loaded on the pumice is arranged in a fixed bed oxidizer and activated by hot air at the temperature of 420-450 ℃ for 24 hours, and then the novel seven-element catalyst is prepared.

The catalyst has the following outstanding advantages by compounding seven compounds:

1. the activity of the catalyst is controlled to be in an optimum state, so that the high conversion rate of raw materials and the high selectivity of main products are ensured;

2. the materials used by the catalyst are all common compounds, and no noble metal compound is used, so that the cost is low;

3. the service life of the catalyst is long, can reach more than five years, and can be activated by introducing hot air every half year to one year according to the production.

Detailed Description

The invention is further illustrated by the following examples:

example 1

1. V₂O₅Preparation of the solution

Weighing 3000 g of vanadium pentoxide, adding 30 kg of distilled water, then adding 3300 g of potassium hydroxide, heating to dissolve, properly stirring to assist dissolution, controlling the dissolution temperature at 70 +/-2 ℃, filtering after complete dissolution, and obtaining filtrate.

2. Preparation of cocatalyst solution

Weighing 7500 g of ferric sulfate, 90 g of manganese sulfate and 150 g of ferrous sulfate, adding 30 kg of distilled water, heating for dissolving, properly stirring for assisting the dissolution, controlling the dissolving temperature to be 50-60 ℃, filtering after full dissolution, and obtaining filtrate.

Weighing 3000 g of potassium sulfate and 240 g of ammonium dihydrogen phosphate, adding 20 kg of distilled water, heating the solution, controlling the dissolving temperature at 50-60 ℃, completely dissolving, and filtering to obtain filtrate.

3. Preparation of impregnation liquid

The above three solutions were mixed slowly with stirring by a wooden stick to prepare a maceration extract.

4. Impregnation

100 liters of dry pumice is added into a frying pan, then the impregnation liquid is added on the pumice, the pumice is evenly impregnated by heating the edge turning while pouring, and the heating is carried out until no impregnation liquid exists in the pan.

5. Drying

And (3) putting the immersed pumice into a dryer for drying, controlling the drying humidity at 130-150 ℃, putting the dried catalyst into a cleaning barrel lined with a plastic bag, and sealing, storing and storing the catalyst in a moisture-proof way for later use.

6. Activation of

Fluorene with the content of 93.2 percent is taken as a raw material, and the load of the catalyst is 16g/m³And s, controlling the reaction temperature at 360 +/-3 ℃, obtaining fluorenone with the content of 98.6 percent and the yield of 98.3 percent, and calculating the conversion rate to be 99.8 percent and the selectivity to be 98.5 percent through testing the composition of a product.

Example 2

Using the same catalyst as in example 1, 95.6% fluorene content was used as a starting material and the catalyst loading was 15g/m³And s, controlling the reaction temperature at 360 +/-3 ℃, obtaining fluorenone with the content of 98.8 percent and the yield of 98.6 percent, and calculating the conversion rate to be 100 percent and the selectivity to be 98.6 percent through testing the composition of a product.

Claims

1. A catalyst for preparing fluorenone by gas-phase oxidation of fluorene is characterized by comprising the following preparation steps:

（1）V₂O₅preparing a solution: weighing a certain amount of V₂O₅Adding into KOH solution, heating to dissolve, stirring properly to aid dissolving, controlling the dissolving temperature at about 70 ℃;

(2) preparation of two cocatalyst solutions: weighing a certain amount of MnSO₄、Fe₂(SO₄)₃、FeSO₄Adding distilled water, heating for dissolving, and properly stirring for assisting dissolution, wherein the dissolving temperature is controlled at 50-60 ℃; in addition, a certain amount of K₂SO₄And NH₄H₂PO₄Adding distilled water to prepare a solution;

(3) preparation of an impregnation liquid: adding the three solutions together under stirring, and stirring to obtain soaking solution;

(4) dipping: firstly, adding dry pumice into a flat container, then adding impregnation liquid onto the pumice, pouring and flanging for heating to ensure that the pumice is uniformly impregnated until no impregnation liquid exists in the container;

(5) and (3) drying: putting the immersed pumice into a dryer for drying, and controlling the drying temperature at 130-150 ℃;

(6) and (3) activation: the dried catalyst loaded on the pumice is arranged in a fixed bed oxidizer and is activated by introducing hot air at the temperature of 420-450 ℃ for 24 hours to prepare the catalyst;

mass ratio V of the above compounds₂O₅∶KOH∶MnSO₄∶Fe₂(SO₄)₃∶K₂SO₄∶FeSO₄ ∶NH₄H₂PO₄=1∶1.1∶0.03∶2.5∶1∶0.05∶0.08。