CN111825510B

CN111825510B - Method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene from anthracene through reaction and then performing catalytic oxidation

Info

Publication number: CN111825510B
Application number: CN201910300499.0A
Authority: CN
Inventors: 郑博; 郄思远; 张月琴; 费建奇; 潘智勇; 朱振兴; 毛俊义; 宗保宁
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-04-15
Filing date: 2019-04-15
Publication date: 2021-05-14
Anticipated expiration: 2039-04-15
Also published as: CN111825510A

Abstract

The invention relates to the field of preparation of 2-alkylanthraquinone, and particularly discloses a method for preparing 2-alkylanthraquinone by separating 2-alkylanthraquinone through reaction of anthracene and then carrying out catalytic oxidation, wherein the preparation method comprises the following steps: (1) preparing a reaction product containing an alkyl anthracene from an anthracene; (2) separating anthracene from a reaction product containing alkyl anthracene through melt crystallization and separating 2-alkyl anthracene through distillation; (3) the 2-alkyl anthracene is contacted with an oxidant under oxidation conditions and in the presence of an oxidation reaction solvent and a catalyst to carry out an oxidation reaction, wherein the oxidant is tert-butyl hydroperoxide, and the catalyst contains a carrier and an active component loaded on the carrier, and the active component is selected from one or more of a group VA element and a transition metal. The invention is a green preparation method of 2-alkyl anthraquinone, wherein the separation method can obviously reduce the difficulty of separation operation, and the product has high yield and high purity; the developed oxidation system has high activity, the conversion rate is up to 96.29 percent, and the selectivity is 98.67 percent.

Description

Method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene from anthracene through reaction and then performing catalytic oxidation

Technical Field

The invention relates to a preparation method of an organic matter, in particular to a method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene through reaction of anthracene and then performing catalytic oxidation.

Background

Hydrogen peroxide is an important green basic chemical, has high industrial relevance, and has become the first major country for hydrogen peroxide production since 2008, and the consumption amount is over 1000 million t/a (calculated by 27.5%) in 2015. At present, the technology for producing hydrogen peroxide at home and abroad is mainly an anthraquinone method. The 2-alkyl anthraquinone in the process is used as a 'carrier' of the process, and the quality and the yield of the hydrogen peroxide are directly influenced. The phthalic anhydride process is the primary method for producing 2-alkylanthraquinones, but this process suffers from serious contamination problems. 1.76 tons of anhydrous AlCl is required to be added for producing 1 ton of 2-ethyl anthraquinone₃And 4.2 tons of fuming H₂SO₄(20%) and the recovery of both is difficult. Therefore, it is very important to develop a green production process of 2-alkylanthraquinone from the viewpoint of environmental protection and clean production.

US 4255343 discloses a method for synthesizing 2-tert-amyl anthracene, which comprises uniformly mixing anthracene, trichlorobenzene and methanesulfonic acid under certain temperature and pressure conditions, and introducing olefin into the system to perform alkylation reaction with anthracene. The solid product was mainly the remaining anthracene and the series of alkyl anthracene products, with 42 wt% anthracene and 47 wt% 2-alkyl anthracene, with the remainder being anthracene disubstituted product and other by-products.

TW 200623958 discloses a method for alkylating anthracene by using ionic liquid catalysis, and the catalytic system of the alkylation reaction is a mixture containing 60-93.7 wt% of ionic liquid and 1-8 wt% of aluminum chloride. In the examplesIn the formula of BmimPF₆As solvent, and adding proper AlCl₃When the alkylation reaction of anthracene and tert-butyl chloride is catalyzed at 70 ℃, the yield of the product 2, 6-tert-butyl anthracene is 90%.

Perezromero et al used H₂O₂Oxidizing anthracene or 2-alkyl anthracene to prepare anthraquinone with Cu-containing Tp as catalyst^xCu (NCMe), after reacting for 2h at 80 ℃, the conversion rate of anthracene is 95%, and the selectivity of anthraquinone is 98%.

In US3953482 a process for the preparation of a catalyst using H is disclosed₂O₂A process for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthraquinone. Using fatty alcohol as solvent, concentrated hydrochloric acid as catalyst and H₂O₂(60%) is an oxidant, and the reaction is carried out for 60min at the normal pressure of 40-100 ℃, so that a better reaction effect can be obtained. The conversion rate of the 2-pentylanthracene is 94 percent, and the selectivity of the 2-pentylanthraquinone is as high as 97 percent.

As can be seen, no complete set of process technology for preparing 2-alkylanthraquinone from anthracene is reported at present.

Disclosure of Invention

The invention aims to provide a novel method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene from anthracene through reaction and then carrying out catalytic oxidation on the 2-alkyl anthraquinone, namely, an integral process for preparing a reaction product containing alkyl anthracene by taking anthracene as a raw material through reaction, separating and preparing the 2-alkyl anthracene, and preparing the 2-alkyl anthraquinone through oxidation reaction on the 2-alkyl anthracene.

The invention provides a method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene from anthracene through reaction and then performing catalytic oxidation, wherein the preparation method comprises the following steps:

(1) preparing a reaction product containing an alkyl anthracene from an anthracene;

(2) separating the reaction product containing alkyl anthracene obtained from step (1), the separation method comprising: melting crystallization separation of anthracene and distillation separation of 2-alkyl anthracene;

(3) and (3) contacting the 2-alkyl anthracene obtained in the step (2) with an oxidizing agent, namely tert-butyl hydroperoxide, under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst to perform an oxidation reaction, wherein the catalyst contains a carrier and an active component loaded on the carrier, and the active component is selected from one or more of a VA group element and a transition metal.

The whole technical route of preparing the 2-alkyl anthraquinone by separating the 2-alkyl anthracene from the anthracene through reaction and then performing catalytic oxidation is reasonable and feasible, and opens up a new direction for the green preparation of the 2-alkyl anthraquinone. The method provided by the invention can obviously reduce the operation difficulty in the separation process of the anthracene-alkyl anthracene product and improve the purity and the total yield of the intermediate target product 2-alkyl anthracene by a melt crystallization-distillation coupling separation technology.

In the method provided by the invention, the constructed 2-alkyl anthracene oxidation system has high raw material conversion rate and good selectivity, the catalyst is low in separation and recovery difficulty, the materials are not corrosive, and the equipment investment is reduced.

In addition, the method provided by the invention also has the advantages of simple process, high efficiency and small pollution.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.

FIG. 1 is a flow diagram of a process for the preparation of 2-alkylanthraquinones by catalytic oxidation of 2-alkylanthraenes separated from anthracene by reaction according to one embodiment of the present invention;

FIG. 2 is a diagram of an embodiment of the present invention for the isolation of an anthracene alkylation product, melt crystallization-multi-step vacuum distillation coupling process;

FIG. 3 is a diagram of an embodiment of the present invention for the isolation of an anthracene alkylation product, melt crystallization-multi-step vacuum distillation coupling process;

FIG. 4 is a flow diagram of the melt crystallization step in the present invention providing for the isolation of the anthracene alkylation product, melt crystallization-vacuum distillation process.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, 2-alkylanthraquinone means 2-alkyl-9, 10-anthraquinone, hereinafter referred to as 2-alkylanthraquinone.

According to the invention, the method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene from anthracene through reaction and then performing catalytic oxidation comprises the following steps:

According to the present invention, the starting material anthracene can be reacted to produce an anthracene containing an alkyl group. The method of producing an alkyl anthracene-containing reaction product from anthracene can be any single reaction or a combination of multiple steps to introduce an alkyl group into an anthracycline to produce an alkyl anthracene. Substances containing anthracene ring structures in the reaction products obtained in the step (1) comprise residual anthracene, 2-alkyl anthracene and other series alkyl anthracene products. It is well known to those skilled in the art that, depending on the reaction method, if the starting anthracene is not completely converted, the reaction product may contain residual anthracene. If the alkyl anthracene is not a single species, the alkyl anthracene may also be a mixture. Therefore, the production of alkyl anthracene-containing reaction products from a starting anthracene typically contains anthracene, 2-alkyl anthracene, and other series of alkyl anthracene products.

According to one embodiment of the present invention, as shown in fig. 1, the method for preparing a reaction product containing an alkyl anthracene from anthracene in step (1) includes: the alkylation reaction is carried out by contacting anthracene with an alkylating agent under alkylation conditions and in the presence of an alkylation solvent and a catalyst.

The mode of contacting anthracene with an alkylating agent and a catalyst according to the present invention can be any of various modes capable of producing alkyl anthracene by alkylation of anthracene. Preferably, for more complete reaction, the contacting is carried out in the following manner: the raw material liquid containing anthracene, catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction.

According to the present invention, the conditions and methods of the anthracycline reaction in step (1) may be performed in a manner conventional in the art.

According to the present invention, in step (1), the alkylating agent may be any alkylating agent known to those skilled in the art capable of introducing an alkyl group into an anthracycline to prepare an alkyl anthracene, for example, the alkylating agent may be one or more of an olefin, an alcohol, a halogenated hydrocarbon, and an ether having 2 to 8 carbon atoms, preferably one or more of an olefin, an alcohol, a halogenated hydrocarbon, and an ether having 4 to 6 carbon atoms, and more preferably a monoolefin having 4 to 6 carbon atoms.

According to the invention, in step (1), the alkylating agent is used in an amount that enables the introduction of alkyl groups into the anthracycline to produce alkyl anthracenes, preferably in a molar ratio of anthracene to alkylating agent of from 0.2:1 to 20:1, more preferably from 0.5:1 to 5: 1.

According to the present invention, in the step (1), the alkylation reaction solvent is an inert organic solvent capable of dissolving anthracene. Specifically, the alkylation reaction solvent is a solvent having a dielectric constant of 1 to 10 at 20 ℃, and more specifically, the alkylation reaction solvent is C₆Above, preferably C₆-C₁₂And one or more of paraffins, naphthenes, and aromatics. Wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of mono-or multi-substituted benzene; more preferably one or more of benzene multi-substituted compounds, the substituent is C₁-C₄And one or more of an alkyl group and a halogen element. IntoPreferably, the alkylation reaction solvent is one or more of polyalkyl substitutes of benzene. Most preferably, the alkylation reaction solvent is selected from one or more of 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5, 6-tetramethylbenzene, and 2,3,5, 6-tetramethylbenzene. The amount of the alkylation reaction solvent is only required to ensure that the anthracene can be fully dissolved so as to achieve the effect of providing a good reaction medium. Preferably, the anthracene is present in an amount of from 5 to 60 weight percent, preferably from 8 to 50 weight percent, based on the total weight of anthracene and alkylation reaction solvent.

According to the present invention, in the step (1), the mode of contacting the anthracene with the alkylating agent under the alkylation conditions and in the presence of the alkylation reaction solvent and the catalyst is not particularly limited, and preferably, in order to ensure that the alkylation reaction can be carried out more favorably, the anthracene, the catalyst and the alkylation reaction solvent are prepared as a raw material solution of the anthracene-catalyst-alkylation reaction solvent, and then the alkylating agent is added to carry out the alkylation reaction. Preferably, the preparation temperature of the raw material liquid of the anthracene-catalyst-alkylation reaction solvent is 100-250 ℃, more preferably 120-200 ℃.

According to the present invention, in step (1), the alkylation reaction conditions generally comprise: the reaction temperature can be 100-250 ℃, preferably 120-200 ℃; the reaction time can be 0.01-48h, preferably 0.5-24 h; the reaction pressure may be from 0 to 1MPa, preferably from 0.05 to 0.5 MPa.

According to the present invention, in step (1), in order to enable the alkylation reaction to be more easily performed, the alkylation reaction is performed in the presence of a catalyst. In particular, the catalyst may be any form and kind of acid catalyst capable of catalyzing the alkylation of anthracene, for example, the catalyst is selected from one or more of liquid acids, preferably methanesulfonic acid and/or p-toluenesulfonic acid; the catalyst may also be used in an amount of 0.01 to 50 wt%, preferably 0.5 to 30 wt%, based on the total weight of the raw material solution containing anthracene, the alkylation reaction solvent and the catalyst, with reference to the amount conventionally used in the art.

According to the present invention, the process for preparing alkyl anthracene from raw material anthracene in step (1) requires the use of a catalyst, and the catalyst after reaction may be separated after step (1) and before step (2) by a separation method that is conventional in the art according to the nature of the catalyst.

According to physical analysis, the boiling point of anthracene is 340 ℃, and the alkyl anthracene product and the anthracene homologue have a boiling point difference, and the product can be separated by a reduced pressure distillation technology. But the technical difficulty is that the melting point of anthracene is as high as 215 ℃, anthracene with a high solidifying point is separated by adopting a vacuum distillation technology alone, the operation difficulty is high, once the pipeline has a problem in heat preservation, the phenomenon of blockage is easy to occur, and the continuous and stable operation of the process is seriously influenced. In addition, anthracene is very easily sublimed, and sublimation temperature is difficult to control, and the chance that the pipeline takes place to block up is showing to increase. Thus, it is impractical to use solely vacuum distillation techniques to achieve separation of the anthracene-alkyl anthracene product.

Therefore, the inventors of the present invention propose to separate anthracene and alkyl anthracene products using a melt crystallization-distillation separation method. The alkyl anthracene destroys the high regularity of an anthracene ring structure due to the existence of a side chain substituent group, so that the melting point of an alkyl anthracene product is obviously reduced, for example, the melting point range of a low-carbon alkyl anthracene product (1< the carbon number j1<8 of an alkyl side chain of anthracene) is 130-150 ℃, the melting point range of a high-carbon alkyl anthracene product (7< the carbon number j2<18 of an alkyl side chain of anthracene) is 150-190 ℃, the melting points are obviously lower than the melting point 215 ℃ of anthracene, and a large melting point difference exists between the alkyl anthracene and the anthracene. For this reason, the inventor of the present invention proposes to first use the melt crystallization technique to separate and remove the anthracene which has the highest melting point and is most difficult to separate by crystallization, and then use one or more reduced pressure distillation techniques to further separate the anthracene from the alkyl anthracene mixture with high boiling point according to the difference of the boiling points.

Based on this, according to the present invention, the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene; the step (2) comprises the following steps:

(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;

(2-3) separating 2-alkyl anthracene from a series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.

According to one embodiment of the present invention, as shown in FIG. 4, the melt crystallization step can be carried out in a melt crystallization system in which the crystalline separation of anthracene from the reaction product mixture can be achieved. The melt crystallization system includes an intermediate melt tank and a melt crystallizer. The melted product containing anthracene and serial alkyl anthracene products heated and melted in the distillation tower is sent into an intermediate melting tank and then is introduced into a melting crystallizer. The apparatus for implementing the melt crystallization process is a melt crystallizer, the crystallization process can be lamellar crystallization or suspension crystallization, and the operation mode can be batch operation or continuous operation, but the invention is not limited to the method, but the batch operation lamellar crystallization mode is more preferable. The temperature increase and decrease in the melt crystallizer is achieved by introducing a heat exchange medium into the melt crystallizer. After the heated and melted material enters the melting crystallizer, the cooling medium is used for cooling, so that the anthracene with a high melting point is crystallized and separated out, and further, the separation of the anthracene and a series of alkyl anthracene products is realized.

According to the present invention, in the melt crystallization step of (2-2), in order to better achieve the crystal separation of anthracene, the melting temperature is controlled to 200-270 ℃, preferably 210-250 ℃.

According to the invention, the melt crystallization process essentially comprises three steps of cooling crystallization, sweating and preferably warming remelting of the anthracene crystals.

According to the present invention, the temperature for cooling crystallization can be 180-210 ℃, preferably 190-200 ℃. In order to better realize the crystal separation of anthracene, the cooling rate of the cooling crystal can be 0.1-10 ℃/h, preferably 0.5-5 ℃/h, and the cooling crystallization time, namely the crystal growth time can be controlled to be 1-5h, preferably 1.5-4 h.

According to the present invention, in order to increase the crystallization rate, in the cooling crystallization process, it is preferable to further include a step of adding seed anthracene, which may be added in an amount according to the details of the cooling crystallization process, and it is further preferable to add the seed anthracene in an amount of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the mass of the molten mixture.

According to the present invention, in order to further increase the purity of the crystalline anthracene, it is necessary to further perform a sweating operation on the anthracene crystal. After the crystal layer is formed, the temperature of the crystal layer is slowly close to the equilibrium temperature by controlling the rising rate of the temperature of the crystal layer, and the local crystal containing more impurities is low in melting point due to uneven distribution of the impurities in the crystal layer and can be firstly melted and separated from the crystal in a sweating mode.

According to the present invention, in the melt crystallization step, the temperature increase rate at which the anthracene crystal undergoes sweating is controlled to 0.1 to 8 deg.C/h, preferably 0.2 to 4 deg.C/h, from the viewpoint of further improving the purity of the crystal and the separation accuracy. The temperature raised to the temperature at which sweating stops cannot melt the crystallized anthracene crystal, and therefore, the temperature raised to the temperature at which sweating stops must be lower than the melting temperature of the anthracene crystal, preferably the temperature raised to the temperature at which sweating stops is 210 ℃ or lower, more preferably, the temperature raised to 5 to 15 ℃ higher than the cooling crystallization temperature, and the sweating stops below 210 ℃. The sweating end temperature may be 190-210 deg.C, more preferably 195-205 deg.C, under the principle of following the above-mentioned sweating stop temperature. In order to further increase the purity of the crystalline anthracene, the amount of perspiration can also be controlled so that the amount of perspiration is 5 to 40% by weight, more preferably 10 to 30% by weight, of the mass of the crystal.

According to the present invention, in order to further improve the separation accuracy, the collected sweat is recycled, that is, the sweat is recycled to the melting and crystallizing step, and the melting and cooling crystallization is carried out by heating together with the reaction product containing alkyl anthracene, that is, the mixture containing anthracene and the series of alkyl anthracene products.

According to the invention, after sweating is finished, the temperature of the separated anthracene crystal can be increased to over 215 ℃, and the crystal anthracene is collected and recycled after being completely melted into liquid.

After melt crystallization according to the process of the present invention, the non-crystallized material collected, i.e., the feed solution of the 2-alkyl anthracene-containing series of alkyl anthracene products consisting essentially of the series of alkyl anthracene products (substantially free of anthracene), is collected.

According to the invention, the boiling points of the serial alkyl anthracene products containing 2-alkyl anthracene are all higher than that of anthracene (340 ℃), so that the distillation technology is needed to further realize the purpose of serial alkyl anthracene product separation. Thus, 2-alkyl anthracenes can be separated from a series of alkyl anthracene products containing 2-alkyl anthracenes by one or more distillation steps.

According to the present invention, in the step (2-3), when the alkyl anthracene product of the series containing 2-alkyl anthracene is a mixture of two substances, or a mixture of three or more substances, the boiling point of 2-alkyl anthracene is the lowest or the highest; then a one-step distillation is performed to separate the 2-alkyl anthracene. In the step (2-3), when the serial alkyl anthracene products containing the 2-alkyl anthracene are a mixture of more than three substances, and the boiling point of the 2-alkyl anthracene is between the substance with the highest boiling point and the substance with the lowest boiling point in the mixture; a multi-step distillation is performed.

According to an embodiment of the present invention, in the step (2-3), the multi-step distillation method comprises:

mode 1: as shown in fig. 2, a feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene is subjected to first distillation and separated to obtain a distillate containing light component Cj 1-anthracene and a bottom product containing heavy component Cj 2-anthracene; subjecting the distillate containing the light component C1 j-anthracene to second distillation to obtain a distillate containing the light component Cj 3-anthracene and a bottom product containing the target product Ci-anthracene;

wherein, the light component Cj 1-anthracene is an alkyl anthracene product with the total carbon number j1 of an alkyl side chain being an integer which is more than 1 and less than j1 and less than i +1, the heavy component Cj 2-anthracene is an alkyl anthracene product with the total carbon number j2 of the alkyl side chain being an integer which is more than i and less than j2 and less than 41, and the light component Cj 3-anthracene is an alkyl anthracene product with the total carbon number j3 of the alkyl side chain being an integer which is more than 1 and less than j3 and less than i;

wherein, in the target product Ci-anthracene, i represents the total carbon number of an alkyl side chain, i is an integer of 4-7, the substitution position is at 2 position, namely 2-alkyl anthracene, and the total carbon number of the alkyl side chain is 4-7.

The conditions of the first distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-. More preferably, the pressure at the top of the column is 0.1 to 10KPa, the temperature at the bottom of the column is 210-340 ℃, the number of theoretical plates is 30 to 75, and the reflux ratio at the top of the column is 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 260 ℃ to 320 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 3. Under this operating condition, the bottoms were predominantly Cj 2-anthracene product (total alkyl side chain carbon number j2 is an integer of i < j2< 41), and the overheads were Cj 1-anthracene product (total alkyl side chain carbon number j1 is an integer of 1< j1< i + 1).

The conditions of the second distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8. More preferably, the pressure at the top of the column is from 0.1 to 10KPa, the temperature at the bottom of the column is from 200 ℃ to 310 ℃, the number of theoretical plates is from 30 to 75, and the reflux ratio at the top of the column is from 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 220-305 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 5. Under the operating conditions, the bottom product is Ci-anthracene (2-alkyl anthracene, the total carbon number of alkyl side chain is 4-7), and the overhead product is Cj 3-anthracene (the total carbon number of alkyl side chain j3 is an integer of 1< j3 < i).

For example, as shown in FIG. 2, the alkyl anthracene mixture is a continuous homolog mixture of C2-anthracene to C20-anthracene, while C5-anthracene is the isolated target product. Through the first distillation, light components including C2-anthracene to C5-anthracene are obtained at the top of the tower, and heavy components including C6-anthracene to C20-anthracene are obtained at the bottom of the tower. The mixture of C2-anthracene to C5-anthracene is subjected to second distillation, light components obtained at the top of the tower comprise the mixture of C2-anthracene to C4-anthracene, and a target product of C5-anthracene is obtained at the bottom of the tower.

Alternatively, the first and second electrodes may be,

mode 2: as shown in fig. 3, the feed liquid of the series alkyl anthracene product containing 2-alkyl anthracene is subjected to third distillation to obtain distillate containing light component Cm 1-anthracene and a bottom product containing heavy component Cm 2-anthracene; carrying out fourth distillation on the bottom product containing the heavy component Cm 2-anthracene to obtain a distillate containing the target product Ci-anthracene and a bottom product containing the heavy component Cm 3-anthracene;

wherein the light component Cm 1-anthracene is an alkyl anthracene product with the total carbon number m1 of an alkyl side chain being an integer of more than 1 and less than m and i, the heavy component Cm 2-anthracene is an alkyl anthracene product with the total carbon number m2 of the alkyl side chain being an integer of more than i and less than m2 and less than 41, and Cm 3-anthracene is an alkyl anthracene product with the total carbon number m3 of the alkyl side chain being an integer of more than i and less than m3 and less than 41;

The conditions of the third distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-. More preferably, the pressure at the top of the column is 0.1 to 10KPa, the temperature at the bottom of the column is 210-340 ℃, the number of theoretical plates is 30 to 75, and the reflux ratio at the top of the column is 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 260 ℃ to 320 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 3. Under this operating condition, the bottoms product was predominantly Cm 2-anthracene product (total alkyl side chain carbon number m2 is an integer from i-1 < m 2< 41), and the overhead product was Cm 1-anthracene product (total alkyl side chain carbon number m1 is an integer from 1< m < i).

The conditions of the fourth distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8. More preferably, the pressure at the top of the column is from 0.1 to 10KPa, the temperature at the bottom of the column is from 200 ℃ to 310 ℃, the number of theoretical plates is from 30 to 75, and the reflux ratio at the top of the column is from 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 220-305 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 5. Under the operating conditions, the overhead product is Ci-anthracene (2-alkyl anthracene, the total carbon number of the alkyl side chain is 4-7) which is the target product, and the bottom product is Cm 3-anthracene (the total carbon number of the alkyl side chain is m3 which is an integer of i < m3 < 41).

For example, as shown in FIG. 3, the alkyl anthracene mixture is a continuous homolog mixture of C2-anthracene to C20-anthracene, while C5-anthracene is the isolated target product. Through the third distillation, light components including C2-anthracene to C4-anthracene are obtained at the top of the tower, and heavy components including C5-anthracene to C20-anthracene are obtained at the bottom of the tower. And (3) carrying out fourth distillation on a mixture of C5-anthracene to C20-anthracene, obtaining a target product C5-anthracene at the tower top, and obtaining a heavy component from the tower bottom, wherein the heavy component comprises C6-anthracene to C20-anthracene.

According to the present invention, the specific operating conditions of each of the vacuum distillations in the multi-step vacuum distillations can be appropriately selected within the operating temperature and pressure ranges thereof according to the different distillation ranges of the overhead product and the bottom product in each vacuum distillation.

According to the present invention, the multi-step vacuum distillation may employ various vacuum distillation apparatuses known in the art, for example: a sieve tray column or a packed column, more preferably a packed column.

According to the present invention, depending on the process and operating conditions of the reaction of step (1), other substances having a boiling point lower than that of anthracene, such as reaction solvents and other by-products (e.g., alkylating agent remaining after the alkylation reaction), may be entrained or generated, and are referred to as light components. Therefore, the reaction product containing an alkyl anthracene obtained via step (1) also contains a reaction solvent. The method further comprises a step (2-1) of separating the reaction solvent before the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation. The method of separating the solvent may be removed using a separation method that is conventional in the art. Preferably, the reaction solvent in the mixed solution containing the alkyl anthracene product is separated by atmospheric distillation from the viewpoint of further improving the separation efficiency and simplifying the operation. According to a specific embodiment of the present invention, the separation method of (2-1) comprises: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene. In addition, the separated reaction solvent may be recycled or collected for disposal as required for the reaction. In addition, other by-product separation methods can also be in the separation of anthracene alkyl anthracene before separation, can pass through conventional separation methods to remove, such as distillation.

Preferably, in the step (2-1), the distillation conditions include: the bottom temperature of the distillation column is 100-300 ℃, preferably 150-200 ℃, and the pressure at the top of the distillation column is normal pressure.

According to the invention, the intermediate product 2-alkyl anthracene is obtained by separation, and can be used for preparing 2-alkyl anthraquinone through reaction. According to the present invention, in the step (3), the 2-alkylanthraquinone is produced from the 2-alkylanthraquinone obtained through the step (2) by subjecting the 2-alkylanthraquinone to an oxidation reaction to produce the 2-alkylanthraquinone. Specifically, in the step (3), the process for producing 2-alkylanthraquinone from 2-alkylanthraquinone obtained via the step (2) comprises: and (3) contacting the 2-alkyl anthracene obtained in the step (2) with an oxidizing agent, namely tert-butyl hydroperoxide, under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst to perform an oxidation reaction, wherein the catalyst contains a carrier and an active component loaded on the carrier, and the active component is selected from one or more of a VA group element and a transition metal.

According to the invention, in the step (3), the combination of the tert-butyl hydroperoxide oxidant and the supported catalyst can improve the conversion rate of raw materials, has good selectivity, low difficulty in separating and recovering the catalyst, mild process conditions and no corrosivity of materials, and can reduce equipment investment.

Preferably, in step (3), the active component in the catalyst is selected from a group consisting of group VA elements and one or more of group VB, group VIB and group VIII metals, preferably a combination of group VA elements and at least one metal selected from group VB, group VIB and group VIII metals. Specifically, the group VA element can be N, P, As, Sb and Bi, the group VB metal can be V, Nb and Ta, the group VIB metal can be Cr, Mo and W, and the group VIII metal can be Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt. Further preferably, the active component is selected from one or more of P, V, Cr, Mo, Fe and Co, most preferably a combination of P and at least one selected from V, Cr, Mo, Fe and Co. The carrier in the catalyst can be selected from one or more of refractory inorganic oxide and molecular sieve, and is preferably refractory inorganic oxide. The heat-resistant inorganic oxide may be one or more selected from silica, magnesia and a silicon-aluminum composite oxide, wherein in the silicon-aluminum composite oxide, SiO is calculated as an oxide₂May be contained in an amount of 0.01 to 70% by weight, preferably 5 to 40% by weight, Al₂O₃The content of (B) may be 30 to 99.9% by weight, preferably 60 to 95% by weight.

The content of the carrier and the active component in the catalyst is not particularly limited, and the content of the carrier and the content of the active component in the catalyst are subject to the catalytic action. More preferably, the active component is present in an amount of from 0.01 to 40 wt%, more preferably from 0.1 to 30 wt%, calculated as elemental content, based on the weight of the support in the catalyst. Further preferably, in order to further improve the catalytic performance of the catalyst, the active component in the catalyst is a combination of a group VA element and a transition metal, and the mass ratio of the transition metal to the group VA element is 1-20:1 in terms of element content.

According to the present invention, the catalyst can be prepared by an impregnation method which is conventional in the art, and for example, a dry impregnation method (i.e., an equivalent-volume impregnation method) can be selected for preparation, or for example, an incipient wetness impregnation method can be selected for preparation. The specific method comprises the following steps: impregnating a carrier with a solution containing a soluble compound of an active component, which is one or more soluble compounds selected from the group consisting of group VA elements and transition metals, drying and calcining the impregnated carrier.

When the elements in the active component are multiple, the method for impregnating the carrier with the solution containing the soluble compound of the active component can be carried out according to the following two methods: (1) the carrier can be impregnated after preparing a mixed solution of a plurality of solutions of soluble compounds of active components; (2) the support may also be impregnated sequentially with soluble compounds of the various active components (the order of impregnation of the support with solutions of soluble compounds of the various elements may be chosen arbitrarily).

According to the present invention, the conditions for impregnating the support with the solution containing the soluble compound of the active ingredient generally include temperature and time, the impregnation temperature may be 0 to 100 ℃, preferably 20 to 80 ℃, and the impregnation time may be appropriately selected depending on the degree of dispersion of the soluble compound of the active ingredient, and preferably, the impregnation time is 4 to 24 hours, more preferably 6 to 12 hours. Furthermore, the amount of solvent in the solution of the soluble compound containing the active ingredient is such that, on the one hand, the compound of the active ingredient is sufficiently soluble in the solvent and, on the other hand, sufficient dispersion of the carrier is ensured, preferably the amount of solvent in the solution of the soluble compound containing the active ingredient is from 0.05 to 10ml, preferably from 0.1 to 5ml, based on 1g of the carrier. According to the present invention, the solvent in the solution may be selected from one or more of water, methanol, ethanol, isopropanol, butanol and pentanol.

According to the invention, the amount of soluble compound of the support and of the active component can be chosen within wide limits, preferably such that the content of active component, calculated as element, is from 0.01 to 40% by weight, more preferably from 0.1 to 30% by weight, based on the weight of the support in the catalyst.

According to the invention, the soluble compound of the active component is a soluble compound selected from elements of group VA and one or more of metals of group VB, group VIB and group VIII. Further preferably, the soluble compound of the active component is a soluble compound of one or more elements selected from P, V, Cr, Mo, Fe, and Co. In order to further improve the catalytic performance of the catalyst, the soluble compound of the active component is preferably a combination of a soluble compound of a group VA element and a soluble compound of at least one metal selected from group VB, group VIB and group VIII. Most preferably a combination of P and a soluble compound of at least one element selected from V, Cr, Mo, Fe and Co.

According to the present invention, the soluble compound is generally a water-soluble compound, and specifically, for example, the soluble compound of a metal in the soluble compounds of P, V, Cr, Mo, Fe, and Co may be one or more of nitrate, chloride, and ammonium salt of the metal, and the like, and the soluble compound of a nonmetal may be ammonium phosphate, ammonium metavanadate, ammonium chromate, ammonium molybdate, ferric nitrate, and cobalt nitrate; preferably one or more selected from the group consisting of ammonium phosphate, ammonium metavanadate, ammonium chromate, ammonium molybdate, iron nitrate and cobalt nitrate.

According to the present invention, after impregnating the carrier with the solution containing the soluble compound of the active ingredient, the drying conditions of the carrier may be conventional drying conditions, for example, the drying temperature may be 90 to 125 ℃ and the drying time may be 1 to 12 hours.

According to the present invention, the conditions for impregnating the support with a solution containing a soluble compound of the active component and then calcining the dried support generally include a calcination temperature, which may be 300-700 ℃, and a calcination time, which may be selected depending on the calcination temperature and may generally be 2-6 hours. The calcination is generally carried out in an air atmosphere, which includes both a flowing atmosphere and a static atmosphere.

According to the present invention, the amount of the oxidizing agent and the catalyst used in step (3) can be selected from a wide range, and preferably, the catalyst is contained in an amount of 0.01 to 50% by weight, preferably 0.5 to 30% by weight, based on the total weight of the catalyst and the oxidation reaction solvent.

According to the present invention, the mode of contacting the 2-alkylanthracene with the oxidizing agent and the catalyst may be various modes capable of achieving the oxidation production of the 2-alkylanthracene to obtain the 2-alkylanthracene. Preferably, for more complete reaction, the contacting is carried out in the following manner: a raw material liquid containing a 2-alkylanthracene, a catalyst and an oxidation reaction solvent is brought into contact with an oxidizing agent to carry out an oxidation reaction.

According to the present invention, in step (3), the conditions and method of the oxidation reaction may be performed in a manner conventional in the art, except for the combination of the above-mentioned t-butyl hydroperoxide oxidizing agent and the specific catalyst.

According to the present invention, in step (3), the oxidizing agent is used in an amount that enables oxidation of 2-alkylanthracene to produce 2-alkylanthracene, preferably in a molar ratio of the oxidizing agent to 2-alkylanthracene of from 0.01:1 to 100:1, more preferably from 1:1 to 50: 1.

According to the present invention, in step (3), the oxidation reaction is generally carried out under conditions including: the reaction temperature can be 10-150 ℃, and preferably 20-100 ℃; the reaction time can be 0.01 to 48 hours, preferably 0.5 to 24 hours; the reaction pressure may be from 0 to 1MPa, preferably from 0 to 0.5 MPa.

According to the present invention, in the step (3), the oxidation reaction solvent is an inert organic solvent capable of dissolving the 2-alkylanthraceneAnd (3) preparing. The oxidation reaction solvent can be a polar organic solvent or a nonpolar organic solvent, and the oxidation reaction solvent can be N-alkyl substituted amide, wherein the number of alkyl substituents is 1-2, and each alkyl substituent is independently C₁-C₄For example, one or more selected from N, N-dimethylformamide, N-dimethylacetamide and N, N-dimethylpropionamide. Preferably, the oxidation reaction solvent is a nonpolar organic solvent, and the oxidation reaction solvent is C₆Above, preferably C₆-C₁₂One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of mono-or poly-substituted benzene. Wherein the substituent is C₁-C₄And one or more of an alkyl group and a halogen element. Wherein, when the substituent is C₁-C₄The oxidation reaction solvent may be one or more selected from the group consisting of 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5, 6-tetramethylbenzene and 2,3,5, 6-tetramethylbenzene. More preferably, the oxidation reaction solvent is one or more of halogen element substitutes of benzene; most preferably, the oxidation reaction solvent is one or more of monochlorobenzene, dichlorobenzene, trichlorobenzene and tetrachlorobenzene. Among them, monochlorobenzene, dichlorobenzene, trichlorobenzene and tetrachlorobenzene include various isomers thereof.

According to the present invention, in the step (3), the oxidation reaction solvent is used in an amount sufficient to ensure that the 2-alkylanthracene is sufficiently soluble to provide a good reaction medium. Preferably, the 2-alkylanthracene is present in an amount of 0.1 to 80 wt%, preferably 5 to 50 wt%, based on the total weight of the 2-alkylanthracene and the oxidation reaction solvent.

According to the present invention, in the step (3), the preparation of 2-alkylanthraquinone from 2-alkylanthracene requires the use of a catalyst, and the catalyst after the reaction can be separated by a separation method which is conventional in the art according to the nature of the catalyst. The 2-alkylanthraquinone in the product is the target product, if other substances including the residual 2-alkylanthraquinone, solvent and generated by-products exist, the 2-alkylanthraquinone can be removed or purified respectively by adopting a conventional separation method or a combined separation method according to the difference of the properties of the substances.

The present invention will be described in detail below by way of examples.

The material composition data are obtained by chromatographic analysis.

The chromatographic analysis method comprises the following steps: agilent 7890A, column DB-1(50 m.times.0.25 mm. times.0.25 μm). Sample inlet temperature: 330 ℃, sample introduction: 0.2 mu L, the split ratio of 20:1, nitrogen as carrier gas, the flow rate of constant flow mode of 0.7mL/min, temperature programming: keeping the temperature at 110 ℃ for 10min, then increasing the temperature to 320 ℃ at the speed of 5 ℃/min, and keeping the temperature for 18 min. FID detector: temperature 350 ℃, hydrogen flow: 35mL/min, air flow: 350mL/min, tail gas blowing is nitrogen, and the flow is as follows: 25 mL/min.

Defining the conversion rate of anthracene as X in the alkylation reaction of step (1)₁The substance selectivity calculated on a molar basis is S (mol%). The mass fraction was expressed as a percentage of the chromatographic peak area of each substance, and the fraction W (% by mol) based on the molar amount of each substance was calculated in combination with the molar mass.

AN is used for representing anthracene, Ci-AN represents 2-alkyl anthracene, and Cj-AN represents other alkyl anthracene.

The conversion of anthracene is shown in formula 1:

the 2-alkyl anthracene selectivity is shown in formula 2:

(II) in the separation process of the step (2), the purity B of a certain substance is the mass fraction of the substance, and the purity of the separated anthracene is B₁The purity of the separated 2-alkyl anthracene is B₂Calculated based on chromatographic data. The anthracene and alkyl anthracene mixture to be separated was chromatographed. Preparing an external standard analysis curve by adopting high-purity 2-alkyl anthracene and mesitylene, and quantitatively calculatingThe content of 2-alkyl anthracene in the mixture of anthracene and 2-alkyl anthracene, denoted W₀And g. The amount of 2-alkylanthracene actually isolated according to the process proposed by the invention is denoted W₁And g. The yield Y of the separation process is calculated as shown in formula 3 below.

(III) in the oxidation reaction of the step (3), the conversion rate of Ci-AN is defined as X₂The substance selectivity calculated on a molar basis is S (mol%). The mass fraction was expressed as a percentage of the chromatographic peak area of each substance, and the fraction W (% by mol) based on the molar amount of each substance was calculated in combination with the molar mass.

Ci-AN is adopted to represent 2-alkyl anthracene, Ci-AO is adopted to represent 2-alkyl anthraquinone, and Ci-X is adopted to represent other byproducts.

The 2-alkyl anthracene conversion is shown as formula 4:

the 2-alkylanthraquinone selectivity is shown in formula 5:

the following examples 1-17 are provided to illustrate the preparation of the 2-alkylanthraquinones provided by the present invention.

Example 1

And (I) alkylation reaction.

The 2-pentylanthracene is prepared by alkylating anthracene and isoamylene, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. 460g of anthracene, 800ml of mesitylene and 42g of methanesulfonic acid were added to a 2L stirred tank at room temperature. After sealing, the temperature is raised to 165 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.3 MPa. 151g of isoamylene was added to the kettle by means of a plunger pump at a feed rate of 6.6 g/min. When the feeding of the isoamylene is finished, the reaction is continued for 270min while the reaction conditions are kept unchanged, and then the reaction is stopped. Reacting for 10 batches under the same condition, separating the catalyst, and uniformly collecting the alkylation reaction product as the raw material for separating the alkyl anthracene.

(II) separating.

The alkylation reaction product is sent to a normal pressure distillation system, the temperature is raised to 165 ℃ under normal pressure, and light components with boiling points lower than that of anthracene, such as residual isoamylene, mesitylene and the like can be separated out successively. The rest is a solid mixture of anthracene-alkyl anthracene, the mixture is heated to 220 ℃ and is in a molten state and sent into an intermittent melting crystallization system, the melting crystallizer is a tubular crystallizer, and cooling medium is introduced to start temperature reduction and crystallization. The cooling rate is 0.5 ℃/h, the cooling crystallization temperature is 200 ℃, the amount of the seed crystal anthracene added is 0.5 weight percent of the mass of the molten mixture, and the crystal growth time is controlled to be 2 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 0.2 ℃/h, the sweating finishing temperature is 205 ℃, the sweating amount is 25 weight percent of the mass of the crystals, and the sweating liquid circulates and is contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 300 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 240 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. And collecting a product 2-pentylanthracene at the bottom of the tower.

(III) oxidation reaction.

Preparation of supported solid catalyst: 7.6g of ammonium phosphate, 54g of ammonium chromate and 80ml of water at 80 ℃ are mixed uniformly, and 133g of SiO carrier is used₂-Al₂O₃Composite (microspheres with an average particle size of 100 μm, wherein Al₂O₃92 wt.%), soaking for 6h, drying in a drying oven at 110 deg.C for 12h to obtain powder, heating to 500 deg.C in a muffle furnace at a heating rate of 5 deg.C/min, and calcining for 5h to obtain the supported solid catalyst. The total amount of the supported elements was 15 wt% calculated as elements based on the weight of the carrier. Wherein the content of the supported P is 1.2% by weight,the content of Cr as a supported metal was 13.8% by weight, and the catalyst was expressed as P (1.2% by weight) -Cr (13.8% by weight)/SiO₂-Al₂O₃(92% by weight). Repeating the steps for a plurality of times to prepare enough catalyst.

The 2-amyl anthracene is oxidized in a liquid phase to prepare the 2-amyl anthraquinone. 3000ml of chlorobenzene, 150g of 2-pentylanthracene, and 587g of the above-mentioned supported solid catalyst were charged into an 8L glass vessel. The reaction was carried out at atmospheric pressure 80 ℃ and 1089g of t-butyl hydroperoxide was added to the kettle by means of a peristaltic pump at a feed rate of 5 g/min. After the feeding is finished, the reaction is continued under the unchanged condition, and the total reaction time is 20 hours. After the reaction is finished, removing the catalyst by settling or filtering, and distilling the reaction liquid to obtain the final product 2-amylanthraquinone.

Conversion rate X of anthracene in the step (I)₁Selectivity of 2-pentylanthracene_Ci-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B₁Intermediate 2-pentylanthracene purity B₂The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X₂And 2-amylanthraquinone-selective S_Ci-AOAs shown in table 1.

Comparative example 1

2-Alkylanthraquinone was prepared according to the method of example 1, except that, in the step (II), after distilling off the light components having a boiling point lower than that of anthracene, anthracene was separated not by melt crystallization but directly by distillation under reduced pressure. The distillation tower for separating anthracene is marked as anthracene-separating reduced pressure distillation system, the pressure at the top of the tower is 8KPa, the distillation temperature is 275 ℃, the number of theoretical plates is 20, and the reflux ratio at the top of the tower is 0.7. The bottom product was subjected to the first vacuum distillation and the second vacuum distillation under the same conditions as in example 1.

In step (III), 3000ml of methanol, 150g of 2-pentylanthracene, and 307g of 36 wt% hydrochloric acid were charged in a 5L glass vessel. The reaction was carried out at atmospheric pressure and 65 ℃ with a peristaltic pump feeding 342g of hydrogen peroxide (30 wt% hydrogen peroxide) into the kettle at a feed rate of 2 g/min. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. After the reaction is finished, transferring the materials in the kettle into a 20L glass stirring kettle, adding 2000ml of mesitylene and 3000ml of deionized water for extraction and washing, standing, separating out the mesitylene phase containing 2-amylanthraquinone on the upper layer, and distilling to obtain the final product 2-amylanthraquinone.

Example 2

2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 5.0 ℃/h, the crystallization temperature was 190 ℃, the amount of anthracene added as a seed crystal was 4% by weight based on the mass of the molten mixture, and the crystal growth time was controlled to 4 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 4 ℃/h, the sweating finishing temperature is 195 ℃, the sweating amount is 10 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer, and then the crystallization operation is carried out together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 300 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 240 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. And collecting a product 2-pentylanthracene at the bottom of the tower.

Example 3

2-Alkylanthraquinone was prepared according to the method of example 1, except that in the step (II), the uncrystallized alkylanthracene mixture was fed to a vacuum distillation system to conduct a third vacuum distillation at a head pressure of 1KPa, a bottom temperature of 290 ℃ C., a theoretical plate number of 65 and a head reflux ratio of 1.5. And carrying out fourth reduced pressure distillation on the tower bottom distillate, wherein the tower top pressure is 1KPa, the tower bottom temperature is 305 ℃, the theoretical plate number is 70, and the tower top reflux ratio is 3. And collecting a product 2-pentylanthracene at the top of the tower.

Example 4

2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 2 ℃/h, the crystallization temperature was 192 ℃, the amount of anthracene added as a seed crystal was 2% by weight of the mass of the molten mixture, and the crystal growth time was controlled to 3 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating and sweating the crystals in the crystallizer, wherein the heating rate is 2.0 ℃/h, the sweating finishing temperature is 197 ℃, the sweating amount is 15 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 300 ℃, the number of theoretical plates is 40, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 240 ℃, the number of theoretical plates is 40, and the reflux ratio at the tower top is 3. And collecting a product 2-pentylanthracene at the bottom of the tower.

Example 5

2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 1 ℃/h, the crystallization temperature was 197 ℃, the amount of anthracene added as a seed crystal was 1% by weight of the mass of the molten mixture, and the crystal growth time was controlled to 1.5 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating and sweating the crystals in the crystallizer, wherein the heating rate is 0.6 ℃/h, the sweating finishing temperature is 202 ℃, the sweating amount is 20 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 0.8KPa, the temperature at the bottom of the tower is 280 ℃, the number of theoretical plates is 75, and the reflux ratio at the top of the tower is 2. And carrying out second reduced pressure distillation on the overhead distillate, wherein the overhead pressure is 1.2KPa, the bottom temperature is 266 ℃, the number of theoretical plates is 75, and the overhead reflux ratio is 4. And collecting a product 2-pentylanthracene at the bottom of the tower.

Example 6

2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 1.5 ℃/h, the crystallization temperature was 195 ℃, the amount of anthracene added as a seed crystal was 1.5% by weight based on the mass of the molten mixture, and the crystal growth time was controlled to 2.5 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 1 ℃/h, the sweating finishing temperature is 199 ℃, the sweating amount is 30 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer, and then the crystallization operation is carried out together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1.2KPa, the temperature at the bottom of the tower is 320 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 0.8KPa, the temperature at the tower bottom is 228 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 1. And collecting a product 2-pentylanthracene at the bottom of the tower.

Example 7

When 2-butylanthraquinone was used as a target product, the other materials and reaction conditions were the same as in example 1 except that in the step (I), 2-methyl-2-butene was changed to isobutylene in an amount of 121g, and the alkylation reaction was carried out in the same manner as in example 1. In the second step, the cooling rate is 0.5 ℃/h, the cooling crystallization temperature is 200 ℃, the amount of the seed crystal anthracene added is 0.5 weight percent of the mass of the molten mixture, and the crystal growth time is controlled to be 2 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 0.2 ℃/h, the sweating finishing temperature is 205 ℃, the sweating amount is 25 weight percent of the mass of the crystals, and the sweating liquid circulates and is contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 291 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 221 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. Collecting the product 2-butylanthracene at the bottom of the tower. In step (three), the amount of catalyst used was changed to 832.5 g.

Conversion rate X of anthracene in the step (I)₁Selectivity of 2-butylanthracene S_Ci-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B₁Intermediate 2-butylanthracene purity B₂The total yield of the 2-butylanthracene separation process is Y, and the step (III)Conversion of 2-butylanthracene to X₂And 2-butylanthraquinone Selective S_Ci-AOAs shown in table 2.

Example 8

When 2-hexylanthracene was used as a target product, the other materials and reaction conditions were the same as in example 1, except that in the step (I), 2-methyl-2-butene was changed to 2-methyl-2-pentene in an amount of 181g, and the alkylation was carried out in the same manner as in example 1. In the second step, the cooling rate is 0.5 ℃/h, the cooling crystallization temperature is 200 ℃, the amount of the seed crystal anthracene added is 0.5 weight percent of the mass of the molten mixture, and the crystal growth time is controlled to be 2 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 0.2 ℃/h, the sweating finishing temperature is 205 ℃, the sweating amount is 25 weight percent of the mass of the crystals, and the sweating liquid circulates and is contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 310 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 251 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. Collecting the bottom product 2-hexyl anthracene. In the third step, the amount of the catalyst used was changed to 175.3 g.

Conversion rate X of anthracene in the step (I)₁S selectivity to 2-hexyl anthracene_Ci-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B₁Intermediate 2-hexyl anthracene purity B₂The total yield of the separation process of the 2-hexyl anthracene is Y, and the conversion rate of the 2-hexyl anthracene in the step (III) is X₂And 2-hexylanthraquinone-selective S_Ci-AOAs shown in table 2.

Example 9

And (I) alkylation reaction.

The 2-pentylanthracene is prepared by alkylating anthracene and isoamylene, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. 76g of anthracene, 800ml of mesitylene and 12g of methanesulfonic acid were added to a 2L stirred tank at room temperature. After sealing, the temperature is raised to 110 ℃ at the rotating speed of 1000 rpm, and the pressure is 0.15 MPa. 60g of isoamylene was added to the kettle by means of a plunger pump at a feed rate of 3 g/min. When the feeding of the isoamylene is finished, the reaction is continued for 270min while the reaction conditions are kept unchanged, and then the reaction is stopped. Reacting for 10 batches under the same condition, separating the catalyst, and uniformly collecting the alkylation reaction product as the raw material for separating the alkyl anthracene.

Both the step (two) and the step (three) were the same as in example 1.

Conversion rate X of anthracene in the step (I)₁Selectivity of 2-pentylanthracene_Ci-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B₁Intermediate 2-pentylanthracene purity B₂The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X₂And 2-amylanthraquinone-selective S_Ci-AOAs shown in table 2.

Example 10

And (I) alkylation reaction.

The 2-pentylanthracene is prepared by alkylating anthracene and isoamylene, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. To a 2L stirred tank, 229g of anthracene, 800ml of mesitylene, and 40g of methanesulfonic acid were added at room temperature. After sealing, the temperature is raised to 130 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.2 MPa. 18g of isoamylene was added to the kettle by means of a plunger pump at a feed rate of 2 g/min. When the feeding of the isoamylene is finished, the reaction is continued for 270min while the reaction conditions are kept unchanged, and then the reaction is stopped. Reacting for 10 batches under the same condition, separating the catalyst, and uniformly collecting the alkylation reaction product as the raw material for separating the alkyl anthracene.

Both the step (two) and the step (three) were the same as in example 1.

Example 11

Both the step (one) and the step (two) were the same as in example 1. Except that in the third step, the amount of the oxidizing agent was changed to 544.5 g.

Example 12

Both the step (one) and the step (two) were the same as in example 1. Except that in the third step, the amount of the oxidizing agent was changed to 272.25 g.

Example 13

Both the step (one) and the step (two) were the same as in example 1. Except that, in the third step, the oxidation reaction solvent was 3000ml of N, N-dimethylformamide, and the amount of the catalyst was changed to 503 g.

Example 14

Both the step (one) and the step (two) were the same as in example 1. Except that in step (III), the catalyst is changed to Cr/SiO₂-Al₂O₃(92% by weight).

The preparation of the supported solid catalyst comprises the following steps: 58.68g of ammonium chromate is evenly mixed with 80ml of water at the temperature of 80 ℃, and 133g of SiO carrier is added₂-Al₂O₃Composite (microspheres with an average particle size of 10)0 μm of which is Al₂O₃92 wt.%), soaking for 6h, drying in a drying oven at 110 deg.C for 12h to obtain powder, heating to 500 deg.C in a muffle furnace at a heating rate of 5 deg.C/min, and calcining for 5h to obtain the supported solid catalyst. The amount of supported metallic Cr was 15% by weight in terms of element based on the weight of the carrier. The catalyst is expressed as Cr/SiO₂-Al₂O₃(92% by weight). Repeating the steps for a plurality of times to prepare enough catalyst.

Example 15

Both the step (one) and the step (two) were the same as in example 1. Except that in step (three), the catalyst was changed to P (1.2 wt%) -Ni (13.8 wt%)/SiO₂-Al₂O₃(92% by weight).

The preparation of the supported solid catalyst comprises the following steps: 7.6g of ammonium phosphate, 57.3g of nickel nitrate and 80ml of water are mixed uniformly, and 133g of carrier SiO₂-Al₂O₃Composite (microspheres with an average particle size of 100 μm, wherein Al₂O₃92 wt.%), soaking for 6h, drying in a drying oven at 110 deg.C for 12h to obtain powder, heating to 500 deg.C in a muffle furnace at a heating rate of 5 deg.C/min, and calcining for 5h to obtain the supported solid catalyst. The total amount of the supported elements was 15 wt% calculated as elements based on the weight of the carrier. Wherein the content of the supported P was 1.2% by weight, the content of the supported metallic Ni was 13.8% by weight, and the catalyst was expressed as P (1.2% by weight) -Ni (13.8% by weight)/SiO₂-Al₂O₃(92% by weight). Repeating the steps for a plurality of times to prepare enough catalyst.

Example 16

Both the step (one) and the step (two) were the same as in example 1. Except that in step (three), the catalyst was changed to P (0.8 wt%) -Cr (9.2 wt%)/SiO₂-Al₂O₃(92% by weight).

The preparation of the supported solid catalyst comprises the following steps: 5.07g of ammonium phosphate, 35.99g of ammonium chromate and 80ml of water at 80 ℃ are mixed uniformly, and 133g of carrier SiO₂-Al₂O₃Composite (microspheres with an average particle size of 100 μm, wherein Al₂O₃92 wt.%), soaking for 6h, drying in a drying oven at 110 deg.C for 12h to obtain powder, heating to 500 deg.C in a muffle furnace at a heating rate of 5 deg.C/min, and calcining for 5h to obtain the supported solid catalyst. The total amount of the supported elements was 10 wt% in terms of elements based on the weight of the carrier. Wherein the content of P supported was 0.8% by weight, the content of Cr supported metal was 9.2% by weight, and the catalyst was expressed as P (0.8% by weight) -Cr (9.2% by weight) -SiO₂-Al₂O₃(92% by weight). Repeating the steps for a plurality of times to prepare enough catalyst.

Example 17

Both the step (one) and the step (two) were the same as in example 1. Except that in step (three), the catalyst was changed to P (1.44 wt%) -Cr (16.56 wt%)/SiO₂-Al₂O₃(92% by weight).

The supported solidPreparation of the catalyst: 9.12g of ammonium phosphate, 64.78g of ammonium chromate and 80ml of water at 80 ℃ are mixed uniformly, and 133g of carrier SiO₂-Al₂O₃Composite (microspheres with an average particle size of 100 μm, wherein Al₂O₃92 wt.%), soaking for 6h, drying in a drying oven at 110 deg.C for 12h to obtain powder, heating to 500 deg.C in a muffle furnace at a heating rate of 5 deg.C/min, and calcining for 5h to obtain the supported solid catalyst. The total amount of the supported elements was 18 wt% calculated as elements based on the weight of the carrier. Wherein the content of the supported P was 1.44% by weight, the content of the supported metal Cr was 16.56% by weight, and the catalyst was expressed as P (1.44% by weight) -Cr (16.56% by weight) -SiO₂-Al₂O₃(92% by weight). Repeating the steps for a plurality of times to prepare enough catalyst.

As can be seen from the results in tables 1 and 2, in the method for preparing 2-alkylanthraquinone by reacting and separating 2-alkylanthraquinone from anthracene and then performing catalytic oxidation, the purity of the separated crystal anthracene, the purity of the intermediate product 2-pentylanthracene (2-butylanthracene, 2-hexylanthracene), and the total yield of the separation process of 2-pentylanthracene (2-butylanthracene, 2-hexylanthracene) are significantly improved by the melt crystallization-distillation coupling separation technique, compared with the prior art, and the total yield of the finally obtained 2-alkylanthraquinone is also improved.

In addition, the 2-alkyl anthracene oxidation technology in the method for preparing the 2-alkyl anthraquinone by separating the 2-alkyl anthracene from the anthracene through reaction and then carrying out catalytic oxidation combines an oxidant tert-butyl hydroperoxide with the supported catalyst for use, and compared with the prior art, the catalyst has the advantages of slightly low conversion rate of raw materials, good selectivity, no corrosivity, no generation of chlorine-containing wastewater, easy recovery of the catalyst, and simple and clean process.

In conclusion, the method provided by the invention opens up a new direction for the green preparation of the 2-alkylanthraquinone.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A method for preparing 2-alkyl anthraquinone by separating 2-alkyl anthracene from anthracene through reaction and then performing catalytic oxidation is characterized by comprising the following steps:

2. The production method according to claim 1, wherein, in the step (1), the method for producing the reaction product containing the alkyl anthracene from the anthracene includes: the alkylation reaction is carried out by contacting anthracene with an alkylating agent under alkylation conditions and in the presence of an alkylation solvent and a catalyst.

3. The method of claim 2, wherein the contacting is performed by: the raw material liquid containing anthracene, catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction.

4. The preparation method according to claim 2 or 3, wherein the alkylating agent is one or more of olefins having 2 to 8 carbon atoms, alcohols, halogenated hydrocarbons and ethers.

5. The preparation method according to claim 4, wherein the alkylating agent is one or more of olefins containing 4 to 6 carbon atoms, alcohols, halogenated hydrocarbons and ethers.

6. The process of claim 5 wherein the alkylating agent is a mono-olefin having from 4 to 6 carbon atoms.

7. The production method according to any one of claims 2,3,5 and 6, wherein in the step (1), the molar ratio of anthracene to the alkylating agent is from 0.2:1 to 20: 1.

8. The production process according to claim 7, wherein in the step (1), the molar ratio of anthracene to the alkylating agent is from 0.5:1 to 5: 1.

9. The production process according to claim 4, wherein in the step (1), the molar ratio of anthracene to the alkylating agent is from 0.2:1 to 20: 1.

10. The production method according to claim 9, wherein in the step (1), the molar ratio of anthracene to the alkylating agent is 0.5:1 to 5: 1.

11. The production process according to claim 2 or 3, wherein in the step (1), the alkylation reaction solvent is a solvent having a dielectric constant of 1 to 10 at 20 ℃, and the alkylation reaction solvent is C₆The above;

based on the total weight of anthracene and alkylation reaction solvent, the content of anthracene is 5-60 wt%.

12. The method according to claim 11, wherein in the step (1), the alkylation reaction solvent is C₆-C₁₂One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted.

13. The method of claim 12, wherein the aromatic hydrocarbon is one or more of a mono-or multi-substituted benzene.

14. The method according to claim 13, wherein the aromatic hydrocarbon is one or more of benzene polybasic substituted compounds, and the substituted group is C₁-C₄And one or more of an alkyl group and a halogen element.

15. The process of claim 14 wherein the alkylation reaction solvent is one or more of a polyalkyl substituent of benzene.

16. The method of claim 15, wherein the alkylation reaction solvent is selected from one or more of 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5, 6-tetramethylbenzene, and 2,3,5, 6-tetramethylbenzene.

17. The production method according to claim 11, wherein the content of anthracene is 8 to 50% by weight based on the total weight of anthracene and the alkylation reaction solvent.

18. The production method according to any one of claims 2,3,5,6, 8 to 10 and 12 to 17, wherein in the step (1), the alkylation reaction conditions include: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

19. The method according to claim 18, wherein in the step (1), the alkylation reaction conditions include: the reaction temperature is 120-200 ℃; the reaction pressure is 0.05-0.5 MPa; the reaction time is 0.5-24 h.

20. The preparation method according to claim 4, wherein in the step (1), the alkylation reaction conditions include: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

21. The preparation method according to claim 7, wherein in the step (1), the alkylation reaction conditions include: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

22. The method according to claim 11, wherein in the step (1), the alkylation reaction conditions include: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

23. The production method according to any one of claims 20 to 22, wherein in the step (1), the alkylation reaction conditions include: the reaction temperature is 120-200 ℃; the reaction pressure is 0.05-0.5 MPa; the reaction time is 0.5-24 h.

24. The production method according to any one of claims 2,3,5,6, 8 to 10 and 12 to 17, wherein, in the step (1), the catalyst is selected from one or more of liquid acids; the catalyst content is 0.01-50 wt% based on the total weight of the raw material liquid containing anthracene, catalyst and alkylation reaction solvent.

25. The production method according to claim 24, wherein, in the step (1), the catalyst is methanesulfonic acid and/or p-toluenesulfonic acid; the catalyst content is 0.5-30 wt% based on the total weight of the raw material liquid containing anthracene, catalyst and alkylation reaction solvent.

26. The production method according to claim 4, wherein, in the step (1), the catalyst is selected from one or more of liquid acids; the catalyst content is 0.01-50 wt% based on the total weight of the raw material liquid containing anthracene, catalyst and alkylation reaction solvent.

27. The production method according to claim 7, wherein, in the step (1), the catalyst is selected from one or more of liquid acids; the catalyst content is 0.01-50 wt% based on the total weight of the raw material liquid containing anthracene, catalyst and alkylation reaction solvent.

28. The production method according to claim 11, wherein, in the step (1), the catalyst is selected from one or more of liquid acids; the catalyst content is 0.01-50 wt% based on the total weight of the raw material liquid containing anthracene, catalyst and alkylation reaction solvent.

29. The production method according to any one of claims 26 to 28, wherein in step (1), the catalyst is methanesulfonic acid and/or p-toluenesulfonic acid; the catalyst content is 0.5-30 wt% based on the total weight of the raw material liquid containing anthracene, catalyst and alkylation reaction solvent.

30. The production method according to any one of claims 1 to 3,5,6, 8 to 10, 12 to 17, 19 to 22, and 25 to 28, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.

31. The production method according to claim 4, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

32. The production method according to claim 7, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

33. The production method according to claim 11, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

34. The production method according to claim 18, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

35. The production method according to claim 23, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

36. The production method according to claim 24, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

37. The production method according to claim 29, wherein the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;

the step (2) comprises the following steps:

38. The preparation method as claimed in claim 30, wherein, in the step (2-2), the melting temperature is 200-270 ℃.

39. The preparation method as claimed in claim 38, wherein, in the step (2-2), the melting temperature is 210-250 ℃.

40. The production method according to any one of claims 31 to 37, wherein, in the step (2-2), the melting temperature is 200 ℃ and 270 ℃.

41. The preparation method as claimed in claim 40, wherein, in the step (2-2), the melting temperature is 210-250 ℃.

42. The preparation method as claimed in claim 30, wherein, in the step (2-2), the cooling crystallization temperature is 180-210 ℃, the cooling rate of the cooling crystallization is 0.1-10 ℃/h, and the cooling crystallization time is 1-5 h.

43. The preparation method as claimed in claim 42, wherein, in the step (2-2), the cooling crystallization temperature is 190-200 ℃, the cooling rate of the cooling crystallization is 0.5-5 ℃/h, and the cooling crystallization time is 1.5-4 h.

44. The preparation method as claimed in any one of claims 31 to 39 and 41, wherein, in the step (2-2), the cooling crystallization temperature is 180-210 ℃, the cooling rate of the cooling crystallization is 0.1-10 ℃/h, and the cooling crystallization time is 1-5 h.

45. The preparation method as claimed in claim 44, wherein, in the step (2-2), the cooling crystallization temperature is 190-200 ℃, the cooling rate of the cooling crystallization is 0.5-5 ℃/h, and the cooling crystallization time is 1.5-4 h.

46. The preparation method as claimed in claim 40, wherein, in the step (2-2), the cooling crystallization temperature is 180-210 ℃, the cooling rate of the cooling crystallization is 0.1-10 ℃/h, and the cooling crystallization time is 1-5 h.

47. The preparation method as claimed in claim 46, wherein, in the step (2-2), the cooling crystallization temperature is 190-200 ℃, the cooling rate of the cooling crystallization is 0.5-5 ℃/h, and the cooling crystallization time is 1.5-4 h.

48. The production method according to any one of claims 42, 43 and 45 to 47, wherein in the step (2-2), during the cooling crystallization, a step of adding seed anthracene in an amount of 0.1 to 10% by weight based on the mass of the molten mixture is further included.

49. The production method according to claim 48, wherein the seed anthracene is added in an amount of 0.2 to 5 wt% based on the mass of the molten mixture.

50. The production method according to claim 44, wherein in the step (2-2), during the cooling crystallization, a step of adding seed anthracene in an amount of 0.1 to 10 wt% based on the mass of the molten mixture is further included.

51. The production method according to claim 50, wherein the seed anthracene is added in an amount of 0.2 to 5 wt% based on the mass of the molten mixture.

52. The production process according to claim 30, wherein in the step (2-2), the temperature increase rate at which the anthracene crystal is subjected to sweating is 0.1 to 8 ℃/h; the temperature is raised to a temperature at which sweating stops and is lower than the melting temperature of the anthracene crystal.

53. The production process according to claim 40, wherein in the step (2-2), the temperature increase rate at which the anthracene crystal is subjected to sweating is 0.1 to 8 ℃/h; the temperature is raised to a temperature at which sweating stops and is lower than the melting temperature of the anthracene crystal.

54. The production process according to claim 52 or 53, wherein in the step (2-2), the temperature increase rate at which the anthracene crystal is subjected to sweating is 0.2 to 4 ℃/h.

55. The production method according to claim 52 or 53, wherein, in the step (2-2), the temperature raised to a temperature at which sweating stops is 210 ℃ or lower.

56. The method according to claim 55, wherein in the step (2-2), the sweating is stopped when the temperature is raised to 5 to 15 ℃ higher than the cooling crystallization temperature and lower than 210 ℃.

57. The preparation method as claimed in claim 56, wherein, in the step (2-2), the sweating end temperature is 190-210 ℃.

58. The preparation method as claimed in claim 57, wherein, in the step (2-2), the sweating finishing temperature is 195-205 ℃.

59. The production method according to any one of claims 31 to 39 and 41, wherein in the step (2-2), the temperature increase rate at which the anthracene crystal is subjected to sweating is 0.1 to 8 ℃/h; the temperature is raised to a temperature at which sweating stops and is lower than the melting temperature of the anthracene crystal.

60. The production method according to claim 59, wherein in the step (2-2), the temperature increase rate at which the anthracene crystal is subjected to sweating is 0.2 to 4 ℃/h.

61. The production method according to claim 59, wherein, in the step (2-2), the temperature raised to a temperature at which sweating stops is 210 ℃ or lower.

62. The production process as claimed in claim 61, wherein in the step (2-2), the sweating is stopped when the temperature is raised to 5 to 15 ℃ higher than the cooling crystallization temperature and lower than 210 ℃.

63. The method as claimed in claim 62, wherein the sweating end temperature is 190-210 ℃.

64. The method as claimed in claim 63, wherein the sweating completion temperature is 195-205 ℃.

65. The production method according to any one of claims 52, 53, 56 to 58, and 60 to 64, wherein the amount of perspiration is 5 to 40 wt% based on the mass of the anthracene crystal.

66. The method of claim 65, wherein the amount of perspiration is 10 to 30 wt% based on the mass of the anthracene crystal.

67. The production method according to claim 54, wherein the amount of perspiration is 5 to 40 wt% based on the mass of the anthracene crystal.

68. The method according to claim 55, wherein the amount of perspiration is 5 to 40 wt% based on the mass of the anthracene crystal.

69. The method of claim 59, wherein the amount of perspiration is 5 to 40 wt.% of the mass of the anthracene crystals.

70. The production method according to any one of claims 67 to 69, wherein the amount of perspiration is 10 to 30 wt% based on the mass of the anthracene crystal.

71. The production method according to any one of claims 52, 53, 56 to 58 and 60 to 64, wherein the method further comprises circulating sweat back to the melt crystallization step to perform melt crystallization together with the reaction product containing alkyl anthracene.

72. The method of claim 54, further comprising recycling sweat back to the melt crystallization step for melt crystallization with the reaction product comprising alkyl anthracene.

73. The method of claim 55, further comprising recycling sweat back to the melt crystallization step for melt crystallization with the reaction product comprising alkyl anthracene.

74. The method of claim 59, further comprising recycling sweat back to the melt crystallization step for melt crystallization with the reaction product comprising alkyl anthracene.

75. The production method according to claim 30, wherein, in the step (2-3), when the series of alkyl anthracene products containing 2-alkyl anthracene is a mixture of two substances, or a mixture of three or more substances, and the boiling point of 2-alkyl anthracene is the lowest or the highest; then a one-step distillation is performed to separate the 2-alkyl anthracene.

76. The production method according to any one of claims 31 to 37, wherein, in the step (2-3), when the series of alkyl anthracene products containing 2-alkyl anthracene is a mixture of two substances, or a mixture of three or more substances, and the boiling point of 2-alkyl anthracene is the lowest or the highest; then a one-step distillation is performed to separate the 2-alkyl anthracene.

77. The production method according to claim 30, wherein, in the step (2-3), when the series of alkyl anthracene products containing 2-alkyl anthracene is a mixture of three or more substances, and the boiling point of 2-alkyl anthracene is between the substance having the highest boiling point and the substance having the lowest boiling point in the mixture; then carrying out multi-step reduced pressure distillation, wherein the multi-step reduced pressure distillation method comprises the following steps:

mode 1:

carrying out first reduced pressure distillation on feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene, and separating to obtain distillate containing a light component Cj 1-anthracene and a bottom product containing a heavy component Cj 2-anthracene; carrying out second reduced pressure distillation on the distillate containing the light component Cj 1-anthracene to obtain a distillate containing the light component Cj 3-anthracene and a bottom product containing the target product Ci-anthracene;

alternatively, the first and second electrodes may be,

mode 2:

carrying out third reduced pressure distillation on feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene to obtain distillate containing light component Cm 1-anthracene and a bottom product containing heavy component Cm 2-anthracene; carrying out fourth reduced pressure distillation on the bottom product containing the heavy component Cm 2-anthracene to obtain a distillate containing the target product Ci-anthracene and a bottom product containing the heavy component Cm 3-anthracene;

wherein the light component Cm 1-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m1 being an integer of 1< m 1< i, the heavy component Cm 2-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m2 being an integer of i-1 < m 2< 41, and Cm 3-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m3 being an integer of i < m3 < 41;

wherein, in the target product Ci-anthracene, i represents the total carbon number of an alkyl side chain, and i is an integer of 4-7.

78. The production method according to any one of claims 31 to 37, wherein, in the step (2-3), when the series of alkyl anthracene products containing 2-alkyl anthracene is a mixture of three or more substances, and the boiling point of 2-alkyl anthracene is between the substance having the highest boiling point and the substance having the lowest boiling point in the mixture; then carrying out multi-step reduced pressure distillation, wherein the multi-step reduced pressure distillation method comprises the following steps:

mode 1:

alternatively, the first and second electrodes may be,

mode 2:

79. The production method according to claim 77, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the first reduced pressure distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.

80. The production method according to claim 78, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the first reduced pressure distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.

81. The production method according to claim 79 or 80, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the first reduced pressure distillation include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

82. The production process according to claim 81, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the first reduced pressure distillation include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.

83. The production method according to any one of claims 77, 79, 80 and 82, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the second reduced pressure distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.

84. The production method according to claim 83, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the second reduced pressure distillation include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

85. The production process according to claim 84, wherein, in the multi-step reduced pressure distillation step, the conditions of the second reduced pressure distillation in mode 1 include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.

86. The production method according to claim 78, wherein in the multi-step reduced pressure distillation step, the conditions of the second reduced pressure distillation in mode 1 include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.

87. The production process according to claim 81, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the second reduced pressure distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.

88. The production method according to claim 86 or 87, wherein in the multi-step reduced pressure distillation step, mode 1, the conditions of the second reduced pressure distillation include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

89. The production method according to claim 88, wherein in the multi-step reduced pressure distillation step, the conditions of the second reduced pressure distillation in mode 1 include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.

90. The production method according to claim 77, wherein in the multi-step reduced pressure distillation step, mode 2, the conditions of the third reduced pressure distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.

91. The production process according to claim 90, wherein in the multi-step vacuum distillation step, mode 2, the conditions of the third vacuum distillation include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

92. The production process according to claim 91, wherein in the multi-step vacuum distillation step, mode 2, the conditions of the third vacuum distillation include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.

93. The production process according to claim 78, wherein in the multi-step vacuum distillation step, mode 2, the conditions of the third vacuum distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.

94. The production process according to claim 93, wherein in the multi-step vacuum distillation step, mode 2, the conditions of the third vacuum distillation include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

95. The production process according to claim 94, wherein in the multi-step vacuum distillation step, mode 2, the conditions of the third vacuum distillation include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.

96. The production method according to any one of claims 77 and 90 to 95, wherein in the multi-step reduced pressure distillation step, mode 2, the fourth reduced pressure distillation conditions include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.

97. The production process according to claim 96, wherein, in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

98. The production process according to claim 97, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.

99. The production process according to claim 78, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.

100. The production process according to claim 99, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions include: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.

101. The production process according to claim 100, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions include: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.

102. The production method according to claim 30, wherein the reaction product containing an alkyl anthracene obtained through step (1) further contains a reaction solvent;

the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;

(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.

103. The production method according to any one of claims 31 to 39, 41 to 43, 45 to 47, 49 to 53, 56 to 58, 60 to 64, 66 to 69, 72 to 75, 77, 79, 80, 82, 84 to 87, 89 to 95, and 97 to 101, wherein the reaction product containing an alkylanthracene obtained through step (1) further contains a reaction solvent;

104. The production method according to claim 40, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

105. The production method according to claim 44, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

106. The production method according to claim 48, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

107. The production method according to claim 54, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

108. The production method according to claim 55, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

109. The production method according to claim 59, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

110. The production method according to claim 65, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

111. The production method according to claim 70, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

112. The production method according to claim 71, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

113. The production method according to claim 76, wherein the reaction product containing an alkyl anthracene obtained through step (1) further contains a reaction solvent;

114. The production method according to claim 78, wherein the reaction product containing an alkyl anthracene obtained through step (1) further contains a reaction solvent;

115. The production method according to claim 81, wherein the reaction product containing an alkyl anthracene obtained through step (1) further contains a reaction solvent;

116. The production method according to claim 83, wherein the reaction product containing an alkyl anthracene obtained through step (1) further contains a reaction solvent;

117. The production method according to claim 88, wherein the reaction product containing an alkyl anthracene obtained by the step (1) further contains a reaction solvent;

118. The production method according to claim 96, wherein the reaction product containing an alkyl anthracene obtained through the step (1) further contains a reaction solvent;

119. The preparation method as claimed in any one of claims 102 and 104-118, wherein in the step (2-1), the distillation conditions include: the bottom temperature of the distillation tower is 100-300 ℃, and the pressure of the top of the distillation tower is normal pressure.

120. The method as recited in claim 119, wherein the distillation column bottom temperature is 150-200 ℃.

121. The production method according to claim 103, wherein, in the step (2-1), the distillation conditions include: the bottom temperature of the distillation tower is 100-300 ℃, and the pressure of the top of the distillation tower is normal pressure.

122. The method as recited in claim 121, wherein the distillation column bottom temperature is 150-200 ℃.

123. The method according to claim 1, wherein in the step (3), the active component is selected from a group VA element and one or more of a group VB, VIB and VIII metal.

124. The method as claimed in claim 123, wherein, in the step (3), the active component is a combination of a group va element and at least one metal selected from group vb, vib and viii.

125. The method of claim 123 or 124, wherein the active component is selected from one or more of P, V, Cr, Mo, Fe, and Co.

126. The method of claim 125, wherein the active component is P in combination with at least one selected from V, Cr, Mo, Fe, and Co.

127. The production method according to claim 1, wherein the support is a heat-resistant inorganic oxide selected from one or more of silica, magnesia and a silicon-aluminum composite oxide in which SiO is contained in terms of oxide₂0.01-70 wt% of Al₂O₃The content of (B) is 30 to 99.9 wt%.

128. The method according to claim 127, wherein SiO is contained in the silicon-aluminum composite oxide on an oxide basis₂Is 5-40 wt% of Al₂O₃Is contained in an amount of 60 to 95% by weight.

129. The preparation method as claimed in any one of claims 1, 123, 124 and 126-128, wherein the content of the active component is 0.01-40 wt% in terms of element content based on the weight of the carrier in the catalyst.

130. The process of claim 129, wherein the active component is present in an amount of from 0.1 to 30% by weight, calculated as elemental content, based on the weight of the support in the catalyst.

131. The process of claim 125, wherein the active component is present in an amount of from 0.01 to 40 wt.% as elemental content, based on the weight of the support in the catalyst.

132. The method of claim 131, wherein the active component is present in an amount of 0.1 to 30 wt% based on the weight of the support in the catalyst, calculated as elemental content.

133. The method of claim 129, wherein the active component in the catalyst is a combination of a group va element and a transition metal, and the mass ratio of the transition metal to the group va element, in terms of element content, is 1-20: 1.

134. The method as claimed in any one of claims 130-132, wherein the active component in the catalyst is a combination of group va and transition metal, and the mass ratio of the transition metal to the group va is 1-20:1 in terms of element content.

135. The preparation method of any one of claims 1, 123, 124, 126 and 130-133, wherein the preparation method of the catalyst comprises: impregnating a carrier with a solution containing a soluble compound of an active component, which is one or more soluble compounds selected from the group consisting of group VA elements and transition metals, drying and calcining the impregnated carrier.

136. The method of claim 125, wherein the catalyst is prepared by a method comprising: impregnating a carrier with a solution containing a soluble compound of an active component, which is one or more soluble compounds selected from the group consisting of group VA elements and transition metals, drying and calcining the impregnated carrier.

137. The method of preparing of claim 129, wherein the method of preparing the catalyst comprises: impregnating a carrier with a solution containing a soluble compound of an active component, which is one or more soluble compounds selected from the group consisting of group VA elements and transition metals, drying and calcining the impregnated carrier.

138. The method of making of claim 134, wherein the method of making the catalyst comprises: impregnating a carrier with a solution containing a soluble compound of an active component, which is one or more soluble compounds selected from the group consisting of group VA elements and transition metals, drying and calcining the impregnated carrier.

139. The method of claim 135, wherein the soluble compound of the active component is a soluble compound selected from a group va element and one or more of a group vb, vib, and viii metal.

140. The method as claimed in claim 139, wherein the soluble compound of the active component is a combination of a soluble compound of group va element and a soluble compound of at least one metal selected from group vb, vib and viii.

141. The method as claimed in any one of claims 136-138, wherein the soluble compound of the active component is a soluble compound selected from a group va element and one or more of a group vb, vib and viii metal.

142. The method as claimed in claim 141, wherein the soluble compound of the active component is a combination of a soluble compound of group va element and a soluble compound of at least one metal selected from group vb, vib and viii.

143. The method of any one of claims 139, 140 and 142, wherein the soluble compound of the active component is a soluble compound of one or more elements selected from P, V, Cr, Mo, Fe and Co.

144. The method of claim 143, wherein the soluble compound of the active component is a combination of P and a soluble compound of at least one element selected from the group consisting of V, Cr, Mo, Fe, and Co.

145. The method of claim 141, wherein the soluble compound of the active component is a soluble compound of one or more elements selected from the group consisting of P, V, Cr, Mo, Fe, and Co.

146. The method of claim 145, wherein the soluble compound of the active component is a combination of P and a soluble compound of at least one element selected from the group consisting of V, Cr, Mo, Fe, and Co.

147. The method of claim 135, wherein the carrier and the soluble compound of the active component are used in an amount such that the active component is present in an amount of 0.01 to 40 wt.% on an elemental basis based on the weight of the carrier in the catalyst.

148. The process of claim 147, wherein the carrier and the soluble compound of the active component are used in an amount such that the active component is present in an amount of 0.1 to 30% by weight, calculated as element, based on the weight of the carrier in the catalyst.

149. The method as recited in any one of claims 136-138, wherein the soluble compound of the active component and the carrier are used in an amount such that the content of the active component in terms of element is 0.01-40 wt% based on the weight of the carrier in the catalyst.

150. The method of claim 149, wherein the carrier and the soluble compound of the active component are used in an amount such that the active component is present in an amount of 0.1 to 30% by weight, calculated as element, based on the weight of the carrier in the catalyst.

151. The process of any one of claims 147, 148 and 150, wherein the soluble compound of the active component is a combination of a soluble compound of a group va element and a soluble compound of a transition metal, and the soluble compound of the active component is used in an amount such that the mass ratio of the transition metal to the group va element, calculated as the elements, in the catalyst is from 1 to 20: 1.

152. The process of claim 149, wherein the soluble compound of the active component is a combination of a soluble compound of a group va element and a soluble compound of a transition metal, and the soluble compound of the active component is used in an amount such that the mass ratio of the transition metal to the group va element, calculated as the elements, in the catalyst is from 1 to 20: 1.

153. The method of claim 135, wherein the impregnating conditions comprise: the dipping temperature is 0-100 ℃, and the dipping time is 4-24 h; drying the impregnated carrier at 90-125 deg.C for 1-12 h; the temperature for roasting the impregnated carrier is 300-700 ℃, and the roasting time is 2-6 h.

154. The method of claim 153, wherein the temperature is 20-80 ℃ and the time is 6-12 h.

155. The method as claimed in any one of claims 136-138, wherein the impregnation conditions include: the dipping temperature is 0-100 ℃, and the dipping time is 4-24 h; drying the impregnated carrier at 90-125 deg.C for 1-12 h; the temperature for roasting the impregnated carrier is 300-700 ℃, and the roasting time is 2-6 h.

156. The method of claim 155, wherein the temperature of the immersion is 20-80 ℃ and the time of the immersion is 6-12 hours.

157. The method of claim 1, wherein the contacting is by: a raw material liquid containing a 2-alkylanthracene, a catalyst and an oxidation reaction solvent is brought into contact with an oxidizing agent to carry out an oxidation reaction.

158. The process of claim 157, wherein the catalyst is present in an amount of 0.01 to 50 wt.%, based on the total weight of catalyst and oxidation reaction solvent.

159. The method of claim 158, wherein the catalyst is present in an amount of 0.5 to 30 wt.%, based on the total weight of catalyst and oxidation reaction solvent.

160. The method as set forth in any one of claims 1, 123, 124, 126, 128, 130, 133, 136, 142, 144, 148, 150, 152, 154 and 156, wherein the oxidation reaction conditions include: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

161. The method of claim 160, wherein the oxidation reaction conditions comprise: the reaction temperature is 20-100 ℃; the reaction pressure is 0-0.5 MPa; the reaction time is 0.5-24 h.

162. The method of claim 125, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

163. The method of claim 129, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

164. The method of claim 134, wherein the oxidation reaction conditions include: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

165. The method of claim 135, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

166. The method of claim 141, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

167. The method of claim 143, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

168. The method of claim 149, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

169. The method of claim 151, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

170. The method of claim 155, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-150 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.

171. The method as claimed in any one of claims 162-170, wherein the oxidation reaction conditions include: the reaction temperature is 20-100 ℃; the reaction pressure is 0-0.5 MPa; the reaction time is 0.5-24 h.

172. The preparation method of any one of claims 1, 123, 124, 126, 128, 130, 133, 136, 140, 142, 144, 148, 150, 152, 154 and 156, 159, wherein the molar ratio of the oxidant to the 2-alkylanthracene is 0.01:1-100: 1.

173. The method of claim 172, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 1:1 to 50: 1.

174. The method of claim 125, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

175. The method of claim 129, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

176. The method of claim 134, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

177. The method of claim 135, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

178. The method of claim 141, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

179. The method of claim 143, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

180. The method of claim 149, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

181. The method of claim 151, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

182. The method of claim 155, wherein the molar ratio of oxidizing agent to 2-alkylanthracene is from 0.01:1 to 100: 1.

183. The method as claimed in any one of claims 174-182, wherein the molar ratio of the oxidant to the 2-alkyl anthracene is from 1:1 to 50: 1.

184. The method as set forth in any one of claims 1, 123, 124, 126, 128, 130, 133, 136, 140, 142, 144, 148, 150, 152, 154 and 156, wherein the oxidation reaction solvent is C₆The above;

the total content of the 2-alkyl anthracene is 0.1 to 80 wt% based on the total weight of the 2-alkyl anthracene and the oxidation reaction solvent.

185. The preparation method of claim 184, wherein the oxidation reaction solvent is C₆-C₁₂One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted.

186. The method of claim 185, wherein the aromatic hydrocarbon is one or more of a mono-or multi-substituted benzene compound with C as a substituent₁-C₄And one or more of an alkyl group and a halogen element.

187. The process of claim 186 wherein said oxidation reaction solvent is one or more of a halogen substituent of benzene.

188. The production method according to claim 187, wherein the oxidation reaction solvent is one or more of monochlorobenzene, dichlorobenzene, trichlorobenzene and tetrachlorobenzene.

189. The production process of claim 184, wherein the 2-alkyl anthracene has a total 2-alkyl anthracene content of 5 to 50 wt.%, based on the total weight of the 2-alkyl anthracene and the oxidation reaction solvent.

190. The method of claim 125, wherein the oxidation reaction solvent is C₆The above;

191. The method of claim 129, wherein the oxidation reaction solvent is C₆The above;

192. The method of claim 134, wherein the oxidation reaction solvent is C₆The above;

193. The method of claim 135, wherein the oxidation reaction solvent is C₆The above;

194. The method of claim 141, wherein the oxidation reaction solvent is C₆The above;

195. The method of claim 143, wherein the oxidation reaction solvent is C₆The above;

196. The method of claim 149, wherein the oxidation reaction solvent is C₆The above;

197. The preparation of claim 151, wherein the oxidation reaction solvent is C₆The above;

198. The preparation of claim 155, wherein the oxidation reaction solvent is C₆The above;

199. The method as claimed in any one of claims 190-198, wherein the oxidation reaction solvent is C₆-C₁₂One or more of paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted.

200. The method of claim 199, wherein the aromatic hydrocarbon is one or more of a mono-or multi-substituted benzene compound with C as a substituent₁-C₄And one or more of an alkyl group and a halogen element.

201. The process of claim 200 wherein the oxidation reaction solvent is one or more of a halogen substituent of benzene.

202. The method of claim 201, wherein the oxidation reaction solvent is one or more of monochlorobenzene, dichlorobenzene, trichlorobenzene and tetrachlorobenzene.

203. The method as claimed in any one of claims 190-198, wherein the total content of the 2-alkylanthracene is 5-50 wt% based on the total weight of the 2-alkylanthracene and the oxidation reaction solvent.