阅读说明：本技术 一种金刚烷胺生产废酸资源化利用的方法 (Method for resource utilization of waste acid in amantadine production ) 是由 李兰花 裘月南 徐冬红 刘志远 吴华强 周珠凤 陈利鸿 蔺珍 于 2020-07-31 设计创作，主要内容包括：本发明属于废液处理及资源化利用技术领域,提供了一种金刚烷胺生产废酸资源化利用的方法。本发明将金刚烷胺生产废酸和尿素混合进行反应,得到硫酸脲；所述金刚烷胺生产废酸具体为废硫酸。本发明提供的方法利用金刚烷胺生产废酸制备硫酸脲,从而将废酸转化成有利用价值的硫酸脲肥料,实现资源化利用的目的。本发明的处理方法节省能耗,安全可靠,解决了金刚烷胺生产废酸的处理困难,实现了内在价值的最大化,具有较高的经济效益和社会效益,且母液可循环利用,处理过程绿色环保。(The invention belongs to the technical field of waste liquid treatment and resource utilization, and provides a method for resource utilization of waste acid in amantadine production. Mixing amantadine production waste acid and urea for reaction to obtain urea sulfate; the waste acid in the amantadine production is specifically waste sulfuric acid. The method provided by the invention utilizes the waste acid produced in amantadine production to prepare urea sulfate, so that the waste acid is converted into urea sulfate fertilizer with useful value, and the purpose of resource utilization is realized. The treatment method disclosed by the invention has the advantages of saving energy consumption, being safe and reliable, solving the problem of difficult treatment of waste acid in amantadine production, realizing maximization of internal value, having higher economic and social benefits, recycling mother liquor and being green and environment-friendly in treatment process.)

1. A method for resource utilization of waste acid from amantadine production is characterized by comprising the following steps: mixing amantadine production waste acid and urea for reaction to obtain urea sulfate; the waste acid in the amantadine production is specifically waste sulfuric acid.

2. The method according to claim 1, wherein the mass fraction of sulfuric acid in the amantadine production waste acid is 40% or less.

3. The method according to claim 1, wherein the mass fraction of sulfuric acid in the amantadine production waste acid is 30-40%.

4. The method according to claim 1, 2 or 3, wherein the molar ratio of sulfuric acid to urea in the amantadine production waste acid is 1 (2-2.3).

5. The method according to claim 1, wherein the reaction temperature is 80-85 ℃.

6. The method according to claim 1 or 5, characterized in that the reaction is in particular: and heating the temperature of the waste acid from the amantadine production to 80-85 ℃, adding urea for reaction, and keeping the temperature for 0.5-5 h after the urea is completely dissolved.

7. The method according to claim 1, wherein after the reaction is completed, the method further comprises cooling, crystallizing and carrying out solid-liquid separation on the obtained product liquid in sequence.

8. The method according to claim 1, wherein the temperature of the cooling crystallization is 10-15 ℃.

9. The method according to claim 1, wherein the solid product obtained by the solid-liquid separation is urea sulfate, and the dry nitrogen content of the urea sulfate is not less than 24%.

10. The method according to claim 1, wherein the mother liquor obtained by the solid-liquid separation is recycled.

Technical Field

The invention relates to the technical field of waste liquid treatment and resource utilization, in particular to a method for resource utilization of waste acid in amantadine production.

Background

At present, more than 1000 of 6000 pharmaceutical enterprises in China produce different types of cold medicines, and the intense market competition causes each cold medicine production enterprise to pay more money in advertising, the promotion means are also various, and at least twenty cold medicine varieties are well known by consumers. The amantadine hydrochloride is the main raw material medicine for preparing the compound anti-cold preparation, the domestic amantadine hydrochloride compound preparation has stable yield, and about 1000 tons of the amantadine hydrochloride raw material is consumed annually. In addition, the amantadine hydrochloride veterinary medicine market is on a growing trend year by year, and the demand of the amantadine hydrochloride is also increasing.

Amantadine hydrochloride is mainly obtained by acidification of amantadine hydrochloride, and the main step for preparing amantadine hydrochloride is the process for preparing amantadine. In the traditional preparation method of amantadine, adamantane is used as a starting material, liquid bromine is used for brominating the adamantane, the brominating liquid bromine reacts with urea at high temperature, and after the reaction is finished, the reaction is alkalized by sodium hydroxide to obtain the amantadine. The method has the defects of long reaction route, high cost of liquid bromine, large environmental pollution, serious corrosion to industrial production equipment and the like.

In addition to the above process, amantadine can be prepared by the following process: taking adamantane as a main raw material, firstly carrying out nucleophilic addition reaction with acetonitrile under the oxidation of fuming sulfuric acid to obtain 1-acetamido adamantane, and hydrolyzing the 1-acetamido adamantane to obtain the amantadine. The method has the advantages of wide raw material source, high product purity, high yield and low production cost. However, a large amount of waste acid is generated in the production process of the method, the main component of the waste acid is sulfuric acid, the waste acid is not treated by a proper method, the environmental protection problem cannot be solved, and the waste of sulfuric acid resources is caused.

Disclosure of Invention

In view of the above, the invention provides a method for resource utilization of waste acid from amantadine production. The method provided by the invention prepares urea sulfate by reacting waste acid from amantadine production with urea, so that the waste acid is converted into urea sulfate fertilizer with useful value, and the purpose of resource utilization is realized.

In order to achieve the above object, the present invention provides the following technical solutions:

a method for resource utilization of waste acid from amantadine production comprises the following steps: mixing amantadine production waste acid and urea for reaction to obtain urea sulfate; the waste acid in the amantadine production is specifically waste sulfuric acid.

Preferably, the mass fraction of sulfuric acid in the amantadine production waste acid is below 40%.

Preferably, the mass fraction of sulfuric acid in the waste acid from amantadine production is 30-40%.

Preferably, the molar ratio of sulfuric acid to urea in the waste acid from amantadine production is 1 (2-2.3).

Preferably, the reaction temperature is 80-85 ℃.

Preferably, the reaction is specifically: and heating the temperature of the waste acid from the amantadine production to 80-85 ℃, adding urea for reaction, and keeping the temperature for 0.5-5 h after the urea is completely dissolved.

Preferably, after the reaction is finished, the method further comprises the steps of sequentially cooling, crystallizing and carrying out solid-liquid separation on the obtained product feed liquid.

Preferably, the temperature of the cooling crystallization is 10-15 ℃.

Preferably, the solid product obtained by the solid-liquid separation is urea sulfate, and the dry-basis nitrogen content of the urea sulfate is more than or equal to 24%.

Preferably, the mother liquor obtained by the solid-liquid separation is recycled.

The invention provides a method for resource utilization of waste acid in amantadine production, which comprises the following steps: mixing amantadine production waste acid and urea for reaction to obtain urea sulfate; the waste acid in the amantadine production is specifically waste sulfuric acid. The method provided by the invention prepares urea sulfate by reacting waste acid from amantadine production with urea, so that the waste acid is converted into urea sulfate fertilizer with useful value, and the purpose of resource utilization is realized. The treatment method disclosed by the invention has the advantages of energy consumption saving, safety, reliability and low treatment cost, solves the problem of difficult treatment of waste acid in amantadine production, and realizes maximization of internal value. According to the calculation, about 15 tons of waste sulfuric acid with the concentration of 40 percent is generated in each ton of amantadine production, the treatment cost is about 3300 yuan according to the traditional treatment method (treatment is carried out according to acid-containing wastewater), the treatment cost is about 1100 yuan by using the method disclosed by the invention, 12.2 tons of the by-product urea sulfate can be obtained, the value of the by-product urea sulfate is 3350 yuan, the cost can be saved by about 5550 yuan per ton of amantadine by comprehensive consideration, the resource utilization value is higher, and the economic benefit and the social benefit are higher.

Furthermore, the mother liquor crystallized in the invention can be recycled, the treatment process is green and environment-friendly, and the treatment cost can be further reduced.

Detailed Description

The invention provides a method for resource utilization of waste acid in amantadine production, which comprises the following steps: mixing amantadine production waste acid and urea for reaction to obtain urea sulfate; the waste acid in the amantadine production is specifically waste sulfuric acid.

In the present invention, the production process of amantadine is as follows:

dissolving adamantane in dichloromethane, simultaneously adding dichloromethane-acetonitrile mixed solution and concentrated sulfuric acid into the dissolved solution to perform nucleophilic addition reaction (to generate 1-acetamido adamantane), standing and layering after the reaction is finished, adding lower-layer reaction solution into water to perform hydrolysis (to generate amantadine), extracting the hydrolysate twice by using an extracting agent after the hydrolysis is finished, performing pressure evaporation drying on organic phase to obtain the amantadine, and obtaining the residual aqueous phase after the extraction, namely the waste acid for producing the amantadine.

In the invention, the main component of the waste acid from the amantadine production is sulfuric acid, and the waste acid also comprises a very small amount of amantadine and an extracting agent (generally dichloromethane), wherein the total mass fraction content of the amantadine and the extracting agent is about 1 percent and can be ignored; the mass fraction of sulfuric acid in the amantadine production waste acid is preferably less than 40%, and more preferably 30-40%.

In the invention, the molar ratio of sulfuric acid to urea in the waste acid from amantadine production is preferably 1 (2-2.3), and more preferably 1 (2.1-2.2).

In the invention, the reaction temperature is preferably 80-85 ℃, and more preferably 82-83 ℃; the reaction is specifically as follows: heating the temperature of waste acid from amantadine production to 80-85 ℃, adding urea for reaction, and keeping the temperature for 0.5-5 h after the urea is completely dissolved; the reaction of urea and sulfuric acid is strongly exothermic, and the urea is preferably added slowly in the invention so as to maintain the temperature of the reaction system within the above range; the invention has no special requirement on the urea, and the solid urea can be directly used.

In the invention, the solubility of the product urea sulfate in the system is greatly influenced by the temperature, the reaction temperature is controlled to be 80-85 ℃, the reaction can be promoted while the high solubility of the urea sulfate is ensured, the reaction time is shortened, the temperature can be directly reduced for cooling crystallization after the reaction is finished, and the operation is simpler.

After the reaction is finished, the invention preferably carries out cooling crystallization and solid-liquid separation on the obtained product feed liquid in sequence. In the invention, the cooling crystallization temperature is preferably 10-15 ℃, and the solid-liquid separation mode is preferably centrifugal separation; the solid product obtained by the solid-liquid separation is urea sulfate, and the dry-basis nitrogen content of the urea sulfate is more than or equal to 24 percent; the mother liquor obtained by the solid-liquid separation is preferably recycled; the mass fraction of sulfuric acid in the mother liquor is less than 0.1%, and the mother liquor is preferably recycled in the preparation process of the next batch of amantadine.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.