阅读说明：本技术 一种稠环芳烃制备烷基金刚烷的方法 (Method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon ) 是由 李晓红 王学明 李文英 荆洁颖 于 2021-01-16 设计创作，主要内容包括：本发明提供一种稠环芳烃制备烷基金刚烷的方法,包括以下步骤：S1,从煤焦油中分离获取纯度≥97％的稠环芳烃,为菲、蒽和芴；S2,选用环己烷为溶剂,利用载体USY负载Pt-Pd形成加氢异构催化剂；S3,将菲、蒽和芴原料分别与溶剂和催化剂混合,并在一定温度下通过加氢异构反应将菲、蒽和芴一步合成烷基金刚烷；S4,在不同反应原料下获得目标产物,并对菲、蒽和芴的加氢异构产物进行定性分析。本发明用煤焦油中高含量的菲、蒽和芴作为原料进行烷基金刚烷的合成,在USY分子筛上负载Pt-Pd催化剂上实现了烷基金刚烷的合成,是稠环芳烃合成烷基金刚烷的新路径,在简化制作步骤的前提下,并且显著提高烷基金刚烷的产率,可以更好的应用于合成金刚烷衍生物,在制药领域、光学领域以及航天领域等有着重要意义。(The invention provides a method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon, which comprises the following steps: s1, separating and obtaining condensed ring aromatic hydrocarbons with purity more than or equal to 97 percent from the coal tar, wherein the condensed ring aromatic hydrocarbons are phenanthrene, anthracene and fluorene; s2, cyclohexane is selected as a solvent, and a carrier USY is used for loading Pt-Pd to form a hydroisomerization catalyst; s3, mixing phenanthrene, anthracene and fluorene raw materials with a solvent and a catalyst respectively, and synthesizing the phenanthrene, the anthracene and the fluorene into alkyl adamantane in one step through a hydroisomerization reaction at a certain temperature; and S4, obtaining target products under different reaction raw materials, and carrying out qualitative analysis on the hydroisomerization products of phenanthrene, anthracene and fluorene. The invention uses phenanthrene, anthracene and fluorene with high content in coal tar as raw materials to synthesize alkyl adamantane, realizes the synthesis of alkyl adamantane on a Pt-Pd catalyst loaded on a USY molecular sieve, is a new path for synthesizing alkyl adamantane by polycyclic aromatic hydrocarbon, obviously improves the yield of the alkyl adamantane on the premise of simplifying the preparation steps, can be better applied to synthesizing adamantane derivatives, and has important significance in the fields of pharmacy, optics, aerospace and the like.)

1. A method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon is characterized by comprising the following steps: the method comprises the following steps:

s1, separating phenanthrene, anthracene, fluorene and other raw materials with the purity of more than or equal to 97% from the coal tar;

s2, cyclohexane is selected as a solvent, and USY is used as a carrier to load Pt-Pd to form a hydroisomerization catalyst;

s3, mixing phenanthrene, anthracene and fluorene serving as raw materials with a solvent and a catalyst respectively, and synthesizing three polycyclic aromatic hydrocarbons into alkyl adamantane in one step by hydrogenation and temperature rise;

and S4, obtaining product yield results under different raw materials, and carrying out qualitative analysis on the three polycyclic aromatic hydrocarbon hydroisomerization products.

2. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: and in the step S1, the coal tar is subjected to a solvent washing crystallization method, phenanthrene, carbazole and fluorene are removed from crude anthracene by utilizing the solubility difference of anthracene, phenanthrene and carbazole in different solvents, the anthracene with the purity of more than or equal to 97% is obtained, phenanthrene and fluorene are separated from the obtained phenanthrene residue by a chemical method, and the phenanthrene and fluorene with the purity of more than or equal to 97% are further refined.

3. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: the catalyst carrier in the step S2 is USY, and the active metal is noble metal.

4. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: and the reaction vessel in the step S3 is a high-pressure reaction kettle connected with a reaction device, and in the stirring reaction process, when the temperature in the reaction kettle is 280 ℃ and the initial hydrogen pressure is 4MPa, the synthetic alkyl adamantane is obtained. .

5. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: the diameter of the USY type molecular sieve micropores in the step S2 is more than or equal to 3 nm.

6. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: the catalyst in the step S2 is prepared by loading active metal Pt-Pd by an equal-volume co-impregnation method, drying at 110 ℃ for 12-24h, roasting at 400 ℃ and reducing at 350 ℃.

7. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: the alkyl adamantane finally synthesized in the step S3 is 1, 3, 5-trimethyl adamantane, 1, 3, 4-trimethyl adamantane, 1-methyl-3-ethyl adamantane, 1, 3, 5, 7-tetramethyl adamantane, 1, 3, 5, 6-tetramethyl adamantane and 1, 3-dimethyl-5-ethyl adamantane.

8. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: when the product yield is checked in the step S4, after the temperature rises to the specified temperature, sampling is started, and then sampling is intermittently performed every 1 h.

9. The method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon according to claim 1, wherein: the product yield in the step S4 was analyzed for organic phase composition by Agilent7980B, 5977A gas chromatograph-mass spectrometer, and the yield of alkyl adamantane was calculated by internal standard method quantification.

Technical Field

The invention relates to the technical field of alkyl adamantane preparation, in particular to a method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon.

Background

In 1957 Schleir (Paul Schleyer), a chemist of Princeton, USA, tried to heat-convert endo-form hydrogenated dicyclopentadiene into exo-isomer using aluminum chloride as a catalyst, and inadvertently found that the product contained about 10% adamantane as a by-product. Schlair seizes this opportunity and improves the yield of adamantane by optimizing the conditions. Thus, adamantane can be obtained in two steps from the inexpensive petrochemical product cyclopentadiene dimer. The price of adamantane is lost like avalanche, and the adamantane becomes a compound which is very cheap and easy to obtain.

For the synthesis of adamantane and derivatives of alkyl adamantanes, Schleyer et al used tetrahydrodicyclopentadiene in the L acid AlCl for the first time₃Adamantane was catalytically synthesized with a yield of adamantane of less than 10%, after which the yield of adamantane was increased to 60% by modifying this catalyst. U.S. Pat. No. (US 6472575) reports that a mixed super acid HF-BF3 supported transition metal is used as a catalyst to obtain a higher adamantane yield, but the synthesis of adamantane still relies on a process route of isomerization reaction using dicyclopentadiene as a raw material, so that there is a certain limitation in the synthesis technology of adamantane, and the realization of conversion of alkyl adamantane by polycyclic aromatic hydrocarbons in coal tar is of great significance.

Disclosure of Invention

The invention aims to provide a method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon, which aims to solve the problem that the existing synthesis of adamantane proposed by the background art still depends on a route of isomerization reaction by taking dicyclopentadiene as a raw material, and the synthesis route is single.

In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon comprises the following steps:

s1, separating phenanthrene, anthracene, fluorene and other raw materials with the purity of more than or equal to 97% from the coal tar;

s2, selecting cyclohexane as a solvent, and loading Pt-Pd on a USY type molecular sieve as a carrier to form a catalyst;

s3, mixing phenanthrene, anthracene and fluorene raw materials with a solvent and a catalyst, and carrying out hydrogenation and temperature rise to synthesize alkyl adamantane from the three polycyclic aromatic hydrocarbons in one step;

and S4, obtaining product yield results under different reaction conditions, and carrying out qualitative analysis on the three polycyclic aromatic hydrocarbon hydroisomerization products.

In order to obtain high-purity phenanthrene, anthracene and fluorene, it is preferable that, in the step S1, the coal tar is subjected to a solvent washing crystallization method, and phenanthrene, carbazole and fluorene are removed from crude anthracene by using the solubility difference of peranthracene, phenanthrene and carbazole in different solvents, so as to obtain anthracene with a purity of more than or equal to 97%, and the obtained phenanthrene residue is separated from fluorene by a chemical method, and further refined into phenanthrene and fluorene with a purity of more than or equal to 97%.

In order to allow experimental comparison and verification, the solvent in the S2 step is cyclohexane as a preferable example of the present invention.

In order to heat and pressurize the mixed raw materials, it is preferable that the reaction vessel in the step S3 is a high-pressure reaction vessel connected to a reaction device, and the synthetic alkyl adamantane is obtained when the temperature in the reaction vessel is 280 ℃ and the initial hydrogen pressure is 4MPa during the stirring reaction.

In order to make the reaction proceed smoothly and obtain the final product, it is preferable that the pore diameter of the USY type molecular sieve in the step S2 is not less than 3 nm.

In order to obtain the catalyst, it is preferable that the catalyst in the S2 step is prepared by loading the active metal Pt — Pd by an equal volume co-impregnation method, drying at 110 ℃ for 12-24h, calcining at 400 ℃ and reducing at 350 ℃.

In order to allow the final product to be obtained, it is preferable in the present invention that the alkyl adamantane finally synthesized in the step S3 is 1, 3, 5-trimethyladamantane, 1, 3, 4-trimethyladamantane, 1-methyl-3-ethyl adamantane, 1, 3, 5, 7-tetramethyladamantane, 1, 3, 5, 6-tetramethyladamantane and 1, 3-dimethyl-5-ethyl adamantane.

In order to allow the product to be sampled a plurality of times, it is preferable that the product yield is checked in the S4 step, the sampling is started after the temperature is raised to a predetermined temperature, and then the sampling is intermittently performed every 1 h.

In order to allow the yield of alkyl adamantane to be obtained quickly, it is preferable in the present invention that the product yield in the step S4 is obtained by analyzing the composition of the organic phase by Agilent7980B, 5977A gas chromatograph-mass spectrometer, quantifying by the internal standard method, and calculating the yield of alkyl adamantane.

Compared with the prior art, the invention has the beneficial effects that:

the method takes the high-content polycyclic aromatic hydrocarbon in the coal tar as the raw material to synthesize the alkyl adamantane, realizes the synthesis of the alkyl adamantane on the Pt-Pd catalyst loaded on the mesoporous USY molecular sieve, is a novel method for synthesizing the alkyl adamantane by the polycyclic aromatic hydrocarbon, obviously improves the yield of the adamantane on the premise of simplifying the preparation steps, can be better applied to the synthesis of adamantane derivatives, and has important significance in the fields of pharmacy, optics, aerospace and the like.

Drawings

FIG. 1 is a total ion flow diagram of a phenanthrene hydroisomerization product GC-MS under the conditions of a reaction temperature of 280 ℃ and an initial hydrogen pressure of 4 MPa;

FIG. 2 is a total ion flow diagram of GC-MS (gas chromatography-Mass spectrometer) of an anthracene hydroisomerization product under the conditions of a reaction temperature of 280 ℃ and an initial hydrogen pressure of 4 MPa;

FIG. 3 is a total ion flow diagram of a fluorine hydroisomerization product GC-MS under the conditions of a reaction temperature of 280 ℃ and an initial hydrogen pressure of 4 MPa;

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1-2, the present invention provides a technical solution: a method for preparing alkyl adamantane from polycyclic aromatic hydrocarbon comprises the following steps:

s1, separating phenanthrene, anthracene, fluorene and other raw materials with the purity of more than or equal to 97% from the coal tar;

s2, selecting cyclohexane as a solvent, and loading Pt-Pd on a USY type molecular sieve as a carrier to form a catalyst;

s3, mixing raw materials such as phenanthrene, anthracene and fluorene with a solvent and a catalyst, and synthesizing three polycyclic aromatic hydrocarbons into alkyl adamantane in one step by hydrogenation at a high temperature;

and S4, obtaining product yield results under different reaction conditions, and carrying out qualitative analysis on the phenanthrene hydroisomerization products.

Specifically, in the step S1, coal tar is subjected to a solvent washing crystallization method, phenanthrene, carbazole and fluorene are removed from crude anthracene by utilizing the solubility difference of anthracene, phenanthrene and carbazole in different solvents, anthracene with the purity of more than or equal to 97% is obtained, phenanthrene and fluorene are separated from obtained phenanthrene residue by a chemical method, and the phenanthrene and fluorene with the purity of more than or equal to 97% are further refined; the solvent in the step S2 is cyclohexane; the reaction vessel in the step S3 is a high-pressure reaction kettle connected with a reaction device, and in the stirring reaction process, when the temperature in the reaction kettle is 280 ℃ and the initial hydrogen pressure is 4MPa, synthetic alkyl adamantane is obtained; the diameter of the USY type molecular sieve micropores in the step S2 is more than or equal to 3 nm; loading an active metal Pt-Pd on the catalyst in the step S2 by an impregnation method, drying at 110 ℃ for 12-24h, roasting at 400 ℃, and reducing at 350 ℃; 1, 3, 5-trimethyladamantane, 1, 3, 4-trimethyladamantane, 1-methyl-3-ethyladamantane, 1, 3, 5, 7-tetramethyladamantane, 1, 3, 5, 6-tetramethyladamantane and 1, 3-dimethyl-5-ethyladamantane finally synthesized in the step S3. (ii) a When the product yield is checked in the step S4, after the temperature is raised to the specified temperature, sampling is started, and then sampling is carried out intermittently every 1 h; and (3) analyzing the organic phase composition of the product yield in the step S4 by an Agilent7980B and 5977A gas chromatograph-mass spectrometer, quantifying by adopting an internal standard method, and calculating the yield of the alkyl adamantane, wherein the calculation formula is as follows:

the absolute correction factor is the content of a certain component represented by a unit area peak, namely:

in the formula (f)_iAbsolute correction factor, C, representing a certain component_iRepresents the mass (or molar amount) of a component, A_iRepresentative is the peak area.

The relative correction factor is the ratio of the absolute correction factor of the component to be detected to the absolute correction factor of the standard component, namely:

data processing involves the following equation:

absolute amount of product:

the product yield is as follows:

Y_total＝∑Y_i

wherein n is_a,0Is the mole number of the reaction raw material, n_iIs the mole number of the product after reaction. Y is_i: 1, 3, 5, 7 tetramethyladamantane, 1, 3, 5, 6 tetramethyladamantane and 1, 3 dimethyl-5-ethyladamantane.

Example 1

Wherein the mesoporous USY molecular sieve is produced by Nankai catalyst factory, 1g of phenanthrene is dissolved in 100mL of cyclohexane, and then transferred to the inner liner of a 300mL reaction kettle after being completely dissolved, and 0.24g of 0.5% Pt-0.5% Pd/USY catalyst is added. The hydrogen pressure is charged to 4MPa, the power supply is turned on, the stirring device is started, the rotating speed is kept at 400r/min, the temperature is increased to 240 ℃ at 5 ℃/min, and then the temperature is increased to 280 ℃ at 2 ℃/min. After the temperature is stable, sampling every 1h, and carrying out constant-temperature continuous reaction for 7 h. After the reaction was completed, the organic phase composition was analyzed by Agilent7980B, 5977A GC, and the yields of several kinds of alkyl adamantanes were calculated.

Example 2

The same procedure as in example 1 was repeated except that the catalyst used in example 1 was used, the starting material was anthracene, and the reaction conditions were the same as in example 1, and the reaction results were as shown in Table 1.

Example 3

Similarly, the catalyst of example 1 was used, the reaction material was fluorene, the reaction conditions were the same as those of example 1, and the reaction results are shown in table 1.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes, modifications, equivalents, and improvements may be made without departing from the spirit and scope of the invention.