阅读说明：本技术 一种利用副产废硫酸生产氨基磺酸技术 (Technology for producing sulfamic acid by using byproduct waste sulfuric acid ) 是由 汪伟国 张维帮 于 2019-10-24 设计创作，主要内容包括：本发明提供一种利用副产废硫酸生产氨基磺酸技术,涉及化学化工技术领域。一种利用副产废硫酸生产氨基磺酸技术,包括以下步骤：(1)将活性炭加入废硫酸中,滴加双氧水,进行氧化反应,得硫酸溶液；(2)将所述硫酸溶液进行高温蒸发浓缩,得到浓硫酸；(3)取部分浓硫酸加热到600-750℃进行裂解,生成三氧化硫、水,收集生成的三氧化硫；(4)将三氧化硫通入浓硫酸,得到发烟硝酸；(5)将发烟硝酸、尿素加入到反应釜中,在45-48℃反应3-4h,然后再升温到80-82℃反应4-5h；(6)经固液分离、提纯,干燥后得到纯氨基磺酸晶体。本发明在制备氨基磺酸过程中避免三氧化硫的流失,操作易控,能够有效利用废硫酸。(The invention provides a technology for producing sulfamic acid by using byproduct waste sulfuric acid, and relates to the technical field of chemistry and chemical engineering. A technology for producing sulfamic acid by using byproduct waste sulfuric acid comprises the following steps: (1) adding activated carbon into waste sulfuric acid, dropwise adding hydrogen peroxide, and carrying out oxidation reaction to obtain a sulfuric acid solution; (2) carrying out high-temperature evaporation concentration on the sulfuric acid solution to obtain concentrated sulfuric acid; (3) heating part of concentrated sulfuric acid to 600-750 ℃ for cracking to generate sulfur trioxide and water, and collecting the generated sulfur trioxide; (4) introducing sulfur trioxide into concentrated sulfuric acid to obtain fuming nitric acid; (5) adding fuming nitric acid and urea into a reaction kettle, reacting for 3-4h at 45-48 ℃, and then heating to 80-82 ℃ for reacting for 4-5 h; (6) and carrying out solid-liquid separation, purification and drying to obtain the pure sulfamic acid crystal. The method avoids loss of sulfur trioxide in the process of preparing sulfamic acid, is easy to operate and control, and can effectively utilize waste sulfuric acid.)

1. A technology for producing sulfamic acid by using byproduct waste sulfuric acid is characterized by comprising the following steps:

(1) adding activated carbon into waste sulfuric acid, then dropwise adding hydrogen peroxide under a stirring state, carrying out oxidation reaction on impurities, then filtering, and taking clear liquid to obtain purified sulfuric acid solution;

(2) carrying out high-temperature evaporation concentration on the sulfuric acid solution to obtain concentrated sulfuric acid;

(3) heating part of concentrated sulfuric acid to 600-750 ℃ for cracking to generate sulfur trioxide and water, and collecting the generated sulfur trioxide;

(4) cooling the sulfur trioxide gas, and introducing the rest concentrated sulfuric acid to ensure that the sulfur trioxide is completely absorbed by the concentrated sulfuric acid to obtain fuming nitric acid;

(5) adding fuming nitric acid and urea into a reaction kettle according to the mass ratio of 7.2-7.6:1, reacting for 3-4h at 45-48 ℃, and then heating to 80-82 ℃ for reacting for 4-5 h;

(6) after solid-liquid separation, a crude product of sulfamic acid is obtained;

(7) purifying, namely putting the crude product of sulfamic acid into distilled water, raising the temperature to a first temperature to ensure that sulfamic acid is dissolved roughly to obtain sulfamic acid solution, and after filtering impurities at high temperature, reducing a second temperature of the sulfamic acid solution to separate out crystals;

(8) and (4) carrying out suction filtration to obtain crystals, and drying to obtain pure aminosulfonic acid crystals.

2. The technology for producing sulfamic acid by using by-product waste sulfuric acid as claimed in claim 1, wherein the activated carbon is one or more of wood chips, rice hulls and crushed olive stones.

3. The technology for producing sulfamic acid by using by-product waste sulfuric acid as claimed in claim 2, wherein the mass ratio of the activated carbon to the waste sulfuric acid is 1: 550-650.

4. The technology of producing sulfamic acid by using by-product waste sulfuric acid as claimed in claim 1,

the drying temperature is 90-100 ℃.

5. The technology of producing sulfamic acid by using by-product waste sulfuric acid as claimed in claim 1,

the first temperature in the step (7) is 80-85 ℃.

6. The technology of producing sulfamic acid by using by-product waste sulfuric acid as claimed in claim 1,

(7) wherein said second temperature is a temperature reduction to 0-4 ℃.

7. The technology of producing sulfamic acid by using by-product waste sulfuric acid as claimed in claim 1,

the mass concentration of the hydrogen peroxide is 25-29%.

Technical Field

The invention relates to the technical field of chemistry and chemical engineering, in particular to a technology for producing sulfamic acid by using byproduct waste sulfuric acid.

Background

Sulfuric acid is one of the most widely used basic chemicals, widely used in many industrial sectors, and its yield and consumption are often used as an important index of the overall industrial development level. Sulfuric acid can be roughly divided into 3 cases during use: is fixed in the product as an integral part of the product; conversion to undesirable by-products such as salt cake, gypsum, ferrous sulfate, etc.; is discharged from the product system in the form of waste sulfuric acid.

The acid consumption of the non-fertilizer industry in China is about 23 Mt, and the production and the use of the sulfuric acid can generate about 1 million tons of waste sulfuric acid,

the acid consumption of China in 2013 in the non-fertilizer industry is about 23 Mt, but the yield of the waste sulfuric acid in China in 2013 is more than 1 hundred million tons. Of the large amount of waste sulfuric acid, the inorganic waste sulfuric acid accounts for about 35%, the organic waste sulfuric acid accounts for about 65%, and the waste sulfuric acid having a waste sulfuric acid concentration of 40% or more accounts for about 46% of the total waste sulfuric acid, and most of the waste sulfuric acids have a low concentration and a large amount. In the industrial production process, reactions such as nitration, esterification, sulfonation, alkylation, drying, catalysis and the like of organic matters can produce a large amount of waste sulfuric acid, and in addition, the waste sulfuric acid is produced in the processes of drying and purifying gas, pickling steel and ores, producing titanium dioxide and the like.

Therefore, the industrial waste sulfuric acid in China has the following characteristics:

(1) the waste sulfuric acid has wide sources and is dispersed in the industry. Except for metal processing, acid washing, titanium white powder and dyeing

Besides main industries such as materials, storage batteries, petrochemical industry and the like, the production of dozens of chemical products is accompanied with the production of waste sulfuric acid in many other chemical industries;

(2) the total amount of waste sulfuric acid is quite large, but the yield of waste sulfuric acid from most individual enterprises is not large.

Many enterprises produce only hundreds of tons of waste sulfuric acid per year;

(3) the waste sulfuric acid contains a large amount of organic or inorganic impurities, and is difficult to be directly utilized or produced

The product quality is poor;

(4) the concentration of the waste sulfuric acid is generally low, and the content of impurities is high.

The common treatment mode of the enterprises in the society for the waste sulfuric acid is direct discharge or simple neutralization

And discharging, in particular to the treatment of low-concentration waste sulfuric acid. Therefore, the treatment cost of the waste sulfuric acid can be greatly saved for enterprises, and the profit of the enterprises is improved. The treatment mode of directly discharging or simply discharging the waste sulfuric acid after neutralization not only wastes a large amount of sulfuric acid resources, but also influences water quality indexes, corrodes a sewer, acidifies soil, releases a large amount of heavy metals in soil ores and water sediments, seriously pollutes the environment and harms the health and living environment of human beings.

Disclosure of Invention

In view of the above, the invention provides a technology for producing sulfamic acid by using byproduct waste sulfuric acid, which can effectively utilize waste sulfuric acid, improve economic benefits, avoid environmental pollution caused by sulfuric acid, and improve the utilization rate of sulfuric acid.

A technology for producing sulfamic acid by using byproduct waste sulfuric acid is characterized by comprising the following steps:

(1) adding activated carbon into waste sulfuric acid, wherein the mass ratio of the activated carbon to the waste sulfuric acid is 1: 550-650, then dropwise adding hydrogen peroxide in a stirring state to perform oxidation reaction of impurities, then filtering, and taking clear liquid to obtain purified sulfuric acid solution;

the principle of the waste sulfuric acid containing a lot of impurities is that organic impurities in the waste sulfuric acid are oxidized and decomposed by using an oxidizing agent under appropriate reaction conditions, and are converted into water, carbon dioxide, nitrogen oxides and the like, which are separated from the sulfuric acid, so that the waste sulfuric acid is purified and recovered. The activated carbon is a carbon material with a developed pore structure and a huge specific surface area, has the characteristics of good adsorption performance, high mechanical strength, good chemical stability, easy regeneration and the like, and is widely applied to various industries such as chemical industry, food, medical treatment and health, environment and the like as a good adsorbent, catalyst and catalytic carrier. The active carbon is used as a catalyst to catalyze the oxidation reaction of hydrogen peroxide, has strong catalytic action on hydrogen peroxide, and can be used for oxidation of sulfur dioxide, reduction of hydrogen chloride, manufacture of phosgene, removal of organic impurities and the like. The active carbon used in the invention is one or more of sawdust, rice hull and olive kernel crushed substances, is low in price, consists of cellulose, hemicellulose and lignin, has a natural high-quality organization structure, is high in compactness, high in mechanical strength and low in ash content, is beneficial to forming a developed microporous structure, and the prepared coconut shell active carbon has a developed microporous structure, large specific surface area, excellent adsorption performance and mechanical strength, and the particle size of the active carbon can be 10-24 meshes of powder. More impurities in the waste sulfuric acid can be removed, and purer dilute sulfuric acid is obtained through the step.

(2) Carrying out high-temperature evaporation concentration on the sulfuric acid solution to obtain concentrated sulfuric acid; the concentration of sulfuric acid is increased by high temperature evaporation.

(3) Heating part of concentrated sulfuric acid to 600-750 ℃ for cracking to generate sulfur trioxide and water, and collecting the generated sulfur trioxide; the temperature in this step must not be too high, which would lead to decomposition of the sulphur trioxide to sulphur dioxide.

(4) Cooling the sulfur trioxide gas, and introducing the rest concentrated sulfuric acid to ensure that the sulfur trioxide is completely absorbed by the concentrated sulfuric acid to obtain fuming nitric acid;

(5) adding fuming nitric acid and urea into a reaction kettle according to the mass ratio of 7.2-7.6:1, reacting for 3-4h at 45-48 ℃, and then heating to 80-82 ℃ for reacting for 4-5 h;

in the step, urea and sulfur trioxide react at 45-48 ℃ to obtain a product ureido sulfonic acid, and then the temperature is raised to 80-82 ℃ to react the ureido sulfonic acid with sulfuric acid to obtain the cinnamyl sulfamic acid. The preparation process is more stable and avoids the loss of sulfur trioxide.

(6) After solid-liquid separation, a crude product of sulfamic acid is obtained; in general, the sulfuric acid is excessive in the reaction process, and the liquid which is easy to separate solid from liquid, namely the sulfuric acid, can be reserved for other purposes.

(7) Purifying, namely putting the crude product of sulfamic acid into distilled water, raising the temperature to 80-85 ℃ to ensure that sulfamic acid is dissolved roughly to obtain sulfamic acid solution, filtering impurities at high temperature, reducing the second temperature of the sulfamic acid solution by 0-4 ℃, and separating out crystals;

the process utilizes the gradual increase of the dissolution reading of the sulfamic acid in the water along with the rise of the temperature, dissolves the crude product of the sulfamic acid into the high-temperature water, and then reduces the temperature to separate out crystals, thereby achieving the purpose of purification.

(8) Obtaining crystals through suction filtration, and drying at 90-100 ℃ to obtain pure aminosulfonic acid crystals.

In addition, the mass concentration of the hydrogen peroxide is 25-29%.

The method has the advantages of high utilization rate of recycling the waste sulfuric acid, low production cost, easy operation control, effective utilization of the waste sulfuric acid, improvement of economic benefit, avoidance of environmental pollution of the sulfuric acid and improvement of the utilization rate of the sulfuric acid, and avoids loss of sulfur trioxide in the process of preparing sulfamic acid.

Detailed Description

The present invention will be described in detail with reference to specific embodiments.