阅读说明：本技术 一种氢化偶氮苯的清洁生产工艺 (Clean production process of hydroazobenzene ) 是由 牛国峰 于 2020-08-24 设计创作，主要内容包括：本发明公开了一种氢化偶氮苯的清洁生产工艺,包括如下步骤：1)硝基苯在碱性溶液中,在聚乙二醇存在下,以醌类化合物为催化剂,用水合肼还原硝基苯,得到氧化偶氮苯；2)步骤1)得到的氧化偶氮苯在碱性溶液中,在聚乙二醇存在下,以雷尼镍为催化剂,用水合肼还原氧化偶氮苯,得到氢化偶氮苯。本发明所公开的氢化偶氮苯的清洁生产工艺无固废污染、碱液可重复使用,能大大节约用碱量,且没有高温高压,易燃易爆等潜在的危险性。(The invention discloses a clean production process of hydroazobenzene, which comprises the following steps: 1) nitrobenzene is reduced by hydrazine hydrate in alkaline solution in the presence of polyethylene glycol and taking quinone compounds as catalysts to obtain azoxybenzene; 2) reducing azoxybenzene with hydrazine hydrate in the presence of polyethylene glycol and in an alkaline solution by taking Raney nickel as a catalyst to obtain the hydrazobenzene. The clean production process of the hydroazobenzene disclosed by the invention has the advantages of no solid waste pollution, reusability of alkali liquor, great saving of alkali consumption, and no potential dangers of high temperature, high pressure, flammability, explosiveness and the like.)

1. The clean production process of the hydroazobenzene is characterized by comprising the following steps of:

1) nitrobenzene is reduced by hydrazine hydrate in alkaline solution in the presence of polyethylene glycol and taking quinone compounds as catalysts to obtain azoxybenzene;

2) reducing azoxybenzene with hydrazine hydrate in the presence of polyethylene glycol and in an alkaline solution by taking Raney nickel as a catalyst to obtain the hydrazobenzene.

2. The clean production process of hydroazobenzene as claimed in claim 1, wherein in step 1), the mass ratio of nitrobenzene to alkaline solution, polyethylene glycol and quinone compound is 1: 2.5-5, 1: 0.02-0.10 and 1: 0.005-0.05 respectively; the molar ratio of nitrobenzene to hydrazine hydrate is 1: 0.75-1.2.

3. The clean production process of hydroazobenzene as claimed in claim 1, wherein in the step 2), the mass ratio of azoxybenzene to the alkaline solution to the polyethylene glycol to the Raney nickel to the hydrazine hydrate is 1:1.3 to 1.8, 1:0.05 to 0.10, 1:0.005 to 0.05, and 1:0.4 to 0.6, respectively.

4. The clean production process of hydroazobenzene as claimed in claim 1, wherein in step 1) and step 2), the alkaline substance in the alkaline solution is an inorganic base or an organic base; wherein the inorganic base is sodium hydroxide, potassium hydrogen hydride or barium hydroxide, and the organic base is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, tributylamine, pyridine, triethylenediamine or 4-dimethylaminopyridine.

5. The clean production process of hydroazobenzene as claimed in claim 4, wherein said inorganic base is sodium hydroxide.

6. The clean production process of hydroazobenzene as claimed in claim 1, wherein in step 1), the concentration of the alkaline solution is 15 to 25%; in the step 2), the concentration of the alkaline solution is 1-5%.

7. The clean production process of hydroazobenzene as claimed in claim 1, wherein in step 1) and step 2), the polymerization degree of polyethylene glycol is 200 to 1500.

8. The clean production process of hydroazobenzene as claimed in claim 1, wherein in step 1), the quinone compound is benzoquinone, naphthoquinone or derivatives thereof.

9. The clean production process of hydroazobenzene as claimed in claim 8, wherein in the step 1), the quinone compound is 1, 4-naphthoquinone.

10. The clean production process of hydroazobenzene as claimed in claim 1, wherein in the step 1), the reaction temperature is 45 to 95 ℃ and the reaction time is 3 to 10 hours; in the step 2), the reaction temperature is 55-85 ℃, and the reaction time is 3-6 hours.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to a clean production process of hydroazobenzene.

Background

The hydrazobenzene is an important intermediate of the medicine phenylbutazone, the industrial synthesis method is a metal reduction method, the cost is high, the pollution is large, iron mud or zinc oxide is difficult to treat, the wastewater amount is large and difficult to treat, high pressure is used in catalytic hydrogenation, the safety risk is large, the equipment investment is high, the catalyst is expensive, the reaction is incomplete, the post-treatment difficulty is large, and the like.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a clean production process of hydroazobenzene.

The purpose of the invention is realized as follows: a clean production process of hydroazobenzene comprises the following steps:

1) nitrobenzene is reduced by hydrazine hydrate in alkaline solution in the presence of polyethylene glycol and taking quinone compounds as catalysts to obtain azoxybenzene;

2) reducing azoxybenzene with hydrazine hydrate in the presence of polyethylene glycol and in an alkaline solution by taking Raney nickel as a catalyst to obtain the hydrazobenzene.

Further, in the step 1), the mass ratio of nitrobenzene to the alkaline solution to the mass ratio of polyethylene glycol to the mass ratio of quinone compounds is 1: 2.5-5, 1: 0.02-0.10 and 1: 0.005-0.05 respectively; the molar ratio of nitrobenzene to hydrazine hydrate is 1: 0.75-1.2.

Further, in the step 2), the mass ratio of azoxybenzene to the alkaline solution to the polyethylene glycol to the Raney nickel to the hydrazine hydrate is 1: 1.3-1.8, 1: 0.05-0.10, 1: 0.005-0.05 and 1: 0.4-0.6 respectively.

Further, in the step 1) and the step 2), the alkaline substance in the alkaline solution is an inorganic base or an organic base; wherein the inorganic base is sodium hydroxide, potassium hydrogen hydride or barium hydroxide, and the organic base is tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, tributylamine, pyridine, triethylenediamine or 4-dimethylaminopyridine.

Further, the inorganic base is sodium hydroxide.

Further, in the step 1), the concentration of the alkaline solution is 15-25%; in the step 2), the concentration of the alkaline solution is 1-5%.

Further, in the step 1) and the step 2), the polymerization degree of polyethylene glycol is 200-1500.

Further, in the step 1), the quinone compound is benzoquinone, naphthoquinone and derivatives thereof.

Further, in the step 1), the quinone compound is 1, 4-naphthoquinone.

Further, in the step 1), the reaction temperature is 45-95 ℃, and the reaction time is 3-10 hours; in the step 2), the reaction temperature is 55-85 ℃, and the reaction time is 3-6 hours.

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

1. no solid waste pollution is caused;

2. the alkali liquor can be repeatedly used, so that the alkali consumption can be greatly saved;

3. and potential dangers such as high temperature, high pressure, flammability, explosiveness and the like do not exist.

Drawings

FIG. 1 shows the preparation of azoxybenzene obtained in example 1¹³C nuclear magnetic spectrum.

FIG. 2 shows the azoxybenzene obtained in example 1¹H nuclear magnetic spectrum.

FIG. 3 shows the preparation of hydroazobenzene as obtained in example 1¹³C nuclear magnetic spectrum.

FIG. 4 shows the preparation of hydroazobenzene as obtained in example 1¹H nuclear magnetic spectrum.

FIG. 5 is a liquid phase diagram of azoxybenzene obtained in example 1.

FIG. 6 is a liquid phase diagram of hydroazobenzene obtained in example 1.

FIG. 7 is a liquid phase diagram of azoxybenzene obtained in example 2.

FIG. 8 is a liquid phase diagram of hydroazobenzene obtained in example 2.

FIG. 9 is a liquid phase diagram of azoxybenzene obtained in example 3.

FIG. 10 is a liquid phase diagram of hydroazobenzene obtained in example 3.

Detailed Description

The present invention will be further described with reference to the following examples.