CN111100022A - Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid - Google Patents
Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid Download PDFInfo
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- CN111100022A CN111100022A CN201911041010.9A CN201911041010A CN111100022A CN 111100022 A CN111100022 A CN 111100022A CN 201911041010 A CN201911041010 A CN 201911041010A CN 111100022 A CN111100022 A CN 111100022A
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- compounds
- acid
- lewis acid
- carboxylic acid
- nitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
Abstract
The invention relates to a method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze by Lewis acid. The method disclosed by the invention is simple to operate, short in reaction time, low in reaction temperature and capable of increasing the yield to 90-99%.
Description
Technical Field
The invention relates to a method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze by Lewis acid.
Background
N-phosphonomethyliminodiacetic acid (PMIDA) is an important intermediate of herbicide glyphosate and other chemical products, the production process is an iminodiacetonitrile method, and the method has two routes, wherein the first route is an alkaline hydrolysis method: after alkaline hydrolysis, acidification and condensation reaction of iminodiacetonitrile, naturally cooling and cooling until crystals are completely separated out, and filtering, washing and drying to obtain the PMIDA product. The method has the advantages of long reaction period, complex process and high energy consumption, can generate a large amount of NaCl in the acidification process, causes the generation of high-salt wastewater, and reduces the yield of iminodiacetic acid.
The second route is an acid hydrolysis: the iminodiacetonitrile is directly acidolyzed and condensed to prepare the N- (phosphonomethyl) iminodiacetic acid. The route adopts hydrochloric acid, sulfuric acid and the like to carry out acidolysis on iminodiacetonitrile, the iminodiacetonitrile is hydrolyzed under the acidic condition to obtain iminodiacetic acid, ammonium salt is directly generated in the hydrolysis process, NaCl is not generated, the ammonium salt can be sold as a byproduct, high-salinity wastewater is not generated, and the pollution problem of glyphosate enterprises is effectively solved.
Nitrile compounds such as iminodiacetonitrile and the like can be hydrolyzed into carboxylic acid compounds under the acid-base condition, but the degree of hydrolysis is not enough under the action of acid or base, the main product is a mixture of amide and carboxylic acid, the yield of iminodiacetic acid is not high, and higher requirements are imposed on reaction temperature and time. The hydrolysis of aromatic nitriles to carboxylic acids is more severe and the yield of carboxylic acid compounds is less efficient than aliphatic nitriles.
Although the hydrolysis process of nitrile compounds is popular and widely used by people, the process is still not mature enough in economic benefit, and the reaction conditions and the productivity still need to be optimized and improved.
Disclosure of Invention
The invention aims to provide a method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid, which is simple to operate and high in yield.
The invention adopts the following technical scheme:
a method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze by Lewis acid is disclosed.
Further, the method specifically comprises the following steps:
(1) mixing hydrochloric acid with the concentration of 30%, distilled water and concentrated sulfuric acid with the concentration of 98% in a volume ratio of 13-20: 4-6: 1 to prepare acid liquor, and stirring and heating to 40-50 ℃;
(2) adding a Lewis acid aqueous solution into the acid liquor, then adding a nitrile compound with the same volume as that of the distilled water in the step (1), carrying out condensation reflux, keeping the temperature at 110-130 ℃, and continuously stirring for 6-8 hours;
(3) adding ammonia water and activated carbon for decoloring treatment for about 30min, wherein the volume ratio of hydrochloric acid to ammonia water is 2-4: 1, the mass ratio of distilled water to activated carbon in the step (1) is 16-35: 1, heating to 100 ℃, and adjusting the pH value to 2-3 to naturally cool;
(4) and (4) carrying out suction filtration on the naturally cooled solution obtained in the step (3), sequentially washing crystals generated by suction filtration with distilled water with the volume of 50-200 ml for 4 times, and drying and crystallizing to obtain the carboxylic acid compound.
Further, in the step (2), the amount of the lewis acid aqueous solution is 1-5% of the volume of the acid solution in the step (1), and is preferably 3%; the mass concentration of the Lewis acid aqueous solution is 1-8%, preferably 3-5%.
Further, the lewis acid is ferric chloride, aluminum chloride or zinc chloride.
Further, the nitrile compound is aliphatic nitrile or aromatic nitrile.
Further, in the step (4), the crystals produced by suction filtration are washed 4 times with 200ml, 150ml, 100ml and 50ml of distilled water in this order.
Further, it still includes:
(5) and (4) mixing the pumped filtrate obtained in the step (4) with flushing liquid, adjusting the pH value to 3-4, heating the mixed liquid, stopping heating when the mixed liquid starts to generate crystals, naturally cooling and cooling, and performing pumping filtration when the mixed liquid is cooled to room temperature to obtain ammonium chloride crystals.
The invention has the beneficial effects that: the method disclosed by the invention is simple to operate, short in reaction time, low in reaction temperature and capable of increasing the yield to 90-99%, and meanwhile, the waste liquid is recycled to prepare the ammonium chloride crystal, so that the economic benefit is increased.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The embodiment takes a small test as an example, and the quality and the yield of the product after industrial scale-up are not lower than the result of the small test.
Example 1
Adding 360ml of hydrochloric acid with the mass concentration of 30%, 100ml of distilled water and 20ml of concentrated sulfuric acid with the mass concentration of 98% into a 1000ml four-neck flask, and heating to 40 ℃ under stirring; adding 15ml of ferric chloride solution with the mass percentage concentration of 5%, stirring and dissolving, adding 100ml of iminodiacetonitrile, heating to 115 ℃ after the reaction is released, starting to condense, reflux and keep the temperature, and continuing to stir for 7 hours; adding ammonia water 120ml and active carbon 6g for decolorizing treatment, stopping heating when the temperature is heated to 100 ℃, starting suction filtration, and adjusting the pH to 2 to naturally cool; and cooling, then, carrying out suction filtration, sequentially washing crystals generated by the suction filtration by using 200ml, 150ml, 100ml and 50ml of distilled water with different volumes, drying the washed crystals in an oven, and drying to obtain the iminodiacetic acid with the yield of about 99%. And (3) mixing the pumped filtrate and the flushing fluid, adjusting the pH value to 3-4, heating the mixed solution, stopping heating when the mixed solution begins to crystallize, naturally cooling, and performing suction filtration when the mixed solution is cooled to room temperature to obtain ammonium chloride crystals.
Example 2
200ml of hydrochloric acid with the mass concentration of 30%, 70ml of distilled water and 10ml of concentrated sulfuric acid with the mass concentration of 98% are added into a 500ml four-neck flask, and the mixture is stirred and heated to 45 ℃; adding 8ml of aluminum chloride solution with the mass percentage concentration of 4%, stirring and dissolving, then dropwise adding 70ml of benzonitrile, heating to 130 ℃ after the reaction is exothermic, starting to perform condensation reflux to keep the temperature, and continuing to stir for 6 hours; adding 100ml of ammonia water and 2g of activated carbon for decoloring, stopping heating when the temperature is heated to 100 ℃, starting suction filtration, and adjusting the pH value to 3 to naturally cool the solution; and cooling, then, carrying out suction filtration, sequentially washing crystals generated by the suction filtration by using 200ml, 150ml, 100ml and 50ml of distilled water with different volumes, drying the washed crystals in an oven, and drying to obtain the benzoic acid with the yield of about 90%. And (3) mixing the pumped filtrate and the flushing fluid, adjusting the pH value to 3-4, heating the mixed solution, stopping heating when the mixed solution begins to crystallize, naturally cooling, and performing suction filtration when the mixed solution is cooled to room temperature to obtain ammonium chloride crystals.
Example 3
Adding 400ml of hydrochloric acid with the mass concentration of 30%, 120ml of distilled water and 30ml of concentrated sulfuric acid with the mass concentration of 98% into a 1000ml four-neck flask, and heating to 50 ℃ while stirring; adding 16.5ml of zinc chloride solution with the mass percentage concentration of 3%, stirring and dissolving, then dropwise adding 120ml of adiponitrile, heating to 110 ℃ after the reaction is released, starting condensation and reflux to keep the temperature, and continuing stirring for 8 hours; adding 100ml of ammonia water and 5g of activated carbon for decoloring, stopping heating when the temperature is heated to 100 ℃, starting suction filtration, and adjusting the pH to 2 to naturally cool the solution; and cooling, then, carrying out suction filtration, sequentially washing crystals generated by the suction filtration by using 200ml, 150ml, 100ml and 50ml of distilled water with different volumes, drying the washed crystals in an oven, and drying to obtain adipic acid with the yield of about 96%. And (3) mixing the pumped filtrate and the flushing fluid, adjusting the pH value to 3-4, heating the mixed solution, stopping heating when the mixed solution begins to crystallize, naturally cooling, and performing suction filtration when the mixed solution is cooled to room temperature to obtain ammonium chloride crystals.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze by Lewis acid is characterized in that under acidic conditions, Lewis acid is used for catalyzing nitrile compounds to hydrolyze into carboxylic acid compounds.
2. The method for preparing carboxylic acid compounds from nitrile compounds by catalyzing hydrolysis with Lewis acid according to claim 1, which is characterized by comprising the following steps:
(1) mixing hydrochloric acid with the concentration of 30%, distilled water and concentrated sulfuric acid with the concentration of 98% in a volume ratio of 13-20: 4-6: 1 to prepare acid liquor, and stirring and heating to 40-50 ℃;
(2) adding a Lewis acid aqueous solution into the acid liquor, then adding a nitrile compound with the same volume as that of the distilled water in the step (1), carrying out condensation reflux, keeping the temperature at 110-130 ℃, and continuously stirring for 6-8 hours;
(3) adding ammonia water and activated carbon for decolorization for about 30min, wherein the volume ratio of hydrochloric acid to ammonia water is 2-4: 1, the mass ratio of distilled water to activated carbon is 16-35: 1, heating to 100 ℃, adjusting the pH value to 2-3, and naturally cooling;
(4) and (4) carrying out suction filtration on the naturally cooled solution obtained in the step (3), sequentially washing crystals generated by suction filtration with distilled water with the volume of 50-200 ml for 4 times, and drying and crystallizing to obtain the carboxylic acid compound.
3. A method for preparing carboxylic acid compounds from nitrile compounds by catalyzing hydrolysis with Lewis acid according to claim 2, wherein the volume of Lewis acid added in step (2) is 1-5% of the volume of acid solution in step (1), and the mass concentration of Lewis acid aqueous solution is 1-8%.
4. A method for preparing carboxylic acid compounds from nitrile compounds by catalyzing hydrolysis with Lewis acid according to claim 2, wherein the Lewis acid is ferric chloride, aluminum chloride or zinc chloride.
5. The method for preparing carboxylic acid compounds by hydrolyzing nitrile compounds catalyzed by Lewis acid according to claim 2, wherein the nitrile compounds are aliphatic nitriles or aromatic nitriles.
6. The method for preparing carboxylic acid compounds from nitrile compounds by catalyzing hydrolysis with Lewis acid according to claim 2, further comprising:
(5) and (4) mixing the pumped filtrate obtained in the step (4) with flushing liquid, adjusting the pH value to 3-4, heating the mixed liquid, stopping heating when the mixed liquid starts to generate crystals, naturally cooling and cooling, and performing pumping filtration when the mixed liquid is cooled to room temperature to obtain ammonium chloride crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911041010.9A CN111100022A (en) | 2019-10-30 | 2019-10-30 | Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911041010.9A CN111100022A (en) | 2019-10-30 | 2019-10-30 | Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid |
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| CN111100022A true CN111100022A (en) | 2020-05-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442892A (en) * | 2020-11-02 | 2021-03-05 | 中国船舶重工集团公司第七一八研究所 | Method for catalytically hydrolyzing polyacrylonitrile material under acidic condition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442892A (en) * | 2020-11-02 | 2021-03-05 | 中国船舶重工集团公司第七一八研究所 | Method for catalytically hydrolyzing polyacrylonitrile material under acidic condition |
| CN112442892B (en) * | 2020-11-02 | 2023-02-28 | 中国船舶重工集团公司第七一八研究所 | Method for catalytically hydrolyzing polyacrylonitrile material under acidic condition |
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