CN106892836B - A kind of new process through in-situ preparation ammonia synthesis oxime - Google Patents
A kind of new process through in-situ preparation ammonia synthesis oxime Download PDFInfo
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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Abstract
The invention discloses a kind of new processes through in-situ preparation ammonia synthesis oxime, which is characterized in that ammonium salt and strong base-weak acid salt in-situ preparation ammonia react to obtain oxime then under titanium molecular sieve catalysis with ketone, hydrogen peroxide.Synthesis technology of the invention has oximation reaction simple, and reaction condition is mild, and by-product is few, product yield height and environmentally friendly feature.Synthetic method of the present invention is simple, and aftertreatment technology is easy, has very strong operability and repeatability, is convenient for industrialized production.
Description
Technical field
The present invention relates to a kind of synthesis technologies of oxime, and in particular to a kind of new process through in-situ preparation ammonia synthesis oxime.Belong to
In technical field of organic synthesis.
Background technique
Oxime (oxime) is the organic compound of the aldehyde containing carbonyl, ketone compounds and azanol effect and generation, general formula
All there is C=NOH base.Claim aldoxime by the oxime that aldehyde is formed, claims ketoxime by the oxime that ketone is formed.Oxime can obtain original aldehyde through hydrolysis
Or ketone.
Oxime can occur rearrangement reaction and generate amide, and the industrial raw material caprolactam for producing polyamide fibre is exactly to be given birth to by cyclohexanone
At rearranged react of oxime obtain.Some oximes can be used as analytical reagent, antioxidant, passivator etc..
Currently, there are mainly two types of the synthetic routes of oxime: (1) hydroxylamine assay uses hydroxylamine hydrochloride or hydroxyl sulfate and reactive ketone
The method for preparing ketoxime is the main route of current synthesizing butanone oxime；(2) ammonia oxidation, generally using TS-1 as catalyst, with ketone
It is raw material with ammonium hydroxide, hydrogen peroxide is added dropwise and obtains oxime.But above-mentioned synthetic method has certain problems, first method
Production line byproduct of reaction is more, and process is complicated；Second method production cyclohexanone oxime technique is more mature, but side reaction
It is difficult to avoid, while the remnants of ammonia are more, post-processing trouble；In addition, since ammonia has certain break to catalyst TS-1
Bad effect, after certain batch, catalyst can not reach the catalytic activity of fresh catalyst by activation again, due to TS-1
Price it is expensive, cause reaction production cost it is higher.
Patent CN103709065A discloses a kind of resource utilization method of low value-added ammonium chloride, but uses alkali
The stronger liquid alkaline of property, it is more serious to the destruction of catalyst Ti-si molecular sieves, it is not suitable for the conjunction of oxime in industrial production actually
At.Even the cyclohexanone oxamidinating technique of current comparative maturity, by-product is also inevitably generated, the remnants of ammonia are more,
Post-processing trouble, and the level of fresh catalyst cannot be fully achieved in catalytic activity after catalyst upon activation.
In conclusion presently, there are following problems for the ammonia deuteration technique of ammonia oxidation: (1) utilization rate of raw material ammonia
Low, side reaction is difficult to avoid that；(2) there are destructions to catalyst for the liquor ammoniae fortis of Ammoximation reaction, influence catalyst company
Continue stable recycled.
Summary of the invention
It is a kind of through the new of in-situ preparation ammonia synthesis oxime the purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, providing
Technique.
To achieve the above object, the present invention adopts the following technical solutions:
A kind of new process through in-situ preparation ammonia synthesis oxime, ammonium salt and strong base-weak acid salt in-situ preparation ammonia, then in titanium silicon
Under molecular sieve catalytic, react to obtain oxime with ketone, hydrogen peroxide.
Preferably, it comprises the concrete steps that: the aqueous solution of ketone, Titanium Sieve Molecular Sieve and ammonium salt, heating being added into reaction vessel
To 50~70 DEG C, the aqueous solution of strong base-weak acid salt is added, until reaction solution pH=10~11, are added dropwise hydrogen peroxide, after the completion of charging
The reaction was continued 1~2 hour, is cooled to room temperature, be filtered to remove Titanium Sieve Molecular Sieve to get.
It is further preferred that the mass concentration of the aqueous solution of ammonium salt is 5%, the mass concentration of the aqueous solution of strong base-weak acid salt
It is 20%.
It is further preferred that ketone, ammonium salt, strong base-weak acid salt and hydrogen peroxide molar ratio be 1:1:0.52~0.57:1.05
~1.3.
It is further preferred that the quality of Titanium Sieve Molecular Sieve is the 1~3% of reaction solution gross mass.
It is further preferred that the ketone is selected from acetone, butanone or cyclohexanone.
It is further preferred that the ammonium salt is selected from ammonium sulfate, ammonium chloride or ammonium acetate.
It is further preferred that the strong base-weak acid salt is selected from sodium carbonate or potassium carbonate.
It is further preferred that the aqueous solution of ammonium salt and the feed time of hydrogen peroxide are 2~3 hours.
It is further preferred that the Titanium Sieve Molecular Sieve is TS-1 type molecular sieve.
It is further preferred that the mass concentration of hydrogen peroxide is 27.3%.
Beneficial effects of the present invention:
The present invention uses ammonium salt and strong base-weak acid salt in-situ preparation ammonia, then with ketone, hydrogen peroxide through titanium molecular sieve catalysis
Oxime is obtained, so that material reaction is more complete, the selectivity of generated in-situ this Quantitative yield of amino, oxime is high.This method solve
The problem that by-product is more in oximation reaction and catalyst service life is short, provides a kind of new method for oximation reaction.The synthesis
Technique has oximation reaction simple, and reaction condition is mild, and by-product is few, product yield height and environmentally friendly feature.This hair
Bright synthetic method is simple, and aftertreatment technology is easy, has very strong operability and repeatability, is convenient for industrial metaplasia
It produces.
The present invention replaces direct plungeing into ammonia using generated in-situ ammonia, both ensure that the basicity of system, and the utilization rate of ammonia >=
98%；And reducing the generation of macromolecular by-product, catalyst service life greatly prolongs, and reaches fresh catalyst after activated
The catalytic activity of agent.
Detailed description of the invention
Fig. 1 is the product gas phase chromatogram of embodiment 1；
Fig. 2 is the product hydrogen spectrogram of embodiment 1.
Specific embodiment
The present invention will be further elaborated with reference to the accompanying drawings and examples, it should which explanation, following the description is only
It is not to be defined to its content to explain the present invention.
Reaction equation of the invention is as follows:
Or
R therein1For methyl, R2For methyl or ethyl.
Embodiment 1:
The aqueous solution of 36g butanone (0.5mol), the ammonium chloride that 535g mass concentration is 5% are added into flask
(0.5mol), 2% catalyst TS-1, turn on agitator is transferred to suitable stirring rate.Temperature is gradually increased to 60 DEG C, simultaneously
The aqueous solution of the sodium carbonate (0.275mol) of 145.75g20% and 27.3% hydrogen peroxide 65.4g (0.525mol) is added dropwise, is added dropwise
Time 3h；After dripping, the reaction was continued, and 2h is cooled to room temperature after reaction, catalyst is filtered out, through gas chromatographic analysis
Obtain diacetylmonoxime 43.4g, yield 99.7%.
Embodiment 2~3:
Butanone replaces with acetone or cyclohexanone, remaining is the same as embodiment 1.It is measured through gas phase, product acetoxime and cyclohexanone
Yield is respectively 99.6% and 99.9%.
Embodiment 4~8:
It is identical as the operating procedure of 1 synthesizing butanone oxime of embodiment and operating condition, the difference is that strong base-weak acid salt and ammonium salt
It is different.It is measured through gas phase analysis, the yield of diacetylmonoxime is shown in Table 1.
The diacetylmonoxime yield of 1. embodiment 4~8 of table
| The ammonium salt of mass fraction 5% | The strong base-weak acid salt of mass fraction 20% | Yield/% | |
| Embodiment 4 | Ammonium chloride | Potassium carbonate | 99.4 |
| Embodiment 5 | Ammonium sulfate | Sodium carbonate | 99.8 |
| Embodiment 6 | Ammonium sulfate | Potassium carbonate | 99.5 |
| Embodiment 7 | Ammonium acetate | Sodium carbonate | 99.6 |
| Embodiment 8 | Ammonium acetate | Potassium carbonate | 99.5 |
Embodiment 9~11:
It is identical as the operating procedure of 1 synthesizing butanone oxime of embodiment and operating condition, the difference is that strong base-weak acid salt additional amount
It is different.The molar ratio of sodium carbonate and ammonium chloride is respectively 0.52,0.55,0.57, is measured through gas phase analysis, diacetylmonoxime yield difference
It is 92.5%, 99.7%, 99.7%.
Embodiment 12:
The aqueous solution of 36g butanone (0.5mol), the ammonium chloride that 535g mass concentration is 5% are added into flask
(0.5mol), 1% catalyst TS-1, turn on agitator is transferred to suitable stirring rate.Temperature is gradually increased to 60 DEG C, simultaneously
The aqueous solution for the sodium carbonate (0.275mol) that mass concentration containing 147.5g is 20% and 27.3% hydrogen peroxide 65.4g is added dropwise
(0.525mol), time for adding 2h；After dripping, the reaction was continued, and 1h is cooled to room temperature after reaction, filters out catalyst,
Diacetylmonoxime 39.5g, yield 90.7% are obtained through gas chromatographic analysis.
Embodiment 13:
The aqueous solution of 36g butanone (0.5mol), the ammonium chloride that 535g mass concentration is 5% are added into flask
(0.5mol), 3% catalyst TS-1, turn on agitator is transferred to suitable stirring rate.Temperature is gradually increased to 60 DEG C, simultaneously
Be added dropwise mass concentration containing 147.5g be 20% sodium carbonate 0.275mol) aqueous solution and 27.3% hydrogen peroxide 65.4g
(0.525mol), time for adding 3h；After dripping, the reaction was continued, and 2h is cooled to room temperature after reaction, filters out catalyst,
Diacetylmonoxime 43.4g is obtained through gas chromatographic analysis, yield 99.6%,
Embodiment 14:
The aqueous solution of 36g butanone (0.5mol), the ammonium chloride that 535g mass concentration is 5% are added into flask
(0.5mol), 3% catalyst TS-1, turn on agitator is transferred to suitable stirring rate.Temperature is gradually increased to 60 DEG C, simultaneously
The aqueous solution for the sodium carbonate (0.275mol) that mass concentration containing 147.5g is 20% and 27.3% hydrogen peroxide 81.0g is added dropwise
(0.65mol), time for adding 3h；After dripping, the reaction was continued, and 2h is cooled to room temperature after reaction, filters out catalyst,
Diacetylmonoxime 41.4g, yield 95.2% are obtained through gas chromatographic analysis, reaction by-product increased significantly.
Comparative example
36g butanone, 10g TS-1 are added into flask, turn on agitator is transferred to suitable stirring rate.Temperature gradually rises
To 60 DEG C, while the hydrogen peroxide 65.4g, time for adding 3h of 25% ammonium hydroxide 34g and 27.3% is added dropwise；After dripping, continue anti-
It answers 2h, after reaction, be cooled to room temperature, filters out catalyst, obtain diacetylmonoxime 36.3g through gas chromatographic analysis, yield is
83.5%, the utilization rate of ammonia is only 83.5%.
It compared with comparative example, by the method for embodiment 1~14, is not only able to successfully prepare oxime, and product yield is high,
Utilization rate >=98% of ammonia.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, based on the technical solutions of the present invention, those skilled in the art are not needed to make the creative labor and can be done
Various modifications or changes out are still within protection scope of the present invention.
Claims (4)
1. a kind of technique through in-situ preparation ammonia synthesis oxime, which is characterized in that ammonium salt and strong base-weak acid salt in-situ preparation ammonia, then
Under titanium molecular sieve catalysis, react to obtain oxime with ketone, hydrogen peroxide；
It comprises the concrete steps that: the aqueous solution of ketone, Titanium Sieve Molecular Sieve and ammonium salt being added into reaction vessel, is warming up to 50~70 DEG C,
It is passed through strong base-weak acid salt and hydrogen peroxide, the reaction was continued after the completion of charging 1~2 hour, is cooled to room temperature, and is filtered to remove titanium silicon molecule
Sieve to get；
The ketone is selected from acetone, butanone or cyclohexanone；
The ammonium salt is selected from ammonium sulfate, ammonium chloride or ammonium acetate；
The strong base-weak acid salt is selected from sodium carbonate or potassium carbonate.
2. a kind of technique through in-situ preparation ammonia synthesis oxime according to claim 1, which is characterized in that ketone, ammonium salt, highly basic
The molar ratio of salt of weak acid and hydrogen peroxide is 1:1:0.52~0.57:1.05~1.3.
3. a kind of technique through in-situ preparation ammonia synthesis oxime according to claim 1, which is characterized in that Titanium Sieve Molecular Sieve
Quality is the 1~3% of reaction solution gross mass.
4. a kind of technique through in-situ preparation ammonia synthesis oxime according to claim 1, which is characterized in that the titanium silicon molecule
Sieve is TS-1 type molecular sieve.
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| CN101560601A (en) * | 2009-05-18 | 2009-10-21 | 中南大学 | Method for improving zinc extraction yield in ammonia solution |
| CN103252252A (en) * | 2013-04-24 | 2013-08-21 | 华东师范大学 | Preparation method of non-binder titaniferous mercerizing molecular sieve catalyst |
| CN103709065A (en) * | 2014-01-04 | 2014-04-09 | 河北工业大学 | Resource utilization method for low value-added ammonium chloride |
| CN103772223A (en) * | 2014-01-10 | 2014-05-07 | 万华化学集团股份有限公司 | Method for preparing 2-amino-2-methyl-1-propionic ester |
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| CN1706818A (en) * | 2005-04-04 | 2005-12-14 | 浙江新宇化工有限公司 | Aldoxime or ketoxime preparing process |
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| CN101560601A (en) * | 2009-05-18 | 2009-10-21 | 中南大学 | Method for improving zinc extraction yield in ammonia solution |
| CN103252252A (en) * | 2013-04-24 | 2013-08-21 | 华东师范大学 | Preparation method of non-binder titaniferous mercerizing molecular sieve catalyst |
| CN103709065A (en) * | 2014-01-04 | 2014-04-09 | 河北工业大学 | Resource utilization method for low value-added ammonium chloride |
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