阅读说明：本技术 烷基蒽醌的制备方法 (Process for preparing alkylanthraquinones ) 是由 洪焱根 于 2021-09-23 设计创作，主要内容包括：本发明请求保护的烷基蒽醌的制备方法,包括如下步骤：(1)将烷基苯、苯酐和三氯化铝在氯苯溶剂中反应生成中间体酮酸；(2)将中间体酮酸、五氧化二磷和发烟硫酸混合成混合物；(3)将混合物送入管式反应器中反应,管式反应器内安装静态混合器；其中,烷基苯、苯酐和三氯化铝三者的总重量与五氧化二磷和发烟硫酸的总重量比例为(0.85-0.9)：1。该制备方法具有反应快,纯度高、废酸少等优点。(The preparation method of the alkylanthraquinone comprises the following steps: (1) reacting alkylbenzene, phthalic anhydride and aluminum trichloride in a chlorobenzene solvent to generate an intermediate ketonic acid; (2) mixing the intermediate ketoacid, phosphorus pentoxide, and oleum to form a mixture; (3) feeding the mixture into a tubular reactor for reaction, wherein a static mixer is arranged in the tubular reactor; wherein, the proportion of the total weight of the alkylbenzene, the phthalic anhydride and the aluminum trichloride to the total weight of the phosphorus pentoxide and the fuming sulfuric acid is (0.85-0.9): 1. the preparation method has the advantages of fast reaction, high purity, less waste acid and the like.)

1. The preparation method of the alkylanthraquinone is characterized by comprising the following steps:

(1) reacting alkylbenzene, phthalic anhydride and aluminum trichloride in a chlorobenzene solvent to generate an intermediate ketonic acid;

(2) mixing the intermediate ketoacid, phosphorus pentoxide, and oleum to form a mixture;

(3) feeding the mixture into a tubular reactor for reaction, wherein a static mixer is arranged in the tubular reactor;

wherein, the proportion of the total weight of the alkylbenzene, the phthalic anhydride and the aluminum trichloride to the total weight of the phosphorus pentoxide and the fuming sulfuric acid is (0.85-0.9): 1.

2. the method of producing alkylanthraquinones according to claim 1, wherein the alkylanthraquinones produced have a purity of more than 98%.

3. The method for producing alkylanthraquinone according to claim 1, wherein the alkylbenzene is any one of toluene, ethylbenzene, n-butylbenzene, isobutylbenzene, tert-pentylbenzene, tert-butylbenzene and sec-pentylbenzene.

4. The process for producing alkylanthraquinone according to claim 1, wherein in the step (1), the weight ratio of the alkylbenzene, the phthalic anhydride and the aluminum trichloride is (0.9 to 1.1): (0.9-1.1): (1.6-2).

5. The process for producing alkylanthraquinones according to claim 1, wherein in the step (2), the weight ratio of phosphorus pentoxide to fuming sulfuric acid is (0.9 to 1.1): (0.9-1.1).

6. The process for preparing alkylanthraquinone according to claim 1, wherein in step (3), the reaction temperature is 120-160 ℃.

7. The process for producing alkylanthraquinone according to claim 1, wherein in the step (3), the reaction time is 13 to 17 min.

8. The process for producing alkylanthraquinones according to claim 1, wherein the static mixer is any of an SV type static mixer, an SK type static mixer, an SX type static mixer, an SH type static mixer and an SL type static mixer.

Technical Field

The invention relates to the technical field of raw material components of alkylanthraquinone and a preparation method thereof, in particular to a preparation method for preparing alkylanthraquinone by using phosphorus pentoxide, fuming sulfuric acid and a static mixer.

Background

The prior preparation process of the alkyl anthraquinone mainly comprises the following steps: the intermediate ketonic acid is prepared by Friedel-crafts reaction of alkylbenzene and phthalic anhydride, then a crude product is prepared by dehydration under the conditions of high temperature and strong acid, and finally the product is purified and extracted. Generally, the strong acid used is sulfuric acid or fuming sulfuric acid, and the amount of the strong acid used is 4 to 10 times of the mass of the keto acid; the dehydration reaction temperature is 70-140 ℃, and the reaction equipment is a stirring kettle or a tubular reactor. The production operation steps are that ketone is dissolved in strong acid and mixed evenly, and then pumped into a reaction device for heating reaction. But the process has the advantages of large waste acid amount, high waste acid treatment cost, long dehydration reaction time, low yield, low product purity (less than or equal to 97 percent) and high product production cost.

Disclosure of Invention

Aiming at the technical problems of slow dehydration reaction time, low purity and more generated waste acid in the existing preparation process of the alkylanthraquinone, the invention prepares the alkylanthraquinone by mixing phosphorus oxide, fuming sulfuric acid and intermediate ketoacid and installing a static mixer in a tubular reactor, thereby improving the reaction efficiency and improving the purity of the product by optimizing the proportion of raw materials.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting alkylbenzene, phthalic anhydride and aluminum trichloride in a chlorobenzene solvent to generate an intermediate ketonic acid;

(2) mixing the intermediate ketoacid, phosphorus pentoxide, and oleum to form a mixture;

(3) feeding the mixture into a tubular reactor for reaction, wherein a static mixer is arranged in the tubular reactor;

wherein, the proportion of the total weight of the alkylbenzene, the phthalic anhydride and the aluminum trichloride to the total weight of the phosphorus pentoxide and the fuming sulfuric acid is (0.85-0.9): 1. in particular, the weight ratio may be 0.85, 0.86, 0.87, 0.88, 0.89 and 0.9.

Wherein, the purity of the alkyl anthraquinone is more than 98 percent.

More specifically, the alkylbenzene is any one of toluene, ethylbenzene, n-butylbenzene, isobutylbenzene, tert-pentylbenzene, tert-butylbenzene, and sec-pentylbenzene.

More specifically, in the step (1), the ratio of the alkylbenzene, the phthalic anhydride and the aluminum trichloride is (0.9-1.1): (0.9-1.1): (1.6-2). The weight ratio of alkylbenzene, phthalic anhydride and aluminium trichloride may be 0.9:0.9:1.6, 1.1: 1.1:2, 0.9:1.1:1.6, 1.1:0.9:2, 1:1:1.8, 1:1:1.6, etc.

More specifically, the weight ratio of phosphorus pentoxide to oleum is (0.9-1.1): (0.9-1.1). The ratio may be 0.9:0.9, 1.1:1.1, 1.1:1, 1.1:0.9, 0.9:1.1, etc.

More specifically, in step (3), the reaction temperature is 120-160 ℃. The reaction temperature may be 160 ℃, 140 ℃, 130 ℃, 120 ℃ or the like.

More specifically, in the step (3), the reaction time is 13-17 min. The reaction time may be 17min, 16min, 15min, 14min, 13min, etc.

More specifically, the static mixer may be any one of an SV type static mixer, an SK type static mixer, an SX type static mixer, an SH type static mixer, and an SL type static mixer.

According to the preparation method of the alkylanthraquinone, the oxidation performance of fuming sulfuric acid can be enhanced by mixing the intermediate ketonic acid, the phosphorus pentoxide and the fuming sulfuric acid, and the mass transfer rate in the tubular reactor can be increased by installing the static mixer in the tubular reactor, so that the dehydration cyclization reaction process in the step (3) is accelerated, the reaction can be completed within 13-17min, and the reaction time is greatly shortened. The ratio of the total weight of the alkylbenzene, the phthalic anhydride and the aluminum trichloride to the total weight of the phosphorus pentoxide and the fuming sulfuric acid is limited to (0.85-0.9): within the range of 1, the purity of the product is ensured to reach more than 98 percent, and the generation of waste acid is reduced.

Detailed Description

In the following, the invention is described in detail by means of a few specific embodiments in order to enhance the understanding of the present solution, but the invention can be implemented in many different ways, which are defined and covered by the claims.

Example 1

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.9t of tert-amylbenzene, 0.9t of phthalic anhydride and 1.7t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid, 2t phosphorus pentoxide and 2t oleum to form a mixture; specifically, the intermediate keto acid and phosphorus pentoxide are dissolved in fuming sulfuric acid together;

(3) and (3) feeding the mixture into a tubular reactor for reaction, installing a static mixer in the tubular reactor, and reacting at the temperature of 150 ℃ for 15min to finally obtain the alkylanthraquinone.

Example 2

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.875t of toluene, 0.875t of phthalic anhydride and 1.65t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid, 2t phosphorus pentoxide and 2t oleum to form a mixture; specifically, the intermediate keto acid and phosphorus pentoxide are dissolved in fuming sulfuric acid together;

(3) and (3) feeding the mixture into a tubular reactor for reaction, installing a static mixer in the tubular reactor, and reacting at the temperature of 120 ℃ for 17min to finally obtain the alkylanthraquinone.

Example 3

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.925t of ethylbenzene, 0.925t of phthalic anhydride and 1.75t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid, 2t phosphorus pentoxide and 2t oleum to form a mixture; specifically, the intermediate keto acid and phosphorus pentoxide are dissolved in fuming sulfuric acid together;

(3) and (3) feeding the mixture into a tubular reactor for reaction, installing a static mixer in the tubular reactor, and reacting at the temperature of 160 ℃ for 13min to finally obtain the alkylanthraquinone.

Example 3

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.925t of n-butylbenzene, 0.925t of phthalic anhydride and 1.75t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid, 2t phosphorus pentoxide and 2t oleum to form a mixture; specifically, the intermediate keto acid and phosphorus pentoxide are dissolved in fuming sulfuric acid together;

(3) and (3) feeding the mixture into a tubular reactor for reaction, installing a static mixer in the tubular reactor, and reacting at the temperature of 130 ℃ for 16min to finally obtain the alkylanthraquinone.

Example 4

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.9t of n-butylbenzene, 0.9t of phthalic anhydride and 1.6t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid, 2t phosphorus pentoxide and 2t oleum to form a mixture; specifically, the intermediate keto acid and phosphorus pentoxide are dissolved in fuming sulfuric acid together;

(3) and (3) feeding the mixture into a tubular reactor for reaction, installing a static mixer in the tubular reactor, and reacting at the temperature of 140 ℃ for 13min to finally obtain the alkylanthraquinone.

Comparative example 1

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.9t of tert-amylbenzene, 0.9t of phthalic anhydride and 1.7t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid and 10t fuming sulfuric acid to form a mixture; specifically, the intermediate keto acid is dissolved in fuming sulfuric acid;

(3) and (3) feeding the mixture into a tubular reactor for reaction, installing a static mixer in the tubular reactor, and reacting at the temperature of 150 ℃ for 30min to finally obtain the alkylanthraquinone.

Comparative example 2

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.9t of tert-amylbenzene, 0.9t of phthalic anhydride and 1.7t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid, 2t phosphorus pentoxide and 2t oleum to form a mixture; specifically, the intermediate keto acid and phosphorus pentoxide are dissolved in fuming sulfuric acid together;

(3) and (3) feeding the mixture into a tubular reactor for reaction, wherein a static mixer is not arranged in the tubular reactor, the reaction temperature is 150 ℃, the reaction time is 30min, and finally the alkylanthraquinone is prepared.

Comparative example 3

A preparation method of alkyl anthraquinone comprises the following steps:

(1) reacting 0.9t of tert-amylbenzene, 0.9t of phthalic anhydride and 1.7t of aluminum trichloride in a chlorobenzene solvent to generate an intermediate keto acid;

(2) mixing the intermediate ketoacid and 10t fuming sulfuric acid to form a mixture; specifically, the intermediate keto acid is dissolved in fuming sulfuric acid;

(3) and (3) feeding the mixture into a tubular reactor for reaction, wherein a static mixer is not arranged in the tubular reactor, the reaction temperature is 150 ℃, the reaction time is 30min, and finally the alkylanthraquinone is prepared.

The alkylanthraquinones prepared in examples 1 to 4 and comparative examples 1 to 3 were measured for purity in accordance with GB/T2405-2013, and the results are shown in Table 1.

TABLE 1 purity of the alkylanthraquinones prepared in examples 1-4 and comparative examples 1-3

As can be seen from examples 1 to 4 in Table 1, in examples 1 to 4, the oxidation performance of oleum is enhanced by mixing the intermediate keto acid, phosphorus pentoxide and oleum, and the mass transfer rate inside the tubular reactor is increased by installing a static mixer in the tubular reactor, so that the dehydration cyclization reaction process in step (3) is accelerated, the reaction can be completed within 13 to 17min, and the reaction time is greatly shortened. The ratio of the total weight of the alkylbenzene, the phthalic anhydride and the aluminum trichloride to the total weight of the phosphorus pentoxide and the fuming sulfuric acid is limited to (0.85-0.9): within the range of 1, the purity of the product is ensured to reach more than 98 percent. In contrast, in comparative examples 1 to 3, the reaction time was prolonged to 30min and the product purity was reduced to below 97% without using phosphorus pentoxide and a static mixer.

The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all modifications of the equivalent structure and equivalent flow path in the present specification, or the direct or indirect application to other related technical fields are included in the scope of the present invention.