阅读说明：本技术 一种由醇类原料制备晕苯类化合物的方法 (Method for preparing coronene compound from alcohol raw material ) 是由 王男 郅玉春 魏迎旭 刘中民 桑石云 于 2019-04-03 设计创作，主要内容包括：本发明涉及一种由醇类原料制备晕苯类化合物的方法。本发明的方法包括以下步骤：将含有醇类化合物的原料与催化剂在反应器中接触反应,得到晕苯类化合物；其中,所述催化剂包括经过活化处理的硅铝分子筛。(The invention relates to a method for preparing coronene compounds from alcohol raw materials. The method of the invention comprises the following steps: the raw material containing the alcohol compound and a catalyst are contacted and reacted in a reactor to obtain the coronene compound; wherein the catalyst comprises an activated aluminosilicate molecular sieve.)

1. A method for preparing coronenes from an alcohol raw material, which is characterized by comprising the following steps:

the raw material containing the alcohol compound and a catalyst are contacted and reacted in a reactor to obtain the coronene compound;

wherein the catalyst comprises an activated aluminosilicate molecular sieve.

2. The method according to claim 1, wherein the reaction is followed by a post-treatment to obtain the coronene compound.

3. The method of claim 1, wherein the post-processing comprises: purifying the product obtained by the reaction in an inorganic strong acid solution to obtain the coronene compound;

preferably, the purification comprises: extracting with an organic solvent;

preferably, the organic solvent comprises one of dichloromethane, chloroform, tetrachloromethane, petroleum ether and diethyl ether;

preferably, the strong inorganic acid comprises: at least one of hydrogen fluoride, hydrochloric acid and nitric acid.

4. The method of claim 1, wherein the coronenes are at least two of coronenes, 8-hydro-phenyl [ bc ] coronenes, methyl-8-hydro-phenyl [ bc ] coronenes, and dimethyl-8-hydro-phenyl [ bc ] coronenes;

the alcohol compound is selected from at least one of methanol, ethanol, propanol, butanol, pentanol and hexanol.

5. The method of claim 1, wherein the feedstock further comprises water;

the mass ratio of the water to the alcohol compound is 0-5;

preferably, the mass ratio of the water to the alcohol compound is 0 to 3.

6. The method of claim 1, wherein the feedstock is introduced into the reactor by a carrier gas or vaporized and introduced into the reactor;

preferably, the carrier gas is selected from at least one of inactive gases.

7. The method of claim 1, wherein the silicoaluminophosphate molecular sieve comprises at least one of a RHO molecular sieve, an ITQ-29 molecular sieve, a UZM-9 molecular sieve, an ECR-18 molecular sieve, a ZSM-25 molecular sieve, a KFI molecular sieve;

the activation treatment comprises: heating at 500-600 deg.c in non-active atmosphere.

8. The method according to claim 1, characterized in that it comprises:

(1) loading a silicon-aluminum molecular sieve catalyst into a reactor, and heating to 500-600 ℃ in an inactive atmosphere to activate the silicon-aluminum molecular sieve catalyst;

(2) adjusting the temperature of the reactor to 450-550 ℃, feeding a raw material containing an alcohol compound into the reactor to be converted on the silicon-aluminum molecular sieve catalyst, and generating a product coronene compound remained in the silicon-aluminum molecular sieve catalyst;

(3) dissolving the silicon-aluminum molecular sieve catalyst in the product of the step (2) in an inorganic strong acid solution, and extracting an organic phase in the inorganic strong acid solution by using an organic solvent to obtain the coronene compound.

9. The method according to claim 1, wherein the feed mass space velocity of the raw material is 1-10 h^-1；

The reaction temperature is 450-550 ℃;

the reaction pressure is 0.1-0.5 MPa;

preferably, the feeding mass space velocity of the raw materials is 2-5 h^-1；

Preferably, the pressure of the reaction is 0.1-0.2 MPa.

10. The method of claim 1, wherein the reactor is a fixed bed reactor or a fluidized bed reactor.

Technical Field

The application relates to a method for preparing coronene compounds, belonging to the field of organic chemistry.

Background

The coronene compound is a condensed ring aromatic compound with highly symmetrical structure, and has a larger conjugated system, a strong rigid structure and coplanarity. Coronene has a maximum absorption wavelength of 255nm and a maximum emission wavelength of 520nm, and has extremely high fluorescence quantum efficiency, and therefore, it occupies an extremely important position in the field of fluorescent materials, particularly ultraviolet fluorescent materials. The coronene compound is an excellent material for preparing an Ultraviolet Charge Coupled Device (UV-CCD), and the Ultraviolet CCD image sensor has wide application in the fields of nuclear explosion, medicine, astronomy, military (radar) and the like.

At present, the preparation method of coronene mainly comprises three methods, namely a Wurtz-Fittig reaction synthesis method, a Diels-Alder reaction synthesis method and an anion reaction synthesis method.

Wurtz-Fittig reaction synthesis method in 1951, Wilson Baker et al synthesized coronene from 2, 7-dimethylnaphthalene under the reduction of Na and palladium black. The synthetic route is shown below. In this preparation method, the final yield of coronene is 4%, the reaction time is long, the conditions are severe and the product isolation is difficult, and thus it is not suitable for mass production.

Diels-Alder reaction synthesis in addition to the Wurtz-Fittig reaction, the Diels-Alder reaction is also an important and efficient method for preparing polycyclic compounds. In 1957, e.clar and e.zander produced coronene with a total reaction yield of 25% using a two-step Diels-Alder reaction and a two-step decarboxylation reaction. Their synthetic routes are shown below. However, the raw material perylene of the method is expensive, and the reaction process involves operations such as high temperature, vacuum decarboxylation, sublimation purification and the like for many times, and the conditions are harsh, so the method is still quite inconvenient in actual operation.

3. Anion reaction synthesis method: in 1996, Van Dijk et al published a method for the synthesis of coronene using the anion of a polycyclic aromatic hydrocarbon, the synthetic route of which is shown below. They still start from perylenes, which are sonicated under the action of Na in THF to give their anions, and subsequently, under the action of concentrated sulfuric acid and ultrasound, produce coronene in 44% overall yield. They also address the mass production of perylenes starting from 3,4,9, 10-perylene tetracarboxylic anhydride in Ba (OH)₂Under the action of the organic solvent, a large amount of perylene can be obtained under the condition of 400 ℃ for several days. The method overcomes the defect of expensive raw material peryleneHowever, the process involves many anhydrous and anaerobic and low-temperature operations, and the intermediate product is extremely unstable, which is inconvenient for industrialization.

Disclosure of Invention

The invention aims to provide a novel method for preparing coronene compounds, which adopts alcohol raw materials and takes a silicon-aluminum molecular sieve as a catalyst to synthesize the coronene compounds.

To this end, the present invention provides a process for the preparation of a coronene compound, said process comprising the steps of:

the raw material containing the alcohol compound and a catalyst are contacted and reacted in a reactor to obtain the coronene compound;

wherein the catalyst comprises an activated aluminosilicate molecular sieve.

In a preferred embodiment, the catalyst consists of an activated aluminosilicate molecular sieve.

In a preferred embodiment, the reaction is followed by a post-treatment to obtain the coronene compound.

In a preferred embodiment, the post-treatment comprises: purifying the product obtained by the reaction in an inorganic strong acid solution to obtain the coronene compound;

preferably, the purification comprises: extracting with an organic solvent;

preferably, the organic solvent comprises one of dichloromethane, chloroform, tetrachloromethane, petroleum ether and diethyl ether.

Preferably, the product is kept stand in inorganic strong acid for 0.5-5 h.

In a preferred embodiment, the strong inorganic acid comprises: at least one of hydrogen fluoride, hydrochloric acid and nitric acid.

In a preferred embodiment, the coronenes are at least two of coronene, 8-hydro-phenyl [ bc ] coronene, methyl-8-hydro-phenyl [ bc ] coronene, and dimethyl-8-hydro-phenyl [ bc ] coronene;

the alcohol compound is selected from at least one of methanol, ethanol, propanol, butanol, pentanol and hexanol.

In a preferred embodiment, the feedstock also includes water;

the mass ratio of the water to the alcohol compound is 0-5;

preferably, the mass ratio of the water to the alcohol compound is 0 to 3.

In a preferred embodiment, the feedstock is introduced into the reactor by a carrier gas or vaporized and then introduced into the reactor;

preferably, the carrier gas is selected from at least one of inactive gases.

Preferably, the inert gas includes nitrogen, an inert gas, and the like.

The silicon-aluminum molecular sieve comprises at least one of an RHO molecular sieve, an ITQ-29 molecular sieve, an UZM-9 molecular sieve, an ECR-18 molecular sieve, a ZSM-25 molecular sieve and a KFI molecular sieve;

the activation treatment comprises: heating at 500-600 deg.c in non-active atmosphere.

In a preferred embodiment, the method comprises:

(1) loading a silicon-aluminum molecular sieve catalyst into a reactor, and heating to 500-600 ℃ in an inactive atmosphere to activate the silicon-aluminum molecular sieve catalyst;

(2) adjusting the temperature of the reactor to 450-550 ℃, feeding a raw material containing an alcohol compound into the reactor to be converted on the silicon-aluminum molecular sieve catalyst, and generating a product coronene compound remained in the silicon-aluminum molecular sieve catalyst;

(3) dissolving the silicon-aluminum molecular sieve catalyst in the product of the step (2) in an inorganic strong acid solution, and extracting an organic phase in the inorganic strong acid solution by using an organic solvent to obtain the coronene compound.

In a preferred embodiment, the feed mass space velocity of the raw material is 1-10 h^-1；

The reaction temperature is 450-550 ℃;

the reaction pressure is 0.1-0.5 MPa;

preferably, the feeding mass space velocity of the raw materials is 2-5 h^-1；

Preferably, the pressure of the reaction is 0.1-0.2 MPa.

In a preferred embodiment, the reactor is a fixed bed reactor or a fluidized bed reactor.

The beneficial effects that this application can produce include:

(1) the simple and feasible method for preparing the coronene compound is provided, and the method has the advantages of simple preparation process, mild reaction conditions and easy operation;

(2) the required raw materials are easy to obtain and the cost is low, so the method is suitable for large-scale production.

Drawings

FIG. 1 is an X-ray diffraction pattern of a sample of a synthesized RHO molecular sieve;

FIG. 2 is an X-ray diffraction pattern of a sample of synthesized ITQ-29 molecular sieve;

FIG. 3 is an X-ray diffraction pattern of a sample of a synthesized UZM-9 molecular sieve;

FIG. 4 is an X-ray diffraction pattern of a sample of synthesized ECR-18 molecular sieve;

FIG. 5 is an X-ray diffraction pattern of a sample of a synthesized ZSM-25 molecular sieve;

fig. 6 is an X-ray diffraction pattern of a sample of the synthesized KFI molecular sieve.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.

In a preferred embodiment of the present invention, the main steps for preparing coronenes from an alcohol feedstock in the presence of a silicoaluminophosphate molecular sieve catalyst in a fixed bed reactor are as follows:

a certain amount of silicon-aluminum molecular sieve catalyst is filled in a fixed bed reactor, and a catalyst bed layer is heated to a certain temperature between 500 ℃ and 600 ℃ for a period of time, for example, 5-60 min, under the atmosphere of inert gas such as nitrogen or helium, so as to complete the catalyst activation process. Adjusting the temperature of the reactor to a certain temperature between 450 ℃ and 550 ℃, introducing inert gas such as nitrogen or helium carrying alcohol steam or mixed steam of alcohol and water into the reactor to contact and react with the catalyst, and cooling the reactor to room temperature after the reaction is finished. After the reaction is completed, the temperature of the reactor is preferably reduced to room temperature, for example, the catalyst (with the product coronene compound remaining inside) is poured out, the catalyst is placed in a strong acid solution such as a hydrogen fluoride solution or a hydrochloric acid solution for a period of time such as 0.5 to 5 hours, and after all solid substances are dissolved, the organic phase is extracted by using an organic solvent such as carbon tetrachloride or petroleum ether to obtain the coronene compound.

In a preferred embodiment of the present invention, the main steps for preparing coronenes from an alcohol feedstock in the presence of a silicoaluminophosphate molecular sieve catalyst in a fluidized bed reactor are as follows:

a certain amount of the silicon-aluminum molecular sieve microspherical catalyst is filled into a fluidized bed reactor, and the reactor is heated to a certain temperature between 500 ℃ and 600 ℃ under the atmosphere of inert gas such as nitrogen or helium and is kept for a period of time such as 5-60 min, so that the catalyst activation process is completed. The reactor temperature is then adjusted to a temperature between 450 c and 550 c and the alcohol feed is introduced into the vaporization furnace, for example, by a feed pump, where it is vaporized and then fed to the fluidized bed reactor to complete the feed. The alcohol raw material contacts with silicon-aluminium molecular sieve catalyst in the reactor and is converted into coronene compound. Preferably, the feeding mass space velocity of the alcohol raw material is 1-10 h^-1The reaction pressure is 0.1-0.5 MPa. And after the reaction is finished, preferably cooling to room temperature, taking out the catalyst, placing the catalyst in a strong acid solution such as a hydrogen fluoride solution or a nitric acid solution for a period of time such as 0.5-5 h, and after the catalyst is completely dissolved, extracting an organic phase by using carbon tetrachloride or chloroform to obtain the coronene compound.

In the present invention, for example, the composition of the organic phase obtained by the extraction is analyzed by an Agilent 7890/5975 chromatograph-mass spectrometer and HP-5 chromatographic column in the examples, and the yield of coronene compound is calculated by combining the weight gain of the catalyst after the reaction (the initial catalyst weight and the catalyst weight after the reaction are determined by an integrated thermal analyzer) and the analysis result of the chromatograph-mass spectrometer, wherein the yield is calculated by the formula:

Y_i＝(ΔW_cat*C_i)/F_j

Y_tatal＝∑Y_i

i: the produced coronenes, including coronene, 8-hydro-phenyl [ bc ] coronene, methyl-8-hydro-phenyl [ bc ] coronene, dimethyl-8-hydro-phenyl [ bc ] coronene;

j: alcohols as raw materials including methanol, ethanol, propanol, butanol, pentanol;

ΔW_cat: catalyst phase weight gain determined by a comprehensive thermal analyzer;

C_i: chromatographically determining the concentration of a coronene compound in the organic phase;

F_j: the feed amount of alcohol as a raw material;

Y_i: the yield of certain coronenes;

Y_total: total yield of coronenes.