阅读说明：本技术 一种新的苯绕蒽酮的生产方法 (Production method of benanthrone ) 是由 熊俊 汤学斌 周坚彪 于 2019-10-24 设计创作，主要内容包括：本发明涉及精细化工领域,具体涉及一种苯绕蒽酮的制备方法,具体包括如下步骤：将蒽醌、钌碳、硫酸、相转移催化剂和溶剂加入压力反应釜中,通入H<Sub>2</Sub>进行反应；反应完成后,冷却反应液,排出剩余H<Sub>2</Sub>后进行过滤,滤液用溶剂洗涤,合并滤液和洗涤液转入第二反应釜中；滤渣用做下一批催化剂重复使用；向第二反应釜中加入丙三醇,并加入催化剂硫酸进行环合反应；反应完成后蒸馏除去溶剂,残余物用热水洗涤、干燥得到苯绕蒽酮。与现有技术相比,本发明优点在于：本发明提供的苯绕蒽酮的生产方法其原材料循环利用率高,工艺易控制,成本低,并且产品质量明显提高的特点。(The invention relates to the field of fine chemical engineering, in particular to a preparation method of benzanthrone, which comprises the following steps: adding anthraquinone, ruthenium carbon, sulfuric acid, phase transfer catalyst and solvent into a pressure reaction kettle, and introducing H 2 Carrying out reaction; after the reaction was completed, the reaction solution was cooled to discharge the remaining H 2 Then filtering, washing the filtrate by using a solvent, combining the filtrate and a washing solution, and transferring the combined filtrate and the washing solution into a second reaction kettle; the filter residue is used as the next batch of catalyst for repeated use; adding glycerol into the second reaction kettle, and adding a catalyst sulfuric acid to carry out cyclization reaction; after the reaction is finished, the solvent is distilled off, and the residue is washed by hot water and dried to obtain the benzanthrone. Compared with the prior art, the invention has the advantages that: the method for producing the benzanthrone has the advantages of high raw material recycling rate, easily controlled process, low cost and productsThe quality is obviously improved.)

1. A production method of benzanthrone is characterized by comprising the following steps:

(1) adding anthraquinone, catalyst, sulfuric acid, phase transfer catalyst and solvent into a pressure reaction kettle, and introducing H₂Carrying out reaction;

(2) after the reaction was completed, the reaction solution was cooled to discharge the remaining H₂Then filtering, washing the filtrate by using a solvent, combining the filtrate and a washing solution, and transferring the combined filtrate and the washing solution into a second reaction kettle; the filter residue is used as the next batch of catalyst for repeated use;

(3) adding glycerol into the second reaction kettle, and adding a catalyst sulfuric acid to carry out cyclization reaction; after the reaction is finished, distilling to remove the solvent, washing the residue with hot water, and drying to obtain the benzanthrone;

2. the method for producing benzanthrone according to claim 1, wherein the mass ratio of the anthraquinone, the catalyst, the sulfuric acid, the phase transfer catalyst and the solvent in step (1) is 1: 0.001-0.05: 0.001-0.01: 0.002-0.02: 2 to 10.

3. The method for producing benzanthrone according to claim 2, wherein the mass ratio of the anthraquinone, ruthenium carbon, sulfuric acid, phase transfer catalyst and solvent in the step (1) is 1: 0.005-0.02: 0.001-0.01: 0.005-0.02: 3 to 8.

4. The method for producing benzanthrone according to claim 1, wherein the solvent in the step (1) is selected from aromatic solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, and bromobenzene.

5. The method of claim 1, wherein the phase transfer catalyst is selected from the group consisting of quaternary ammonium salts such as sodium lauryl sulfate and tetrabutylammonium bromide.

6. The method according to claim 1, wherein the pressure in the pressure reactor in step (1) is 1000 to 1800kPa, and the reaction temperature is 150 to 200 ℃.

7. The method for producing benzanthrone as claimed in claim 1, wherein the catalyst in step (1) is ruthenium carbon.

8. The method according to claim 1, wherein the catalyst in step (1) contains 1-10% by mass of palladium on carbon, and the balance is ruthenium on carbon.

9. The method for producing benzanthrone according to claim 1, wherein the molar ratio of anthraquinone, glycerol and sulfuric acid in step (3) is 1: 1-3: 1 to 5.

10. The method for producing benzanthrone according to any of claims 1 to 9, wherein the addition rate of sulfuric acid in step (3) is controlled so that the reaction temperature is controlled to 100 to 120 ℃.

Technical Field

The invention relates to the field of fine chemical engineering, in particular to a novel production method of benzanthrone.

Background

The dye is an indispensable fine chemical in modern society, has been used as a traditional dye with complete chromatogram, bright color and good fastness for thousands of years, is a high-grade dye variety widely used for dyeing cotton, and is widely applied to the pad dyeing of main cotton components in cellulose fibers and polyester/cotton blends. Some of these vat dyes are also used for dyeing polyester fibers and vinylon. As for the environment, the vat dye does not contain azo substances which can generate carcinogenic aromatic amine by cracking under specific conditions, is comfortable to wear after dyeing, does not cause allergy to people, does not have carcinogenic acute toxicity, does not contain environmental hormone, has low chroma of waste water during use, and has small toxicity to fishes, so the vat dye is also a substitute for forbidden dye in recent years. However, the problem of great environmental pollution is always accompanied in the production and use processes for a long time, the green technology in the dye production process is researched and developed, novel production equipment is designed, manufactured and applied, industrial production and application are carried out, raw material and energy consumption are reduced, the discharge amount of three wastes and treatment difficulty are reduced, clean process production is realized, the purposes of energy conservation and emission reduction are achieved, important economic and social meanings are achieved, and the method is also very urgent work.

Because of high requirements on technical equipment, complex process and low yield in the production process of vat dyes, the pollution of three wastes is serious, especially the development of other dyes in recent years reduces the importance of vat dyes in the textile printing and dyeing industry, in some developed countries, because of the limits of environmental regulations and production cost, the economic benefit of producing vat dyes is reduced, a plurality of companies stop the production and development of vat dyes, and the variety of dyes is updated slowly. However, the demand of the international market for vat dyes is still large, so that the development of new vat dye varieties, the reduction of environmental pollution in the production and use processes of vat dyes and the improvement of the existing backward production process are hot spots in the research field of vat dyes nowadays.

The benzanthrone is also called benzanthrone, is an important dye intermediate, and is used for producing various high-grade vat dyes for dyeing cotton fibers, such as the intermediates of vat olive green B, vat olive green T, vat blue BO, vat grey M, vat brilliant green FFB and the like.

The structural formula of benzanthrone is as follows:

chemical name: benzanthrone

English name: benzanthrone

Number ca S: 82-05-3

The molecular formula is as follows: c₁₇H₁₀O

Molecular weight: 230.26g/mol

The existing synthetic methods for preparing the benzanthrone are various, and can be divided into the following steps according to different starting raw materials: anthraquinone is used as a raw material, anthrone is used as a raw material, benzanthracene is used as a raw material, and 1,4,6, 9-tetrahydroanthraquinone and 1, 4-dihydroanthraquinone are used as raw materials. The methods are comprehensively compared, anthraquinone is easy to obtain as a raw material, and the reaction is simple and feasible, so that the existing general method for synthesizing the benzanthrone mainly adopts the anthraquinone method.

The method for synthesizing the benzanthrone used in the existing factory is to prepare the benzanthrone in a concentrated sulfuric acid solution by taking anthraquinone and glycerol as raw materials and iron powder as a reducing agent. The process has the following disadvantages: the recovery of iron ions generated after the reaction is time-consuming and labor-consuming, and the direct discharge also causes pollution to the environment; the concentrated sulfuric acid is difficult to recover after reaction, and the environment is polluted due to improper treatment. The process method provided by the invention takes ruthenium carbon as a reducing agent, reduces the concentration of sulfuric acid, and is obtained by dehydration and ring closure under the condition of reflux. The raw material has high recycling rate, the process is easy to control, the cost is low, and the product quality is obviously improved.

Disclosure of Invention

The first purpose of the invention is to overcome the defect that the raw materials and reaction byproducts are not easy to recover in the prior art, and provide the production method of the benzanthrone, which has high recycling rate of the raw materials and easy control of the process.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a production method of benzanthrone comprises the following steps:

(1) adding anthraquinone, catalyst, sulfuric acid, phase transfer catalyst and solvent into a pressure reaction kettle, and introducing H₂Carrying out reaction;

(2) after the reaction was completed, the reaction solution was cooled to discharge the remaining H₂Then filtering, washing the filtrate by using a solvent, combining the filtrate and a washing solution, and transferring the combined filtrate and the washing solution into a second reaction kettle; the filter residue is used as the lower partReusing a batch of catalyst;

(3) adding glycerol into the second reaction kettle, and adding a catalyst sulfuric acid to carry out cyclization reaction; after the reaction is finished, distilling to remove the solvent, washing the residue with hot water, and drying to obtain the benzanthrone;

preferably, the mass ratio of the anthraquinone, the catalyst, the sulfuric acid, the phase transfer catalyst and the solvent in the step (1) is 1: 0.001-0.05: 0.001-0.01: 0.002-0.02: 2-10; further, the mass ratio of the anthraquinone, the catalyst, the sulfuric acid, the phase transfer catalyst and the solvent in the step (1) is 1: 0.005-0.02: 0.001-0.01: 0.005-0.02: 3 to 8. The purpose of the sulfuric acid in the step (1) is to provide an acidic environment required by the reaction.

Preferably, the solvent in step (1) is selected from aromatic solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene or bromobenzene.

Preferably, the phase transfer catalyst is selected from quaternary ammonium salts such as sodium dodecyl sulfate or tetrabutylammonium bromide.

Preferably, the pressure in the pressure reaction kettle in the step (1) is 1000-1800 kPa, and the reaction temperature is 150-200 ℃; further, the pressure in the pressure reaction kettle in the step (1) is 1200-1600 kPa, and the reaction temperature is 160-180 ℃.

Preferably, the catalyst in step (1) is ruthenium carbon.

Preferably, the catalyst in the step (1) contains 1-10% of palladium carbon by mass fraction, and the balance is ruthenium carbon. The catalyst containing 1-10% of palladium-carbon by mass has a better effect of catalyzing the reaction.

Preferably, the molar ratio of anthraquinone, glycerol and sulfuric acid in the step (3) is 1: 1-3: 1 to 5. Further, in the step (3), the molar ratio of anthraquinone to glycerol to sulfuric acid is 1: 1.5-3: 2-5; the amount of the anthraquinone is based on the amount of the anthraquinone put into the step (1).

Preferably, the adding speed of the sulfuric acid in the step (3) is controlled, so that the reaction temperature is controlled to be 100-120 ℃.

Compared with the prior art, the invention has the advantages that: the method for producing the benzanthrone has the characteristics of high raw material recycling rate, easily controlled process, low cost and obviously improved product quality.

Detailed Description

The present invention will be further specifically described below with reference to examples, but is not limited thereto.