JPS629522B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new method for producing hydroxylamine-O-sulfonic acid. Hydroxylamine-O-sulfonic acid has various industrial uses, such as as an intermediate for dyes, medicines, agricultural chemicals, etc., or as a polymerization catalyst. Conventionally, a method for producing hydroxylamine-O-sulfonic acid by reacting a mineral acid salt of hydroxylamine with oleum is known. For example, when hydroxylamine sulfate is used as a raw material, hydroxylamine-O-sulfonic acid can be obtained according to the following formula. (NH ₂ OH) ₂・H ₂ SO ₄ +2SO ₃・H ₂ SO ₄ →2NH ₂ OSO ₃ H＋3H ₂ SO _4However , in this method, the target hydroxylamine-O-sulfonic acid is suspended in mineral acid. However, since it is obtained in the form of microcrystals, it is extremely difficult to purify it, and hydroxylamine-O-sulfonic acid is highly hygroscopic and decomposes into hydroxylamine when it comes into contact with moisture, making it a time-consuming purification method. It also has the problem that it cannot be adopted. Therefore, research has been carried out as a means of purification. For example, Japanese Patent Publication No. 47-49999 proposes a method in which a halide such as methylene chloride or chloroform is present as a diluent in the reaction system. This method attempts to increase the superactivity of the reaction mixture by keeping the reaction system in a liquid state through the use of a diluent. However, in this method, the more the amount of diluent used, the more the target substance may be eluted into the diluent. However, the disclosed diluent has poor compatibility with mineral acids, so The effect cannot be expected unless a very large amount is used, and the use of a diluent causes the target product to become even more microcrystalline, which poses industrial problems such as the ability to separate and obtain the target product with simple operations. ing. As described above, all known methods for producing hydroxylamine-O-sulfonic acid are carried out in a solvent, which has the disadvantage of separating and purifying the target product, and as a result, the purity and yield of the target product are also low. They also have common drawbacks, such as requiring complicated operations for solvent recovery and purification. The present inventors conducted extensive research with the aim of improving the above-mentioned drawbacks of conventionally known devices. As a result, solid hydroxylamine mineral acid salt,
The inventors have discovered that hydroxylamine-O-sulfonic acid can be produced very industrially advantageously by bringing it into contact with sulfur trioxide gas, and that the object can be achieved, and the present invention has been achieved. 〓〓〓
In the present invention, as the hydroxylamine mineral salt, sulfate of hydroxylamine is particularly preferred, but other salts such as hydrochloride, nitrate, and phosphate can also be used. The present invention is a so-called solid-gas reaction in which these solid hydroxylamine mineral salts are brought into contact with gaseous sulfur trioxide. Therefore, in order to uniformly contact the two and increase the reactivity, it is preferable that the hydroxylamine mineral salt is usually ground to about 40 to 250 mesh before use. Sulfur trioxide gas may be pure, but it may also be diluted with an inert gas such as nitrogen, argon, or methane, and sulfur trioxide-containing gas obtained in the sulfuric acid manufacturing process can also be used as is. . The higher the contact temperature, the better the reactivity; however, if the contact temperature is too high, scattering of the hydroxylamine mineral salt occurs, so it is usually preferred to carry out the contact at a temperature of 20 to 100°C. The contact time depends on the contact temperature and the amount of sulfur trioxide gas aerated, but it is usually sufficient to carry out the contact for 0.5 to 10 hours, preferably 1 to 5 hours. In the present invention, after the hydroxylamine mineral acid salt and the sulfur trioxide gas come into contact with each other, the target product is obtained in a wet state with free mineral acid attached thereto. However, the mineral acid can be easily removed by washing with ether or acetate, and highly pure hydroxylamine-O-sulfonic acid can be easily obtained. In this way, the present invention, compared to conventionally known methods,
This method has many advantages, such as easy separation and purification of the target product, and because no solvent is used, recovery and purification steps are omitted, and the purity and yield of the target product are significantly improved. It is recognized that the method for producing hydroxylamine-O-sulfonic acid of the invention is extremely superior. Example 1 100 to 170 in a gas cleaning bottle with a glass filter
5 g of mesh hydroxylamine sulfate was charged and the temperature of the washing bottle was maintained at 40°C. After approximately 4 vol % of sulfur trioxide gas (the remainder being nitrogen gas) was circulated through the bottom of the packed bed at a rate of 2/min for 4.5 hours, the contents of the washing bottle were cooled to room temperature. Next, add 50 ml of dry ether at about 0°C to the washing bottle.
After adding and thoroughly suspending, filter, dry, and crystallize.
6.85g was obtained. As a result of quantifying this crystal by iodo-reduction titration, it was found that hydroxylamine-O-sulfonic acid
It contained 6.70g. Therefore, the purity of hydroxylamine-O-sulfonic acid is 97.8%, and the yield based on hydroxylamine sulfate is 97.1%. Examples 2 and 3 Experiments were conducted in the same manner as in Example 1, except that the contact temperature between hydroxylamine sulfate and sulfur trioxide gas was 60°C (Example 2) and 80°C (Example 3). Ivy. The following table shows the results of Examples 1 to 3.

[Table] *: Consumption amount of sulfur trioxide is per mole of hydroxylamine sulfate in each example.
Approximately 2-2.5 moles.
Comparative Example 6.2 g of hydroxylamine sulfate was gradually mixed with 32.2 g of 30 wt % fuming sulfuric acid over a period of 40 minutes, and then the reaction was carried out at 60° C. for 2 hours with stirring. After the reaction, the reaction mixture was cooled to 10° C., stirred for 1 hour, and then filtered under suction. Analysis of 9.0 g of the obtained crystals revealed that it contained 7.5 g of hydroxylamine-O-sulfonic acid. Therefore, the yield based on hydroxylamine sulfate of the target product was 87.8%, and the purity was 83.3%. 〓〓〓

Claims (1)

[Claims] 1. A method for producing hydroxylamine-O-sulfonic acid, which comprises contacting a solid mineral acid salt of hydroxylamine with sulfur trioxide gas.