CN101391759B - Sulfamic acid production process - Google Patents
Sulfamic acid production process Download PDFInfo
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- CN101391759B CN101391759B CN2008102264155A CN200810226415A CN101391759B CN 101391759 B CN101391759 B CN 101391759B CN 2008102264155 A CN2008102264155 A CN 2008102264155A CN 200810226415 A CN200810226415 A CN 200810226415A CN 101391759 B CN101391759 B CN 101391759B
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Abstract
The invention discloses a novel sulfamic acid after-treatment process, which comprises: carbamide is adopted to be sulfonated with oleum for preparing sulfamic acid; after the reaction the dilute sulphuric acid with the concentration of 5 to 30 percent is added to regulate the concentration of the sulphuric acid in an reaction kettle to be about 70 percent, and the sulphuric acid is isolated after holding; then the dilute sulphuric acid with the concentration of 1 to 10 percent or water is added into the reaction kettle for a second time acidity regulation to regulate the concentration of the sulphuric acid in the reaction kettle to be 5 to 20 percent; then the high pure product with the purity greater than 99.9 percent can be obtained after recrystallization, filtering and drying. The after-treatment process is easy for operation and the labor hardship is lower; and the purity of the product is high and the quality is better.
Description
Technical field
The invention belongs to inorganic synthetic field, be specifically related to a kind of sulfamic acid production process.
Technical background
Thionamic acid is a kind of important fine chemicals, is mainly used in the production of amidosulfonic acid sodium of happy prime ring in recent years, also has the multiple uses such as softening and SYNTHETIC OPTICAL WHITNER that are used for weedicide, fireproofing agent, metal and ceramic sanitising agent, paper and textiles.The main production of Description on Production of Sulfaminic Acid producer is that urea is through oleum method of sulfonation both at home and abroad at present.Throughput is big because this technology has, good product quality, safety, advantage that quantity of three wastes is few, so people are constantly studying, making every effort to further to improve to this technology and perfect always.For example, Russ P RU 2240997C had been improved, proposed a kind of new simplification aftertreatment technology to post-treating method in 2004: sulfonated bodies is without the dilution direct filtration, and the paste that obtains carries out recrystallization with the circulating mother liquor of sulfuric acid content 22%.The invention people claims this simplification technology can reduce sulfuric acid consumption, utilizes small device, low power consumption and low laboring fee usefulness, obtains high yield, high-quality purpose product simultaneously.But in fact this technology still can't be avoided because a series of problems that the sad filter of sulfonated products is brought.In the actually operating, reaction product particle is very thin, though adopt the press filtration mode to accelerate filtration velocity owing to increasing of pressure, it is self-evident that the expense that filtering equipment brought increases.Only be paste owing to what obtain simultaneously, obtain highly purified qualified product and must carry out recrystallization.Need great amount of manpower and labour intensity very big yet this paste is transferred to the crystallization kettle recrystallization process, this shortcoming is particularly outstanding when throughput is big.Can not substitute fully and manually finish this step operation even if use mechanism instead, also can increase power consumption simultaneously.Therefore the aftertreatment technology of thionamic acid becomes the bottleneck problem of restriction whole production flow process.
Summary of the invention
For solve the material filtering difficulty that exists in the sulfamic acid production process prior art, paste shifts problems such as difficulty, the present invention proposes a kind of more succinct, aftertreatment technology rapidly.
The present invention adopts ordinary method to prepare thionamic acid.So-called ordinary method refers to the method for urea through oleum sulfonation production thionamic acid.Its preparation method can be known for example feed molar ratio, reaction conditions and operation steps or the like from many pieces of reference for a person skilled in the art.The creative contribution that the present invention made has provided a kind of new aftertreatment technology, make people can abandon the post processing mode of bibliographical information in the past, adopt a kind of material that need not repeatedly to shift, need not specific installation, and can obtain the purpose product of high quality, high yield.
The technical scheme of sulfamic acid production process provided by the invention is as follows:
Reaction finishes the back and adds in the dilute sulphuric acid conditioned reaction still that concentration is 5-30% sulfuric acid concentration and tell upper strata sulfuric acid after leaving standstill between the 60-75%; Adding concentration again in still is dilute sulphuric acid or the water of 1-10%, regulates the interior sulfuric acid concentration of still between the 5-20%, and recrystallization, filtration, drying obtain high purity purpose product.
According to aftertreatment technology of the present invention, react the first material in end back and be cooled to about 40 ℃, carry out the acidity conciliation processing first time by the mode that adds dilute sulphuric acid.The dilute sulphuric acid preferred concentration that this time adds in reactor is about 10-25%.Because in the actual production, its concentration of filtrate that product recrystallization after-filtration obtains in this scope, can recycle as this adjusting acidity used just.The concentration of acidity conciliation for the first time is preferably between 65-70%.The solubleness of thionamic acid in 70% sulfuric acid is minimum under the room temperature, and the two difference in specific gravity is bigger, therefore suitable when acidity adjustment, stop to stir, leaving standstill after a moment, very carefully be difficult to filtration although from 70% sulfuric acid, separate out the thionamic acid particle, can settle down quickly.Utilizing these characteristics (almost not have entrained product) easily tells the sulfuric acid on upper strata.Can adopt a removable pipe that has suitable position of opening that this part sulfuric acid (accounting for whole more than 70% of sulfuric acid total amount in the still) is extracted out by the top of reactor in the actually operating.The sulfuric acid of extracting out (concentration about 70%) can be used as by-product sale and uses for other producers.
Afterwards, the material in the still needn't shift and can directly carry out the recrystallization operation.The concrete operations mode is: at first carry out the acidity adjustment second time, add concentration and be the dilute sulphuric acid of 1-10% or directly add water, regulate the interior sulfuric acid concentration of still to being not more than 20%, suitable acid concentration is controlled between the 5-20%.Concentration is higher than 20% and can causes quality product to descend; Concentration is lower than 5% then spent acid amount increasing, increases the cost of the disposal of three wastes.In the actual production, for the second time the amount of used dilute sulphuric acid of acidity adjustment or water be the weight ratio of thionamic acid and dilute sulphuric acid or water between 1:2-1:7, so both can guarantee to obtain high-quality product, can control the spent acid amount effectively again.Heat temperature raising makes the thionamic acid CL, notices that temperature should be above 75 ℃.The thionamic acid crystalline particle is separated out in cooling afterwards.Filter, drying, obtain purity and be the thionamic acid more than 99.5%, yield about 85%.
Aftertreatment technology of the present invention has the following advantages: the acid discharge in the Description on Production of Sulfaminic Acid process, purification operations are arranged in the same reactor carry out, solved thoroughly that high labour intensity shifts material, multiple times of filtration in the prior art, repeatedly recrystallization is purified or used pressure exerting device to increase problems such as production cost.Only need in the post-processing operation once to filter, and because the product crystal formation is good, filter operation is easy to.Use conventional equipment, filter 850 kilograms of products and can finish in 0.5～1 hour.Therefore aftertreatment technology provided by the invention is easy and simple to handle, labor strength is low, and product yield height, quality are good.Can reclaim simultaneously the sulfuric acid of 70% concentration to greatest extent and sell as byproduct, most of dilute sulphuric acid is capable of circulation to be applied mechanically, and has reduced useless vitriolic quantity discharged.
Embodiment
Following examples are used to further specify the present invention, but the present invention is not limited only to these embodiment.
Example 1
Add the oleum of 1000 liters 23% in 5000 liters of reactors, add 300 kilograms of urea in batches, controlled temperature is no more than 45 ℃ when reinforced.After adding urea, slowly be warming up to 90 ℃ and insulation reaction 1 hour, reaction is finished.Reaction finishes the back stirring and is cooled to 40 ℃, adds 20% sulfuric acid, 300 liters with vitriolic concentration adjustment to 70% in the still.Stop to stir, material left standstill 1 hour, and vacuum is extracted upper strata sulfuric acid out.Sulfuric acid 4200 liters of adding 10% are regulated sulfuric acid concentration in still again, are heated to 70 ℃, and material all dissolves.Be cooled to 20 ℃ afterwards, filter, dry 849 kilograms of thionamic acids, purity 99.5%, the yield 86% of getting.
Example 2
Add the oleum of 1350 liters 23% in 5000 liters of reactors, add 450 kilograms of urea in batches.Reaction conditions is with example 1.Reaction finishes the back stirring and is cooled to 40 ℃, adds and filters filtrate 540 liters that obtain in the example 1, with vitriolic concentration adjustment to 67% in the still.Stop to stir, material left standstill 2.5 hours, and vacuum is extracted upper strata sulfuric acid out.Sulfuric acid 4500 liters of adding 5% are regulated sulfuric acid concentration in still again, are heated to 70 ℃, and material all dissolves.Be cooled to 10-20 ℃, filter, dry 1255.8 kilograms of thionamic acids, purity 99.5%, the yield 85% of getting.
Example 3
The reinforced reaction conditions that reaches is with example 1.Post-processing operation is with example 1.Not existing together only is that for the first time 10% sulfuric acid is adopted in acid adjustment, and acid adjustment for the second time is with 1800 kilograms of deionized waters.Dry 828.4 kilograms of thionamic acids, purity 99.6%, the yield 84% of getting.
Claims (2)
1. sulfamic acid production process, adopt urea to prepare thionamic acid through the oleum sulfonation, it is characterized in that: reaction finishes the first material in back and is cooled to 40 ℃, adds concentration and is in the dilute sulphuric acid conditioned reaction still of 5-30% sulfuric acid concentration and tell upper strata sulfuric acid after leaving standstill between the 60-75%; The dilute sulphuric acid or the water that add concentration again and be 1-10% in reactor carry out acidity adjustment second time, and the interior sulfuric acid concentration of conditioned reaction still is between the 5-20%, and recrystallization, filtration, drying obtain purity and be higher than 99.5% purpose product.
2. according to the described production technique of claim 1, it is characterized in that: it is the dilute sulphuric acid of 10-25% that reaction finishes back adding concentration, and vitriolic concentration is between the 65-70% in the conditioned reaction still.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102264155A CN101391759B (en) | 2008-11-10 | 2008-11-10 | Sulfamic acid production process |
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| CN2008102264155A CN101391759B (en) | 2008-11-10 | 2008-11-10 | Sulfamic acid production process |
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| CN101391759B true CN101391759B (en) | 2010-10-13 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058373B (en) * | 2014-03-27 | 2016-01-20 | 荆门市熊兴化工有限公司 | A kind of Description on Production of Sulfaminic Acid line |
| CN104058374B (en) * | 2014-03-27 | 2015-11-11 | 荆门市熊兴化工有限公司 | A kind of dilute sulphuric acid reutilization system on sulfuric acid production line |
| CN108017374B (en) * | 2017-12-29 | 2023-05-02 | 清大国华环境集团股份有限公司 | Method and device for comprehensively utilizing cyanide tailings |
| CN108101011A (en) * | 2018-01-05 | 2018-06-01 | 荆门市熊兴化工有限公司 | A kind of refuse reclamation method and device of sulfamic acid by-product dilute sulfuric acid |
| CN112755930B (en) * | 2020-12-30 | 2022-09-27 | 莱州市中大贵合化工有限公司 | Production equipment and production process of sulfamic acid |
| CN113401883B (en) * | 2021-07-12 | 2023-03-17 | 烟台三鼎化工有限公司 | Continuous reaction process and continuous reaction equipment for sulfamic acid |
| CN115594157A (en) * | 2022-11-09 | 2023-01-13 | 荣成青木高新材料有限公司（Cn） | Preparation method of bis (chlorosulfonyl) imide |
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