CN111777480A - Method for preparing coronene compound by using molecular sieve catalyst - Google Patents

Method for preparing coronene compound by using molecular sieve catalyst Download PDF

Info

Publication number
CN111777480A
CN111777480A CN201910264943.8A CN201910264943A CN111777480A CN 111777480 A CN111777480 A CN 111777480A CN 201910264943 A CN201910264943 A CN 201910264943A CN 111777480 A CN111777480 A CN 111777480A
Authority
CN
China
Prior art keywords
molecular sieve
sieve catalyst
reactor
alcohol
catalyst
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.)
Granted
Application number
CN201910264943.8A
Other languages
Chinese (zh)
Other versions
CN111777480B (en
Inventor
王男
郅玉春
魏迎旭
刘中民
桑石云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201910264943.8A priority Critical patent/CN111777480B/en
Publication of CN111777480A publication Critical patent/CN111777480A/en
Application granted granted Critical
Publication of CN111777480B publication Critical patent/CN111777480B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings

Abstract

The invention relates to a method for preparing coronene compounds by using a molecular sieve catalyst. Specifically, the method disclosed by the invention comprises the following steps of: (1) activating the molecular sieve catalyst; wherein the molecular sieve catalyst comprises a SAPO molecular sieve catalyst; (2) carrying out contact reaction on the raw material and the molecular sieve catalyst activated in the step (1) in a reactor to obtain the coronene compound; wherein the raw material comprises an alcohol compound.

Description

Method for preparing coronene compound by using molecular sieve catalyst
Technical Field
The invention relates to the preparation of chemicals, in particular to a method for preparing coronene compounds from alcohol raw materials.
Background
Coronene is an organic fluorescent material. Coronene has a maximum absorption wavelength of 255nm and a maximum emission wavelength of 520nm and has a high quantum efficiency, and thus coronene can be used in uv-ccd devices as well as in radar.
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.
Figure BDA0002016480760000011
Diels-Alder reaction synthesis is also an important and efficient method for the preparation of 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.
Figure BDA0002016480760000021
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. Although the method overcomes the defect that the price of the raw material perylene is high, the process involves multiple anhydrous and anaerobic and low-temperature operations, and the intermediate product is extremely unstable, which brings inconvenience to industrialization.
Figure BDA0002016480760000022
Disclosure of Invention
In view of the defects of the prior art, the invention provides a method for preparing coronene compounds by using a molecular sieve catalyst, which is characterized by at least comprising the following steps:
(1) activating the molecular sieve catalyst; wherein the molecular sieve catalyst comprises a SAPO molecular sieve catalyst;
(2) carrying out contact reaction on the raw material and the molecular sieve catalyst activated in the step (1) in a reactor to obtain the coronene compound;
wherein the raw material comprises an alcohol compound.
In a preferred embodiment, the method comprises the steps of:
(1) filling an SAPO molecular sieve catalyst into a reactor, heating to 500-600 ℃ under inert atmosphere, and activating the SAPO molecular sieve catalyst;
(2) after the temperature of the reactor is adjusted to 450-550 ℃, feeding an alcohol raw material into the reactor to perform conversion on the SAPO molecular sieve catalyst to generate a product coronene compound remaining inside the SAPO molecular sieve catalyst;
(3) dissolving the SAPO molecular sieve catalyst with the product in a strong inorganic acid solution, and extracting an organic phase therein by using an organic solvent to obtain the coronene compound.
In a preferred embodiment, the alcohol is selected from at least one of methanol, ethanol, propanol, butanol, pentanol and hexanol.
In a preferred embodiment, the alcohol raw material is a mixture of alcohol and water, and the mass ratio of water to alcohol is 0 to 5, preferably 0 to 3.
In a preferred embodiment, the coronene-based compound is at least two of coronene, 8-hydro-phenyl [ bc ] coronene, methyl-8-hydro-phenyl [ bc ] coronene, and dimethyl-8-hydro-phenyl [ bc ] coronene.
In a preferred embodiment, the SAPO molecular sieve is at least one of DNL-6, SAPO-42, ZK-21, ZK-22, DNL-1, cloverite; preferably, the SAPO molecular sieve catalysts are DNL-6, SAPO-42, and ZK-21.
In a preferred embodiment, the alcohol feedstock is fed by entraining its vapor with an inert gas into the reactor or by vaporizing the alcohol feedstock in a vaporizer and then feeding into the reactor.
In a preferred embodiment, the strong inorganic acid solution is a hydrogen fluoride solution, a hydrochloric acid solution, or a nitric acid solution.
In a preferred embodiment, the organic solvent used for extraction is dichloromethane, chloroform, tetrachloromethane, petroleum ether or diethyl ether.
In a preferred embodiment, the reactor is a fixed bed reactor or a fluidized bed reactor.
In a preferred embodiment, the feeding mass space velocity of the alcohol raw material is 1-10 h-1The reaction pressure is 0.1-0.5 MPa; preferably, the feeding mass airspeed of the alcohol raw material is 2-5 h-1The reaction pressure is 0.1-0.2 MPa.
The beneficial effects that this application can produce include:
1) the simple method for preparing the coronene compound is provided, and has the advantages of simple preparation process, mild reaction conditions and easy operation;
2) the raw materials are easy to obtain, the cost is low, and the method is suitable for large-scale production.
Drawings
FIG. 1 is an X-ray diffraction analysis of a sample of the synthesized DNL-6 molecular sieve.
FIG. 2 is an X-ray diffraction analysis of a sample of a synthesized SAPO-42 molecular sieve.
FIG. 3 is an X-ray diffraction analysis of a sample of synthesized ZK-21 molecular sieve.
FIG. 4 is an X-ray diffraction analysis of a sample of synthesized ZK-22 molecular sieve.
FIG. 5 is an X-ray diffraction analysis of a sample of the synthesized DNL-1 molecular sieve.
FIG. 6 is an X-ray diffraction analysis of a sample of the synthesized clofarite 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.
In a preferred embodiment of the present invention, the main steps for preparing coronenes from an alcohol feedstock in the presence of a SAPO molecular sieve catalyst in a fixed bed reactor are as follows:
a certain amount of SAPO 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 that the catalyst activation process is completed. 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 reactor is preferably cooled 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 SAPO molecular sieve catalyst in a fluidized bed reactor are as follows:
a certain amount of SAPO molecular sieve microsphere catalyst is loaded 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 SAPO 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. After the reaction is completed, the temperature is preferably lowered to room temperature, and the catalyst is taken out of the reaction solution in a strong acid solutionFor example, hydrogen fluoride solution or nitric acid solution is placed for a period of time, for example, 0.5-5 hours, after the catalyst is completely dissolved, carbon tetrachloride or chloroform is used for extracting an organic phase, and the product coronene compound is obtained.
In the present invention, the composition of the organic phase obtained by extraction can be analyzed by Agilent 7890/5975 chromatograph-mass spectrometer and HP-5 chromatographic column, and the yield of coronene compound can be calculated by combining the weight gain of the catalyst after reaction (the initial catalyst weight and the catalyst weight after reaction are determined by comprehensive thermal analyzer) and the analysis result of chromatograph-mass spectrometer, wherein the yield is calculated by the formula:
Yi＝(ΔWcat*Ci)/Fj
Ytatal＝∑Yi
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;
ΔWcat: catalyst phase weight gain determined by a comprehensive thermal analyzer;
Ci: chromatographically determining the concentration of a coronene compound in the organic phase;
Fj: the feed amount of alcohol as a raw material;
Yi: the yield of certain coronenes;
Ytotal: total yield of coronenes.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1: synthesis of DNL-6 molecular sieve catalyst
Initial gel molar composition ratio 2N-methylbutylamine (as organic structure directing agent): 0.3SiO2：0.4P2O5：0.5Al2O3：50H2O: 0.2 (20%) hexadecyltrimethylammonium bromide (as seed) directed metered amounts of organic structure toMixing the agent, silica sol, phosphoric acid, aluminum isopropoxide, deionized water and seed crystal in a beaker, fully stirring to form gel, then putting the gel into a stainless steel autoclave lined with polytetrafluoroethylene, and carrying out rotary crystallization for 24 hours at a constant temperature of 200 ℃ and a rotating speed of 75 r/min. Centrifuging at 3000 rpm for 3min, washing the solid product with deionized water to neutrality, and drying at 120 deg.C overnight to obtain XRD analysis result shown in FIG. 1. As can be seen from the results in FIG. 1, the synthesized product was DNL-6 molecular sieve raw powder, which was calcined at 550 ℃ for 5 hours to give DNL-6 molecular sieve, which was designated as catalyst 1.
Example 2: synthesis of SAPO-42 molecular sieve catalyst
1.852, 2-dimethyl-2, 3-dihydro-1H-phenyl [ de ] in initial gel molar composition ratio]Isoquinoline (as organic structure directing agent): 0.296SiO2：0.85P2O5：1Al2O3：60H2And O, mixing the metered organic structure directing agent, silica sol, phosphoric acid, pseudo-boehmite and deionized water in a beaker, fully stirring to form gel, then filling the gel into a stainless steel autoclave lined with polytetrafluoroethylene, and crystallizing at the constant temperature of 175 ℃ for 120 hours. Centrifuging at 3000 rpm for 3min, washing the solid product with deionized water to neutrality, and drying in air at 100 deg.C overnight to obtain XRD analysis result shown in FIG. 2. As can be seen from the results of FIG. 2, the synthesized product is SAPO-42 molecular sieve raw powder, which is calcined at 600 ℃ for 5 hours to obtain SAPO-42 molecular sieve, which is marked as catalyst 2.
Example 3: synthesis of ZK-21 molecular sieve catalyst
6.1g of sodium aluminate (1.11 Na)2O·Al2O3·3.5H2O) and a small amount of deionized water are mixed, 23g of phosphoric acid with the concentration of 85 percent is added to prepare 220ml of aqueous solution, 10.3g of sodium metasilicate pentahydrate and 80ml of deionized water are added while stirring, gel is obtained after full stirring, then the gel is filled into a stainless steel autoclave lined with polytetrafluoroethylene, and the constant temperature crystallization is carried out for 69 hours at 100 ℃. Centrifuging at 3000 rpm for 3min, washing the solid product with deionized water to neutrality, drying at 100 deg.C overnightThe results of XRD analysis are shown in FIG. 3. As can be seen from the results in FIG. 3, the synthesized product was ZK-21 molecular sieve raw powder, which was calcined at 600 ℃ for 5 hours to obtain ZK-21 molecular sieve, which was designated as catalyst 3.
Example 4: synthesis of ZK-22 molecular sieve catalyst
6.1g of sodium aluminate (1.11 Na)2O·Al2O3·3.5H2O) and a small amount of deionized water are mixed, 23g of phosphoric acid with the concentration of 85 percent is added to prepare 220ml of aqueous solution, 10.3g of sodium metasilicate pentahydrate and 80ml of deionized water are added while stirring, the gel is obtained after full stirring, the pH value of the solution is adjusted to 10.2, and then the solution is filled into a stainless steel autoclave lined with polytetrafluoroethylene and crystallized at the constant temperature of 100 ℃ for 69 hours. After crystallization, the solid product obtained by separation was washed to neutrality with deionized water and dried overnight in air at 100 ℃ with a centrifuge of 3000 rpm for 3min, and the results of XRD analysis are shown in FIG. 4. As can be seen from the results in FIG. 4, the synthesized product is ZK-22 molecular sieve raw powder, which is calcined at 600 ℃ for 5 hours to obtain ZK-22 molecular sieve, which is marked as catalyst 4.
Example 5: synthesis of DNL-1 molecular sieve catalyst
1Al in initial gel molar composition ratio2O3：1P2O5: 801-ethyl-3-methylimidazolium bromide: 2, hydrofluoric acid: 11, 6-hexanediamine (as organic structure directing agent) is prepared by mixing weighed pseudoboehmite, phosphoric acid, ionic liquid and organic structure directing agent in a beaker, fully stirring to obtain gel, then placing into a stainless steel autoclave lined with polytetrafluoroethylene, and crystallizing at constant temperature of 200 ℃ for 2 h. After crystallization, the solid product obtained by separation was washed to neutrality with deionized water and dried overnight at 110 ℃ in air, and the results of XRD analysis are shown in FIG. 5. As can be seen from the results in FIG. 5, the synthesized product was DNL-1 molecular sieve raw powder, which was calcined at 600 ℃ for 5 hours to give DNL-1 molecular sieve, which was designated as catalyst 5.
Example 6: synthesis of cloverite molecular sieve catalyst
1Ga in initial gel molar composition ratio2O3：1P2O5: 6 quinine: 0.75 hydrofluoric acid: 64H2And O, mixing metered gallium sulfate, phosphoric acid, quinine, hydrofluoric acid and water in a beaker, fully stirring to form gel, then filling the gel into a stainless steel autoclave lined with polytetrafluoroethylene, and crystallizing at the constant temperature of 150 ℃ for 24 hours. After crystallization, the solid product obtained by separation was washed to neutrality with deionized water and dried overnight at 110 ℃ in air, and the results of XRD analysis are shown in FIG. 6. From the results in fig. 6, it can be seen that the synthesized product is clovierite molecular sieve raw powder, which is calcined at 600 ℃ for 5h to obtain clovierite molecular sieve, which is denoted as catalyst 6.
The following examples illustrate the preparation of coronenes using the catalysts 1 to 6 prepared above and an alcohol starting material.
Example 7
A fixed bed reactor having an internal diameter of 10mm was charged with 600mg of the DNL-6 molecular sieve catalyst of example 1 (catalyst 1), and the reactor was heated to 550 ℃ and held for 30min in a nitrogen stream of 155ml/min to complete the catalyst activation process. Then the reaction temperature of the reactor is adjusted to 475 ℃, methanol steam is carried into the reactor from a methanol saturation tube which is kept at 25 ℃ by nitrogen flow of 155ml/min to contact and react with the catalyst, the reaction pressure is 0.1MPa, and the reaction mass space velocity is 4h-1. And stopping the reaction after the reaction time reaches 1h, and cooling the reactor to room temperature. Directly pouring out the reacted catalyst (at the moment, the reaction product is remained in the catalyst), taking 10mg of the catalyst, determining the total amount of the catalyst deposition species by a TA Q-600 type comprehensive thermal analyzer, additionally taking 50mg of the catalyst, putting into 1ml of hydrogen fluoride solution (20 wt%), standing for 1h, adding 0.5ml of carbon tetrachloride after all solid substances are dissolved, extracting the organic phase, standing and layering overnight. Then separating the carbon tetrachloride on the lower layer by using a separating funnel to be detected. The composition of the organic phase obtained was analyzed by means of an Agilent 7890/5975 chromatograph and HP-5 column, combining the weight gain of the catalyst after the reaction and the corresponding chromatographic peak area of the coronene compound, and the yield of the coronene compound therein was calculated by the above-mentioned calculation formula, with the reaction conditions and results shown in Table 1.
Examples 8 to 12
The same procedure as in example 7 was followed, except that the SAPO-42 molecular sieve catalyst (catalyst 2), the ZK-21 molecular sieve catalyst (catalyst 3), the ZK-22 molecular sieve catalyst (catalyst 4), the DNL-1 molecular sieve catalyst (catalyst 5) and the cloverite molecular sieve catalyst (catalyst 6) prepared in examples 2 to 6 were respectively used as catalysts, and the hydrogen fluoride solution was replaced with a hydrochloric acid solution and a nitric acid solution in examples 11 and 12, respectively, to prepare a product coronene compound, with the reaction conditions and results shown in table 1.
Examples 13 to 16
The product coronene was prepared by the same procedure as in example 7 except that the reaction temperature of the reactor was adjusted to 425 deg.C, 450 deg.C, 500 deg.C and 525 deg.C, respectively, and the reaction conditions and results are shown in Table 1.
Example 17
The product coronenes were prepared by the same procedure as in example 7, except that a mixture of the DNL-6 molecular sieve catalyst of example 1 (catalyst 1) and the SAPO-42 molecular sieve catalyst prepared in example 2 (catalyst 2) was used as the catalyst, wherein the masses of catalyst 1 and catalyst 2 were 300mg and 300mg, respectively, and the reaction conditions and results are shown in Table 1.
Example 18
The product coronene was prepared by the same procedure as in example 7, except that a mixture of the DNL-6 molecular sieve catalyst in example 1 (catalyst 1), the SAPO-42 molecular sieve catalyst prepared in example 2 (catalyst 2) and the DNL-1 molecular sieve prepared in example 5 (catalyst 5) was used as the catalyst, wherein the weights of catalyst 1, catalyst 2 and catalyst 5 were 300mg, 150mg and 150mg, respectively, and the reaction conditions and results are shown in Table 1.
Example 19
10g of DNL-6 molecular sieve microspherical catalyst was charged into a fluidized bed reactor and treated in a helium atmosphere at 600 ℃ for 1h, and then the reaction temperature of the reactor was adjusted to 475 ℃. Introducing methanol and water into preheater via feed pump, introducing the raw material into fluidized bed reactor after vaporizing in preheater at 250 deg.C, contacting methanol vapor and water vapor with catalyst in the reactor and catalyzingThe agent is fluidized, and the feeding space velocity of the methanol is 2h-1The mass ratio of water/methanol was 1.5, and the reaction pressure was 0.1 MPa. And stopping the reaction after the reaction time reaches 1h, and cooling the reactor to room temperature. Directly pouring out the reacted catalyst (at the moment, the reaction product is remained in the catalyst), taking 10mg of the catalyst, determining the total amount of the catalyst deposition species by a TA Q-600 type comprehensive thermal analyzer, additionally taking 50mg of the catalyst, putting into 1ml of hydrogen fluoride solution (20 wt%), standing for 1h, adding 0.5ml of carbon tetrachloride after all solid substances are dissolved, extracting the organic phase, standing and layering overnight. Then separating the carbon tetrachloride on the lower layer by using a separating funnel to be detected. The composition of the organic phase obtained was analyzed by means of an Agilent 7890/5975 chromatograph and HP-5 column, combining the weight gain of the catalyst after the reaction and the corresponding chromatographic peak area of the coronene compound, and the yield of the coronene compound therein was calculated by the above-mentioned calculation formula, with the reaction conditions and results shown in Table 1.
Examples 20 to 24
The coronene product was prepared by the same procedure as in example 19 except that the reaction raw materials were changed to ethanol, propanol, butanol, pentanol and hexanol, respectively, and the reaction conditions and results were as shown in table 1.
Example 25
The same procedures as in example 19 were repeated except that the mass ratio of water to methanol was adjusted to 1, the reaction pressure was adjusted to 0.2MPa, and the reaction mass space velocity was adjusted to 2h-1To prepare the product coronene compound, the reaction conditions and results are shown in table 1.
Example 26
The same procedures as in example 19 were repeated except that the mass ratio of water to methanol was adjusted to 3, the reaction pressure was adjusted to 0.5MPa, and the reaction mass space velocity was adjusted to 10 hours-1To prepare the product coronene compound, the reaction conditions and results are shown in table 1.
Example 27
The same procedure as in example 19 was followed, except that the mass ratio of water to methanol was adjusted to 5 and the reaction mass space velocity was adjusted to 10h-1To prepare the product coronene compound, the reaction conditions and results are shown in table 1.
TABLE 1 reaction conditions and yield of coronenes prepared
Figure BDA0002016480760000101
Figure BDA0002016480760000111
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A method for preparing coronenes using a molecular sieve catalyst, the method comprising at least the steps of:
(1) activating the molecular sieve catalyst; wherein the molecular sieve catalyst comprises a SAPO molecular sieve catalyst;
(2) carrying out contact reaction on the raw material and the molecular sieve catalyst activated in the step (1) in a reactor to obtain the coronene compound;
wherein the raw material comprises an alcohol compound.
2. Method according to claim 1, characterized in that it comprises the following steps:
(1) filling an SAPO molecular sieve catalyst into a reactor, heating to 500-600 ℃ under inert atmosphere, and activating the SAPO molecular sieve catalyst;
(2) after the temperature of the reactor is adjusted to 450-550 ℃, feeding an alcohol raw material into the reactor to perform conversion on the SAPO molecular sieve catalyst to generate a product coronene compound remaining inside the SAPO molecular sieve catalyst;
(3) dissolving the SAPO molecular sieve catalyst with the product in a strong inorganic acid solution, and extracting an organic phase therein by using an organic solvent to obtain the coronene compound.
3. The method according to claim 1, wherein the alcohol compound is at least one selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol and hexanol;
preferably, the alcohol raw material is a mixture of alcohol and water, and the mass ratio of the water to the alcohol is 0-5, preferably 0-3.
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.
5. The method of claim 1, wherein the SAPO molecular sieve is at least one of DNL-6, SAPO-42, ZK-21, ZK-22, DNL-1, clovorite; preferably, the SAPO molecular sieve catalysts are DNL-6, SAPO-42, and ZK-21.
6. The process of claim 2 wherein the alcohol feedstock is fed by entraining a vapor thereof with an inert gas into the reactor or by vaporizing the alcohol feedstock in a vaporizer and then feeding the vaporized alcohol feedstock into the reactor.
7. The method according to claim 2, wherein the strong inorganic acid solution is a hydrogen fluoride solution, a hydrochloric acid solution, or a nitric acid solution.
8. The method according to claim 2, wherein the organic solvent used for extraction is dichloromethane, chloroform, tetrachloromethane, petroleum ether or diethyl ether.
9. The method of claim 2, wherein the reactor is a fixed bed reactor or a fluidized bed reactor.
10. The method of claim 2, wherein the feeding mass space velocity of the alcohol raw material is 1-10 h-1The reaction pressure is 0.1-0.5 MPa; preferably, the feeding mass airspeed of the alcohol raw material is 2-5 h-1The reaction pressure is 0.1-0.2 MPa.
CN201910264943.8A 2019-04-03 2019-04-03 Method for preparing coronene compound by using molecular sieve catalyst Active CN111777480B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910264943.8A CN111777480B (en) 2019-04-03 2019-04-03 Method for preparing coronene compound by using molecular sieve catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910264943.8A CN111777480B (en) 2019-04-03 2019-04-03 Method for preparing coronene compound by using molecular sieve catalyst

Publications (2)

Publication Number Publication Date
CN111777480A true CN111777480A (en) 2020-10-16
CN111777480B CN111777480B (en) 2021-06-15

Family

ID=72754767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910264943.8A Active CN111777480B (en) 2019-04-03 2019-04-03 Method for preparing coronene compound by using molecular sieve catalyst

Country Status (1)

Country Link
CN (1) CN111777480B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008129024A1 (en) * 2007-04-24 2008-10-30 Basf Se Porous organometallic framework materials loaded with catalyst metal components
CN105801333A (en) * 2016-04-29 2016-07-27 王占奇 Preparation method of coronene
CN106582797A (en) * 2016-11-25 2017-04-26 厦门大学 Preparation method for HZSM-5 methanol aromatization molecular sieve catalyst with skeleton containing molybdenum
CN108236966A (en) * 2016-12-23 2018-07-03 北斗航天卫星应用科技集团有限公司 Aromatization of methanol catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008129024A1 (en) * 2007-04-24 2008-10-30 Basf Se Porous organometallic framework materials loaded with catalyst metal components
CN105801333A (en) * 2016-04-29 2016-07-27 王占奇 Preparation method of coronene
CN106582797A (en) * 2016-11-25 2017-04-26 厦门大学 Preparation method for HZSM-5 methanol aromatization molecular sieve catalyst with skeleton containing molybdenum
CN108236966A (en) * 2016-12-23 2018-07-03 北斗航天卫星应用科技集团有限公司 Aromatization of methanol catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Z. A. MANSUROV ET AL.: "Study of polyaromatic hydrocarbons - products of low-temperature combustion of methane", 《PETROCHEMISTRY》 *

Also Published As

Publication number Publication date
CN111777480B (en) 2021-06-15

Similar Documents

Publication Publication Date Title
Wang et al. Hollow TS-1 crystals formed via a dissolution–recrystallization process
KR20030055264A (en) Method for heteroatom lattice substitution in large and extra-large pore borosilicate zeolites
CN106145138B (en) A kind of method for synthesizing the zeolite molecular sieve with chabazite structure
CN107337215B (en) Silicate-1 molecular sieve containing noble metal ions and preparation method thereof
Luan et al. Alcohol-assisted synthesis of high-silica zeolites in the absence of organic structure-directing agents
Käldström et al. Pillared H-MCM-36 mesoporous and H-MCM-22 microporous materials for conversion of levoglucosan: Influence of varying acidity
Shamzhy et al. Direct incorporation of B, Al, and Ga into medium-pore ITH zeolite: Synthesis, acidic, and catalytic properties
Lu et al. Topotactic conversion of Ge-rich IWW zeolite into IPC-18 under mild condition
CN111777480B (en) Method for preparing coronene compound by using molecular sieve catalyst
CN101402049A (en) Process for producing catalyst for producing propylene with methanol
CN103301880A (en) Preparation method of heteroatom boron contained ZSM-5 molecular sieve and application of heteroatom boron contained ZSM-5 molecular sieve for preparing formaldehyde through methanol dehydrogenation
CN111777483B (en) Method for preparing coronene compound from acyclic olefin
CN111777487B (en) Method for preparing coronene compound from alcohol raw material
CN111777482B (en) Preparation method of coronene compound
CN107262140B (en) 2, 6-dimethylnaphthalene catalyst prepared from 2-methylnaphthalene, preparation and application thereof
CN108794288B (en) Method for preparing low-carbon olefin and co-producing p-xylene
Zhang et al. Efficient synthesis of niobium pentoxide nanowires and application in ethanolysis of furfuryl alcohol
CN104140352B (en) A kind of method being prepared adamantane compound by alcohols feedstock
US20230405547A1 (en) M-xylene Adsorbent and Preparation Method Therefor
CN115043805A (en) Method for preparing liquid methyl tetrahydrophthalic anhydride by isomerization catalysis
Wang et al. Forming pure shaped ZSM-5 zeolite bodies by a steam-assisted method and their application in methanol to aromatic reactions
CN114249637A (en) Method for preparing dimethyl ether by dehydrating methanol
CN109020947B (en) Preparation method of 2-methyl-1, 3-dioxolane
CN110893337A (en) Preparation method of EMT molecular sieve and application of EMT molecular sieve in adsorption of volatile organic gas
JP4503021B2 (en) Process for producing N-vinylcarbazoles

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