Reaction-extraction coupling method for preparation of hydroxylamine salt / hydroxylamine

Abstract

A oxime hydrolysis and solvent extraction coupling method for one step preparation of hydroxylamine salt / hydroxylamine. The invention is characterized in that oxime (ketoxime or aldoxime) is used as a raw material, and the hydrolysis reaction of oxime in an acidic solution and organic solvent extraction and separation are coupled, so that an extraction agent extracts the correspondingly generated ketone or aldehyde into an organic phase while the hydrolysis reaction is carried out, thus breaking the restrictions of oxime hydrolysis reaction chemical equilibrium under mild conditions, introducing the reaction to the direction for generation of hydroxylamine salt / hydroxylamine, and improving the reaction conversion rate and yield of hydroxylamine salt / hydroxylamine. The hydroxylamine salt preparation method provided by the invention has the characteristics of simple process and operation, mild reaction conditions, high conversion rate and selectivity, and low energy consumption, etc.

Description

technical field

[0001] The invention relates to a method for preparing hydroxylamine salt / hydroxylamine through the coupling of oxime hydrolysis reaction and solvent extraction. Background technique

[0002] Hydroxylamine salt or hydroxylamine is a class of fine chemical products with a very wide range of uses. The molecular formula of hydroxylamine is NH 2 OH is an unstable white crystal at room temperature, which is easy to deliquesce and decompose. Therefore, hydroxylamine is usually stored, transported and used in the form of aqueous solution or salt. Hydroxylamine salts are mainly compounds formed from inorganic acids and hydroxylamine, such as hydroxylamine hydrochloride, hydroxylamine sulfate, hydroxylamine phosphate, and hydroxylamine nitrate. Hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine phosphate are mainly used in the synthesis of medicines, pesticides, spices, rubber chemicals, dyes, and organic materials; hydroxylamine nitrate is mainly...

Examples

Embodiment 1

[0077] Example 1: Press H + The molar ratio to cyclohexanone oxime is 2:1, measure 50ml of 2mol / L sulfuric acid, weigh 11.5g of cyclohexanone oxime with a purity of 99.0%, mix it and add it to a 250ml three-necked flask equipped with a condensing device , and then added 50ml of cyclohexane, heated and stirred at 25°C for 1h. After the reaction, stand for stratification, cyclohexanone oxime and cyclohexanone are dissolved in the upper oil phase, and the lower layer is the water phase, mainly hydroxylamine sulfate; the oil phase is quantitatively analyzed by gas chromatography internal standard method, and the water phase is analyzed by oxidation-reduction titration The content of hydroxylamine salt was analyzed; the conversion rate of cyclohexanone oxime was 32.7%, and the selectivity of hydroxylamine sulfate was 99.2%.

Embodiment 2

[0078] Embodiment 2: reaction step is as embodiment 1, and difference is that the ketoxime in the reaction is 8.7g purity and is the butanone oxime of 99.5%; The conversion rate of butanone oxime is 39.8%, and the selectivity of hydroxylamine sulfate is 99.4%.

Embodiment 3

[0079] Embodiment 3: The reaction steps are as in Example 1, the difference is that the ketoxime in the reaction is 7.3g of acetone oxime with a purity of 99.7%; the conversion rate of acetoxime is 42.5%, and the selectivity of hydroxylamine sulfate is 99.6% .

technical field

[0001] The invention relates to a method for preparing hydroxylamine salt / hydroxylamine through the coupling of oxime hydrolysis reaction and solvent extraction. Background technique

[0002] Hydroxylamine salt or hydroxylamine is a class of fine chemical products with a very wide range of uses. The molecular formula of hydroxylamine is NH 2 OH is an unstable white crystal at room temperature, which is easy to deliquesce and decompose. Therefore, hydroxylamine is usually stored, transported and used in the form of aqueous solution or salt. Hydroxylamine salts are mainly compounds formed from inorganic acids and hydroxylamine, such as hydroxylamine hydrochloride, hydroxylamine sulfate, hydroxylamine phosphate, and hydroxylamine nitrate. Hydroxylamine hydrochloride, hydroxylamine sulfate, and hydroxylamine phosphate are mainly used in the synthesis of medicines, pesticides, spices, rubber chemicals, dyes, and organic materials; hydroxylamine nitrate is mainly...

Examples

Embodiment 1

[0077] Example 1: Press H + The molar ratio to cyclohexanone oxime is 2:1, measure 50ml of 2mol / L sulfuric acid, weigh 11.5g of cyclohexanone oxime with a purity of 99.0%, mix it and add it to a 250ml three-necked flask equipped with a condensing device , and then added 50ml of cyclohexane, heated and stirred at 25°C for 1h. After the reaction, stand for stratification, cyclohexanone oxime and cyclohexanone are dissolved in the upper oil phase, and the lower layer is the water phase, mainly hydroxylamine sulfate; the oil phase is quantitatively analyzed by gas chromatography internal standard method, and the water phase is analyzed by oxidation-reduction titration The content of hydroxylamine salt was analyzed; the conversion rate of cyclohexanone oxime was 32.7%, and the selectivity of hydroxylamine sulfate was 99.2%.

Embodiment 2

[0078] Embodiment 2: reaction step is as embodiment 1, and difference is that the ketoxime in the reaction is 8.7g purity and is the butanone oxime of 99.5%; The conversion rate of butanone oxime is 39.8%, and the selectivity of hydroxylamine sulfate is 99.4%.

Embodiment 3

[0079] Embodiment 3: The reaction steps are as in Example 1, the difference is that the ketoxime in the reaction is 7.3g of acetone oxime with a purity of 99.7%; the conversion rate of acetoxime is 42.5%, and the selectivity of hydroxylamine sulfate is 99.6% .

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